US3543292A - Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts - Google Patents

Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts Download PDF

Info

Publication number
US3543292A
US3543292A US647324A US3543292DA US3543292A US 3543292 A US3543292 A US 3543292A US 647324 A US647324 A US 647324A US 3543292D A US3543292D A US 3543292DA US 3543292 A US3543292 A US 3543292A
Authority
US
United States
Prior art keywords
parts
bis
isoxazole
photographic
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US647324A
Other languages
English (en)
Inventor
Donald M Burness
Jerome J Looker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3543292A publication Critical patent/US3543292A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • This invention relates to a new class of nitrogen-containing compounds, their ammonium salts, and uses of such materials.
  • this invention relates to the rendering of hydrophilic colloid compositions, capable of forming layers, resistant to the effects of swelling from aqueous solutions.
  • this invention relates to photographic elements comprising a layer hardened by bisisoxazolium salts and having reduced staining properties.
  • these compounds are conveniently used in the form of their ammonium salts which are water-soluble and can be easily incorporated into aqueous compositions comprising carboxyl-containing polymers such as gelatin or synthetic polymers.
  • Such salts can be effectively used in any concentration for hardening purposes, although suitable hardening concentrations are generally in the range of about 1 to about 5 percent, by weight, based on the weight of harden able material such as carboxyl-containing polymer.
  • the hardeners described herein are particularly effective in color photography since their use results in reducing the stain usually exhibited by multiple layer photographic silver halide systems which contain a color coupler and hydrophilic colloid layers.
  • Such layers generally comprise hardenable carboxyl-containing polymers such as gelatin, vinyl polymers, or mixtures thereof.
  • Suitable carboxyl-containing polymers are film-forming and suitable vinyl polymers are exemplified by ethyl-acrylate-acrylic acid polymer (4:1 by weight), butyl acrylate-acrylic acid polymer (9:1 by weight), and the like.
  • the various following examples are illustrative in contrasting the photographic effects of prior art hardening agents in comparison to those agents of the present invention.
  • One embodiment of this invention relates to his heterocyclic compounds comprising two isoxazole rings linked through carbon atoms at ring positions 2, 4, and 5 of said isoxazole rings, each of said rings being unsubstituted in the 3 position.
  • Another embodiment of this invention relates to a his isoxazole or its quaternary salt comprising two isoxazole rings unsubstituted in their 3 positions and linked at their 2, 4, or 5 positions through a divalent aliphatic or aromatic group.
  • each Z is a divalent aliphatic or aromatic radical
  • each R is aliphatic hydrocarbon of 1-4 carbons
  • each R' is alkyl, cycloalkyl, or aryl, provided R is not linked to a ring in the 3 position
  • each n is an integer of from 0 to 2 and each X is an anion.
  • Another embodiment relates to a photographic element comprising a support, and a layer comprised of a carboxyl-containing polymer hardened with a bis isoxazolium salt.
  • Still another embodiment relates to a composition
  • a composition comprising a hydrophilic colloid containing a his isoxazolium salt in hardening concentration.
  • the bis heterocyclic compounds of this invention comprise at least two heterocyclic rings.
  • the hetero atoms in each of these rings are nitrogen and oxygen in the 1-2 position with respect to each other.
  • Suitable linking groups are divalent aliphatic or aromatic groups. Suitable aliphatic groups, including cycloaliphatic groups, can be straight chain or branched and include alkylene, cycloalkylene, and the like. Generally, a linking group contains not more than carbon atoms and includes alkylene groups such as tetramethylene, pentamethylene, hexamethylene, and araylene groups, such as phenylene, and the like.
  • Linking groups are preferably hydrocarbon but such groups can also contain atoms other than carbon, for example, oxygen, sulfur, nitrogen, and the like.
  • the nitrogen atoms in the two isoxazole rings present in the compounds of this invention carry aliphatic substituents, designated as R in the above formulas.
  • Suitable R substituents contain 1-4 carbon atoms and include for example, methyl, ethyl, propyl, butyl, allyl, tertiary butyl, isopropyl, and the like.
  • Each isoxazole ring can carry substituents, designated R in the above formulas.
  • substituents occur at the various available isoxazole ring positions other than 3 and include alkyl, cycloalkyl, and aryl groups as exemplified by methyl, ethyl, hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, and the like.
  • groups can be hydrocarbon or can contain atoms other than carbon and hydrogen, e.g. oxygen or halogen as in hydroxyalkyl or chloroalkyl groups.
  • the anion previously shown as X can be, for example, perchlorate, p-toluenesulfonate, chloride, nitrate, tetrafiuoroborate, or the like. It is most desirable that the anion contributes to the water solubility of the base compound and that the entire radical possesses a negative valence of two.
  • a convenient method for preparing the his isoxazole compounds of this invention comprises reacting an ap limbate hydroxylamine salt, such as hydroxylamine hydrochloride, and a suitable substance comprising two fl-ketoaldehyde moieties, such as p-phenylenebis(diethylamino-propenone), 2,2-phenylenebis-(S-dimethylamino acrolein) and the like, or its equivalent precursor substance in situ.
  • the novel salts of these compounds are prepared by reacting these bis isoxazole compounds with compounds capable of producing the desired anion in a suitable solvent. All such reactions are carried out in the presence of organic solvents at moderate temperatures.
  • the reaction forming the his isoxazole compounds is complete in hours or less but may take as long as 72 hours and the resulting compounds are isolated by conventional procedures.
  • the reactions are not pressure dependent and therefore superatmospheric or subatmospheric pressures are employed.
  • the specific reaction conditions for example, temperature, pressure, and the like, depend upon the particular reactants employed.
  • the compounds described in this application can be used eifectively in combination with hardenable materials in general but are most advantageously used with hydrophilic colloid coating compositions used in preparing photographic elements added either in solution or as addition salts.
  • Specific materials which can be hardened according to the practice of this invention include hardenable carboxyl-containing polymers such as gelatin, binding materials such as colloidal albumin, water-soluble vinyl polymers, cellulose derivatives, proteins, water-soluble poly acrylamides, dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials as exemplified by polymers of alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates, methacrylates, maleic-acid and the like.
  • the hardening agents described herein can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic panchromatic and in frared emulsions, they are also useful in X-ray and other nonoptically sensitized emulsions. They can be added to the emulsions before or after any optically sensitizing dyes which may be used. They are effective in sulfur and gold sensitized silver halide emulsions.
  • Various silver salts can be used as sensitive salts, including, for example, silver bromide, silver iodide, silver chloride, silver chlorobromide silver bromoiodide, or silver chloriodide.
  • Typical supports include those generally employed for photographic elements, as exemplified by cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and related film or resinous materials as well as glass, paper, metal, wood, and the like.
  • Supports such as paper that are coated with a-olefin polymers, particularly polymers of a-olefins containing 2-10 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers, and the like, can also be employed.
  • photographic emulsions and elements can also contain additional additives, particularly those known to be beneficial in photographic emulsions, as exemplified by optical sensitizers, speed increasing materials, other hardeners, plasticizers, and the like.
  • Example 1 .5 ,5 p-phenylene bisisoxazole 3.2 parts of p-diacetylbenzene and 15 parts of ethyl formate by weight are dissolved in parts of benzene. This solution is hten added to a suspension of 6.5 parts of sodium methoxide in 50 parts of benzene at 10 C. The mixture is allowed to warm to 25 C. and is left standing for 16 hours. The benzene is then distilled 01f, and the residue dissolved in methanol, and a solution of 9.8 parts of dimethylamine hydrochloride in methanol is added.
  • Example 3 5,5'- (p-phenylene)bis-N-methylisoxazolium methosulfate
  • a mixture of 2.1. parts of 5,5'-(p-phenylene)bis isoxazole and 50 parts of dimethyl sulfate is heated for one hour on a steam bath.
  • a solid material separate which is washed with ether giving 2.3 parts of 5,5'-(p-phenylene) bis(N-methylisoxazolium methosulfate), M.P. l84 C.
  • Example 4.-5,5'-tetramethylenebis(Z-ethylisoxazolium fluoroborate 5,5-tetramethylenebis(isoxazole) is prepared by known methods, as for example in a process described by A. E. Pohland and W. R. Benson, Chemical Reviews, vol. 66, page 161, 1966, starting with adipyl chloride.
  • Example 5.2,5-dimethylhexane-2,5-diyl-2,2"-bis(5- methylisoxazolium fluoroborate A mixture of 2.9 parts of 2,5-dimethylhexane-2,5-diol, 3.3 parts of S-methylisoxazole, and 7.2 parts of 48 percent fluorobon'c acid is allowed to stand for three days and the solvent is removed. The residue is dissolved in acetone (20 parts) and ether is added. The oil that separates crystallizes on washing with ether and the solid recrystallizes from acetone, 1.65 parts (18 percent), with a melting point of 130-132 C. A form melting at 126-127 C. and having the correct elemental analysis is also obtained.
  • a hot solution of 2.1 parts of 4,4-p-phenylenebis(isoxazole) in 50 parts of 1,2-dichloroethane is added in one portion to a solution of 10 parts of triethyloxonium fluoroborate in 20 palts of the same solvent.
  • the solid, 4,4-p-phenylenebis(N-ethylisoxolium fluoroborate) is collected, 4.4 parts (100 percent), M.P. 241 C., decompose. Recrystallization from acetonitrile gives material melting at 244 C. decompose.
  • Example 7 As previously indicated, the compounds described herein give very good results when used as hardeningagents in photographic applications.
  • the compounds prepared in Examples 2 and 3 are added in various concentrations to separate portions of a high-speed gelatino silver bromoiodide photographic emulsion. Each emulsion sample is coated onto a cellulose acetate film support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. Each film coating is exposed on an Eastman 1B sensitometer, processed for five minutes in Kodak Developer DDK-SO, fixed, washed, and dried. The resistance to swell, relative speed, contrast, and fog are determined and are as follows:
  • Example 7 The procedure of Example 7 is repeated using the compounds prepared in Examples 46.
  • the results obmixture of 67 parts of the perchlorate, 500 parts of chlorotained are as follows:
  • Example 10 TABLE 5 Percent by weight of gelatin Percent swell Hardener
  • Example 11 As already indicated, the hardeners employed in accordance with our invention are particularly useful in photographic emulsions in which color couplers have been incorporated. In contrast to some prior art hardeners, it has been found that the hardeners described herein result in reduced stain with no significant adverse photographic effects. Also no adverse effect upon dye hue or stability of the emulsion has been noted. To illustrate, two separate elements are prepared having the following layer arrangement. The use of the hardener is varied between the two elements as described hereinafter.
  • Layer l.Blue-sensitive silver chlorobromide gelatin emulsion consisting of 98 mole percent bromide plus an acyl acetanilide yellow coupler of the type described in U.S. Pat. 2,875,057.
  • mucochloric acid is the hardener used in all six layers in concentration of 0.54 percent by weight of gelatin and in the other element all six layers contain 1 percent by weight of the hardener of Example 3.
  • the above layers are coated on paper support in the order given, layer 1 being immediately adjacent to the paper.
  • Exposure of the two samples and processing by a color development process used in making color prints indicates the improvement in stain in the case of hardeners in accordance with the invention as compared to an aldehyde type hardener as represented by mucochloric acid.
  • the improvement in stain is shown by the increase in percent of reflectance, measured by a recording spectrophotometer and compared with the sample in which the aldehyde-type hardener has been used.
  • a photographic element comprising a support, and a layer comprised of a carboxyl-containing polymer hardened with a bis isoxazolitun quaternary salt comprising two isoxazole rings unsubstituted in their 3 positions and linked at their 2, 4 or 5 positions through a divalent aliphatic or aromatic group.
  • a photographic element comprising a support, a photographic silver halide, a color coupler, a carboxylcontaining polymer and a his isoxazolium quaternary salt in hardening concentration, said salt comprising two isoxazole rings unsubstituted in their 3 positions and linked at their 2, 4 or 5 positions through a divalent aliphatic or aromatic group.
  • a composition comprising a hydrophilic colloid containing a his isoxazolium quaternary salt in hardening concentration, said salt comprising two isoxazole rings unsubstituted in their 3 positions and linked at their 2, 4 or 5 positions through a divalent aliphatic or aromatic group.
  • composition of claim 8 in which said hydrophilic colloid comprises gelatin.
  • composition of claim 8 in which said hydrophilic colloid comprises gelatin and alkyl acrylate-acrylic acid copolymer.
  • a composition comprising a gelatin silver halide photographic emulsion comprising a his isoxazolium quaternary salt in a hardening concentration, said salt having the formulae:
  • a composition comprising a hardenable carboxylcontaining polymer and a quaternary salt in hardening FIGHTER, Assistant Examiner concentration, said salt comprising two isoxazole rings unsubstituted in their 3 positions and linked at their 2, 4 or 5 positions through a divalent aliphatic or aromatic 10 10 .425; 2 7 group.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US647324A 1967-06-20 1967-06-20 Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts Expired - Lifetime US3543292A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US64732467A 1967-06-20 1967-06-20

Publications (1)

Publication Number Publication Date
US3543292A true US3543292A (en) 1970-11-24

Family

ID=24596510

Family Applications (1)

Application Number Title Priority Date Filing Date
US647324A Expired - Lifetime US3543292A (en) 1967-06-20 1967-06-20 Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts

Country Status (5)

Country Link
US (1) US3543292A (enrdf_load_stackoverflow)
BE (1) BE716824A (enrdf_load_stackoverflow)
DE (1) DE1770239A1 (enrdf_load_stackoverflow)
FR (1) FR1570191A (enrdf_load_stackoverflow)
GB (1) GB1225179A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
WO2008038764A1 (fr) 2006-09-28 2008-04-03 Fujifilm Corporation Écran à émission spontanée, procédé de fabrication d'un écran à émission spontanée, film conducteur transparent, dispositif électroluminescent, électrode transparente de cellule solaire et électrode transparente de papier électronique
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316095A (en) * 1965-10-13 1967-04-25 Eastman Kodak Co Hardeners for incorporated coupler emulsions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3316095A (en) * 1965-10-13 1967-04-25 Eastman Kodak Co Hardeners for incorporated coupler emulsions

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
WO2008038764A1 (fr) 2006-09-28 2008-04-03 Fujifilm Corporation Écran à émission spontanée, procédé de fabrication d'un écran à émission spontanée, film conducteur transparent, dispositif électroluminescent, électrode transparente de cellule solaire et électrode transparente de papier électronique
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Also Published As

Publication number Publication date
GB1225179A (enrdf_load_stackoverflow) 1971-03-17
BE716824A (enrdf_load_stackoverflow) 1968-12-02
FR1570191A (enrdf_load_stackoverflow) 1969-06-06
DE1770239A1 (de) 1972-03-16

Similar Documents

Publication Publication Date Title
US3642908A (en) Vinyl and ether containing sulfones
US2983611A (en) Gelatin compositions containing hardeners
US3137578A (en) Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants
US3880665A (en) Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer
US3301678A (en) Process for stabilizing photographic images with heat
US3397986A (en) Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides
US3232764A (en) Gelatin compositions adapted for the preparation of hardened coatings
US3549377A (en) Method of hardening photographic gelatin-containing layers with non-ionic dichlorotriazinyl amino compounds
US3071465A (en) Fog reduction in silver halide emulsions by 2h-tetrazolium halides
US3042521A (en) Antifoggants and stabilizers for photographic silver halide emulsion
US3543292A (en) Photographic gelatin hardened with bis isoxazole compounds and their quaternary salts
US3909268A (en) Tetrazolium C-oxy-betaine compounds as antifog agents for silver halide photographic emulsions
US2964404A (en) Hardening of gelating with aziridinylsulfonyl compounds
EP0084290B1 (en) Photographic silver halide material containing substituted hydroquinone compounds
CA1146172A (en) Derivatives of 2-hydroxy-naphtalene and use thereof as coupling components in diazotype materials
GB1135112A (en) Linear condensation polymers
JP2557252B2 (ja) ハロゲン化銀写真感光材料
US3026201A (en) Antifoggants and stabilizers for photographic silver halide emulsions
US3671255A (en) Silver halide emulsion fog inhibited with quaternary ammonium,triazole and tetrazaindene compounds
US2948615A (en) Antifoggants and stabilizers for photographic silver halide emulsions
US3625697A (en) Sensitization of light-sensitive silver halide photographic emulsions
US2184303A (en) Photographic color-forming developer and emulsion
US3681372A (en) Bis-isoxazole compounds and their quaternary salts
US3174861A (en) Photographic elements containing bischloroacylamido hardening agents
US3779763A (en) Phenol color couplers