US2940851A - Sensitization of photographic emulsions - Google Patents

Sensitization of photographic emulsions Download PDF

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US2940851A
US2940851A US699197A US69919757A US2940851A US 2940851 A US2940851 A US 2940851A US 699197 A US699197 A US 699197A US 69919757 A US69919757 A US 69919757A US 2940851 A US2940851 A US 2940851A
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emulsion
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Dorothy J Beavers
Charles V Wilson
James L Graham
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US699197A priority patent/US2940851A/en
Priority to US699198A priority patent/US2944898A/en
Priority to DEE16772A priority patent/DE1110520B/de
Priority to DEE16773A priority patent/DE1110521B/de
Priority to FR780270A priority patent/FR1221622A/fr
Priority to GB3830858A priority patent/GB911501A/en
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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
    • C07D213/06—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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances

Definitions

  • This invention relates to the sensitization of photographic silver halide emulsions with certain quaternary ammonium salts, e. g., pyridinium and quinolinium salts.
  • Emulsions containing the compounds of the invention are appreciably more stable than emulsions containing the mentioned quaternary compounds. Accordingly, upon the aging of emulsions containing the new sensitizing agents, less fog is developed and the emulsion speed is maintained. Also, photographic emulsions containing the new quaternary nitrogen compounds maintain their speed over a wider range of development conditions than do emulsions sensitized with previously known alkylenebis-pyridinium salts such as decamethylene-l,10-bispyridinium perchlorate.
  • emulsions containing the latter compound as a sensitizing agent can be expected to lose an appreciable amount of speed when developed with a developing solution of high sulfite content of the order of 100 grams of anhydrous sodium sulfite per liter, whereas the emulsion speed is maintained in such developers when the emulsion is sensitized with the quaternary salts of the present invention.
  • the first development step with the usual Metol-hydroquinone developer produces less fog than when the emulsions are sensitized with other quaternary salts such as that of the above Carroll invention.
  • the quaternary salt sensitizing agents of the invention are bis-quaternary salts having the following general formulas:
  • I QRCONH(A),, NHCOR'Q' and II QRCONHAQ' where Q and Q represent the same or different organic radicals containing quaternary nitrogen atoms such as trialkyl ammonium salt radicals and cyclammoniumsalt radicals, e.g., pyridinium salt radicals or quinolinium salt radicals, R and R represent the same or different radicals, which may be alkylene, such as (CH and including a carbon chain separated by other atoms such as O or S, 2)n 2)n' or 2)n 2)nb n and n' being integers of from about 1 to 10.
  • the total chain length of R and R must be such that the number of atoms in the linear chain joining Q to Q does not exceed about 30.
  • atoms as used herein refers solely to the actual elements that compose the chain and not to any groups that these elements may carry. For example, --(CH is considered to be a IO-atom chain, the hydrogen atoms being disregarded;
  • a compound of the above structure wherein the chain contains 34 atoms has been found not to be useful as a sensitizing agent.
  • compounds having less than about 14 atoms in the chain are not very useful sensitizing agents, the sensitizing activity of the compounds decreasing rapidly in compounds having less than about 14 or more than about 30 atoms in the linear chain connecting Q to Q.
  • the compounds contain from about 14 to about 30 atoms in the chain.
  • group A represents a linear chain of one or more atoms of carbon which may or may not contain sulfur, oxygen or nitrogen as an intermediate linkage. Since n represents the positive integers 1 or 2,
  • tween Q and Q contains from about 14 to about 30 'atoms.
  • the quaternary nitrogen compounds obtained as the halide salts are preferably converted to inert salts such as the perchlorate as illustrated in the syntheses hereafter.
  • X represents a halogen atom, e.g., chlorine, bromine or iodine or alkyl or aryl sulfonate ester; R, R, A and n, Q and Q have the significance given above.
  • Representative bis-quaternary salts of this type are synthesized as follows:
  • COMPOUND VI w-Bromocaproic acid w-Bromocapronitrile, 202 g. (1.15 mole), 350 ml. of 48% hydrobromic acid and 350 ml. of glacial acetic acid were refluxed vigorously for fifteen hours.
  • the product was diluted with 500 m1. of ice water and extracted three times with 500 ml. portions of ether. The solvent was removed on the steam bath and the residue stripped under reduced pressure to remove any acetic acid which may have been extracted along with the product.
  • the 216 g. of crude oil was fractionated under vacuum to yield 181 g. (81.5% yield) of a colorless oil, B.P. 120-140/ 1.2 mm. which solidified to white platelets M.P. 27-29".
  • the dibromide is dissolved in a minimum of methanol, filtered, ether added to the cloudpoint, and the solution chilled in a Dry Ice acetone bath. With vigorous scratching a crystalline solid of excellent melting point is obtained.
  • the analytical sample was obtained as white needles from acetone and melted at l10-1l2.5.
  • the oil was dissolved in 500 ml. of methanol in a flask equipped with an efiicient stirrer.
  • a solution of 95.0 g. (0.68 mole) of sodium perchlorate monohydrate in 500 ml. of acetone was added and the thick slurry heated for one-half hour on the steam bath.
  • the sodium bromide which had precipitated was filtered off and the solution concentrated to about 21-300 ml. volume.
  • Acetone, 300 ml. was added and the mixture heated.
  • the sodium bromide which precipitated was filtered off.
  • the solution was chilled in a Dry-Ice acetone bath and with vigorous scratching, dry ether was slowly added to the cloud point. The scratching was continued until a solid precipitate appeared, or if an oil appeared, the excess ether was removed, the solution chilled and the agitatediorJS minutes.
  • Oneppound of sodium chloride was added to -the-resulting grey liquid slutry and the mixture stirred -vigorously with two 2"1.portions of-hot benzene, thebenzene layers: being decanted each time.
  • the benzene was removed r' from .the -extracts gorrtheistearn bath under. vacuum leaving 129 g.
  • the oil was dissolvedjin 500 ml. of methanohand withl eflicient sti'" g a solution of182-g. (1.30 mole;
  • bromide formed a thick slurry.
  • the 'solu-' tion was now concentrated to about 400' ml. andthis sticky residue heated'andslurried with one l. of acetone.
  • COMPOUND XVH Ethyl N-w-bromocaproylglycinate
  • 19.5 g. (0.10 mole) of w-bromocaproic acid and 12.9 g. (0.10 mole) of carbethoxymethyl isocyanate (mildly exothermic) was heated on the steam bath under anhydrous conditions for six hours. An evolution of carbon dioxide was evident during the reaction. A yellow oil resulted which was dissolved in 50 ml. of dry ether, cooled, and petroleum ether added slowly. A white crystalline solid weighing 18.4 g. (65.7 percent) and melting at 46.548.5 was filtered from the mixture.
  • the analytical sample of the ester was obtained as matted white needles from ether-petroleum ether, melting point 46.5-48.5
  • N-w-bromocaproylglycz'ne N-w-bromocaproylglycine ethyl ester was prepared as above from 52 g. (0.27 mole) of w-bromocaproylglycine and 34.4 g. carbethoxymethyl isocyanate (0.27 mole) and used without further purification for the hydrolysis.
  • the pale yellow ester was dissolved in 100 ml. methanol and hydrolyzed by slowly adding a solution of 21.2 g. (0.53 mole) sodium hydroxide in 22 ml. of water. The temperature was not allowed to rise above 50 during the addition. After one-half hour, the solution was poured into a large volume of ether, precipitating the sodium salt. The White solid weighed 86 g. (contained some NaOH) and melted cloudy at 174177.
  • the powder was dissolved in 250 ml. of methanol, filtered, and crystallized; melting point -175 softening at 150. A recrystallization from ethanol gave 10.3 g. (41 percent) of white powder of melting point -178 (softens at 160).
  • the gum was dissolved in 25 ml. of methanol and a solution of 2.1 g. (0.015 mole) of sodium perchlorate monohydrate in 50 ml. of acetone added. The solution was heated until only 20 ml. of a slurry remained and the precipitated sodium bromide filtered off.
  • the product was precipitated from ethanol-ether as a sticky white solid when chilled in a Dry Ice-acetone bath. This sticky solid was recrystallized from methanolacetone as a Wax which when triturated with ether turned to 2.0 g. of a white solid of melting point 90100 dec. (38 percent).
  • a high-speed bromoiodide emulsion wasprepared, chemically sensitizedwith sulfur and gold; compounds and-optically sensitized with'a cyanine dye.
  • the amounts of the bisquaternary nitrogen compounds-shown in Table 1 below were added to samples of-theemulsion alone and *together with an azainde'ne stabilizing agent; The emulsionv samples were thencoated; exposed'on. a sensito'meteriand developed-for' S -minutes at 68 F. .inithe developer givenabelow: The speed, gamma and'fogvalues obtained by sensitometric evaluation of the-:developed samples" are also .sh'ownririthe table.
  • Test- 90 F 32 C te in was carried out as EX 1 1 th fr m SOdll-llll hexametaphosphate grams 2.0 g m amp 6 upon es N-methyl p-aminophenol sulfate ..do.. 6.0 coated emulsion samples and other samples of each emul- Sodium sulfite desiccated do 50 0 o men were incubated for 1 week at 120 F. and 50 per- Hydmquinone 64) cent relative humidity. Still other samples of each Sodium carbonate, monohydrated 3 5 0 emulsion were stored under room conditions 78 F.
  • EXAMPLE 6 The use of the bis-quaternary salts of the invention in color photography is illustrated in this example.
  • a sulfur and gold sensitized gelatino silver bromoiodide emulsion was ripened to maximum sensitivity.
  • an optical sensitizing dye that extended the light sensitivity to 6000-7000 A. and a hydrophobic cyan color former suitably dispersed in a high boiling organic solvent.
  • a portion of this liquid emulsion received no further treatment; to another portion was added one of the compounds described below. Both portions were coated on film support, and the dry films were exposed to red light in an intensity scale sensitometer.
  • the exposed films were processed in reversal Color Process 1 and in the 5248 Negative Color Process 2 with the results shown in the following table. Color Process 2 was carried out as described by Hanson and Kisner JSMPTE, 61, 667-701 (1953) for Color Negative Film, type 5248 involving the steps of color development,
  • the color developing solution above had the following composition:
  • the silver bleaching solution above had the following. composition:
  • Potassium bromide do Determined by measuring the shift of the reversal dye curve on the log E axis at a given density below maximum density.
  • EXAMPLE 7 A high-speed bromoiodide emulsion chemically sensitized with sulfur and gold compounds and optically sensitized with a cyanine'fidyewas-providedr Tcr'various' mg, (3) the second digestion or after-ripening;-to olgvtairi increased, sensitivity (Mees, ,The Theory of, the Photo: graphic Process,-1942,,page'3).
  • the sensitizing agents may be added 'ataiiy 'stage,,preferably after the final. digestion.
  • the emulsions arechemically sensitizedbyany of the accepted procedures in addition to sensitizing with the bis-quaternary salts of the invention.
  • a stabilizing agent into the emulsion sensitized'with'the bis-quaternary salts of-the invention .towredu'ce fogitoj'normaljlevels'l 'Azaindenes particularlysuib able forthis purpose are those described the patrol et al'; U.S. 'patent application Serial'No s. 627,135 and 627; 186;,file'cl- Dec. 10, 195 6,1- foneiample-fthe' following: 5-
  • the emulsions may also be treated with salts of the noble mans such as ruthenium, rhodium, palladium, iridium and platinum, all of which belong to group VIII of the periodic table of'elements and have anatomic weight greater than 100.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for'sensitizing:
  • emulsions may also be-chemically 'sensitized with. gold salts asrdescribed inwalle'r" and-D'odd-KJLS. Patent.
  • Patent 2,487,850 polyamines such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698), polyamines such as spetmine (Lowe and Allen U.S. Patent 2,521,925), or bis-(*fl-anrinoethyl) sulfide and'rits waten solubleisalts (Lowe andJones; U.S;1Patent-2,521,926); v.
  • Other compounds useful:for-,suppressingJthe-iogdcivl: of the emulsion sensitized with the bis-quaternary;:con'1-;-'v pounds of the invention include the mercury compounds of Allen et a1.
  • the chemical-z sensitizing agents tangl other addenda 21 which we have described may; be used in valfiqnskindsoi photographic emulsions, e.g., various silver salts may be 17 used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the dispersing agent for the silver halide may be gelatin or other hydrophilic material such as collodion, albumin, cellulose derivatives or synthetic resins.
  • the coupler-containing emulsions sensitized as described with the bis-quaternary salts are adapted particularly for use in color photography, they Will ordinarily comprise the emulsion layers of multilayer color films which emulsion layers are customarily difierentially sensitized to the primary regions of the visible spectrum and contain coupler compounds producing dye images of colors complementary to the sensitivity of the emulsion layers.
  • one or more of the differentially sensitized emulsion layers may be sensitized with the bis-quaternary salts, and in a typical example emulsions sensitized to the red, green and blue regions of the spectrum are superimposed on the support in that order and contain cyan, magenta and yellow color-forming coupler compounds respectively.
  • a yellow filter layer is advantageously interposed between the blue and greensensitive emulsion layers.
  • the emulsion layers sensitized with the bis-quaternary salts of the invention may contain coupler compounds they can be readily processed by well known methods to yield color negatives directly or positive images by means of well known reversal processes. That is, after initial exposure of the emulsion to a subject a developer of the p-phenylene diamine type will produce a colored image negative in respect to the subject. Likewise, if development of the emulsion layer is first carried outwith a non-color-forming developer followed by reversal exposure of the residual silver halide and then color development, a colored positive is obtained as described in the examples above.
  • the coupler compounds used in the emulsion layers sensitized with the bis-quaternary salts are any of the well known compounds which combine with the oxidation product of primary aromatic amino (p-phenylene diarnines) silver halide color developing agents to form dyes, for example, the phenolic couplers of U.S. Patents 2,266,- 452, 2,362,598, 2,589,004, 2,474,293, 2,521,908, 2,423,730 and Fierke U.S. patent application 476,561; the pyrazolone couplers of U.S.
  • the emulsions may contain colored color-forming couplers as described in U.S. Patents 2,521,908, 2,706,- 684, 2,455,169, 2,694,703, 2,455,170 and 2,453,661.
  • the couplers may be dispersed in the emulsion layers by means of an oily coupler solvent according to the methods of U.S. Patents 2,304,940 and 2,322,027; However, if as may be the case, the couplers contain solubilizing groups such as SO H groups which render the couplers soluble in alkaline solution, the oily coupler solvent may be dispensed with and the couplers can be added to the emulsion from aqueous solutions as their alkali metal salts.
  • solubilizing groups such as SO H groups which render the couplers soluble in alkaline solution
  • p e n positive integers or. from about 1 to 10 there being from about 14 to, about '30 at ms p e nt in he h rtes l nea hain of atom i k said quaternary nitrogen atoms.
  • alkylcne groups linked directly to the quaternary nitrogen atoms "of said radicals, A represents an alkylene group of from about 1 to carbon atoms, there being from about 14 to about 30 atoms present in the shortest-linear'chain of atoms linking said quaternaryfnitrogen atoms.
  • a photographic silver halide emulsion containing the compound 12,15-diaza-11,16'- dioxohexacosane- 1,26- bis(pyridini1im perchlorate). 8. A photographic silverhalide emulsion containing the compound, 12,19-diaza- 11,20 dioxotriacontane-1',30 bis(pyridinium perchlorate). l J 1 9. The emulsion of claim 1 furthefcontaining a coupler compound reactive with the'oxidation products of a p-phenylcne diamine silver halide devcloping agent to forma'diei' i 10. The emulsion of claim 2 further containing a coupler compound reactive with the oxidation products of a p-phenylene diamine silver halide developing agent to form a dye.
  • a method for increasing the speed of'a silver halide '5'20 emulsion which comprises developing said emulsionin the presence of a quaternary ammonium salt having a general formula of the class consisting of V QRCQNH(A) NHCOR'Q' wherein Q and Q each represent radicals of the class consisting of wherein R R and R represent lower alkyl groups, Z represents the atoms necessary to complete a heterocycliclnucleusof the class consisting of pyridinium and quinolinium,-R and R each represent alkylene groups linked directly to the quaternary nitrogen atoms of said radicals,'n represents a positive integer of from 1 to 2, A represents a member of the class consisting of 2)n' 2)n' n" V z)n- N a)a" 2)n"- I-( a)n' z)n" -'(CH,) 'COO(CH V z)nz)n'" cH ),,.NHco
  • n and 11 represent ,positive integers of from about 1 to 10, there being firom about 14 to about 30 atoms present in the shortest linear chain of atoms linking said quaternary nitrogen atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
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US699197A 1957-11-27 1957-11-27 Sensitization of photographic emulsions Expired - Lifetime US2940851A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US699199A US2940855A (en) 1957-11-27 1957-11-27 Sensitization of photographic emulsions
US699197A US2940851A (en) 1957-11-27 1957-11-27 Sensitization of photographic emulsions
US699198A US2944898A (en) 1957-11-27 1957-11-27 Sensitization of photographic emulsions
DEE16772A DE1110520B (de) 1957-11-27 1958-11-26 Verfahren zum Entwickeln, besonders Farbentwickeln, belichteter photo-graphischer Halogensilberemulsionsschichten und photographisches Material zur Durchfuehrung des Verfahrens
DEE16773A DE1110521B (de) 1957-11-27 1958-11-26 Verfahren zum Entwickeln, besonders Farbentwickeln, belichteter photo-graphischer Halogensilberemulsionsschichten und photographisches Material zur Durchfuehrung des Verfahrens
FR780270A FR1221622A (fr) 1957-11-27 1958-11-27 Nouvelle émulsion photographique sensibilisée et procédé pour accroître la sensibilité des émulsions photographiques
GB3830858A GB911501A (enrdf_load_stackoverflow) 1957-11-27 1958-11-27

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US699197A US2940851A (en) 1957-11-27 1957-11-27 Sensitization of photographic emulsions
US699198A US2944898A (en) 1957-11-27 1957-11-27 Sensitization of photographic emulsions

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers
US3062646A (en) * 1959-03-06 1962-11-06 Eastman Kodak Co Sensitization of silver halide emulsions with macrocyclic compounds
US3189457A (en) * 1961-09-11 1965-06-15 Eastman Kodak Co Sensitized photographic emulsions containing quaternary ammonium compounds
US3212899A (en) * 1961-08-17 1965-10-19 Eastman Kodak Co Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations
US3275440A (en) * 1963-08-12 1966-09-27 Metalphoto Corp Process for developing photosensitized anodized aluminum plates
US3717560A (en) * 1972-05-05 1973-02-20 Hercules Inc Modification of ethylenically unsaturated polymers with polyfunctional quaternary amidoximidinium salts
US3772021A (en) * 1969-10-09 1973-11-13 Fuji Photo Film Co Ltd Process for the development of silver halide light-sensitive material
US3878220A (en) * 1972-05-05 1975-04-15 Hercules Inc Polyfunctional quaternary amidoximidinium salts
US3893862A (en) * 1973-09-24 1975-07-08 Eastman Kodak Co Reduced pyridine compounds
US4135931A (en) * 1976-08-27 1979-01-23 Fuji Photo Film Co., Ltd. Method of image formation
US4247476A (en) * 1977-06-10 1981-01-27 Ciba-Geigy Corporation Polymeric quaternary ammonium salts containing specific cationic recurring units

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3046134A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions with polymeric compounds containing a plurality of sulfur atoms
US3106468A (en) * 1961-11-28 1963-10-08 Eastman Kodak Co Hardeners for gelatin
US3666792A (en) * 1969-10-13 1972-05-30 Wisconsin Alumni Res Found Polymeric tetrahaloterephthalate esters
FR2257580B1 (enrdf_load_stackoverflow) * 1974-01-10 1977-06-10 Kodak Pathe
US6130248A (en) * 1996-12-30 2000-10-10 Bar-Ilan University Tricarboxylic acid-containing oxyalkyl esters and uses thereof
US5939455A (en) * 1997-03-11 1999-08-17 Beacon Laboratories, Inc. Therapeutic augmentation of oxyalkylene diesters and butyric acid derivatives
US6030961A (en) * 1997-03-11 2000-02-29 Bar-Ilan Research & Development Co., Ltd. Oxyalkylene phosphate compounds and uses thereof
US6110970A (en) * 1997-03-11 2000-08-29 Beacon Laboratories, Inc. Nitrogen-containing oxyalkylene esters and uses thereof
US6110955A (en) * 1997-03-11 2000-08-29 Beacon Laboratories, Inc. Metabolically stabilized oxyalkylene esters and uses thereof
US6124495A (en) * 1997-03-11 2000-09-26 Beacon Laboratories, Inc. Unsaturated oxyalkylene esters and uses thereof
US6043389A (en) * 1997-03-11 2000-03-28 Mor Research Applications, Ltd. Hydroxy and ether-containing oxyalkylene esters and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2288226A (en) * 1940-02-29 1942-06-30 Eastman Kodak Co Photographic emulsion
US2419975A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Increasing speed and contrast of photographic emulsions
US2784090A (en) * 1952-11-08 1957-03-05 Eastman Kodak Co Stabilization of emulsions sensitized with onium compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE466375A (enrdf_load_stackoverflow) * 1939-03-30

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2288226A (en) * 1940-02-29 1942-06-30 Eastman Kodak Co Photographic emulsion
US2419975A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Increasing speed and contrast of photographic emulsions
US2784090A (en) * 1952-11-08 1957-03-05 Eastman Kodak Co Stabilization of emulsions sensitized with onium compounds

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers
US3062646A (en) * 1959-03-06 1962-11-06 Eastman Kodak Co Sensitization of silver halide emulsions with macrocyclic compounds
US3212899A (en) * 1961-08-17 1965-10-19 Eastman Kodak Co Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations
US3189457A (en) * 1961-09-11 1965-06-15 Eastman Kodak Co Sensitized photographic emulsions containing quaternary ammonium compounds
US3275440A (en) * 1963-08-12 1966-09-27 Metalphoto Corp Process for developing photosensitized anodized aluminum plates
US3772021A (en) * 1969-10-09 1973-11-13 Fuji Photo Film Co Ltd Process for the development of silver halide light-sensitive material
US3717560A (en) * 1972-05-05 1973-02-20 Hercules Inc Modification of ethylenically unsaturated polymers with polyfunctional quaternary amidoximidinium salts
US3878220A (en) * 1972-05-05 1975-04-15 Hercules Inc Polyfunctional quaternary amidoximidinium salts
US3893862A (en) * 1973-09-24 1975-07-08 Eastman Kodak Co Reduced pyridine compounds
US4135931A (en) * 1976-08-27 1979-01-23 Fuji Photo Film Co., Ltd. Method of image formation
US4247476A (en) * 1977-06-10 1981-01-27 Ciba-Geigy Corporation Polymeric quaternary ammonium salts containing specific cationic recurring units

Also Published As

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US2944898A (en) 1960-07-12
FR1221622A (fr) 1960-06-02
DE1110520B (de) 1961-07-06
US2940855A (en) 1960-06-14
DE1110521B (de) 1961-07-06
GB911501A (enrdf_load_stackoverflow) 1962-11-28

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