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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
• • 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
  • G03C1/12—Methine and polymethine dyes

Definitions

• This invention relates to photographic emulsions and more particularly to sensitized photographic emulsions.
• polyammonium salts need not be surface-active, and their effect (as in the foregoing case) is generally independent of spectral sensitization and involves no appreciable change in the distribution of spectral sensltivity.
• These polyammonium salts are also effective in low concentrations.
• these polyammonium quaternary salts have an advantage over the aforesaid cationic surface active ammonium salts, in that the polyammonium quaternary salts show little or no tendency to diffuse from the emulsions into the film support upon which the emulsions are coated.
• substantially non-surface active, substantially colorless cyclammonium quaternary salts and certain substantially non-surface active, substantially colorless non-quaternary cyclammonium salts sensitize photographic emulsions.
• these cyclammonium salts increase sensitivity in a manner different from that of the aforesaid surface-activ quaternary ammonium salts, in that the instant salts frequently alter the distribution of spectral sensitivity of spectrally sensitized emulsions.
• the instant salts must ordinarily be employed in much larger concentrations than the aforesaid surface active salts in order to secure maximum eiiects.
• substantially non-surface active we mean no more surface activity than of the order of that encountered with such cyclammonium salts as pyridine c-phenylethyl bromide or a-picoline 'y-phenyl-n-propyl bromide.
• substantially non-surface active, substantially colorless cyclammonium salts in a photographic silver halide emulsion, such as a silver bromide emulsion, a silver chlorobromide emulsion or a silver bromiodide emulsion.
• a photographic silver halide emulsion such as a silver bromide emulsion, a silver chlorobromide emulsion or a silver bromiodide emulsion.
• the eyelammonium salts which we employ have no action on silver chloride emulsions, and silver chloride emulsions are not within the purview of our invention.
• cyclammonium salts we employ cyclammonium quaternary (with no hydrogen atoms on the cyclammonium nitrogen atom) salts, as well as non-quaternary cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitro atom are employed in the formation of a cyclic nucleus.
• Pyridine quaternary salts such as pphenylethyl pyridinium bromide:
• N-alkylpiperidine salts such as N-(fi-phenylethyl)-piperidine bromide:
• the cyclammonium salts which we employ are substantially non-surface active and substantially colorless and contain not more than one quaternary nitrogen atom and contain only carbon and nitrogen atoms in the cyclic nucleus embodying the cyclammonium nitrogen atom and contain no quaternary nitrogen atom linked by a conjugated carbon chain to a ternary nitrogen atom.
• the most effective cyclammonium quaternary salts appear to be (1) those in which the quaternary nitrogen atom is the nitrogen atom of a pyridine nucleus, such as pyridine quaternary salts, quinoline quaternary salts, isoquinoline quaternary salts and benzoquinoline quaternary salts, (2) those in which the quaternary nitrogen atom is the nitrogen atom of a reduced pyridine nucleus, such as quaternary salts derived from N-alkyl piperidines and (3) those in which the quaternary nitrogen atom is the nitrogen atom of a benzimidazole or indazole nucleus.
• the cyclammonium salts employed are aralkyl cyclammonium salts, especially good efiects having been obtained with sphenylethyl and v-phenylpropyl salts.
• the nature of the acid radical of the cylammonium salt is of small import, except that iodides should not be employed in high concentrations.
• the cyclammonium salts may carry substituents, e. g. alkyl, alkoxyl, arylmercapto, carboxylalkyl, halogen, carboxyl or thioalkyl.
• substituents e. g. alkyl, alkoxyl, arylmercapto, carboxylalkyl, halogen, carboxyl or thioalkyl.
• nitro, sulfonic acid or sulfonate groups should be avoided, since such derivatives usually do not exert a desirable effect.
• chlorobromide emulsions In such emulsions, cyclammonium bromides or iodides are undesirable and are advantageously replaced by chlorides or perchlorates.
• the cyclammonium salts are advantageously incorporated in the emulsions in the form of aqueous or methyl alcoholic solutions.
• the salts should be thoroughly distributed throughout the emulsion.
• the quantity of cyclammonium salt which gives th maximum effect will, of course, vary with the nature of the salt and the type of emulsion. Ordinarily this quantity lies between about 0.2 gram to about 4 grams of cyclammonium salt per gram-mole of silver halide in the emulsion. ,The optimum concentration for any particular salt can readily be determined by examining the effect of a series of difierent concentrations.
• the cyclammonium salt can be incorporated in the emulsion before, simultaneously with or after the sensitizing dye, except in the case of cyclammonium perchlorates, when the cyclammonium salt is advantageously incorporated in the emulsion after the sensitizing dye.
• sensitizing dyes in emulsions are, of course, well known to those skilled in the art.
• the dyes are advantageously incorporated in the emulsions in the form of methyl alcoholic solutions.
• Acetone or ethyl alcohol may be employed where the solubility of the sensitizing dye is low in methyl alcohol.
• the sensitizing dye can be employed in any desired concentration. Frequently the optimum concentration (at which greatest sensitivity is conferred) of a sensitizing dye is within the range, 10 mg. to 30 mg. of dye per liter of emulsion containing about 0.25 gram-mole of silver halide.
• the greatest two-fold response (change of distribution of spectral sensitivity and increase of general sensitivity) is obtained with emulsions spectrally sensitized with the oxacarbocyanines, oxathiacarbocyanines, oxaselenacarbocyanines, thiacarbocyanines, selenathiacarbocyanines and selenacarbocyanines.
• a flowable gelat-v ino-silver-halide emulsion containing about 0.23 gram-mole of silver halide was added, with stirring, a methyl alcoholic solution of a sensitizing dye. The dye was thoroughly dispersed throughout the emulsion.
• a sensitized emulsion was then added, with stirring, an aqueous solution of one of our cyclammonium salts, The salt was thoroughly dispsersed throughout the emulsion.
• the resulting emulsion can then be coated, dried and exposed in the usual manner.
• Our cyclammonium salts are advantageously added to the washed, finished emulsions.
• the following table represents the relative effectiveness of several cyclammonium salts. The greater the number of plus signs the greater the efiicacy.
• N-p-phenylethyl piperidinium bromide- N-methyl-N-p-phenylethyl piperidinium cyclammonium quaternary salts which we employ can be prepared by heating heterocyclic nitrogen bases with esters (alkyl salts), e. g., alkyl halides or alkyl-p toluenesulfonates. Ordinarily an excess of the alkyl salt is advantageously employed.
• esters alkyl salts
• alkyl halides or alkyl-p toluenesulfonates Ordinarily an excess of the alkyl salt is advantageously employed.
• an aqueous solution of a quaternary halide or p-toluenesulfonate can be treated with an aqueous solution of a soluble perchlorate, e.
• Hydroxyalkyl quaternary salts are described in United States Patent 2,213,238, dated September 3, 1940. Substituted alkyl quaternary salts are described in United, States Patent 2,231,658, dated February 11, 1941. Benzyl, p-phenylethyl and 'Y- henylpropy1 quaternary salts are described in United States Patent 2,233,511, dated March 4, 1941. Alkylmercaptoand arylmercapto-substituted quaternary salts are described in United States Patent 2,231,- 657, dated February 11, 1941, and in United States Patent 2,117,936, dated May 17, 1938.
• N-phenyl pyridinium chloride can be prepared according to the process described by Zincke in Ann. 333, 329.
• N-phenyl pyridinium bromide can be pre pared from the chloride by treating a concentrated aqueous solution of the chloride with an aqueous solution of potassium bromide.
• Emulsions sensitized with the following dyes have been found to undergo especially useful changes in the distribution of spectral sensitivity with our cyclammonium quaternary salts.
• R, R and R" each represents an alkyl group and X represents an acid radical, especially those dyes wherein R, R and R" each represent an alkyl group of the formula CnH2n+1 wherein n represents a positive integer of from 1 to 2, e. g.
• R, R' and R" each represent alkyl groups and X represents an acid radical, especially those dyes wherein R, R and R" each represent an alkyl group of the formula CnH2n+1 wherein n represents a positive integer of from 1 to 2, e. g., 3,3-diethyl-9-methylselenathiacarbocyanine iodide; 5-chloro-3,3'-diethyl-9-methylselenathiacarbocyanine iodide and 3,3'-diethyl-9-methylselenathiacarbocyanine bromide.
• R and R each represents an alkyl group and X represents an acid radical, especially those dyes where R and R each represents an alkyl group of the formula CnH2n+1 wherein n represents a positive integer of from one to two, e. g., 1,1diethyl-2,2-carbocyanine iodide;
• R, R and R" each represent alkyl groups and X represents an acid radical, especially those dyes wherein R, R and R each represents an alkyl group of the formula CnHZn-l-l wherein n represents a positive integer of from one to 2, e. g., 3,3-diethyl-9-methyloxathiacarbocyanine iodide.
• Our invention is primarily directed to the customarily employed gelatino-silver halide developing-out emulsions.
• the carrier is other than gelatin, e. g., a cellulose derivative or a resinous material, can also be employed.
• Emulsions prepared in accordance with our inventlon can be coated in the usual manner upon any desired support, such as cellulose nitrate support, cellulose acetate support, polyvinyl acetal resin support, glass support, metal support or paper support.
• non-quaternary cyclammonium salts which we employ in practicing our invention can be prepared by heating the appropriate heterocyclic nitrogen base with esters (alkyl salts).
• esters alkyl salts
• N-(fl-phenylethyl) piperidinium bromide it is only necessary to heat piperldine with p-phenylethyl bromide.
• a photographic silver halide emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide emulsions, containing in a concentration of from more than 0.2 gram to about 4 grams per grammole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of cyclammonium quaternary salts and cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitrogen atom are employed in the formation of a cyclic nucleus, said cyclammonium salt containing not more than one quaternary nitrogen atom and containing only carbon and nitrogen atoms in the cyclic nucleus embodying the cyclammonium nitrogen atom, any acid dye in said emulsion being present in a concentration low enough that more than 0.2 gram of cyclammonium salt
• a photographic silver halid developing-out emulsion selected from the group consisting of silver chlorobromide developing-out emulsions, silver bromide developing-out emulsions and silver bromiodide developing-out emulsions, containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion.
• a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of cyclammonium quaternary salts and cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitrogen atom are employed in the formation of a cyclic nucleus, said cyclammonium salt containing not more than one quaternary nitrogen atom and containing only carbon and nitrogen atoms in the cyclic nucleus embodying the cyclammonium nitrogen atom, any acid dye in said emulsion bein present in a concentration low enough that more than 0.2 gram of cyclammonium salt per grammole of silver halide in the emulsion is uncom bined with said acid dye.
• a photographic silver halide developing-out emulsion selected from the group consisting of silver chlorobromide developing-out emulsions, silver bromide developing-out emulsions and silver bromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of cyclammonium quaternary salts and cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitrogen atom are employed in the formation of a cyclic nucleus, said cyclammonium salt containing not more than one quaternary nitrogen atom and containing only carbon and nitrogen atoms in the cyclic nucleus embod
• a photographic gelatino-silver-halide developing-out emulsion selected from the o p consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non surface active, substantially colorless cyclammonium salt selected from the group consisting of cyclammonium quaternary salts and cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitrogen atom are employed in the formation of a cyclic nucleus, said cyclammonium salt containing not more
• a photographic silver halide emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of cyclammonium quaternary salts and cyclammonium salts in which there is one hydrogen atom on the cyclammonium nitrogen atom and but two of the remaining valences of the cyclammonium nitrogen atom are employed in the formation of a cyclic nucleus, said cyclammonium salt containing not more than one quaternary nitrogen atom and containing only carbon and nitrogen atoms in the cyclic nucleus embodying the cyclammonium nitrogen atom and being free from groups having the eifect of
• a photographic silver halide emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide emulsions, spectrally sensitized with nonacidic sensitizing dye containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of pyridine and quinoline quaternary salts, said cyclammonium salt containing not more than one quaternary nitrogen atom, any acid dye in said emulsion being in a concentration low enough that more than 0.2 gram of cyclammonium salt per grammole of silver halide in the emulsion are uncombined with said acid dye.
• a photographic silver halide developingout emulsion selected from the group consisting of silver chlorobromide developing-out emulsions, silver bromide 'developing-out emulsions and silver bromiodide developing-out emulsions, spectrally sensitized with non-acidic sensitizing dye containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of pyridine and quinoline quaternary salts, said cyclammonium salt containing not more than one quaternary nitrogen atom, any acid dye in said emulsion being in a concentration low enough that more than 0.2 gram of cyclammonium salt per gram-mole of silver' halide in the emulsion are uncombined with said acid dye.
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with non-acidic sensitizing dye containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a substantially non-surface active, substantially colorless cyclammonium salt selected from the group consisting of pyridine and quinoline quaternary salts, said cyclammonium salt containing not more than one quaternary nitrogen atom, any acid dye in said emulsion being in a concentration low enough that more than 0.2 gram of cyclammonium salt per gram-mole of silver halide in the emulsion are uncombined with
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatinosilver-bromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in concentration of from more than 0.2 gram to about 4 grams per grammole of silver halide in the emulsion, a substan-- tially colorless cyclammonium salt selected from the group consisting of pyridine and quinoline quaternary salts, said cyclammonium quaternary salt containing not more than one quaternary nitrogen atom and being free from groups having the effect of nitro, sulfonic acid and sulfonate groups, any acid dye in said emulsion being present in a concentration low enough that more than 0.2
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silverchlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye selected from the group consisting of oxacarbocyanine dyes, thiacarbocyanine dyes, selenacarbocyanine dyes, thiaselenacarbocyanine dyes, oxathiacarbocyaninedyes, oxaselenacarbocyanine dyes and 2,2'carbocyanine dyes, containing in a concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a non-surface active, substantially colorless cyclam
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentration of from than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion a non-surface active, substantially colorless cyclammonium aralkyl quaternary salt selected from the group consisting of pyridine and quinoline aralkyl quaternary salts, said cyclammonium aralkyl quaternary salt containing not more than one quaternary nitrogen atom and being free from groups having the effect of nitro, sulfonic acid and sulfonate groups, any acid dye in
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentraton of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion a non-surface active, substantially colorless cyclammonium pphenylethyl quaternary salt selected from the group consisting of pyridine and quinoline pphenylethyl quaternary salts, said cyclammonium p-phenylethyl quaternary salt containing not more than one quaternary nitrogen atom and being free from groups having the effect of .nitro, sulfonic acid
• acid dye in said emulsion being present in a concentration low enough that more than 0.2 gram of p-phenylethyl cyclammonium salt per gram-mole of silver halide in the emulsion is uncombined in said acid dye.
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye and containing in a concentration of from more than 0.2 gram to about Qgrams per gram-mole of silver halide in the emulsion a non-surface active, substantially colorless cyclammonium yphenyl-n-propyl quaternary salt selected from the group consisting of pyridine and quinoline 'y phenyl n propyl quaternary salts, said cyclammonium -phenyl-n-propyl quaternary salt containing not more than one quaternary nitrogen atom and being free from groups having the effect of
• a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of gelatino-silver-chlorobromide developing-out emulsions, gelatino-silver-bromide developing-out emulsions and gelatino-silverbromiodide developing-out emulsions, spectrally sensitized with a non-acidic sensitizing dye selected from the group consisting of oxacarbocyanine dyes, thiacarbocyanine dyes, selenacarbocyam'ne dyes, thiaselenacarbocyanine dyes, oxathiacarbocyanine dyes, oxaselenacarbocyanine dyes and 2,2'-carbocyanine dyes, containing in a, concentration of from more than 0.2 gram to about 4 grams per gram-mole of silver halide in the emulsion, a non-surface active, substantially
• H CERT] FICATE 0F C0 RREC TI 0N Patent No. 2,55 h86h- November 25, 1915.

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• 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)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

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Cited By (7)

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• 0
  • BE BE467068D patent/BE467068A/xx unknown
• 1942
  • 1942-02-02 US US429282A patent/US2334864A/en not_active Expired - Lifetime
  • 1942-04-28 GB GB5716/42A patent/GB560082A/en not_active Expired
• 1946
  • 1946-06-14 FR FR942831D patent/FR942831A/fr not_active Expired
• 1950
  • 1950-10-02 DE DEE2753A patent/DE857308C/de not_active Expired

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