US2944896A - Process for sensitizing silver halide emulsions - Google Patents

Process for sensitizing silver halide emulsions Download PDF

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Publication number
US2944896A
US2944896A US585146A US58514656A US2944896A US 2944896 A US2944896 A US 2944896A US 585146 A US585146 A US 585146A US 58514656 A US58514656 A US 58514656A US 2944896 A US2944896 A US 2944896A
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Prior art keywords
emulsion
silver halide
sensitivity
mixture
minutes
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Expired - Lifetime
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US585146A
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English (en)
Inventor
Riester Oskar
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Agfa Gevaert NV
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Agfa AG
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    • 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
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds

Definitions

  • the efiect of the glass intercalated between the light source and the emulsion layer is to cut off by far the greatest part of this sensitivity.
  • the main effect of this is seen when the exposure is made with artificial light, because the short-Wavespetra-l zone. thereof is veryslight.- Therefore, with the photographic copying process, only a smalli'pa-rtof 1118 eifectivelight is utilized.
  • R stands-for alkylgsuchias methyl, ethyl, propyl, butyl, amyl, 'alkyl, dfldflQYl,.iSQPIOP1,.-i$0r butyl, isoamyl, cycloalkyl, such as cyclohexyl, ary-l such 2,944,896 HatentedsJuly; 12,1950.
  • radicals. which contain a free carboxylic acid groupysuch' as alkylenecarboxy-i groups as for instance group, organic. radicals'which: contain an. esterified acid groups such as -CH CO0H, CH CH COOH groups which are esterified with aliphatic and cycloaliphatic alcohols such as methyl-, ethyl, cyclohexylalcohol, organic radicals which contain asulfonic. acid group such as alkylensulfonic and groups as for instance propylene-w sulfonic acid, butylene-w sulfonic acid groups, and
  • R and R stand for alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical without nitrogen, such as furyl or thienyL. any- -such:rad-ical..being. substituted in place :of anzappropriatenumber of hydrogen atoms. of the CH groups, the. left; handaring, .onralternatively the I left; hand ring may be :unsubstitutei R and R ,being-the same omdiif'erenhmhilerR, and R3 or R and R may be. joined to form. aring;
  • n awholenumber fr'orni3, to 12;
  • the entire dyestutf molecule can also be multiplied, forexample, bythe. ring nitrogen. atoms being combined with one another by a divalent organic radical, such as for example an alkylene group.
  • a divalent organic radical such as for example an alkylene group.
  • Such dyestufis may be (H2 a Bi and.
  • Imtheseiormulae n, R R R and A have the same significance. as. in the; first. formula, whereasR stands for abivalentorganic radical such as an alkylene group.
  • neutrocyanines are producedlaccording. to the prQQess-ofiGennan Patent 927,043.
  • An additional advantage is their stability with respect to the conventional-emulsion additives, such as stabilisers, wetting agents, fluorescing substances, etc.
  • the sensitisers are added in amounts of for example 3 to mg. per litre. of emulsion, depending on the increase in sensitivity which is desired. It can be added at mega, Hyman)...
  • any desired time for example, as a casting additive to the finished emulsion or already in the final digestion, or the sensitisers are used in the so-called bath process.
  • Example 1 The yellow dyestuff of the following constitution:
  • Sensitization maximum is in the region of 434 me.
  • the dyestuff is prepared as follows: 7
  • 2-piperidone is dissolved in chloroform and treated with excess phosphorpentasulfide at a temperature of 40.
  • the resultant Z-thiopiperidone has the boiling point l84l85 at 13-14 mm.
  • the thiopiperidone is reacted in an alcoholic sodium 'alcoholate solution With methyliodide to form 2-methyl-mercapto-3,4,4,6-tetrahydropyridine, which latter is a liquid of the boiling point 71-79 at 13 mm.
  • Z-methylmercaptotetrahydropyridine and 1 ml. of 'dimethylsulfate are heated with one another, the mixture substantially rises in temperature and reacts vigorously.
  • Example 3 The dyestufi of the following constitution: v
  • the dyestufi is prepared as follows:
  • N-phenyl-Z-thiopyrrolidone-metbiodide which is obtainable from N-phenyl-Z-pyrrolidone by melting with excess phosphorus pentasulfide at 130 C. and reacting the thus obtained thiopyrrolidone with methyliodide.
  • N-ethylrhodanine are mixed and treated with 20 cc. of absolute alcohol and 2 cc. of triethylarnine. The mixture is refluxed on a Water bath for 30 minutes. The dyestufl re-crystallizes upon cooling. It is re-crystallized from 50 cc. of methanol.
  • Example 4 yields an increase of about 6 times in the initial sensitivity of a contrasty silver chloride emulsion with the addition of 30 mg. to 1 kg. of emulsion.
  • the sensitization maximum is in the region of 434 m
  • the dyestuff is prepared as follows:
  • T he thiolactam as obtained from caprolactam by sulfurization with p s is methylated with dimethyl-sulfate in diluted caustic soda solution and distilled in vacuum t ture'i's'heated on an oil bath for 5 minutes at 90 C.
  • the reaction mixture is cooledin ice water, 1.6 g. N-ethylrhodanine are added and treated with'20 cc. of absolute alcohol and 2 cc. of trieth-ylamine.
  • the mixture is heated to boiling on the water bath for 30 minutes.
  • the hot yellow dystutf solution is mixed with 20 cc. of Water, the mixture is cooled in ice water. A yellow, crystallized dyestuflf is obtained. It is dried in the exsiccatorov'er sulfuric acid and i e-crystallizes from methylisoheptane.
  • Example 5 The increase is sixfold.
  • the sensitization maximum is in the region of 436 mu.
  • the dyestuft' is prepared as follows:
  • Example 6 1 The-increase 7 to 8 times.
  • the sensitization maximum is in the region of 456 me.
  • the dyestufl is prepared as follows:
  • 3-cyclohexyl-pyrrolidone-(2) are converted, as described in the foregoing example, in 2-mercaptomethyl-3- cyclohexyl-l-pyrroline.
  • the pyrroline is a liquid of the boiling point 151C. at 21 mm. Hg. 2 g. of pyrroline thus obtained and 1 cc. of dimethylsulfate are heated in the oil bath for 10 minutes to 100 C.
  • the reaction mixture is cooled, 2,6 ggof N-phenyl-selenorhodanine 10 cc. bf piiridiiie'and 1.5 cc.oftriethylamine are added.
  • the mixture is heated to 100 C. in the oil bath for 1 hour.
  • olic solution ofthe dyestufl absorbs the ultraviolet specand added to a silver chloride emulsion prior to casing.
  • the increase in sensitivity is 6 to 7 times the sensitization maximum is in the region of 439 m
  • the dyestufl: is prepared as follows:
  • the hexamethylene-bis-(pyrrolidone-Z) is prepared by heating 116 g. of hexamethylenediamine with 175 g. of butyrolactone in the autoclave at 260 280 C. for 3 h61irs andsubsequent distil1ation (B.P. 226-228 C. 100 g. of this pyrrolidone are stirred with 86fg.phosphorus pentasulfide in 350cc. of xylene .and 53g. of magnesia at 12044 0 for 30 minutes. Thereu on it isdecomposed with ca. 200 cc. of water and '100 'cc.,of sodium hydroxide. solution, the oil is separated, dried with potash and distilled The "N,N'- hexamethylene-bis-(thiopyrrolidone) distilled -over at 280295 under 2 miii. Hg.
  • the dyestufr' is prepared as follows: a
  • the mixture is slowly cooled and 2 g. of ethylenerhodanine in 20 cc. of pyridine are added and the mixture is heated to about 40 C. for 12 hours.
  • the formed dye stufi is thereafter precipitated by addition of water and re-crystallized from methanol and chloroform (1:1).
  • the methanolic solution absorbs the spectral violet and ultraviolet.
  • R stands for a substituent selected frqm the C2115 3.
  • a method formakingphotographic reproductions including the steps of providing a support that carries the optically sensitized silverh'alide emulsion of claim 2; exposing .the emulsion to the desired optical 'image, and developing the; exposed emulsion in a developer for exposed silver halide and in a relatively bright yellow light.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US585146A 1955-05-25 1956-05-16 Process for sensitizing silver halide emulsions Expired - Lifetime US2944896A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA22746A DE1009020B (de) 1955-05-25 1955-05-25 Verfahren zur Sensibilisierung von Halogensilberemulsionen

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US2944896A true US2944896A (en) 1960-07-12

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US (1) US2944896A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE548014A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH (1) CH348872A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE1009020B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR1153538A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB814375A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923524A (en) * 1973-10-29 1975-12-02 Eastman Kodak Co Fogged direct positive silver halide emulsions containing photographic sensitizing dyes derived from substituted salicylaldehydes
US3976493A (en) * 1975-02-18 1976-08-24 Polaroid Corporation Photosensitive compositions containing linked spectral sensitizers
US4144070A (en) * 1976-11-22 1979-03-13 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4156611A (en) * 1974-01-22 1979-05-29 Fuji Photo Film Co., Ltd. Heat-developable photosensitive materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2166736A (en) * 1937-04-23 1939-07-18 Eastman Kodak Co Photographic emulsion
US2213730A (en) * 1937-04-26 1940-09-03 Eastman Kodak Co Benzothiazinomerocyanine dyes
US2322015A (en) * 1939-05-25 1943-06-15 Eastman Kodak Co Dye and photographic emulsion containing the same
DE927043C (de) * 1943-04-14 1955-04-28 Agfa Ag Fuer Photofabrikation Verfahren zur Herstellung von Methinfarbstoffen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2166736A (en) * 1937-04-23 1939-07-18 Eastman Kodak Co Photographic emulsion
US2213730A (en) * 1937-04-26 1940-09-03 Eastman Kodak Co Benzothiazinomerocyanine dyes
US2322015A (en) * 1939-05-25 1943-06-15 Eastman Kodak Co Dye and photographic emulsion containing the same
DE927043C (de) * 1943-04-14 1955-04-28 Agfa Ag Fuer Photofabrikation Verfahren zur Herstellung von Methinfarbstoffen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923524A (en) * 1973-10-29 1975-12-02 Eastman Kodak Co Fogged direct positive silver halide emulsions containing photographic sensitizing dyes derived from substituted salicylaldehydes
US4156611A (en) * 1974-01-22 1979-05-29 Fuji Photo Film Co., Ltd. Heat-developable photosensitive materials
US3976493A (en) * 1975-02-18 1976-08-24 Polaroid Corporation Photosensitive compositions containing linked spectral sensitizers
US4144070A (en) * 1976-11-22 1979-03-13 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials

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Publication number Publication date
DE1009020B (de) 1957-05-23
BE548014A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH348872A (de) 1960-09-15
FR1153538A (fr) 1958-03-12
GB814375A (en) 1959-06-03

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