US2860981A - Supersensitization of photographic silver halide emulsions - Google Patents

Supersensitization of photographic silver halide emulsions Download PDF

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US2860981A
US2860981A US586053A US58605356A US2860981A US 2860981 A US2860981 A US 2860981A US 586053 A US586053 A US 586053A US 58605356 A US58605356 A US 58605356A US 2860981 A US2860981 A US 2860981A
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pyridine
emulsions
carbon atoms
emulsion
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Jean E Jones
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Eastman Kodak Co
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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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances

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  • This invention relates to photographic silver halidev emulsions containing certain polymethine dyes, and in supersensitizing combination therewith, pyridine bases.
  • the sensitization produced by a given dye varies somewhat with the typeof emulsion in which the dye is incorporated.
  • the sensitization of a given emulsion by a given dye may be altered by varying the conditions in the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e., increasing the alkalinity) or both.
  • sensitization can be increased by bathing plates, coated with a spectrally sensitized emulsion, in water or in aqueous solutions of ammonia.
  • Such a process of altering the sensitivity of a sensitized emulsion by-increasing the silver ion concentrationand/or-by decreasing the hydrogen ion concentration is commonly.
  • Hypersensitization Hypersensitized emulsions have generally poor keeping qualities.
  • polymethine dyes 'usefuli in practicing my invention are sometimes referred to asb en-chain merocyanines, and can be represented by the following general formula:
  • R represents an alkyl group, such as .methyl, ethyl, propyl, butyl, 'car'b'ethoxymethyl, benzyl (phenylmethyl), etc. (e. g., an alkyl group containing from 1 to 4 carbon atoms)
  • R represents a hydrogen atom or a lower alkyl group, such as methyl, ethyl, etc.
  • R represents a hydrogen atom, a lower alkyl group, such as methyl, ethyl, etc., a lower alkoxyl group, such as methoxyl, ethoxyl, etc., a monocyclic aryl group, such as phenyl, tolyl, etc., or a heterocyclic group, such as thienyl
  • R and R can together represent an alkylene group "ice (ie.
  • n a positive integer of from 1 to 2
  • Z represents the non metallic atoms necessary to complete a heterocyclic nucleus containing from too atoms in the heterocyclic ring, such as those selected from the group consisting of those of the benzothiazole series (e.
  • benzothiazole 4- chlorobenzothiazole, 5 chlorobenzothiazole, 6 chlorobenzothiazole, 7 chlorobenzothiazole, 4 methylbenzothiazole, 5-methylbenzothiazo1e, 6-methylbenzothiazole,, S-bromobenzothiazole, 6-bromobenzothiazole; .4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, o-methoxybenzothia- 'zole, S-iodobenzothiazole, o-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimetho iybenzothiazole, 5,6-dio xymethylenebenzothiazole, 5- hydroxybenzothiazole, G-
  • those of the benzoselenazole series e. g., benzoselenazole, S-chlorobenzoseleriazole, S-methoxybenzoselenazole,, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • those of the naphtho selenazole series e. g., naphtho[l,2]selenazole, naphtho2,1] selenazole,
  • those of the thiazoline series e. g., thiazoline, 4- methylthiazoline, etc.
  • those of the benzimidazoleseries zimidazole, etc. those of the 3,3-dialkylindolenine series (e. g., 3,-3-dimethylinclolenine, 3,3,5-trimethylindolenine,
  • pyridine bases useful in practicingmy invention comprise those represented by the following general formula:
  • Typical bases include pyridine, oc-, 13-,and 7-picoline, etc.
  • Polymethine dyes selected from which can be used in my invention comprise those of formula I those rep- 2-(5. 1 mm arkn n a ieny ld e)e hy b n ml I 2-(5,5 dicyapp-2,4-pentadlepylldene)fimethylbenzothiazoline Patented Nov. s, 1958,
  • I incorporate one or more of the polymethine dyes of Formula I with one or more of the pyridine bases of Formula II in a photographic silver halide emulsion.
  • My invention is particularly directed to the ordinarily employed gelatino-silver-halide emul- 'sions.
  • my supersensitizing combinations can be employed in silver halide emulsions in which the carrier is other than gelatin, e. g., a resinous substance or cellulosic material which has no deteriorating eifect on the silver, halide.
  • My invention is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g., gelatino-silver-chloride, -chlorobrornide, -chloroiodide, -chlorobromiodide, -bromide and -bromiodide developing-out emulsions. While the results in the following examples were obtained using gelatino-silverbromiodide emulsions, useful results have also been obtained using gelatino-silver-chlorobromide emulsions.
  • emulsions prepared in accordance with my invention can be coated in the usual manner on any suitable support, e. g., glass, cellulose nitrate film, cellulose acetate art.
  • polymethine sensitizing dyes of Formula I and v represented by Formula II above have little or no sensitizing action on the emulsions.
  • the optimum concentration of a sensitizing dye can be determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of test portion of the same emulsion, each portion containing a different concentration of the sensitizing dye.
  • the optimum concentration of my supersensitizing combinations can, of course, be readily determined in the same manner, by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing a different concentration of the sensitizing dye used in the combination.
  • the optimum or near optimum concentration of the dyes selected fromthose represented by Formula I above which I employ in practicing my invention is of the order of from 0.05 to 0.30 gram per mol. of silver halide in.the emulsion.
  • the pyridine bases selected from those represented by Formula II above are advantageously employed in concentrations on the order of from 10.0 to 50.0 grams per mol. of silver halide in the emulsion.
  • the concentration of the dye of Formula I to the pyridine base of Formula II can vary rather widely in my combinations, e. g., from 1:30 to 121000 (by weight) in many cases.
  • the sensitizing dyes can be directly added to the emulsions, or they can be added to the emulsions in the form of their solutions.
  • the sensitizing dyes of Formula I can be dissolved in an appropriate solvent, such as acetone, methanol, etc., and these olutions added to the photographic emulsions. Since the pyridine bases of Formula II are liquids and are compatible with the photographic emulsions, the sensitizing dyes of Formula I can frequently be dissolved in these pyridine bases and the resulting solutions added to the emulsions.
  • the sensitizing dyes and pyridine bases of my invention are advantageously incorporated in the finished, washed emulsions and should be uniformly distributedthroughout the emulsions. The following procedure is satisfactory: Stock,so-'
  • lutions of the sensitizing dyes described above are preemulsion Stirring is continued until the vdye (or dyes)- is thoroughly incorporated in the emulsion. Then, the desired amount of the pyridine base is slowly added to theemulsion, while stirring. If desired, the pyridine base can be added prior to the solution of sensitizing dye (or dyes), or a mixture of these two ingredients can'be added 'in a single operation. arately added, stirring'is continued until all ingredients have been uniformly dispersed throughout the emulsions.
  • the supersensitized emulsion can then be coated out on a suitable support, such as glass, cellulosenitratefilm, cellulose acetate film, polyvinyl acetal resin film, paper, etc., to a suitable thickness and allowed to dry.
  • a suitable support such as glass, cellulosenitratefilm, cellulose acetate film, polyvinyl acetal resin film, paper, etc.
  • the details of such coating methods are well known to those skilled in the art.
  • sensitizing dye and pyridine'base actually incorporated in the' emulsion will vary somewhat,
  • any emulsion containing a com- The following examples will serve to illustrate further the manner of practicing my invention: To different proportions of the same batch of photographic gelatinosilver-bromiodide emulsion were added (1) a sensitizing dye selected from those of Formula I above and (2) a combination of the sensitizing dye of Formula I and a pyridine base, such as those represented by Formula II above. No data on the coating containing the pyridine base of Formula II alone are given, inasmuch as'it has been found that these compoundshave little or no measureable sensitizing action of their own when so employed in these emulsions. While different emulsion batches were employed in some of these examples, the same emulsion batches were employed for the coatings in each individual example.
  • the 30/,E speed, gamma and fog obtained after development of V the exposed emulsions are given below.
  • the de- 8 urements for these emulsions are givenjn Example ,9 of the above table.
  • curve C represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized veloper employed had the following composition: 5 with 2-(5,5-dicyano-2,4-pentadienylidene) 3 methyl- G benzothiazoline, while curve D represents the sensitivity N th 1 h n 1 If t 6 of the same emulsion sensitized with 2-(5,5-dicyano- 2, 4-
  • curve E represents the sensitivity of an potassmm bromlda. "r ordinary gela-tino-silver-bromiodide emulsion sensitized water to make one liter with 2(5,5-dicy-ano 2,4 pentadienylidene) 1 ethyl B- Wratten No. 12 filter transmits substantially no light naphthothiazoline, while curve F represents the sensitivof wavelength shorter than about 495 mu, Wratten No.
  • cal sensitizers e. g., sulfur scnsitizers (e. g., allyl thio- Without Base With Base Dye No. Exposure Example (gJmol. Base Filter AgX) (cc./mo1. AgX) /E 30/E No.
  • the accompanying drawing illustrates the supersensitizing effect obtained with three of my new combinations of polymethine dyes and pyridine bases in gelatino-silverbromiodide emulsions.
  • Each figure of the drawing is a diagrammatic reproduction of two spectrograms.
  • the sensitivity of the emulsion containing only the polymethine dye of Formula I is represented by the solid curve.
  • the sensitivity of the emulsion containing both the polymethine dye of Formula I and the pyridine base of Formula II is represented by the curve consisting of short dashes. No curve showing the sensitivity of the emulsion containing the pyridine base of Formula II is shown, since these compounds have no measureable effect on the emulsion employed.
  • curve A represents the sensitivity of an ordinary gelatino-silver bromiodide emulsion sensitized with 2-(3,3-dicyanoallylidene) 3 ethylbenzothiazoline
  • curve B represents the sensitivity of the same emulsion sensitized with 2-( 3,3-d1'cyano-ally1idene)-3-ethylbenzothiazoline and pyridine.
  • palladium chloride U. S. 2,540,086)
  • potassium chloropalladate U. S. 2,598,079
  • antifoggants such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinitc (U. S. 2,566,263)
  • benzotriazole nitrobenzimidazole, S-nitro
  • polymethine dyes represented by Formula I above can be prepared according to known methods.
  • U. S. Patent 2,697,707, issued December 21, 1954 describes the preparation of certain of these dyes.
  • French Patent 1,099,380, granted March 16, 1955, and corresponding Belgian Patent 519,732, granted May 30, 1952 also describe the preparation of certain of these polymethine dyes.
  • Belgian Patent 506,549, granted No vember 14, 1951 also describes the preparation of certain of these polymethine dyes.
  • Example A 2-(3,3-dicyanoallylidene) 3 ethylbenzoxazoline
  • Example B -2-(5,5-dicyono-2,4-pentadienylidene)-1 ethylnaphtho-[1,2lthiazline
  • Dye 2 was prepared in the manner shown inExarnple B above and was obtained as a solid melting at 250-251 C. with decomposition.
  • Dye 4 was obtained as a solid melting at 194-195 C. with decomposition.
  • Dye 9' was obtained as a solidmelting at207 208 'C. with decomposition.
  • Dye 10 was obtainedas a solid melting at 212 -213 C. with decomposition.
  • Dye l7 was'obtained as. a solid melting at 225 226 C. 'with" decomposition.
  • Dye 18 was obtained as a solid melting at 273-274" C. with decomposition.
  • 'Dye 20 was obtained as a 'solid melting at 301-302 C. with decomposition.
  • polyniethine dyes of my invention represented by Formula I abovewherein R and R together. represent an .alkylene group can be prepared according to the method described in U. S. Patent 2,697,707 (corresponds to British 704,770 and 704,840). The following examples illustrate thismethod. 1
  • Example 'c.-'-1-ditana ah iene-z weih i-z 3H) benzothiazolylidene)cyclopentane A mixture of 18.35 g. (1 mol.) of 3-methyl-2-methyl mercaptobenzothiazolium p-toluenesulfonate, 13.2 g. (1 mol. plus excess) of l-dicyanomethylenecyclo pentane, 35 ml. of absolute ethyl alcohol and 5.05 g. (1 mol.) of triethylamine was heated at the refluxing temperature of 20 minutes. After chilling, the solid was collected on a filter and washed with methyl alcohol. The yield of product was 89% crude and 69% after two recrystallizations from ethyl alcohol. The red crystals had M. P. 208 209 C. with decomposition.
  • Example E.1-dicyan0methylene-2- (3-methyl-2 (3H) benzothiazolylidene) cyclohexane H2O CH2 I C O CH2 1 o N H on ON O tions from ethyl alcohol.
  • the scarlet needles had Pg 220-221 C. with'decompositio'n.
  • lower alkyl as used herein means an alkyl group containing from 1 to 2 carbon atoms.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms and groups which, together with R represent the atoms necessary to complete a cycloalkane ring containing from 5 to 6 carbon atoms
  • R when R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, an alkoxyl group containing from 1 to 2 .carbon atoms, a monocyclic aryl group of the benzene series and a thienyl group
  • n represents a positive integer of from 1 to 2
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R ' represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms and groups which, together with R represent the atoms necessary to complete a cycloalkane ring containing from 5 to 6 carbon atoms, ,R-,,, when .R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms, represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2carbon atoms, an alkoxyl group containing from 1 to 2carbon atoms, a monocyclic aryl group of the benzene'series and a thienyl group
  • n represents a positive integer of from *1 to 2
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothi
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from l to 2 carbon atoms, an alkoxyl group containing from 1 to 2 carbon atoms, a monocyclic aryl group of the benzene series, and a Z-thienyl group
  • Z represents the non-metallic atoms necessary to complete a heterocyclicnucleus of the benzothiazole series.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus ofthe benzothiazole. series.
  • R represents an alkyl group containing from t 1 to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms and groups which, together with R,,-represent the atoms necessary to complete a cycloalkane ring containing from 5 to 6 carbon atoms
  • R when R represents a member selected from the group. consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms
  • n a positive integer of from 1 to 2
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series, and at least one pyridine base selected from those represented by the following general formula:
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms. 7
  • R represents an alkyl group containing froml to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, an alkoxyl group containing from 1 to 2 carbon atoms, a monocyclic aryl group of the benzene series, and a Z-thienyl group
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R represents a 2-thienyl group
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms and groups which, together with R represent the atoms necessaryto complete a cycloalkane ring containing from 5 to 6 carbon atoms
  • R when R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, an alkoxyl group containing from 1 to 2 carbon atoms, a monocyclic aryl group of the benzene series and a thienyl group
  • n represents a positive integer of from 1 to 2
  • Z represents the non-metallic atoms necessary to complete a hetero
  • R represents a member selected from the group taining from 1 to 2 carbon atoms.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, analkoxyl group containing from 1 to 2 carbon atoms, a monocyclic aryl group of the benzene series, and a 2-thienyl group
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the naphthothiazole series.
  • R represents an alkyl group containing from 1 to 2 carbon atoms
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the naphthothiazole series.
  • I 1 R-N represented by the following general' 15 ofihe benzene series, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus ref-the napthothiazole series.

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US586053A 1956-05-21 1956-05-21 Supersensitization of photographic silver halide emulsions Expired - Lifetime US2860981A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293626A (en) * 1977-07-25 1981-10-06 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
US4307183A (en) * 1979-10-12 1981-12-22 Minnesota Mining And Manufacturing Company Silver halide photographic emulsions including dye sensitizers and supersensitizing or stabilizing amounts of a polymeric compound and photographic elements, particularly radiographic elements including said emulsions
US20060266571A1 (en) * 2005-05-26 2006-11-30 Mattson Marlin J Combined truck and trailer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE519732A (enrdf_load_html_response) *
US2398778A (en) * 1942-11-24 1946-04-23 Eastman Kodak Co Sensitized photographic emulsion
US2478369A (en) * 1945-12-29 1949-08-09 Eastman Kodak Co Supersensitized silver halide photographic emulsion
US2638473A (en) * 1948-10-02 1953-05-12 Ilford Ltd Methine dyestuffs
US2697707A (en) * 1950-12-05 1954-12-21 Ilford Ltd Process of producing cyanine dyestuffs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE519732A (enrdf_load_html_response) *
US2398778A (en) * 1942-11-24 1946-04-23 Eastman Kodak Co Sensitized photographic emulsion
US2478369A (en) * 1945-12-29 1949-08-09 Eastman Kodak Co Supersensitized silver halide photographic emulsion
US2638473A (en) * 1948-10-02 1953-05-12 Ilford Ltd Methine dyestuffs
US2697707A (en) * 1950-12-05 1954-12-21 Ilford Ltd Process of producing cyanine dyestuffs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293626A (en) * 1977-07-25 1981-10-06 Eastman Kodak Company Electrophotosensitive materials for migration imaging processes
US4307183A (en) * 1979-10-12 1981-12-22 Minnesota Mining And Manufacturing Company Silver halide photographic emulsions including dye sensitizers and supersensitizing or stabilizing amounts of a polymeric compound and photographic elements, particularly radiographic elements including said emulsions
US20060266571A1 (en) * 2005-05-26 2006-11-30 Mattson Marlin J Combined truck and trailer
US7658397B2 (en) 2005-05-26 2010-02-09 Mattson Marlin J Combined truck and trailer

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