US3615635A - Silver halide photographic emulsion - Google Patents

Silver halide photographic emulsion Download PDF

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Publication number
US3615635A
US3615635A US779022A US3615635DA US3615635A US 3615635 A US3615635 A US 3615635A US 779022 A US779022 A US 779022A US 3615635D A US3615635D A US 3615635DA US 3615635 A US3615635 A US 3615635A
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United States
Prior art keywords
group
silver halide
general formula
halide photographic
photographic emulsion
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Expired - Lifetime
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US779022A
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English (en)
Inventor
Keisuke Shiba
Akira Sato
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • 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
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

Definitions

  • This invention relates to a spectrally sensitized silver halide photographic emulsion and more particularly to a super-sensitized silver halide emulsion containing at least one organic heterocyclic compound, having a high spectral sensitivity and a suitable spectral sensitivity distribution.
  • Spectral sensitivity is affected by the chemical structure of a sensitizing dye and by various properties of an emulsion, such as the halogen composition of the silver halide; crystal habit; crystal system; silver ion concentration; and the pH of the emulsion.
  • the spectral sensitivity is also affected by additives present in an emulsion, such as a stabilizer, an antifoggant, a coating agent, a floculating agent, agents for modifying the physical properties of a film. In many cases, the spectral sensitivity of the film is lowered thereby.
  • a further technique has been known for making a light-sensitive material wherein two or more sensitizing dyes, or a sensitizing dye and an organic heterocyclic compound, are used in combination.
  • two or more sensitizing dyes, or a sensitizing dye and an organic heterocyclic compound are used in combination.
  • a spectral sensitivity which is lower than either individual component. This is known as antisensitization.
  • the spectral sensitivity obtained by the use of a sensitizing dye in combination with one or more sensitizing dyes or organic heterocyclic compounds is superadditively" increased, much beyond the results obtained by the use of a single sensitizing dye. This is known as supersensitization.
  • a multilayer color light-sensitive material for subtractive color processes comprises a blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer.
  • the distribution of the spectral sensitivity of emulsion layer is the main factor in determining the color reproducing character of the color light-sensitive material. It is required that a green-sensitive emulsion layer have a sensitivity which is as high as possible, that the maximum spectral sensitivity not occur in the long wavelengths and that a high spectral sensitivity be present only in the green region.
  • the maximum wavelength of the spectral sensitivity is preferably not at the longer wavelength side, for example, longer than 670 millimicrons.
  • the requirement of a red-sensitive emulsion is to have a high spectral sensitivity in the narrow red region.
  • a silver halide photographic emulsion comprising at least one sensitizing dye represented by general formula 1:
  • Z and Z are atoms necessary to complete a heterocyclic ring selected from the group consisting of a benzimidazole ring, a benzothiazole ring, a naphthothiazole ring and a benzoselenazole ring;
  • R and R are a member selected from the group consisting of an unsubstituted alkyl group, a substituted alkyl group, a monovalent aliphatic unsaturated hydrocarbon group and an aralkyl group;
  • R is a member selected from the group consisting of a hydrogen atom and an alkyl group, said R being a hydrogen atom when Z and Z, are atoms forming benzimidazole ring;
  • X is an anion group and at least one organic heterocyclic compound selected from the formulas represented by general formula ll and I], wherein general formula II is:
  • Z is the atoms necessary to complete a heterocyclic ring selected from the group consisting of a benzimidazole ring and a naphthoimidazole ring;
  • R is a member selected from the group consisting of an unsubstituted alkyl group.
  • R is a member selected from the group consisting of a hydrogen atom and an alkylene group necessary to complete a ring when R and R, are bonded to form the ring; and A is a member selected from the group consisting of an unsubstituted phenyl group and a substituted phenyl group and general formula III is wherein X is an anion group and A, 2;, R and R have the same meaning as in general formula II.
  • the object of the invention can be accomplished by adding to a silver halide photographic emulsion at least one sensitizing dye represented by general formula I, and at least one organic heterocyclic compound represented by the general formula II, or, at least one organic heterocyclic compound represented by general formula III, in combination.
  • Z, and Z are atoms necessary to complete a benzimidazole ring, a benzothiazole ring, a naphthothiazole ring or a benzoselenazole ring;
  • R, and R are an alkyl group, a substituted alkyl group, a monovalent aliphatic unsaturated hydrocarbon group or an aralkly group;
  • R is a hydrogen atom or an alkyl group, said R being a hydrogen atom when Z, and 2 are the atoms to complete a benzimidazole ring;
  • X is an anion group
  • Z is the atoms necessary to complete a benzimidazole ring or a naphthoimidazole ring;
  • R is an alkyl group, a substituted alkyl group, a monovalent aliphatic unsaturated hydrocarbon group or an aralkyl group;
  • R represents hydrogen atoms or an alkylene group necessary t complete a ring when R and R are bonded to form the ring;
  • A is an unsubstituted or a substituted phenyl group.
  • R,, R and R are an alkyl group such as methyl, ethyl or propyl group, a substituted alkyl group such as 2-hydroxyethyl, 2-methoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carb0xybutyl, 2- sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl or a 2-carboethoxyethyl group, a monovalent aliphatic unsaturated hydrocarbon group such as an aryl group, and an aralkyl group.
  • a substituted alkyl group such as 2-hydroxyethyl, 2-methoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carb0xybutyl, 2- sulfoethyl, 3-sulfopropyl, 4-sulfobut
  • R is a hydrogen atom or an alkyl group such as methyl or ethyl group.
  • the ring may be substituted with a substituent, for example, a halogen atom, cyano, trifluoromethyl, phenyl, carboalkoxy, alkyl, hydroxyl or alkoxy group.
  • X, and X need not be present when the quaternary nitrogen atom and R, and R or R, form a betaine structure. The details thereof will be understood by making reference to the following examples of suitable compounds, which are not intended to limit the invention.
  • organic heterocyclic compounds of the invention represented by general formula II and Ill, can be synthesized by known methods.
  • Compounds of general formula II can readily be obtained by treating compounds of the general formula III with an aqueous alkaline solution.
  • IlIC can be obtained by similar methods to the ones above Wlth f developer hereafter descnbed, Passed thfough 3510p described. 20 solutlon and a fixing solution and then washed wlth water to The sensitizing dye or organic heterocyclic compound used give a strip.
  • the density thereof was measured by means of S- in the invention is dissolved inawater-soluble organic solvent, yp Densiiometef (Trade Mark, made y j Photo Film for example, methanol, ethanol, butanol or pyridine, and C0., Ltd.) to determine the degree of spectral sensitization. added to a silver halide photographic emulsion.
  • yp Densiiometef Trade Mark, made y j Photo Film for example, methanol, ethanol, butanol or pyridine, and C0., Ltd.
  • the addition he standard optical density for determining the sensitivity may be carried out in solution form separately, or after being Was the P of! g denslty lmixed.
  • the type of silver halide used in this photographic I The degrees of spectral sensltlzatlon are shown (relatively) emulsion may be silver bromide, silver iodobromide, silver table chlorobromide and silver chloroiodobromide.
  • the halide emulsion there may be incorporated, in addition to the foregoing manner a sublecled to p l exposure "Sing a gelatin, a silver halide, a sensitizing dye and an organic heteroreflection-type 8 8 spectl'al and cyclic compound, a chemical sensitzer, a stabilizer an antifogdeveloped, descllbed abovei t0 g a p; Measurement gam, a coating agent, a photographic dye ff Such as an antiof the denslty thereof y elded aspectral sensltlvlty curve as irradiation dye, a filter dye or an antihalation dye, a binder Show" the accompanying drawmg- (besides gelatin) and, if necessary, a color former. 35
  • FIG. 1 and FIG. 2 of the drawing show the spectral sensitiviwith citric acid to a pH of 6.5.
  • a hardener and surface active ty curves in the cases of using a sensitizing dye alone and with agent (for coating) were then added thereto, and the resultant solution coated onto a film support, and dried, to obtain a sample of a red-sensitive color sensitive material.
  • Curve I is a spectral sensitivity curve resulting from using 4 ml. of IA (4Xl0 molar concentration) alone per g. of the photographic emulsion
  • Curve II is that for using 4 ml. of HF (4xl0molar concentration) alone
  • Curve Ill and Curve IV are those resulting from using 4 ml. of the foregoing IA with 4 ml. and 8 ml., respectively, of the foregoing IIF in example I.
  • Curve V is a spectral sensitivity curve resulting upon using 4 ml. of IH (4Xl0 molar concentration alone per 100 g.
  • Curve VI and Curve VII are the curves resulting from using 4 ml. of the foregoing III with 4 ml. and 8 ml., respectively, of 118 (4X10 molar concentration) in combination, as in example 2.
  • the dye represented by general 7 formula I is generally present in amounts of from about lXl mole to about 0.40 mole per kilogram of silver halide emulsion. Further, the amount of the materials represented by general formulas ll or III will generally range from about l to about 5 times the amount of the dye represented by general formula 1 (molar basis).
  • the alkyl group per se as for example represented by R, has from one to five carbon atoms.
  • R and R are a member selected from the group consisting of an alkyl group of one to five carbon atoms, a substituted alkyl group wherein the alkyl group has from one to five carbon atoms and wherein the substituent is hydroxy, alkoxy having from one to five carbon atoms, carboxy, sulfoor carboxy-alkoxy wherein the alkoxy group has from one to five carbon atoms, an aryl group and an aralkyl group wherein the alkyl moiety has from one to five carbon atoms;
  • R is a member selected from the group consisting of a hydrogen atom and an alkyl group having from one to five carbon atoms, said R being a hydrogen atom when 2, and
  • R is a member selected from the group consisting of an alkyl group having from one to five carbon atoms, a substituted alkyl group wherein the alkyl group has from one to five carbon atoms and wherein the substituent is hydroxy, alkoxy of one to five carbon atoms, carboxy, sulfoor carboxy-alkoxy wherein the alkoxy moiety has from one to five carbon atoms, an aryl group and an aralkyl group wherein the alkyl moiety has from one to five carbon atoms;
  • R is a member selected from the group consisting of a hydrogen atom and an alkylene group necessary to complete a ring when R. and R are bonded to form the ring; and
  • A is a member selected from the group consisting of phenyl and substituted phenyl; wherein formula III is:
  • X is an acid anion group
  • A, 2 R and R have the same meaning as in formula ll, wherein said heterocyclic compound is present in an amount of from 1/10 to 5 times the amount of said sensitizing dye, on a molar basis.
  • sensitizing dye represented by the general formula 1 is a member selected from the group consisting of:

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (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)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US779022A 1967-11-27 1968-11-26 Silver halide photographic emulsion Expired - Lifetime US3615635A (en)

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JP7607167 1967-11-27

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BE (1) BE724467A (enrdf_load_html_response)
DE (1) DE1811069C3 (enrdf_load_html_response)
FR (1) FR1600926A (enrdf_load_html_response)
GB (1) GB1235369A (enrdf_load_html_response)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2711267A1 (de) * 1976-03-15 1977-09-22 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsion
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4581329A (en) * 1983-03-11 1986-04-08 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US4659654A (en) * 1984-09-28 1987-04-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive emulsion
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
US5807666A (en) * 1995-11-30 1998-09-15 Eastman Kodak Company Photographic elements with j-aggregating carbocyanine infrared sensitizing dyes
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19711143A1 (de) * 1997-03-18 1998-09-24 Agfa Gevaert Ag Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im roten Spektralbereich

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152163A (en) * 1976-03-15 1979-05-01 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion containing cyanine and hemicyanine sensitizing dyes
DE2711267A1 (de) * 1976-03-15 1977-09-22 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsion
US4581329A (en) * 1983-03-11 1986-04-08 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4659654A (en) * 1984-09-28 1987-04-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive emulsion
EP0202784A2 (en) 1985-04-23 1986-11-26 Konica Corporation Silver halide photographic light-sensitive material
EP0200206A2 (en) 1985-04-30 1986-11-05 Konica Corporation Silver halide photographic light-sensitive material
EP0201027A2 (en) 1985-04-30 1986-11-12 Konica Corporation Silver halide photographic light-sensitive material
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
US5389511A (en) * 1991-11-06 1995-02-14 Konica Corporation Silver halide photographic emulsion and light-sensitive silver halide photographic material making use of the same
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
US5807666A (en) * 1995-11-30 1998-09-15 Eastman Kodak Company Photographic elements with j-aggregating carbocyanine infrared sensitizing dyes
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

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BE724467A (enrdf_load_html_response) 1969-05-02
DE1811069C3 (de) 1980-08-07
DE1811069B2 (de) 1979-11-15
FR1600926A (enrdf_load_html_response) 1970-08-03
GB1235369A (en) 1971-06-16
DE1811069A1 (de) 1969-07-17

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