Classifications

• • 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
  • C09B23/107—The polymethine chain containing an even number of >CH- groups four >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
  • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
• • 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
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• • 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
• • 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
  • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
  • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >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
• • 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
  • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
• • 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

• Photographic silver halide emulsions are spectrally sensitized by protonating a sensitizing dye having the amidinium ion auxochromophore system, and adding the protonated dye to a liquid photographic silver halide emulsion which has a pH sufiiciently high to convert the dye to its colored, unprotonated form, to spectrally sensitize the silver halide.
• the protonated dye can be dispersed in a hydrophilic colloid and the dispersion of dye in hydrophilic colloid can subsequently be combined with a fluid silver halide emulsion, either the colloid or the emulsion having a pH sufficiently high to convert the dye to its unprotonated, colored form.
• the invention avoids introduction of organic solvent into photographic emulsions, and thereby eliminates defects in emulsion coatings which are caused by organic solvent.
• This invention relates to improved methods for spectrally sensitizing photographic silver halide emulsions. It also relates to aqueous solutions of certain protonated spectral sensitizing dyes.
• Spectral sensitizing dyes containing the amidinium ion auxochromophore system are substantially water insoluble. Most of these spectral sensitizing dyes have been incorporated in silver halide emulsions by dissolving them in organic solvent solutions. Relatively large amounts of organic solvents are generally required to dissolve these dyes. When dye solutions containing substantial quantities of organic solvent are added to silver halide emulsions, coating defects frequently occur in applying the emulsion to a support. The presence of organic solvent in the emulsion tends to cause bare spots in the emulsion coating. In addition, organic solvent solutions of such dyes cannot be stored in light without damaging the dye.
• One object of this invention is to provide improved methods for spectrally sensitizing photographic silver halide emulsions with dyes containing the amidinium ion auxochromophore system. Another object of this invention is to provide highly light-stable aqueous solutions of protonated spectral sensitizing dyes having the amidinium ion auxochromophore system. A further object of this invention is to provide a method for spectrally sensitizing photographic silver halide emulsions with dyes having the amidinium ion auxochromophore system which does not involve the use of organic solvents.
• a method for spectrally sensitizing photographic silver halide grains dispersed in an alkali permeable colloid which comprises protonating a spectral sen sitizing dye having the amidinium ion auxochromophore system, dissolving the protonated dye in an aqueous solution, and adding the solution of protonated dye to a dis- 3,482,981 Patented Dec. 9, 1969 persion of silver halide grains in the alkali permeable colloid, which dispersion has a pH sufliciently high to convert the protonated dye to its colored form.
• this method of spectrally sensitizing silver halide dispersions substantially reduces or eliminates the addition of organic solvents to the system.
• coating defects caused by organic solvent are eliminated.
• the aqueous solutions of protonated dye have substantially greater stability to light than aqueous organic solvent solutions of the corresponding unprotonated dyes.
• photographic silver halide emulsions are spectrally sensitized by protonating a spectral sensitizing dye havingthe amidinium ion auxachromophore system, forming an aqueous solution of said protonated dye, adding said aqueous solution of protonated dye to a hydrophilic colloid, dispersing said dye in said colloid; and then adding said dispersion of dye in colloid to a fluid photographic silver halide emulsion to spectrally sensitize said silver halide, the pH of at least one of said hydrophilic colloid and said silver halide emulsion being sufficiently high to convert the dye to its protonated form.
• the invention also provides novel aqueous solutions of protonated photographic spectral sensitizing dyes containing the amidinium ion auxochromophore system. These solutions, as noted above, exhibit superior stability to light.
• amidinium ion auxochromophore system is used broadly as in Mees, The Theory of the Photographic Process published in 1954 by Macmillan Company, pages 373, 375 and 376.
• the characteristic amidinium ion auxochromophore system is described below:
• n can be 0 or an integer of from 1 to 4.
• Dyes containing the amidinium ion auxochromophore system include the cyanine dyes and the hemicyanine dyes (including styryl dyes) which are photographic spectral sensitizers.
• dyes containing the amidinium ion auxochromophore system are employed which, in the protonated form thereof, are soluble in water in the absence of any organic solvent.
• organic solvent may be added to dissolve certain dyes which, even in their protonated form, are difiicultly soluble in water.
• organic solvent may be added, preferably in relatively small quantities, to obtain more concentrated solutions of the dye if desired.
• the most useful dyes are those which can be protonated at a pH of over 1, e.g., pH 1 to 4.
• Typical useful cyanine dyes which may be protonated and employed in accordance with this invention have the following general formula:
• thiazole 4-phenylthiazole, 4,5-diphenylthiazole, 4 (2 thienyDthiazole, 4-methylthiazole, benzothiazole, 4-chlorobenzothiazole, 4-methylbenzothiazole, 4-methoxybenzothiazole, 4-ethoxybenzothiazole, 4-phenylbenzothiazole, 5 ehlorobenzothiazole, 5 bromobenzothiazole, 5- methyl-benzothiazole, S-rnethoxybenzothiazole, S-ethoxybenzothiazole, S-phenylbenzothiazole, 6-chlorobenzothiazole, 6 bromobenzothiazole, 6 methylbenzothiazole, 6- rnethoxybenzothiazole, 6-ethoxybenzothiazole, 4-phenyloxazole, benzoxazole, S-chlorobenzoxazole, S-methylbenzoxazole, S-methylbenzoxazole, S
• sulfatoalkyl such as 'y-sulfatopropyl and fi-sulfatobutyl, etc.
• acid anion represented by X in the above formula
• R such as dyes containing the betaine type structure.
• Typical hemicyanine dyes (including p dialkylaminostyryl dyes) which may be protonated and employed in the processes and solutions of the invention have the following general formula:
• R X, Z L, d and m have the meanings given above; and, R and R each represents a substituent selected from the group consisting of hydrogen, an alcohol radical, e.g., an alkyl substituent (including substituted alkyl) of from 1 to 18, and preferably 1 to 8 carbon atoms, including the specific substituents given for R and R above, or an aryl substituent such as phenyl and naphthyl, or R and R taken together represent the atoms required to form a ring, such as a heterocyclic nucleus having 5 to 6 atoms, e.g., piperidine, morpholine or pyrrolidine.
• specific hemicyanine dyes which can be protonated and employed in this invention include the p-dialkylaminostyryl dyes such as 2-p-dimethylaminostyrylbenzothiazole ethiodide; l-methyl-2 p dimethylaminostyryl pyridinium iodide; B-methyl-Z-p-dimethylaminostyryl thiazolinium iodide; 3,5 -dimethyl 4 phenyl- Z-pdimethylarninostyrylthiazolinium iodide; and, the dye having the following structural formula:
• Protonation of dyes containing the amidinium ion auxochrornophore system can be effected in any convenient manner, such as reaction of the dye with any acid of sufiicient strength to protonate the dye, and which does not adversely affect the dye.
• Acids which protonate dyes having the amidinium ion auxochromophore system include, for example, sulfuric, sulfonic, phosphoric, and phosphonic acids.
• the most convenient method for pr! tonation is to dissolve the dye in an aqueous solution containing sufficient acid to protonate the dye.
• the strength of the acidic solution will depend, of course, on the particular dye being protonated. PH of 1 to 4 is preferred.
• Emulsions usually have a pH on the order of about 5.5 to 7. Emulsions having a pH in this range, or a higher pH, convert the protonated dyes to their unprotonated form. In some instances, it is desirable to adjust the pH of the emulsion after addition of the aqueous solution of protonated dye thereto.
• the pH of the emulsion can be conveniently regulated, for example by addition of a suitable base, e.g., sodium hydroxide.
• the colloid itself may have a suificiently high pH to convert the dye to its unprotonated form. It is possible, however, to use colloids having a sufliciently low pH that the dye remains therein in its protonated form, and is not converted to its protonated form until added to a photographic silver halide emulsion.
• Typical hydrophilic colloids in which the protonated dye is dispersed and typical hydrophilic colloids which can be used as binder for the silver halide, include gelatin, polyvinyl alcohol and the other colloids (or dispersing agents) disclosed and referred to in Beavers U.S. Patent 3,039,873 (issued June 19, 1962), column 13.
• Emulsion spectrally sensitized in accordance with this invention may contain other spectral sensitizing dyes which do not have the amidinium ion auxochromophore system, e.g., merocyanine dyes.
• the emulsion can also contain various supersensitizers for the dyes added to the emulsion in accordance with the invention. Supersensitization can be accomplished in such emulsion with the same materials, and using the same techniques, as disclosed in the prior art.
• Photographic silver halide emulsions spectrally sensitized in accordance with this invention may contain any of the usual addenda, such as speed increasing compounds, hardeners, antifoggants, color-formers etc.
• the processes and solutions of the invention are effective in sensitizing any of the light sensitive silver halides, such as silver chloride, silver bromide, silver iodide and mixed halides such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
• concentration of dye required to spectrally sensitize the emulsion varies with the particular dye used and the effects desired. Generally, concentrations of dye in the range of about 5 to about 100 mg. per liter of flowable emulsion (or from 0.01 to 1 g. dye per mole of silver halide) gives good spectral sensitization.
• Example 1 A spectral sensitizing dye having the amidinium ion auxochromophore system anhydro 5,5,6' tetrachlorol,1,3 triethyl 3' (4-sulfobutyl)-benzimidazolocarbocyanine hydroxide was protonated by dissolving 30 mg. of the dye in 1.0 ml. of 2.0 N sulfuric acid, and brought up to a total of 30 ml. with distilled water. The protonated form of the dye is soluble in water, colorless and may be represented by the following structure:
• the coatings were exposed on a sensitometer, developed for 2 /2 minutes in Kodak developer D-l9, fixed, washed and dried.
• the relative speed and the percent maximum absorption (at 580 m were essentially the same.
• the control coating showed defects (bare spots) due to the use of methanol therein. There were no coating defects using the protonated dye in accordance with the invention.
• the emulsions also contained an oxacarbocyanine spectral sensitizer of the type described in Belgian Patent 659,853 at a concentration of mg. per mole of silver.
• the relative speed and percent maximum absorption were essentially the same with each coating.
• the control coating showed defects due to the presence of methanol therein, whereas the coating prepared with protonated dye in accordance with the invention was free from coating defects.
• Example 2 The dye, anhydro 5,5,6,6'-tetrachloro-1,1'-diethyl-3,3'- di (4-sulfobutyl)-benzimidazolocarbocyanine hydroxide, is protonated in the same manner as in Example 1 but using 0.25 ml. of 2.0 N sulfuric acid. An emulsion is sensitized, coated and tested as in Example 1, a control being made with a methanolic solution with the unprotonated form of the dye as in Example 1. The results obtained with the test and control coatings with respect to coating properties and percent maximum absorption (at 570 m are similar to those of the test and control coatings in Example 1.
• the coating sensitized using the protonated form of the dye shows an unexpected increase of about 25% in relative speed.
• Good results, similar to those obtained in Example 1, are obtained when the emulsion also contains 160 mg. per mole of silver of an oxacarbocyanine spectral sensitizer of the type described in Belgian Patent 659,853.
• Examples 3-12 Good coating and spectral sensitization, similar to the results obtained with the test coating in Example 1, are obtained when the following dyes are protonated, added to an emulsion and tested as in Example 1:
• Example 13 The procedure of Example 1 is followed except that the aqueous solution of protonated dye is dispersed in an aqueous gelatin solution having a pH of about 6. The protonated dye is converted to its colored, unprotonated form. The mixture is homogenized and dried. The dispersion of dye in gelatin is then added to a liquid silver halide emulsion as in Example 1, and results similar to the test coating in Example 1 are obtained with respect to coating properties and spectral sensitization.
• novel, stable dye solutions of this invention are useful in spectrally sensitizing photographic silver halide emulsions and for spectrally sensitizing other forms of silver halide, such as binderless deposits of silver halide on a support, e.g., evaporated silver halide films, by bathing such films in the novel solutions of the invention after the pH of the solution is raised to convert the dye to its unprotonated form.
• Photographic emulsions and materials spectrally sensitized in accordance with the method of this invention may be used in any products in which conventionally sensitized silver halide emulsions are employed, such as reversal films, direct positive films, emulsions having color couplers, dye bleach photographic elements and the like.
• the method of spectrally sensitizing photographic silver halide grains dispersed in an alkali-permeable colloid which comprises:
• Z and Z each represents the atoms required to complete a nucleus selected from the group con sisting of a thiazole nucleus, a benzothiazole nucleus, an oc-IlflPhihOthliZOlG nucleus, a ,B-naphthothiazole nucleus, a benzoxazole nucleus, a l-alkyl imidazole nucleus, 21 l-aryl imidazole nucleus, a l-alkyl benzirnidazole nucleus, a l-aryl benzimidazole nucleus, a 1-alky1naphth[1,2-d]imidazole nucleus, a l-arylnaphth[l,2-d]imidazole nucleus, a selenazole nucleus and a benzoselenazole nucleus; R and R each represents an alkyl substitu
• Z and Z each represents the atoms required to complete a nucleus selected from the group consisting of a thiazole nucleus, a benzothiazole nucleus, an a-naphthothiazole nucleus, a fi-naphthothlazole nucleus, a benzoxazole nucleus, a l-alkyl imidazole nucleus, a l-aryl imidazole nucleus, a l-alkyl benzimidazole nucleus, a l-aryl benzimidazole nucleus, a l-alkylnaphth[l,2-d]imidazole nucleus, a l-arylnaphth[1,2-d]imidazole nucleus, a selenazole nucleus and a benzoselenazole nucleus, at least one of Z and Z being selected from the group consisting of a l-
• Z and Z each represents the atoms required to complete a l-alkyl benzimidazole nucleus; R and R each represents an alkyl substituent containing from 1 to 4 carbon atoms; L represents a methine group; and X represents an acid anion; and,
• a method of spectrally sensitizing photographic silver halide grains dispersed in an alkali-permeable colloid which comprises:
• Z and Z each represents the atoms required to complete a nucleus selected from the group consisting of a thiazole nucleus, a benzothiazole nucleus, an :x-naphthothiazole nucleus, a B-naphthothiazole nucleus, a benzoxazole nucleus, a l-alkyl imidazole nucleus, a l-aryl imidazole nucleus, a l-alkyl benzimidazole nucleus, a l-aryl benzimidazole nucleus, a l-aryl benzimidazole nucleus, a l-alkylnaphth[1,2-d]imidazole nucleus, a l-arylnaphth[l,2-d]imidazole nucleus, a selenazole nucleus and a benzoselenazole nucleus; R and R each
• a method for spectrally sensitizing photographic silver halide grains dispersed in an alkali-permeable colloid which comprises:
• Z and Z each represents the atoms required to complete a nucleus selected from the group consisting of a thiazole nucleus, a benzothiazole nucleus, an a-naphthothiazole nucleus, a ,B-naphthothiazole nucleus, a benzoxazole nucleus, a l-alkyl imidazole nucleus, a l-aryl imidazole nucleus, a l-alkyl benzimidazole nucleus, 21 l-aryl benzimidazole nucleus, a 1-alkylnaphth[1,2-d]imida- 'zole nucleus, a 1-arylnaphth[l,2-d]imidazole nucleus, a selenazole nucleus and benzoselenazole nucleus, at least one of Z and Z being selected from the group consisting of a thiazole nucle
• Z and Z each represents the atoms required to complete a nucleus selected from the group consisting of a thiazole nucleus, a benzothiazole nucleus an a-naphthothiazole nucleus, 9.
• R and R each represents an alkyl substituent
• L represents a methine group
• in represents an integer of from l to 3
• X represents an acid anion
• Z and Z each represents the atoms required to complete a nucleus selected from the group consisting of a thiazole nucleus, a benzothiazole nucleus, an a-naphthothiazole nucleus, a fi-naphthothiazole nucleus, a benzoxazole nucleus, a l-alkyl imidazole nucleus, 21 l-aryl imidazole nucleus, a l-alkyl benzimidazole nucleus, a l-aryl benzimidazole nucleus, a l-alkylnaphth[1,2-d]imidazole nucleus, a l-arylnaphth[1,2-d]imidazole nucleus, a selenazole nucleus and benzoselenazole nucleus, at least one of Z and Z being selected from the group consisting of a l-alkyl-benz
• Z and Z each represents the atoms required to complete a l-alkyl benzimidazole nucleus; R and R each represents an alkyl substituent containing from 1 to 4 carbon atoms; L represents a methine group; and, X represents an acid anion;
• the method of spectrally sensitizing a photographic gelatin silver halide emulsion which comprises protonating anhydro 5,5',6,6-tetrachloro-l,l'-diethyl3,3'-di-(4- sulfobutyl)benzimidazolocarbocyanine hydroxide by dissolving said dye in an aqueous solution of sulfuric acid; and, adding said solution of protonated dye to a photographic gelatin silver halide emulsion having a pH of at least 6.0 whereby said protonated dye is converted to its unprotonated, colored form, and the silver halide is spectrally sensitized.

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• 1966
  • 1966-03-08 US US532593A patent/US3482981A/en not_active Expired - Lifetime
• 1967
  • 1967-02-13 DE DE19671547775 patent/DE1547775A1/de active Pending
  • 1967-03-07 BE BE695140D patent/BE695140A/xx unknown
  • 1967-03-07 GB GB00613/67A patent/GB1177141A/en not_active Expired
  • 1967-03-07 CH CH332867A patent/CH471406A/fr not_active IP Right Cessation
  • 1967-03-08 FR FR97835A patent/FR1513197A/fr not_active Expired

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