US3062646A - Sensitization of silver halide emulsions with macrocyclic compounds - Google Patents

Sensitization of silver halide emulsions with macrocyclic compounds Download PDF

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US3062646A
US3062646A US797577A US79757759A US3062646A US 3062646 A US3062646 A US 3062646A US 797577 A US797577 A US 797577A US 79757759 A US79757759 A US 79757759A US 3062646 A US3062646 A US 3062646A
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issued
compound
emulsions
silver halide
macrocyclic
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John R Dann
Jr John W Gates
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US797577A priority patent/US3062646A/en
Priority to DEE18919A priority patent/DE1124349B/de
Priority to GB5922/60A priority patent/GB942865A/en
Priority to FR820261A priority patent/FR1377252A/fr
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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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
    • C07D291/02—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/08—Bridged systems

Definitions

  • This invention relates to photographic silver halide emulsions, andmore particularly, to an improved means for sensitizing such photographic silver halide emulsions.
  • the compounds used in our invention do not appear to be chemical sensitizers in the usual sense, since they increase speed by their presence during exposure and processing and require no digestion with the photographic emulsion to produce the increase in speed, nor does their chemistry indicate that they are likely to react with silver halide under normal emulsion conditions.
  • novel'sensitizers of our invention are quite unique in that the effects produced are additive in photographic emulsions which have already been sensitized to their optimum, or near-optimum, with conventional chemical sensitizers, such as labile sulfur compounds.
  • the novel sensitizers of our invention can be used to sensitize photographic silver halide emulsions containing no other sensitizers, if desired.
  • the novel sensitizers of our invention are not strictly chemical sensitizers, since chemical sensitizers do not generally provide the additive effects of the type mentioned.
  • Another object of our invention is to increase the sensitivity of ordinary photographic silver halide emulsions which have already been sensitized with chemical sensitizers, such 'as *gold compounds and/ or compounds .containing labile sulfur atoms.
  • the sensitivity of an ordinary photographic silver halide emulsion can be materially increased byincorporating therein a macrocyclic compound containing at least twelve atoms in the ring. At least eight of these atoms'in the ringare carbon atoms andat least one of these atoms is a sulfur atom.
  • Identificationcrocyclic compounds of our'invention also contain at least one oxygen atom and/or one nitrogen atom in the heterocyclic ring.
  • the macrocyclic compounds of our invention can contain various functional groups as substituents-to the macrocyclic ring, or they can actually contain these functional groups within the heterocyclic, macrocyclic ring. Typical functional groups include carboxylicester linkages, carboxylicamide linkages, thioether linkages, ether linkages, etc. Polar functional groups have been foundto provide especially useful results in our macrocyclic compounds.
  • the macrocyclic compounds of our invention should have sufficient dispersibility in water (or a dilute alkaline solution), or in an organic solvent, such as acetone, the lower aliphatic alcohols (e.g., ethanol, propanol,'butano1, etc.), 1,4-dioxane, ethylacetate, etc. (directly, .or in a colloid mill, or by other means, such as by a dispersing agent, e.g., sodium laurylsulfate, etc.), so that a sensitizing amount of the macrocycliccompound can be adsorbed by or associated with the silver halidegrains.
  • an organic solvent such as acetone
  • the lower aliphatic alcohols e.g., ethanol, propanol,'butano1, etc.
  • 1,4-dioxane ethylacetate, etc.
  • a dispersing agent e.g., sodium laurylsulfate, etc.
  • the macrocyclic compounds useful in practicing our invention can be called thiacycloalkanes, .which contain In general, we have found that particularly useful compounds contain from about eight to sixteen carbon atoms .in the .macrocyclic ring, from about one to .foursulfur atoms wherein-R and "R each represents a hydrocarbon alkylene 'group or an alkylene group, the carbon chain'of'which is interrupted by an oxygen atom, a sulfur atom, a carboxylic ester linkage, a carbonic ester linkage, or a carboxylic amide linkage, and Q represents an oxygen atom or a sulfur atom, provided, of course, that said macrocyclic compound contains at 'least twelve carbon atoms in the marocyclic ring and contains at least one oxygen atom and/ or onenitrogen atom.
  • Macrocyclic compounds embraced by Formula Iabove which can be used in our invention, comprise compounds selected from the class'representedby the following general formula:
  • R and R" each represents an alkylene group, such as ethylene, methyl-substituted ethylene, ethyl-substituted ethylene, propylene, butylene, etc.
  • Q represents -a I and la above
  • these compounds can be prepared by heating together an alkali metal sulfide (e.g., potassium sulfide, sodium sulfide, etc.) with a compound selected from those represented by the following general formula: hal-Rhal wherein hal represents a halogen atom, such as chclorine or bromine, and R has the values given above.
  • the reaction of one molecule of a compound of Formula II with one molecule of an alkali metal sulfide produces the compounds of Formula Ia wherein Q is an oxygen atom.
  • the reaction of two molecules of a compound of Formula II with two molecules of an alkali metal sulfide produces the compound of Formula Ia Where Q represents a sulfur atom.
  • These condensations can advantageously be carried out in a reaction medium containing substantial quantities of diluent, which favors the formation of macrocyclic compounds.
  • Typical diluents include the lower aliphatic alcohols, such as ethyl alcohol, propyl alcohol, etc., which may or may not be diluted with water.
  • the desired macrocyclic compounds can be readily extracted from the reaction mixture with a suitable solvent, such as one of the lower aliphatic alcohols.
  • the compounds of Formula I above can be prepared by reacting together one molecule of a compound of Formula II with one molecule of a dimercaptan selected from those represented by the following general formula:
  • R represents an alkylene group, such as ethylene, methylene, propylene, etc.
  • X represents a hydrocarbon alkylene group, such as ethylene, propylene, butylene, etc., an alkylene group, the carbon chain of which is interrupted by an oxygen atom or a sulfur atom, or the group:
  • R represents a hydrogen atom, a hydroxyl group, a sulfo group, a carboxyl group, or an amino group
  • Y represents a hydrocarbon alkylene group, such as methylene, ethylene, propylene, butylene, etc., or an alkylene group, the carbon chain of which is interrupted by an oxygen atom or a sulfur atom.
  • the carbon atoms in the macrocyclic compounds of our invention can contain various substituents, such as alkyl groups, aryl groups, substituted alkyl groups, such as carboxymethyl hydroxymethyl, etc.
  • certain of'the compounds represented 'by Formula IV above can be prepared by conventional methods, such as by acylation of an amine by a carboxylic acid, anhydride, or halide. This method of preparation -is illustrated in one of the following examples.
  • These "compounds can also be prepared by reacting a dibasic acid or halide (or anhydride) with an aliphatic diamine, care being taken in all of these reactions to provide a large quantity'of-diluent for the reactions in order to favor the formation of macrocyclic compounds. In general, it has been 'found that the concentration of the reactants should not be greater than about 0.02 molar to obtain optimum results.
  • the same reaction may be run in a higher state of dilution, for example, in 400 ml. of ethyl alcohol and 400 ml. of water. Such dilute conditions favor the intramolecular reactions leading to cyclic compounds.
  • Compound 2 above was prepared in exactly the manner illustrated in Example A by replacing the substituted ethane compound of that example by a molecularly equivalent amount of his (2-chloroethyl)ether.
  • Compound 3 was prepared in like manner by replacing the substituted ethane compound of Example A by a molecularly equivalent amount of bis(3-chloro-n-propyl) ether.
  • Compound 4 was prepared in like manner by replacing the substituted ethane compound of Example A by a molecularly equivalent amount of bis(2-chloroisopropyl) ether.
  • Compound 5 was prepared according to the method of Example A above by replacing the substituted ethane compound of that example by a molecularly equivalent amount of bis(2-chloroethyl)carbonate.
  • EXAMPLE B.COMPOUND 2 A reaction mixture composed of 14.3 g. of bis(2-chloroethy1)ether, 13.8 of bis(2-mercaptoethyl)ether, 10.6 g. of sodium carbonate, .3000 ml. of ethyl alcohol, and 3000 ml. of water was refluxed on a steam bath for 63 hours, and the solvents were then removed by distillation in vacuum. Extraction of the residue with hot ethyl acetate removed the organic product which was then recovered from the ethyl acetate by evaporation and distillation in vacuum to give a colorless oil, B.P. 118 C./1 mm.
  • C H O S The calculated analysis for the above product, C H O S is as follows: C, 46.1; H, 7.7; S, 30.8; mol. wt. 208. The analysis found was: C, 45.2; H, 7.7; S, 30.3; mol wt. 218.
  • the concentration of reactants was 0.002 molar.
  • the desired "8 product was found to have a molecular weight of 410 by boiling point elevation.
  • This compound was also prepared by reacting 1,2-bis(2- mercaptoethoxy)ethane with N,N'-methylene bis(B-propionamide) at a dilution of 0.00025 molar. A mixed melting point determination of this material with that obtained immediately above showed no depression. The melting point was 197-199 C.
  • N,N'-methylene bis chloroacetamide was prepared (Ann., vol. 343, page 282) and 1.9 g. (0.01 mole) were dissolved in 4 liters of 50% ethanol containing 1.1 g. of Na CO To this solution were added 1.82 g. (0.01 mole) of 1,2-bis(2-mercaptoethoxy)ethane, and the mixture was heated under reflux for 48 hours. The solvent was removed and the residue was recrystallized twice from ethanol to give 2.4 g. (78%) of material melting sharply at 2092l0 C.
  • EXAMPLE B.COMPOUND 8 The reaction of acrylamide with bis(2-mercaptoethyl)- ether followed by reaction with formaldehyde. A mixture of 6.9 g. (0.05 mole) of bis(2-mercaptoethyl)ether and 7.1 g. (0.10 mole) of acrylamide in 500 ml. of absolute ethanol containing 10 drops of benzyl trimethyl ammonium hydroxide solution (30% in methanol) was heated under reflux for two hours, and upon cooling the white precipitate of 3,9-dithia-6-oxa-Lll-undecane dicarboxamide, was filtered ofl and washed with ethanol.
  • EXAMPLE F.COMPOUND 9 fi-Chloropropionyl chloride, 25.4 g. (0.2 mole), was dissolved in 50 ml. of dry diethyl ether and placed in a flask equipped with a stirrer, reflux condenser and dropping funnel. The flask was cooled in an ice bath, and with rapid stirring 6.0 g. (0.1 mole) of ethylenediamine were added dropwise over a 30-minute period. The reaction mixture was then left overnight at room temperature, and a white precipitate was filtered oil and recrystallized from ethanol.
  • EXAMPLE G.COMPOUND 10 Methylene bis acrylamide, 6.28 g. (0.04 mole), and 2,3-dimercapto-1-propanol, 4.32 g. (0.04 mole), were dissolved in 1600 ml. of ethyl alcohol and 10 drops of a 35% solution in methanol of benzyl trimethyl ammonium hydroxide were added as a catalyst. The reaction mixture was heated under reflux for 72 hours. The solvent was partially removed and precipitate A was filtered olf. Upon removal of the remainder of the solvent, a residue, B, was found. Both A and B were recrystallized from ethanol. A-M.P. l93-l98 C. BM.P. 214215 C. '5
  • EXAMPLE H.COMPOUND 11 A reaction mixture composed of 32.0 g. of bis 2-(2- bromoethoxy)ethyl ether, 24.0 g. of sodium sulfide nonahydrate, 2000 ml. of ethyl alcohol and 2000 ml. of water 315 was refluxed on a steam bath for 41 hours, and the solvents were then removed by distillation in vacuum. Extraction of the residue with hot ethyl acetate removed the organic product which was then recovered from the ethyl acetate by-evaporation and distillation in vacuum to give a clear colorless oil. B.P. 90-95 C./1 mm.
  • C H O S The calculated analysis for the above product, C H O S is as follows: C, 50.0; H, 8.3; S, 16.7; mol. wt. 384. The analysis found was: C, 50.2; H, 8.7; S, 16.3;mol. Wt. 352.
  • EXAMPLE K.-COMPOUND 14 Glycol dimercaptoacetate, 21.0 g. (0.1 mole), and .N,N'-methylene bis acrylamide, 15.4 g. (0.1 mole), were dissolved in 2 liters of ethyl alcohol and added dropwise 0 bath for 7 hours.
  • the macrocyclic compounds of our invention can be added to ordinary photographic silver halide emulsions for the purpose of increasing the sensitivity thereof. These macrocyclic compounds are conveniently added to the emulsions in the form of their solutions -or dispersions in organic solvents or organic solvents diluted with water.
  • the preparation of photographic silver halide emulsions involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess water-soluble salts, usually by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity.
  • the sensitizers of our invention can be added to the emulsion before the final digestion or after-ripening, or they can be added immediately prior to the coating. Our new photographic sensitizers require no special final digestion or after-ripening.
  • the particular quantity of macrocyclic compound used in a given emulsion can vary, depending upon the effects desired, degree of ripening, silver content of the emulsion, etc. The amount 'used is also dependent upon the particular stage at which the sensitizer is added during the preparation of the emulsion. We have found that from about 50 mg. to about 5 g. of macrocyclic compounds per mole of silver halide is quite adequate to accomplish the desired sensitization of many of the common photographic silver halide emulsions.
  • the sensitizers of our invention can be added to photographic emulsions using any of the well-known techniques in emulsion making.
  • the sensitizers can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color-forming compounds (couplers) in a photographic emulsion.
  • Techniques of this type are described in Jelley et al. US. Patent 2,322,- 027, issued June 15, 1943, and Fierke et al. US. Patent 2,801,171, issued July 30, 1957.
  • the solvent should be selected so that it has no harmful efiect upon the emulsion, and generally solvents or dlluents which are miscible with water are to be preferred.
  • Water or diute alkali is a dispersing medium for some of the sensitizers of the invention.
  • the sensitizer can be dissolved in solvents, such as ethanol, acetone, pyridine, N,N-dimet'nylformamide, etc., and added to the emulsion in this form.
  • certain of the sensitizers can be prepared in finely-divided form and dispersed in water alone, or in the presence of a suitable dispersing agent (such as alkali metal salts of aromatic or aliphatic sulfonic acids) and added to the emulsion in this form.
  • a suitable dispersing agent such as alkali metal salts of aromatic or aliphatic sulfonic acids
  • the sensitizers of our invention should have sufiicient water-dispersibility so that they can be adsorbed to the grains of the silver halide present in the emulsion in sufficient amount to sensitize the emulsion. It is apparent that the optimum amount for each of the sensitizers will vary somewhat from emulsion to emulsion and from sensitizer to sensitizer.
  • the optimum amount for any given sensitizer can be determined for any particular emulsion by running a series of tests in which the quantity of sensitizer is varied over a given range. Exposure of the treated emulsion in conventional photographic testing apparatus, such as an intensity scale sensitometer, will reveal the most advantageous concentrations for that sensitizer in that particular emulsion. Such matters are well understood by those skilled in the art.
  • photographic emulsions used in practicing our invention are, of course, of the developing-out type.
  • the emulsions can be chemically sensitized by any of the accepted procedures.
  • the emulsions can be digested with naturally active gelatin, or sulfur compounds can be added such as those described in Sheppard US. Patent 1,574,944, issued March 2, 1926, Sheppard et al. US. Patent 1,623,499, issued April 5, 1927, and Sheppard and Brigham US. Patent 2,410,689, issued November 5, 1946.
  • the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli US. Patent 2,448,060, issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith US. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller et al. US. Patent 2,399,- 083, issued April 23, 1946, or stabilized with gold salts as described in Damschroder US. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers US. Patent 2,597,915, issued May 27, 1952.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll US. Patent 2,487,850, issued November 15, 1949, polyamines, such as diethyltriamine (Lowe and Jones US. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen US. Patent 2,521,925, issued September 12, 1950), or bis([3-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones US. Patent 2,521,- 926, issued September 12, 1950).
  • reducing agents such as stannous salts (Carroll US. Patent 2,487,850, issued November 15, 1949, polyamines, such as diethyltriamine (Lowe and Jones US. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen US. Patent 2,521,925, issued September 12, 1950), or bis([3-aminoethyl) sulf
  • the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker US. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White US. Patent 1,990,507, issued February 12, 1935; Brooker and White US. Patents 2,112,-
  • Patent 2,493,7408 issued January 10, 1950; Sprague US. Patents 2,503,776, issued April 11, 1950, and 2,519,001, issued August 15, 1950; Heseltine and Brooker US. Patent 2,666,761, issued January 19, 1954; Heseltine US. Patent 2,734, 900, issued February 14, 1956; Van Lare US. Patent 2,739,149, issued March 20, 1956; and Kodak Limited British Patent 450,958, accepted July 15, 1936.
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers, and Murray US. Patent 2,728,663, issued December 27, 1955; Carroll and Murray US. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray US. Patent 2,728,665, issued Decrnber 27, 1955; the triazoles of l-leimbach and Kelly US. Patent 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly US. Patents 2,444,605 and 2,444,- 606, issued July 6, 1948; Heimbac'n US. Patents 2,444,- 607, issued July 6, 1948, and 2,450,397, issued September 28, 1948; Heimbach and Clark US. Patent 2,444,609, issued July 6, 1948; Allen and Reynolds US.
  • Patent 2,694,716, issued November 16, 1954 e.g., decamethylene bis benzothiazolium perchlorate
  • zinc and cadmium salts of Jones US. patent application Serial No. 493,047, filed March 8, 1955 now US. Patent 2,839,405, issued June 17, 1958.
  • the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll US. Patent 2,271,623, issued February 3, 1942; Carroll and Allen US. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence US. Patent 2,334,864, issued November 23, 1943; and the polyethylene glycol type of Carroll and Beach US. Patent 2,708,162, issued May 10, 1955.
  • the emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murray US. application Serial No. 588,951, filed June 4, 1956 (now US. Patent 2,960,404, issued November 15, 1960); an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton US. application Serial No. 662,564, filed May 31, 1957 (now US. Patent 2,904,- 434, issued September 15, 1959); bis-(ethoXy diethylene glycol) succinate as described in Gray US. application Serial No. 604,333, filed August 16, 1956 (now US.
  • Patent 2,940,854, issued June 14, 1960 or a polymeric hydrosol as results from the emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in Tong US. patent application Serial No. 311,319, filed September 24, 1952 (now US. Patent 2,852,386, issued September 16, 1958).
  • the plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
  • the emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo(2,2,2)-7-0ctene-2,3,5, 6-tetracarboxylic dianhydride, or a dicarboxylic or a disulfcnic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfor1yl chloride as described in Allen 13 and Carroll U.S.
  • any suitable hardener for gelatin such as formaldehyde
  • a halogen-substituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937
  • Patent 2,726,162 issued'December 6, 1955 1,3-dihydroxymethylbenzimidazol-Z-one as described in July, Knott and Pollak U.S. Patent 2,732,316, issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 23 carbon atoms, such as fi-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness Canadian Patent 588,- 451, issued December 8, 1958; a bisaziridine carboxamide such as trimethylene 'bis(1-aziridine carboxamide) as described in Allen and Webster U.S. patent application Serial No.
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis US. Patent 2,831,766, issued April 22, 1958; a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955; an acylatedalkyl taurine such as the sodium salt of N-oleoyl- N-methyl taurine as described in Knox, Twardokus and Davis U.S.
  • a coating aid such as saponin
  • a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis US. Patent 2,831,766, issued April 22, 1958
  • a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955
  • an acylatedalkyl taurine such
  • Patent 2,739,891 issued March 27, 1956; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxy butane as described in Knox, Stenberg and Wilson U.S. patent application Serial No. 485,812, filed February 2, 1955 (now U.S. Patent 2,843,487, issued July 1, 1958); a water-soluble maleopim arate or a mixture of a watersoluhle maleopimarate and a substituted glutamate salt as described in Knox and Fowler U.S.
  • Patent 2,823,123 issued February 11, 1958; an alkali metal salt of a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypentaethoxy) glutamate as described in Knox and Wilson U.S. patent application Serial No. 600,679, filed July 30, 1956 (now U.S. Patent 3,038,804, issued June 12, 1962); or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate as described in Knox and Stenberg U.S. patent application Serial No. 691,125,, filed October 21, 1957 (now U.S. Patent 2,992,108, issued July 11, 1961).
  • a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypenta
  • the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitiveemulsions. They may be added to the emulsion before or after any sensitizing dyes which are used.
  • Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the agents may be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type, such as described in Godowsky U.S. Patent 2,698,794, issued January 4, 1955; or emulsions of the mixed-grain type, such as described in-Carroll and Hanson U.S. Patent 2,592,243, issued April 8, 1952.
  • These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystals, such as those described in Davey and Knott U.S. Patent 2,592,250, issued April 8, 1952.
  • the dispersing agent for the silver halide in its preparation gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • colloidal albumin colloidal albumin
  • a cellulose derivative a cellulose derivative
  • synthetic resin for instance, a polyvinyl compound.
  • colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in U.S.
  • Patent 2,768,154 issued October 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,808,331, issued October '1, 1957; or a polymeric material which results from polymerizing .a protein or a saturated acylated protein with a monomer having a vinyl group .as described in U.S. application Serial No. 527,872 of Illingsworth, Dann and Gates, filed August 11, 1954 (noW U.S. Patent 2,852,382, issued September 16, 1958).
  • -con1patible mixtures of two-or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Combinations of these antifoggants, sensitizers, hardeners, etc., may be used.
  • the sensitized emulsions of our invention can be used in the preparation of color photographs. This may be accomplished either by using photographic emulsions containing color-forming compounds or couplers, or by the use of photographic emulsions which are developed in color developers containing color-form ing compounds or couplers.
  • Color-forming compounds or couplers which can be incorporated in photographic silver halide emulsions to provide the useful results of our invention include the couplers listed in Graham and SagalU'S. application Serial No. 779,839, filed December 12, 1958. Typical couplers include the following:
  • Couplers Producing Cyan Images Nnoo-ou-o- -ouu Couplers Producing Magenta Images etc.
  • sensitizers can be added to ordinary photographic silver halide emulsions of the type used in black-and-White photography, such as gelatino-silverbromiodide emulsions, and the emulsions exposed in an intensity scale sensitometer to daylight quality radiation for a fraction of a second (usually and processed for about 15 minutes in a phenylenediamine color developer, to which has been added 10 g. per liter of H- acid.
  • the pH of this developer is usually adjusted to 10.8 by adding sodium hydroxide.
  • a suitable developer composition for this screening technique is as follows.
  • the relative speed, as compared with a portion of the emulsion containing no macrocyclic compound, and fog for each of the coatings was then measured.
  • Table II is shown the effect produced by one of our macrocyclic compounds in an ordinary negative speed silver bromiodide emulsion which had been digested to optimum sensitivity with a mixture of a labile sulfur compound of the type shown in Sheppard US. Patent 1,623,499, mentioned above, and a gold compound of the type shown, for example, in US. Patent 2,448,060, mentioned above, and which had been red-sensitized (ca. 600-700 mg) with a spectral sensitizing dye.
  • the emulsion contained a macrocyclic compound in the amount indicated in the table, and also contained a coupler dispersion of one of the color-forming compounds for producing the cyan image upon color development, as identified further below.
  • Two series of coatings were prepared for each of the emulsions, one for processing in a color negative process and another series for processing in a reversal color process.
  • Each of the emulsions was coated on a transparent support, such as cellulose acetate film, dried, and then exposed in an Eastman Type Ib Sensitometer to daylight quality radiation for approximately 4 second.
  • Each was then processed through the color negative process or the reversal color process.
  • a typical negative color process is described in detail by W. T. Hanson, Jr. and W. I. Kisner in an article in the Journal of the Society of Motion Picture and Television Engineers, vol. 61 (1953), pages 667-701.
  • the reversal color process was as follows:
  • the exposed film was developed in a developer having the following composition:
  • Potassium dichromate g 5.0 Potassium ferricyanide g 70.0 Potassium bromide g 200 Water to make 1 liter.
  • the element was again washed and treated once again with the clearing and fixing bath identified above.
  • the element was again washed and treated in a stabilizing bath having the following composition:
  • Triton X-100 i.e., an alkylaryl polyether alcohol (octylphenoxy polyethoxy ethanol).
  • the emulsion contained a dispersion of a phenol coupler, e.g., one of the couplers numbered 1 to 6 of Fierke et al. US. Patent 2,801,171 (column 2), in a suitable solvent, such as tri-o-cresyl phosphate, or dibutyl phosphate.
  • a suitable solvent such as tri-o-cresyl phosphate, or dibutyl phosphate.
  • the emulsions contained a dispersion in tri-o-cresylphosphate of a pyrazolone coupler, e.g., couplers Nos. 7, etc., of Fierke et al. US. Patent 2,801,171 (column 2) and a phenylazopyrazolone coupler, e.g., coupler No. 8 of US Patent 2,801,171.
  • the speed and density for each of the coatings is shown in the following table after the coatings were exposed in an Eastman Type Ib Sensitometer to daylight quality radiation and after processing in the color negative process or the reversal color process.
  • the macrocyclic compounds of our invention can be added to photographic developers, which may or may not contain color-forming compounds, in order to increase the effective speed of photographic emulsions which have not been previously sensitized by incorporation of one of the macrocyclic compounds of our invention.
  • This discovery has been found to apply to the number of photographic silver halide emulsions, including emulsions containing color-forming compounds or couplers, as well as photographic silver halide emulsions containing no such color-forming compounds.
  • the latter emulsions can be used in black-and-white photography, or alternatively, they can be used in a photographic, color process wherein the color-forming components are incorporated in the color developers.
  • photographic silver halide emulsions can be sensitized with macrocyclic compounds similar to those illustrated above, wherein the sulfur atoms of the macrocyclic ring are replaced by oxygen atoms.
  • macrocyclic compounds similar to those illustrated above, wherein the sulfur atoms of the macrocyclic ring are replaced by oxygen atoms.
  • two molecules of ethylenediamine can be condensed with two molecules of methylmethacrylate at a temperature of about 3040 C., over a period of about 65 minutes to provide 1,5,8,12-tetraza-3,lO-dimethyl-2,9-cyclotetradecanedione.
  • This compound was particularly effective in photographic emulsions intended for color photography and produced a speed increase of 100% in such emulsions.
  • Similar compounds can be prepared by replacing the ethylenediamine with other aliphatic or aromatic primary diarnines, including diethylenetriamine, cystine, djenkolic acid, 1,3-diamino-2-propanol, etc. It has been found, in general, that these oxygen analogues do not provide sensitizing properties comparable to those provided by the sulfur compounds of the present invention.
  • Macrocyclic compounds of the classes represented by Formulas I, Ia and IV containing less than 12 atoms in the ring can also be added to photographic silver halide emulsions to alter the sensitivity thereof, although macrocyclic compounds as hereinafter claimed have been found to be especially useful.
  • R and R each represents a member selected from the class consisting of alkylene and alkylene-W- alkylene, wherein w represents a member selected from the class consisting of an oxygent atom, a sulfur atom, a carboxylic ester radical, a carbonic ester radical and a carboxylic amide radical, and Q represents a member selected from the class consisting of an oxygen atom and a sulfur atom, said marcocylic compound containing at least 12 atoms in a monocyclic, macrocyclic ring, and containing at least one atom selected from the class consisting of an oxygen atom and a nitrogen atom in said monocyclic, macrocyclic ring, said monocyclic, macrocyclic ring consisting of from 8 to 16 carbon atoms, from 1 to 4 sulfur atoms, from 0 to 6 oxygen atoms and from 0 to 4 nitrogen atoms.
  • R represents alkylene containing from 1 to 3 carbon atoms
  • X represents a member selected from the class consisting of (1) alkylene containing from 2 to 4 carbon atoms, and (2) alkylene-w-alkylene, wherein W represents a member selected from the class consisting of an oxygen atom and a sulfur atom, and (3) a group wherein R represents a member selected from the class consisting of a hydrogen atom, a hydroxyl group, a sulfo group, a carboxyl group and an amino group, and Y represents a member selected from the class consisting of alkylene containing from 1 to 4 carbon atoms and alkylene-w-alkylene, wherein w represents a member selected from the class consisting of an oxygen atom, and a sulfur atom, said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring.
  • a photographic silver halide emulsion which has been sensitized with a labile sulfur compound and a gold salt, said photographic silver halide emulsion containing a sensitizing amount of a macrocyclic compound selected 21 from the class represented by the following general formual:
  • R and R each represents a member selected from the class consisting of alkylene and alkylene-walkylene
  • w represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a carboxylic ester radical, a carbonic ester radical and a carboxylic amide radical
  • Q represents a member selected from the class consisting of an oxygen atom and a sulfur atom
  • said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring, and containing at least one atom selected from the class consisting of an oxygen atom and a nitrogen atom in said monocyclic, macrocyclic ring, said monocyclic, macrocyclic ring consisting of from 8 to 16 carbon atoms, from 1 to 4 sulfur atoms, from to 6 oxygen atoms and from 0 to 4 nitrogen atoms.
  • a photographic silver halide emulsion which has been sensitized with a labile sulfur compound and a gold compound, said photographic silver halide emulsion containing a sensitizing amount of a macrocyclic compound selected from the class represented by the following general formula:
  • R and R" each represents alkylene containing from 2 to 4 carbon atoms
  • Q represents a member selected from the class consisting of a sulfur atom and an oxygen atom
  • m and n each represents a positive integer of from 1 to 3, said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring.
  • a photographic silver halide emulsion containing a sensitizing amount of a labile sulfur compound and a gold salt said photographic silver halide emulsion containing a sensitizing amount of a macrocyclic compound selected from the class represented by the following general formula:
  • R represents alkylene containing from 1 to 3 carbon atoms
  • X represents a member selected from the class consisting of (1) alkylene containing from 2 to 4 carbon atoms, (2) alkylene-w-alkylene, wherein W represents a member selected from the class consisting of an oxygen atom and a sulfur atom
  • W represents a member selected from the class consisting of an oxygen atom and a sulfur atom
  • Y represents a member selected from the class consisting of alkylene containing from 1 to 4 carbon atoms and alkylene-w-alkylene, wherein w represents a member selected from the class consisting of an oxygen atom, and a sulfur atom, said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring.
  • R and R each represents a member selected from the class consisting of a alkylene and alkylene-walkylene
  • w represents a member selected from the class consisting of an oxygen atom, a sulfur atom, a carboxylic ester radical, a carbonic ester radical and a carboxylic amide radical
  • Q represents a member selected from the class consisting of an oxygen atom and a sulfur atom
  • said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring, and containing at least one atom selected from the class consisting of an oxygen atom and a nitrogen atom in said monocyclic, macrocyclic ring, said monocyclic, macrocyclic ring consisting of from 8 to 16 carbon atoms, from 1 to 4 sulfur atoms, from O to 6 oxygen atoms and from 0 to 4 nitrogen atoms.
  • a method for producing a photographic image comprising developing an exposed photographic silver halide emulsion in the presence of a macrocyclic compound selected from the class represented by the following general formula:
  • R and R each represents a member selected from the class consisting of alkylene and alkylene-w-alkylene, wherein w represents a member selected from the class consisting of an oxygent atom, a sulfur atom, a carboxylic ester radical, a carbonic ester radical and a carboxylic amide radical, and Q represents a member selected from the class consisting of an oxygen atom and a sulfur atom, said macrocyclic compound containing at least 12 atoms in a monocyclic, macrocyclic ring, and containing at least one atom selected from the class consisting of an oxygen atom and a nitrogen atom in said monocyclic, macrocyclic ring, said monocyclic, macrocyclic ring consisting of from 8 to 16 carbon atoms, from 1 to 4 sulfur atoms, from to 6 oxygen atoms and from 0 to 4 nitrogen atoms.
  • Rgi loRsoi lRz carbon atoms and R represents alkylene containing from 2 to 4 carbon atoms.
  • a photographic silver halide emulsion containing a sensitizing amount of a labile sulfur compound and a gold compound said photographic silver halide emulsion containing a sensitizing amount of a macrocyclic compound selected from the class represented by the following general formula:
  • R represents alkylene containing from 1 to 3 carbon atoms and R represents alkylene containing from 2 to 4 carbon atoms.

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DEE18919A DE1124349B (de) 1959-03-06 1960-02-18 Verfahren zur Sensibilisierung photographischer Emulsionen und zugehoerige sensibilisierte Emulsion
GB5922/60A GB942865A (en) 1959-03-06 1960-02-19 Photographic silver halide emulsions of increased sensitivity
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271157A (en) * 1962-09-11 1966-09-06 Eastman Kodak Co Light-developable direct-print silver halide emulsions
US3419393A (en) * 1965-02-24 1968-12-31 Ilford Ltd Cyclic thioether silver halide development accelerators
US3531289A (en) * 1966-12-02 1970-09-29 Eastman Kodak Co Silver halide photographic emulsions improved by new precipitation methods
US4017314A (en) * 1976-01-07 1977-04-12 E. I. Du Pont De Nemours And Company Use of crown compounds (cyclic polyethers) in litho developers to improve halftone dot quality and gradation
US4198240A (en) * 1977-06-03 1980-04-15 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4251617A (en) * 1979-10-01 1981-02-17 Polaroid Corporation Novel silver complexing agents
US4267256A (en) * 1979-10-01 1981-05-12 Polaroid Corporation Novel silver complexing agents
US4267254A (en) * 1979-10-01 1981-05-12 Polaroid Corporation Photographic process
US4272632A (en) * 1979-10-01 1981-06-09 Polaroid Corporation Novel silver complexing agents
US4297439A (en) * 1978-06-02 1981-10-27 Agfa-Gevaert Ag Production of photographic silver halide emulsion
US4311638A (en) * 1979-10-01 1982-01-19 Polaroid Corporation Silver complexing agents
US4353976A (en) * 1979-10-01 1982-10-12 Polaroid Corporation Novel silver complexing agents
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4752560A (en) * 1985-09-24 1988-06-21 Eastman Kodak Company Photographic element containing a cyclic thioether compound
US4782013A (en) * 1987-07-23 1988-11-01 Eastman Kodak Company Photographic element containing a macrocyclic ether compound
US4865965A (en) * 1987-06-12 1989-09-12 Eastman Kodak Company Light sensitive emulsion and element containing a cyclic ether compound and process for using same
EP0509810A1 (en) * 1991-04-16 1992-10-21 Konica Corporation Light-sensitive silver halide photographic material
US5252455A (en) * 1992-03-04 1993-10-12 Eastman Kodak Company Photographic silver halide material comprising gold (I) complexes comprising sulfur- and/or selenium-substituted macrocyclic polyether ligands
EP0691569A1 (en) 1994-07-04 1996-01-10 Kodak-Pathe Photographic emulsion with improved sensitivity
US5500337A (en) * 1991-10-15 1996-03-19 Eastman Kodak Company Dyes comprising thioether macrocycles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU206781B (en) * 1990-01-15 1992-12-28 Forte Fotokemiai Ipar Method for chemical sensibilizing silver-halogenide photo emulsion

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Publication number Priority date Publication date Assignee Title
US2131038A (en) * 1932-05-26 1938-09-27 Eastman Kodak Co Photographic emulsion containing alkyl quaternary salts of thiazoles and the like asantifoggants
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds
US2940851A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131038A (en) * 1932-05-26 1938-09-27 Eastman Kodak Co Photographic emulsion containing alkyl quaternary salts of thiazoles and the like asantifoggants
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds
US2940851A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271157A (en) * 1962-09-11 1966-09-06 Eastman Kodak Co Light-developable direct-print silver halide emulsions
US3419393A (en) * 1965-02-24 1968-12-31 Ilford Ltd Cyclic thioether silver halide development accelerators
US3531289A (en) * 1966-12-02 1970-09-29 Eastman Kodak Co Silver halide photographic emulsions improved by new precipitation methods
US4017314A (en) * 1976-01-07 1977-04-12 E. I. Du Pont De Nemours And Company Use of crown compounds (cyclic polyethers) in litho developers to improve halftone dot quality and gradation
US4198240A (en) * 1977-06-03 1980-04-15 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4297439A (en) * 1978-06-02 1981-10-27 Agfa-Gevaert Ag Production of photographic silver halide emulsion
US4311638A (en) * 1979-10-01 1982-01-19 Polaroid Corporation Silver complexing agents
US4267254A (en) * 1979-10-01 1981-05-12 Polaroid Corporation Photographic process
US4272632A (en) * 1979-10-01 1981-06-09 Polaroid Corporation Novel silver complexing agents
US4267256A (en) * 1979-10-01 1981-05-12 Polaroid Corporation Novel silver complexing agents
US4251617A (en) * 1979-10-01 1981-02-17 Polaroid Corporation Novel silver complexing agents
US4353976A (en) * 1979-10-01 1982-10-12 Polaroid Corporation Novel silver complexing agents
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4752560A (en) * 1985-09-24 1988-06-21 Eastman Kodak Company Photographic element containing a cyclic thioether compound
US4865965A (en) * 1987-06-12 1989-09-12 Eastman Kodak Company Light sensitive emulsion and element containing a cyclic ether compound and process for using same
US4782013A (en) * 1987-07-23 1988-11-01 Eastman Kodak Company Photographic element containing a macrocyclic ether compound
EP0509810A1 (en) * 1991-04-16 1992-10-21 Konica Corporation Light-sensitive silver halide photographic material
US5246828A (en) * 1991-04-16 1993-09-21 Konica Corporation Light-sensitive silver halide photographic material
US5500337A (en) * 1991-10-15 1996-03-19 Eastman Kodak Company Dyes comprising thioether macrocycles
US5252455A (en) * 1992-03-04 1993-10-12 Eastman Kodak Company Photographic silver halide material comprising gold (I) complexes comprising sulfur- and/or selenium-substituted macrocyclic polyether ligands
US5391727A (en) * 1992-03-04 1995-02-21 Eastman Kodak Company Photographic silver halide material comprising novel gold compound
EP0691569A1 (en) 1994-07-04 1996-01-10 Kodak-Pathe Photographic emulsion with improved sensitivity

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