US3057724A - Internal amide, nonpolymeric thioether sensitizers for photographic emulsions - Google Patents

Internal amide, nonpolymeric thioether sensitizers for photographic emulsions Download PDF

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US3057724A
US3057724A US858872A US85887259A US3057724A US 3057724 A US3057724 A US 3057724A US 858872 A US858872 A US 858872A US 85887259 A US85887259 A US 85887259A US 3057724 A US3057724 A US 3057724A
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issued
emulsions
silver halide
emulsion
photographic
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William G Lovett
Peter P Chiesa
John R Dann
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US858872A priority patent/US3057724A/en
Priority to DEE19995A priority patent/DE1124351B/de
Priority to FR845595A priority patent/FR1280802A/fr
Priority to GB31738/64A priority patent/GB976837A/en
Priority to GB41509/60A priority patent/GB976836A/en
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Priority to US357801A priority patent/US3165552A/en
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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

Definitions

  • This invention relates to photographic silver halide emulsions, and more 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 an increase in speed, nor does their chemistry seem to 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 he 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.
  • an object of our invention to provide "ice photographic silver halide emulsions which have been sensitized with various non-polymeric compounds containing a plurality of sulfur atoms.
  • Another object of our invention is to increase the sensitivity of ordinary photographic silver halide emulsions whichhave been sensitized with chemical sensitizers, such as compounds containing labile sulfur atoms, or gold-containing compounds.
  • chemical sensitizers such as compounds containing labile sulfur atoms, or gold-containing compounds.
  • thioether we mean a linkage wherein the sulfur atom is divalent and is joined to two non-oxocarbonylic carbon atoms.
  • Compounds useful in sensitizing photographic silver halide emulsions according to the present invention are to be distinguished from the polymeric thioether compounds described in U.S. Patent application Serial No. 779,874, filed December 12, 1958, by I. R. Dann and J. J. Chechak.
  • the polymeric compounds described in this latter application are generally characterized as having high molecular weights and as containing characteristic sulfur-containing repeating units or groups.
  • sensitizing compounds useful in practicing our invention are non-polymeric and can be represented by the following general formula:
  • R represents a methylene group, a substituted methylene group (e.g., methyl-substituted, ethyl-substituted, propyl-substituted, isopropyl-substituted, etc., methylene groups) or a p,p'-hexahydroxylylenyl group .(i.e., a cyc1ohexylene-p,p'-bismethylene group), R represents a hydrogen atom or a methyl group and R represents an alkyl group, such as methyl, ethyl, propyl, butyl, etc., an alkoxyalkyl group, such as methoxyethyl, ethoxyethyl, butoxyethyl, methoxypropyl, etc., an alkoxyalkoxy-alkyl group, such as ethoxyethoxyethyl, methoxyethoxyethyl, etc.
  • R and R each have the values given above and R represents either two hydrogen atoms or a propen-lylidene-3 group.
  • the compounds of Formulas I, II and III can be prepared according to methods illustrated below. Certain of these compounds can be prepared by the addition of a mercaptan compound across an olefinic double bond.
  • Compounds containing a hydrazine group can be prepared by condensing hydrazine with the product resulting from the condensation of a carbethoxythiol compound across an dlefinic double bond, while hydrazide compounds can be prepared by condensing the hydrazine compounds with an aldehyde, such as acrolein.
  • Method B The reaction of an alkyl halide with a thiolacetate compound in the presence of sufiicient alkali to hydrolyze the thiolacetate to a rnercaptan and, if desired, simultaneously effect its reaction with the alkyl halide. This allows the reaction to proceed without the isolation of the free rnercaptan with its attendant difiiculties of purification and danger of oxidation to a disulfide, e.g.,
  • Method D The reaction of hydrazides of the type shown in Method C with aldehydes or ketones, e.g.,
  • EXAMPLE 1 7,9-Diaza-I,15-Dihydroxy-3,13-Dithiapentadecane- 6,10-Dione ll (HO CHzCHzSCHzCHrC-NHhCH Methylene bis acrylamide, 7.7 g. (0.05 mole), and 2- mercaptoethanol, 7.8 g. (0.10 mole), were dissolved in 50 ml. of absolute ethanol containing 10 drops of a 30% methano'lic solution of benzyl trimethylammonium hydroxide. The reaction mixture was heated for 2 hours on the steam bath under a reflux condenser. The product was filtered from the cooled reaction mixture and recrystallized from ethanol. M.P. 17l173 C.
  • This compound was made by the same general method as Example 2.
  • the melting point was 129-131 C.
  • the reaction product obtained by adding 0.2 mole of ethylmercaptoacetate to 0.1 mole of methylene bis acrylamide was heated in 75 ml. of 64% hydrazine hydrate for one hour on the steam bath under a reflux condenser. After standing for 2 days at room temperature, white crystals were formed. These were washed with water and recrystallized from ethanol to give a product melting at 199201 C.
  • Acrolein, 0.23 g. (0.004 mole) and the dihydrazide of 6,8 diaZ-a 1,13 dicarboxy-Z,l2-dithiatridecane-5,9- dione, 0.72 g. (0.002 mole) were dissolved in 37 ml. of water and 12 ml. of ethanol.
  • the reaction mixture was heated on the steam bath for 45 minutes and the white precipitate was filtered off and washed with ethanol.
  • the melting point was 260 C. dec.
  • EXAMPLE 7 8,10-Diaza-1,1 7-Dihydroxy-4,14-Dithiaheptaziecane- 7,1 1 -Dine Reaction of methylene bis acrylamide thiolacetate and 3 bromo-1-propanol 0 (CHa SCH2CHz( JNH)zOHz 2110 CHQCEQGHZBI 0 (HO OHZOEHOHQSOHZOHZ NHhCH
  • This compound was made by the same general method as Example 2. The melting point was 163-165 C.
  • This compound was made -by refluxing the above ingredients for 7 hours, evaporating the solvents and extracting the desired product with hot absolute ethanol. Upon cooling, the precipitate obtained was filtered and recrystallized from ethanol. M.P. 157-159 C.
  • Nnzonwonmm 2o1om01-12ooo1 01011201120 oernonQ-onmno 0 0112011201 HCI OH; HCHO 2CH CHCONH2
  • acrylamide 71 g.
  • isobutyraldehyde 36 g.
  • the mixture was warmed to 3035 C. for 15 minutes, then cooled, the product filtered off, and recrystallized from ethanol. The yield of material was 44 g. M.P. 270 C.
  • the sensitizing compounds of our invention can be added to ordinary photographic silver halide emulsions for the purpose of increasing the sensitivity thereof, as has been indicated above.
  • the preparation of photographic silver halide emulsions involves three separate operations: 1) emulsification and digestion of silver halide, (2) the freeing of the emulsions of excess water-soluble salts, usually by washing with water, and (3) the second digestion or afterripening to obtain increased emulsion speed or sensitivity (Mees, The Theory of the Photographic Process, 1954).
  • 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.
  • sensitizer 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 Was added during the preparation of the emulsion. We have found that generally from about 50 mg. to about 5 g. of sensitizer per mole of silver halide are quite adequate to accomplish the desired sensitization.
  • 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. U.S. Patent 2,322,027, issued June 15, 1943, and Fierke et al. U.S. Patent 2,801,171, issued July 30, 1957.
  • the solvent should be selected so that it has no harmful eifect upon the emulsion, and generally solvents or diluents which are miscible with water are to be preferred.
  • Water or dilute alkali is a dispersing medium for some of the sensitizers of the invention.
  • the sensitizers can be dissolved in a solvent, such as ethanol, acetone, pyridine, N,N-dimethylformamide, etc., and added to the emulsion in this form.
  • certain of the sensitizers can be prepared in finelydivided 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 suflicient water-dispersibility so that they can be adsorbed to or associated with the grains of the silver halide present in the emulsion in sufiicient 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 compound to compound.
  • the optimum amount of any given sensitizer can be determined from 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 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. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et al. U.S. 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 U.S. Patent 2,448,060, issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. 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. U.S. Patent 2,399,- 083, issued April 23, 1946, or stabilized with gold salts as described in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichlon'de and 2- aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,- 518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis(fi-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,- 926, issued September 12, 1950).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,- 518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis(f
  • the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,- 854, issued January 9, 1934; White U.S. Patent 1,990,- 507, issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747 issued January 10, 1950, and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S.
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,- 728,663, issued December 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,- 444,606, issued July 6, 1948; Heimbach US. Patents 2,- 444,607, issued July 6, 1948, and 2,450,397, issued September 28, 1948; Heimbach and Clark U.S.
  • Patent 2,444,- 609 issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955, and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27, 1956, and those disclosed by Birr in Z. wiss. Phot., vol.
  • the emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the thiopolymers of Graham and Sagal U.S. application Serial No. 779,839, filed December 12, 1958, or Dann and Chechak U.S. application Serial No. 779,874, filed December 12, 1958, or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1957.
  • 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 U.S. application Serial No. 588,951, filed June 4, 1956; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. application Serial No. 662,564, filed May 31, 1957 (now U.S. Patent 2,904,- 434, issued September 15, 1959); bis-(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No. 604,333, filed August 16, 1956 (now U.S.
  • a suitable gelatin plasticizer such as glycerin
  • a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murray U.S. application Serial No. 588,951, filed June 4, 1956
  • an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as
  • Patent 2,904,854, 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 U.S. 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 halogensubstituted aliphatic acid such as mucobromic acid as described in White U.S. 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-octene-2,3,
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. 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 acylated alkyl 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 oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. 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 acylated alkyl 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 tetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a water-soluble 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-ptert. octylphenoxypentaethoxy)-glutamate as described in Knox and Wilson U.S. patent application Serial No. 600,679, filed July 30, 1956; 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.
  • 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 sensitive emulsions. 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 crystal, 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 US. 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 US.
  • Patent 2,563,791 issued August 7, 1951; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unruh and Smith US. 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 US. Patent 2,808,- 311, issued October 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group as described in US. Patent 2,852,382, of Illingsworth, Dann and Gates, issued September 16, 1958.
  • compatible 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 sensitizing compounds of our invention can be used both in emulsions intended for black-and-white photography, or emulsions intended for color photography. When used for this latter purpose, they can be used in emulsions containing color-forming compounds or couplers, or they can be used in emulsions which are to be color-developed in developers containing the colorforming compounds or couplers. In either type of color photography, the particular color-forming compounds or couplers react with the oxidation products of color developers (particularly phenylenediamine developers) to provide subtractively-colored images.
  • the color-forming compounds can be of the customary types employed in color photography, such as pyrazolone couplers for formation of the magenta image, phenolic couplers for formation of the cyan image and open-chain compounds containing a reactive methylene group for formation of the yellow image.
  • Such couplers can be of the type which can be dispersed in a high-boiling, crystalloidal compound, which can be used as a vehicle for incorporating the color-forming compound in the photographic emulsion, or such couplers can be of the fat-tail varieties (see, for example, F.I.A.T., Final Report, No. 721 for examples thereof) which can be dispersed in the photographic silver halide emulsions.
  • Couplers are characterized by non-diffusing properties from the particular silver halide emulsions in which they are incorporated.
  • the couplers or color-forming compounds can be incorporated in the silver halide emulsions by any of the common methods known to those skilled in the art.
  • Typical color-forming compounds or couplers which are useful in color photography, according to our invention include the following:
  • amylphenyl)naphthamide 8-hydroxy-1-a-naphthoyl-1,2,3,4-tetrahydroquinoline 2-lauryl-4-chlorophenol 1-naphthol-2-carboxylic-a-naphthalide 1-naphthol-S-sulfo-cyclohexylamide 5 -phenoXyacetamino-1-naphthol 5 -flphenylpropionylamino-1-naphthol Monochlor-S-(N yphenylpropyl-N p sec.
  • amylbenzoylamino)-1-naphthol Z-acetylamino-S-methylphenol 2-benzoylamino-3,S-dimethylphenol 2-tx(p-tert. amylphenoxy)n-butyrylamino-S-methylphenol 6- ⁇ 'y- ⁇ 4-['y-(2,4 di tert. amylphenoxy)butyramidoJphenoxy ⁇ acetamido ⁇ -2,4-dichloro-3 -methylphenol 1-hydroxy-2- 6-(2,4-di-tert. amylphenoxy) -n butyl] naph.
  • amylsulfanilide 2-cyanoacetylcoumarone-S-SuIfon-N-n-butylanilide 2cyanoacetyl-S-benzoylamino-coumarone Z-cyanoacetylcoumarone-S-sulfondimethylamide 2-cyanoacetylcoumarone-S-sulfon-N-methylanilide Z-cyanoacetylnaphthalene sulfon-N-methylanilide 2-cyanoacetylcoumarone-5- (N-q-phenylpropyl) -p-tert.
  • amylbenzoylami no) -5-pyrazolone 1-phenyl-3-diamylbenzoylamino-S-pyrazolone 1-phenyl-3-B-n-aphthoylamino-5-pyrazolone 1-phenyl-3-phenylcarbamylamino-S-pyrazolone 1-phenyl-3-palmitylamino-S-pyrazolone 1-phenyl-3-benzenesulfonylamino-5-pyrazolone 1-( p-phenoxyphenyl) -3-(p-tert.
  • sensitizers can be added to ordinary photographic silver halide emulsions of the type used in black-and-White photography, such: as gelatino-silver-bromiodide 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 adjustedto 10.8 by adding sodium hydroxide.
  • a suitable developer composition for this screening technique is as fol-lows;
  • DK-SO G. N-methyl-p-aminophenol sulfate 2.5 Hydroquinone 2.5 Sodium sulfite (dry) 30.0 Sodium 'borate 10.0 Potassium bromide 0.5
  • the following data show the effect produced by adding a sensitizing compound of our invention to 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 U.S. Patent 1,623,- 499 and a gold compound of the type shown in U.S. Patent 2,448,060.
  • the emulsion had been red-sensitized to that region of the spectrum lying between about 600 and 700 m and it contained a coupler dispersion of one of the color-forming compounds for producing the cyan image upon color development, such as a dispersion of a phenol coupler, e.g., any one of couplers Nos. 1 to 6 of Fierke U.S.
  • Patent 2,801,171 (column 2) in a suitable solvent, such as tri-o-cresylphosphate or dibutylphthalate.
  • a suitable solvent such as tri-o-cresylphosphate or dibutylphthalate.
  • internal amide sensitizers as identified in the table.
  • the emulsions were then coated on conventional film supports and dried.
  • the coatings were exposed in an Eastman type Ib sensitometer for 1 sec. to the light emitted by a SOD-watt tungsten lamp adjusted to 6100 K. and further modulated by a Wratten No. 15 filter.
  • the exposed coatings were then processed through a reversal process, such as the following:
  • the exposed film was developed in a developer having the following compositions:
  • the element was treated in a color developer having the following composition:
  • the element was treated in a bleach bath having the following composition:
  • 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:
  • Formaldehyde (37% by weight) cc 7.0 Dispersing agent 1 g 0.5 Water to make 1 liter.
  • Triton X-100 i.e., an alkylaryl polyether alcohol (octylphenoxy polyethoxy ethanol).
  • a photographic silver halide emulsion sensitized with a non-polymeric sensitizer selected from those represented by the following general formula:
  • R 0 (R SCHfl JHfI JNHMR wherein R represents a member selected from the class consisting of a methylene group, an alkyl-substituted methylene group and a cyclohexylene-p,p-bis methylene group, R represents a member selected from the class consisting of a hydrogen atom and a methyl group, and
  • R represents a member selected from the class consisting of an alkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a hydroxyalkoxyalkoxyalkyl group, and an aryloxyalkyl group.
  • R represents a member selected from the class consisting of a methylene group, an alkyl-substituted methylene group, and a cyclohexylene-p,p'-bis methylene group
  • R represents a member selected from the class consisting of a hydrogen atom and a methyl group
  • R represents a member selected from the class consisting of a hydrogen atom, an alkyl group and an aryl group
  • n represents a positive integer of from 1 to 4.
  • R4NNH( JCHZSCHz( JHCNH)2R wherein R represents a member selected from the class consisting of a methylene group, an alkyl-substituted methylene group and a cyclohexylene-p,p'-bis methylene group, R represents a member selected from the class consisting of a hydrogen atom and a methyl group and R represents a member selected from the class consisting of two hydrogen atoms and a propen-1-ylidene-3 group.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US858872A 1959-12-11 1959-12-11 Internal amide, nonpolymeric thioether sensitizers for photographic emulsions Expired - Lifetime US3057724A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE597819D BE597819A (en)van) 1959-12-11
US858872A US3057724A (en) 1959-12-11 1959-12-11 Internal amide, nonpolymeric thioether sensitizers for photographic emulsions
DEE19995A DE1124351B (de) 1959-12-11 1960-10-01 Sensibilisierte photographische Halogensilberemulsion
FR845595A FR1280802A (fr) 1959-12-11 1960-12-01 Nouveaux thioéthers et leurs applications, notamment comme sensibilisateurs des émulsions photographiques aux halogénures d'argent
GB31738/64A GB976837A (en) 1959-12-11 1960-12-02 Bis- (thioether amide) derivatives
GB41509/60A GB976836A (en) 1959-12-11 1960-12-02 Photographic silver halide emulsions of increased sensitivity
US357801A US3165552A (en) 1959-12-11 1964-04-06 Internal amide, nonpolymeric thioether sensitizers for photographic emulsions

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Application Number Priority Date Filing Date Title
US858872A US3057724A (en) 1959-12-11 1959-12-11 Internal amide, nonpolymeric thioether sensitizers for photographic emulsions

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US3057724A true US3057724A (en) 1962-10-09

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US858872A Expired - Lifetime US3057724A (en) 1959-12-11 1959-12-11 Internal amide, nonpolymeric thioether sensitizers for photographic emulsions

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US (1) US3057724A (en)van)
BE (1) BE597819A (en)van)
DE (1) DE1124351B (en)van)
FR (1) FR1280802A (en)van)
GB (2) GB976837A (en)van)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same
US3419392A (en) * 1965-02-24 1968-12-31 Ilford Ltd 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
US4113488A (en) * 1975-05-13 1978-09-12 Fuji Photo Film Co., Ltd. Method for improving the light fastness of color photographic dye images
US4276374A (en) * 1978-05-30 1981-06-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion with thioether sensitizer
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4665017A (en) * 1983-12-08 1987-05-12 Fuji Photo Film Co., Ltd. Process for preparing silver halide emulsion and silver halide photographic light-sensitive material
US4678745A (en) * 1984-06-15 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same
US5162405A (en) * 1987-12-24 1992-11-10 Elf Atochem North America, Inc. Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP1122280A3 (en) * 2000-02-05 2001-10-04 Eastman Kodak Company Nonionic surface active oligomers as coating aids for the manufacture of photographic products
EP1122279A3 (en) * 2000-02-05 2002-10-02 Eastman Kodak Company Nonionic oligomeric surfactants and their use as dispersants and stabilisers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2419974A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Silver halide emulsions containing water-insoluble hydrazine derivatives
US2640776A (en) * 1947-08-29 1953-06-02 Eastman Kodak Co Sensitized photographic emulsion containing color couplers
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers
US2856427A (en) * 1956-04-25 1958-10-14 American Home Prod Substituted glycinamides
US2927942A (en) * 1956-05-21 1960-03-08 American Cyanamid Co Stabilization of acrylamide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2419974A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Silver halide emulsions containing water-insoluble hydrazine derivatives
US2640776A (en) * 1947-08-29 1953-06-02 Eastman Kodak Co Sensitized photographic emulsion containing color couplers
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers
US2856427A (en) * 1956-04-25 1958-10-14 American Home Prod Substituted glycinamides
US2927942A (en) * 1956-05-21 1960-03-08 American Cyanamid Co Stabilization of acrylamide

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same
US3419392A (en) * 1965-02-24 1968-12-31 Ilford Ltd 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
US4113488A (en) * 1975-05-13 1978-09-12 Fuji Photo Film Co., Ltd. Method for improving the light fastness of color photographic dye images
US4276374A (en) * 1978-05-30 1981-06-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion with thioether sensitizer
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4665017A (en) * 1983-12-08 1987-05-12 Fuji Photo Film Co., Ltd. Process for preparing silver halide emulsion and silver halide photographic light-sensitive material
US4678745A (en) * 1984-06-15 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same
US5162405A (en) * 1987-12-24 1992-11-10 Elf Atochem North America, Inc. Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP1122280A3 (en) * 2000-02-05 2001-10-04 Eastman Kodak Company Nonionic surface active oligomers as coating aids for the manufacture of photographic products
EP1122279A3 (en) * 2000-02-05 2002-10-02 Eastman Kodak Company Nonionic oligomeric surfactants and their use as dispersants and stabilisers
US6472139B1 (en) 2000-02-05 2002-10-29 Eastman Kodak Company Nonionic surface active oligomers as coating aids for the manufacture of photographic products

Also Published As

Publication number Publication date
DE1124351B (de) 1962-02-22
FR1280802A (fr) 1962-01-08
BE597819A (en)van)
GB976837A (en) 1964-12-02
GB976836A (en) 1964-12-02

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