US3021215A - Polythialkylenediols as sensitizers for photographic silver halide emulsions - Google Patents

Polythialkylenediols as sensitizers for photographic silver halide emulsions Download PDF

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US3021215A
US3021215A US843638A US84363859A US3021215A US 3021215 A US3021215 A US 3021215A US 843638 A US843638 A US 843638A US 84363859 A US84363859 A US 84363859A US 3021215 A US3021215 A US 3021215A
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emulsions
silver halide
emulsion
compounds
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Jack L R Williams
Bernard C Cossar
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to FR839865A priority patent/FR1281263A/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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

Definitions

  • This invention relates to photographic silver halide emulsions, and more particularly, to an improved means for sensitizing such photographic silver halide emulsions.
  • a number of methods have been previously described for increasing the sensitivity of photographic silver halide emulsions, other than methods of optical or spectral sensitization which involve the incorporation of certain colored compounds or dyes in the emulsions.
  • Such chemical sensitizers are believed to react with the silver halide to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of other noble metals, and these processes are capable of increasing the sensitivity of developing-out emulsions by very large factors.
  • the process of chemical sensitization reaches a definite limit beyond which further addition of sensitizer, or of further digestion with the sensitizer present, merely increases the fog of the photographic emulsion with constant or decreasing speed.
  • 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 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.
  • nonpolymeric compounds which can be characterized as polythia-alkylenediols.
  • These non-polymeric compounds contain their sulfur atoms in the form of thioether linkages.
  • thioether linkages we mean a linkage wherein the sulfur atom is a divalent atom joined to two nonoxocarbonylic carbon atoms.
  • Compounds useful in sensitizing photographic silver halide emulsions according to our invention are to be distinguished from the polymeric thioether compounds described in US. application Serial No. 779,874, filed December 12, 1958, by J. R Dann and J. J. Chechak.
  • the polymeric compounds described in this latter application are generally characterized as having a relatively high molecular weight and containing characteristic repeating groups.
  • the sensitizing compounds useful in practicing our invention include compounds represented by the followi ing general formula: (I) HOR(SR S-ROH wherein R and R each represents an alkylene group, such as ethylene, trimethylene, tetramethylene (butylene), methyl-substituted trimethylene, pentamethylene, ethyl substituted tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc.-
  • the compounds of Formulas I and Ia above can be prepared according to methods which have been previously described in the prior art.
  • these compounds can be prepared by condensing a dihalogenated compound together with an alkali metal salt of a mercaptoalkanol.
  • these sensitizing compounds can be prepared by condensing an alkylene chlorohydrin with an alkali metal salt of an alkanedithiol.
  • Still another method for preparing the higher alkylene derivatives is by reaction of a diene with a mercapto alcohol.
  • Method A Reaction of an alkylene dihalide with a mercapto alcohol 2)6 2)5 2)6
  • Method B Reaction of an alkylene chlorohydrin with a dithiol NaS (CH SNa+2Cl CH 0H 2)6 2)5 2)6
  • Method C Reaction of a diene with a mercapto alcohol Another object of EXAMPLE 3 v M ethod C.7,13-dithianonadecan-l ,1 9-di0l A mixture of 13.6 g. (0.2 mole) of 1,4-pentadiene and 5 5 3.6 g.
  • non-pol meric sensitizers embraced by Formula I above can be V, prepared.
  • Those sensitizers containing 3 or 4 sulfur 0 m 5011x1011 0f 8- atOm) Sodium 5 atoms can be prepared by using reactants which contain in 500 ml. of methanol, there were added with cooling 68
  • 1,19-nonadecanediol was prepared by method B above by replacing the disodium salt with a molecularly equivalent
  • 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 emulsion of excess water-soluble salts, usually by washing With water, and (3) the second digestion or afterripening 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.
  • sensitizer used in a given emulsion can vary, depending upon the eiiects 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 a1.
  • 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 seusitizers of the invention.
  • the sensitizer can be dissolved in a solvent, such as ethanol, acetone, pyridine, N,N-dimethylfor1n.- amide, 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 sufficient 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 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. Sach 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 U.S. Patent 1,574,944, issued March 2, 1926; Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard and Brigham 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.
  • 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 anti-foggants 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 trichloride and 2-aurosulfobenzothiazole methochloiide.
  • 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 diethyltriamine (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 diethyltriamine (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-
  • 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 Mur- Y ray 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 U.S. 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 Carroll and Spence U.S. Patent 2,334,864, issued Novem tion Serial No. 779,839, filed December 12, 1958, or
  • 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, now U.S. Patent No. 2,960,404; an ester of an ethylene bisglycolic 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 No. 2,904,343; bis- (ethoxy diethylene glycol) succiuate as described in Gray U.S. application Serial No. 604,333, tiled August 16, 1956, now U.S. Patent No.
  • 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, now U.S. Patent No. 2,960,404
  • 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, 195 8.
  • 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; :1 halogen-substituted 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,- 5,6-tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disu1fonyl chloride as described in Allen and Carroll U.S.
  • any suitable hardener for gelatin such as formaldehyde; :1 halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having
  • dialdehyde or a sodium bisulfite derivative thereof the aldehyde groups of which are separated by 2-3 carbon atoms, such as fl-methyl glutaraldehyde bis-sodium bisul- -fite as described in Allen and Burness U.S. patent application Serial No. 556,031, filed December 29, 1955, now abandoned; a bisaziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster U.S. patent application Serial No. 599,891, filed July 25, 1956, now U.S. Patent No. 2,950,197; or 2,3-dihydroxy dioxane as described in Jeifreys U.S. Patent 2,870,013, issued January 20, 1959.
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleoyl 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 oleoyl 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
  • 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-p-tert. octaylphenoxypentaethoxy ⁇ glutamate as described in Knox and Wilson U.S. patent application Serial No. 600,679, filed July 30, 1956; or a sulfosuccinamate such as tetrasodiurn N-(1,2-dicarboxyethyl)-N-octadecy1 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 -rnay be used in various grinds of photographic 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 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 alcoholvinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. 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 US. Patent 2,852,382 of lllingsworth, Dann and Gates, issued September 16, 1958.
  • cyano-acetyl groups such as the vinyl alcoholvinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. 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 US. Patent 2,852,382 of lllingsworth, 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 bl-ack-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 colorforming compounds can be of the customary types employed in color photography, such as pyrazolone couplers for formation of the magenta image, phenolic couple-rs 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-difiusing 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)naphtharnide S-hydroxy-1-a-naphthoyl-1,2,3,4-tetrahydroquinoline 2-lauryl-4-chlorophenol 1-naphtho1-2-carboxylic-a-naphthalide 1-naphthol-S-sulfo-cyclohexylamide S-phenoxyacetamino-l-naphthol 5-;3-phenylpropionylamino-l-naphthol Monochlor-S- (N-'y-phenylpropyl-N-p-sec.-amylb enzoylamino)-l-naphthol 2-acetylamino-S-methylphenol 2-benzoylamino-3,S-dimethylphenol 2-u(p-tert.
  • amylsulfanilide Z-cyanoacetylcoumarone-S sulfon-N-n-butylanilide 2-cyanoacetyl-5-benzoylamino-coumarone 2-cyanoacetylcoumarone-S-sulfondimethylamide Z-cyanoacetylcoumarone--sulfon-N-methylanilide 2-cyanoacetylnaphthalene sulfon-N-methylanilide 2-cyanoacetylcoumarone-5-(N-y-phenylpropyl) -p-ter-t.
  • amylbenzoylarnino -5-pyrazolone 1-phenyl-3-diamylbenzoylamino-i-pyrazolone 1-phenyl-3-B-naphthoylamino-S-pyrazolone 1-phenyl-3-phenylcarbamylamino-S-pyrazolone 1-phenyl-3paImityIaminod-pyrazolone I l-plienyl-3-benzenesulfonylaminod-pyrazolone 1- (p-phenoxyphenyl -3- (.p-tert.
  • Especially useful color developers are those derived from p-phenylenediamines containing at least one primary amino group, such as N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N-carbamidomethyl N -methyl p-phenylenediamine, N -carbamidomethyl N tetrahydrofurfuryl 2 methyl-p-phenylenediarnine, N -ethyl-N -carboxymethyl-2 methyl-p-phenylenediamine, N -carbamidomethyl-N -ethyl 2 methyl-pphenylenediamine, N ethyl N tetrahydrofurfuryl 2- methyl-p-aminophenol, 3-acetylamino-4-aminodirnethylaniline, N ethyl-N-fl-methanesulfonamidoethyl-4-a
  • 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 scnsitorneter to daylight quality radiation for a fraction of a second (usually 1/25) 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 so dium hydroxide.
  • a suitable developer composition for 13 H-acid (1 amino 8 naphtho1-3,6-disulfonic acid g 10.0 4-amino-3-methyl-N-ethyl N-(p methyl sulfonamidoethyl aniline sulfate g 8.0 Sodium carbonate monohydrate g 40.0 Sodium bromide g 1.5 Sodium thiocyanpteg 0.2 Benzotriazole g .03
  • Control 100 1.29 14 (j) 7,13-dithia-1,19-n0nadecandiol 3 148 1. 18 21 It has also been found that while tetraethylene glycol is of no practical use in increasing the sensitivity of photographic silver halide emulsions, the corresponding compounds of our invention are quite useful in sensitiz ing photographic silver halide emulsions in the manner described.
  • 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 my and it contained a conpler dispersion of one of the color-forming compounds for producing the cyan image upon color development, such as a dispersion ofaphenol 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.
  • polythiaalkylenediol sensitizers as identified in the table.
  • the emulsions were then coated on conventional film support and dried.
  • the coatings were exposed in an Eastman Type Ib Sensitometer for 1/50 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 element was again washed and treated once again with the clearing and fixing bathidentified above.
  • the element was again Washed and treated in a stabilizing bath having the following composition:
  • Formaldehyde 37% by weight c 7.0 Dispersing agent* g 0.5 Water to make 1 liter.
  • TritnX 100 i.e., an ulky'laryl polyether alcohol (octylphenoxypolyethoxyethanol).
  • the sensitizers are effective not only-in red-sensitized emulsions but in emulsions whichhave their maximum sensitivity in the blue region of the spectrum, or inemulsions which have their maximum sensitivity in the green region of the spectrum.
  • n and it each represents a positive integer of from about 2 to 10.
  • R and R each represents a hydrocarbon alkylene group containing from about 2 to 10 carbon atoms and d represents a positive integer of from about 1 to 3.
  • n each represents a positive integer of from about 2 to 10.
  • a photographic silver halide emulsion containing a color-forming compound capable of coupling with the oxidation products of a color developer containing at least one primary aminoaryl group to produce a colored compound said emulsion containing a sensitizing amount of a compound selected from those represented by the following general formula:
  • n each represents a positive integer of from about 2 to 10.

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US843638A 1959-10-01 1959-10-01 Polythialkylenediols as sensitizers for photographic silver halide emulsions Expired - Lifetime US3021215A (en)

Priority Applications (5)

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BE595533D BE595533A (enrdf_load_stackoverflow) 1959-10-01
US843638A US3021215A (en) 1959-10-01 1959-10-01 Polythialkylenediols as sensitizers for photographic silver halide emulsions
DEE19975A DE1124350B (de) 1959-10-01 1960-09-28 Sensibilisierte, vorzugsweise ausentwickelbare photographische Halogensilberemulsion
FR839865A FR1281263A (fr) 1959-10-01 1960-09-29 Nouvelle émulsion photographique aux halogénures d'argent
GB33560/60A GB950089A (en) 1959-10-01 1960-09-30 Photographic silver halide emulsions of increased sensitivity

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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers
US3128184A (en) * 1960-01-25 1964-04-07 Eastman Kodak Co Antifoggants for gold sensitized emulsions in the presence of reduction sensitizers
US3201242A (en) * 1961-09-11 1965-08-17 Eastman Kodak Co Accelerators for reversal color development
US3271157A (en) * 1962-09-11 1966-09-06 Eastman Kodak Co Light-developable direct-print silver halide emulsions
US3419392A (en) * 1965-02-24 1968-12-31 Ilford Ltd Thioether silver halide development accelerators
JPS5036978B1 (enrdf_load_stackoverflow) * 1970-03-20 1975-11-28
US4049829A (en) * 1974-09-23 1977-09-20 Societe Anonyme Dite: Laboratoire L. Lafon Sulphur containing hydroxy aliphatic compounds
US4072526A (en) * 1975-01-22 1978-02-07 Agfa-Gevaert, N.V. Development of photographic silver halide material
US4072523A (en) * 1975-01-22 1978-02-07 Agfa-Gevaert, N.V. Development of photographic silver halide material
EP0006543A1 (de) * 1978-06-27 1980-01-09 Agfa-Gevaert AG Lichtempfindliches photographisches Material, Verfahren zu dessen Herstellung sowie Verwendung zur Herstellung photographischer Bilder
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
FR2463431A1 (fr) * 1979-08-11 1981-02-20 Du Pont Procede pour la preparation d'emulsions photographiques d'halogenures d'argent monodispersees d'une sensibilite amelioree et emulsions ainsi produites
US4272632A (en) * 1979-10-01 1981-06-09 Polaroid Corporation Novel silver complexing agents
US4276374A (en) * 1978-05-30 1981-06-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion with thioether sensitizer
US4292400A (en) * 1979-09-27 1981-09-29 Agfa-Gevaert, N.V. Photographic silver halide development in the presence of thioether development activators
US4297439A (en) * 1978-06-02 1981-10-27 Agfa-Gevaert Ag Production of photographic silver halide emulsion
US4407825A (en) * 1981-02-05 1983-10-04 Sandoz Ltd. Novel bis- and poly-disulfides having immunostimulant activity
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4551421A (en) * 1983-02-14 1985-11-05 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US4551419A (en) * 1983-02-10 1985-11-05 Fuji Photo Film Co., Ltd. Method of developing silver halide photographic material
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
US4695534A (en) * 1986-12-29 1987-09-22 Eastman Kodak Company Silver halide photosensitive material
US4713322A (en) * 1986-12-29 1987-12-15 Eastman Kodak Company Silver halide photosensitive material
US5015567A (en) * 1983-10-07 1991-05-14 Fuji Photo Film Co., Ltd. Method for producing silver halide photographic emulsion and silver halide photographic material
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
US5500337A (en) * 1991-10-15 1996-03-19 Eastman Kodak Company Dyes comprising thioether macrocycles
EP0772079A2 (en) 1995-10-31 1997-05-07 Eastman Kodak Company Light-sensitive silber halide emulsions and processes for their preparation
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2757089A (en) * 1954-01-05 1956-07-31 Du Pont Phytic acid sensitizer for silver halide emulsions
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2757089A (en) * 1954-01-05 1956-07-31 Du Pont Phytic acid sensitizer for silver halide emulsions
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers
US3128184A (en) * 1960-01-25 1964-04-07 Eastman Kodak Co Antifoggants for gold sensitized emulsions in the presence of reduction sensitizers
US3201242A (en) * 1961-09-11 1965-08-17 Eastman Kodak Co Accelerators for reversal color development
US3271157A (en) * 1962-09-11 1966-09-06 Eastman Kodak Co Light-developable direct-print silver halide emulsions
US3419392A (en) * 1965-02-24 1968-12-31 Ilford Ltd Thioether silver halide development accelerators
JPS5036978B1 (enrdf_load_stackoverflow) * 1970-03-20 1975-11-28
US4049829A (en) * 1974-09-23 1977-09-20 Societe Anonyme Dite: Laboratoire L. Lafon Sulphur containing hydroxy aliphatic compounds
US4072526A (en) * 1975-01-22 1978-02-07 Agfa-Gevaert, N.V. Development of photographic silver halide material
US4072523A (en) * 1975-01-22 1978-02-07 Agfa-Gevaert, N.V. Development of photographic silver halide material
US4198240A (en) * 1977-06-03 1980-04-15 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4276374A (en) * 1978-05-30 1981-06-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion with thioether sensitizer
US4297439A (en) * 1978-06-02 1981-10-27 Agfa-Gevaert Ag Production of photographic silver halide emulsion
EP0006543A1 (de) * 1978-06-27 1980-01-09 Agfa-Gevaert AG Lichtempfindliches photographisches Material, Verfahren zu dessen Herstellung sowie Verwendung zur Herstellung photographischer Bilder
FR2463431A1 (fr) * 1979-08-11 1981-02-20 Du Pont Procede pour la preparation d'emulsions photographiques d'halogenures d'argent monodispersees d'une sensibilite amelioree et emulsions ainsi produites
US4292400A (en) * 1979-09-27 1981-09-29 Agfa-Gevaert, N.V. Photographic silver halide development in the presence of thioether development activators
EP0026520B1 (en) * 1979-09-27 1983-09-14 Agfa-Gevaert N.V. Photographic silver halide development in the presence of thioether development activators; method, developer and photographic element
US4272632A (en) * 1979-10-01 1981-06-09 Polaroid Corporation Novel silver complexing agents
US4251617A (en) * 1979-10-01 1981-02-17 Polaroid Corporation Novel silver complexing agents
US4407825A (en) * 1981-02-05 1983-10-04 Sandoz Ltd. Novel bis- and poly-disulfides having immunostimulant activity
US4551419A (en) * 1983-02-10 1985-11-05 Fuji Photo Film Co., Ltd. Method of developing silver halide photographic material
US4551421A (en) * 1983-02-14 1985-11-05 Fuji Photo Film Co., Ltd. Silver halide photographic materials
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5015567A (en) * 1983-10-07 1991-05-14 Fuji Photo Film Co., Ltd. Method for producing silver halide photographic emulsion and silver halide photographic material
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
US4695534A (en) * 1986-12-29 1987-09-22 Eastman Kodak Company Silver halide photosensitive material
US4713322A (en) * 1986-12-29 1987-12-15 Eastman Kodak Company Silver halide photosensitive material
US5500337A (en) * 1991-10-15 1996-03-19 Eastman Kodak Company Dyes comprising thioether macrocycles
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
EP0772079A2 (en) 1995-10-31 1997-05-07 Eastman Kodak Company Light-sensitive silber halide emulsions and processes for their preparation
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

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GB950089A (en) 1964-02-19
DE1124350B (de) 1962-02-22
BE595533A (enrdf_load_stackoverflow)

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