Classifications

• • 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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
  • C07H15/02—Acyclic radicals, not substituted by cyclic structures
  • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
  • C07H15/08—Polyoxyalkylene derivatives

Definitions

• This invention relates to photographic silver halide emulsions, and more particularly, to an improved means for sensitizing such photographic silver halide emulsions,
• My process is to be distinguished from hypersensitization which is produced by bathing a finished coating with water or with solutions of ammonia, amines or silver salts. Such processes act primarilyon optically sensitized photographic emulsions and tend to increase the free silver ion concentration of the emulsion and greatly diminish its stability.
• novel sensitizers of my invention are unique in that the eifects 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 my invention can be used to sensitize photographic silver halide emulsions containing no other sensitizers if desired.
• novel sensitizers of my invention are not strictly chemical sensitizers since chemical sensitizers do not generally provide the additive elfects of the type mentioned. It is therefore an object of my invention to provide photographic silver halide emulsions which have been sensitized with polyhydroxy compounds containing three or more ethylene oxide chains, their sulfonic acid esters and their polyquaternary salts.
• a further object is to provide a novel class of sensitizers which disperse readily in emulsion dispersions.
• a still further object is to provide a novel class of sensitizers which when added to silver halide photographic emulsions, produce their sensitizing effects without requiring further digestion of the emulsion.
• the sulfonic acid esters and quaternary salts of tertiary amine derivatives of the condensation products of alkylene oxides and these pyranose ring compounds of my invention are particularly useful since they have a rather high degree of water solubility and are easily incorporated in conventional photographic silver halide emulsions in sensitizing amounts.
• Z Z Z Z Z Z Z Z has a total of from 8 to 680;
• R represents a hydroxy substituted polymethylene chain having from 2 to 4 carbon atoms; at is from 1 to 2;
• X is a lower alkyl sulfonate radical 5 such as methylsulfonate, ethylsulfonate, propylsulfonate I and butylsulfonate, etc., an arene sulfonate radical such 0112032) TX as p-toluenesulfonate, a pyridinium group or an ammonium group;
• Y is an anion such as the lower alkyl sulfonate X'WHZCHZOHTH ions, methylsulfonate, ethylsulfonate, propylsulfonate, 19 butylsulfonate, etc., an arene sulfonate ion, a perchlorate
• the sensitizing compounds of my invention have molecules with a total of r- 2 from 8 to 680 ethylene oxide units per molecule.
• the total molecular weight of the ethylene oxide units in a molecule may thus vary from 350 to about 30,000.
• the preferred compounds of my invention have a total of from 20 to 460 ethylene oxide units per molecule.
• the Zs represent a compounds the range of molecular weight of the total ethylene oxide units per mole varies from 880 to 20,240.
• Typical examples that illustrate compounds of my in- R(OCHZCHZ)D R vention that have structures described by Formula I are given in Table I.
• R represents a methyl substituted methylene chain compounds and describes their structures by indicating having from 2 to 6 carbon atoms
• n is a positive integer the groups represented by X and the values of m-l-m of at least 1 such that the sum of the ns in the groups and of d.
• the pound Name X of Formula I represents sum of value of N o. m-l-m; d is 1 Poly(oxyethylene)sorbitan monolaurate tris(methanesulfonate) -0SO2CH; 10 1 2 Poly(oxyethylene)sorbitan monostearate tris(2-methyl-5-ethyl pyridlnium N/ OH3SO3 16 1 rnethanesulfonate) 3 .l Poly(oxyethylene)sorbitan monolaurate tris(pyridlniurn methanesultonate) CH3S03- 10 1 +CHa 4 Poly(oxyethylene)sorbltan monolaurate tris (dimethyl-fl-hydroxyethylammonlum -NOH:CH;OH CHaSO 10 1 methanesulfonate).
• the acylated polyhydroxy compound, or if desired the unacylated polyhydroxy compound, can be reacted directly with epoxides at 60 C. or above by the use of an acid catalyst, a Lewis acid-type catalyst such as borontrifluoride or a basic catalyst such as sodium hydroxide or triethylamine.
• a Lewis acid-type catalyst such as borontrifluoride
• a basic catalyst such as sodium hydroxide or triethylamine.
• the ratio of the ethylene oxide molecules to the polyhydroxy molecule can be easily controlled.
• the ethylene oxide may add to one or all of the free hydroxy groups in equal or varying chain lengths.
• the polyquaternary derivatives are prepared by dissolving the polyhydroxy polyethylene oxide products in cold pyridine and esterifying the w-hydroxy groups with benzene, p-toluene, or methanesulfonyl chloride.
• the polyesters are converted to the polyquaternary derivatives by reacting with tertiary bases such as trialkylamines or heterocyclic compounds such as pyridine.
• Example I Poly(oxyerhylene)sorbitan monolaurate tris(methaneszllfonate).45.2 grams of poly(oxyethylene) sorbitan monolaurate dried by dissolving in benzene, azeotroping oi the Water and then removing the benzene, was dissolved in 150 ml.
• Example II Poly(oxyethylene)sorbitan monosteamte tris(2-metlzyl- 5-ethylpyridinium methanesulf0nate).-A mixture of 3 parts of poly(oxyethylene)sorbitan monostearate tris- (methanesulfonate) prepared in the same manner as was used in Example I excepting that poly(oxyethylene)sorbitan monostearate was used inplace of the corresponding monolaurate, and 5 parts of 5-ethyi-2-methylpyridine Was heated for 5 hours at C. The mixture was cooled and shaken vigorously with 30 of ether. The oily layer was separated from the ether wash and the washing repeated 3 times with fresh ether. The last traces of ether were removed under reduced pressure. Two parts or" a 60 dark colored oil remained.
• Example III P0ly(0xyethylene)sorbitczn monolaurate trz's(pyridinium methanesulfonate).This compound was prepared by the same procedure used in Example 11 by using the molar equivalent amount of poly(oxyethylene)sorbitan monolaurate in place of the corresponding monostearate, and pyridine in place of Z-methyl-S-ethyl pyridine.
• Example IV Poly(0xyethylene)s0rbitan monolaurate tris(dimethyl- B-hydroxyethylammonium methanesulfonate).-Po1y(oxyethylene)sorbitan monolaurate tris(methanesulfonate), 4 parts, was heated for 15 hours at C. with 10 parts of dimethylaminornethanol. he excess amine was re- 75 moved under reduced pressure and the residue washed 4 times with 25 ml. portions of ether. The last traces of ether were removed under reduced pressure. Two parts of a very dark, viscous oil remained. Decolorizing carbons were inefiective.
• Example V Poly(oxyethylene)sorbitan mouolaurate tris(triethylammonium metlzanesulfonate).-To a mixture of parts 7
• Example VI Poly(oxyethylene)sorbitan monostearate tris(pyridinium mezhanesulfonate) .-This compound was prepared by the same procedure as described in Example III by using the molar equivalent amount of poly(oxyethylene) sorbitan monostearate in place of the corresponding monolaurate.
• Example V11 Poly(oxyerhylene)sorbitan monostearate tris(methanesulf0nate).This compound was prepared by the same procedure described in Example I by using the molar equivalent amount of poly(oxyethylene)sorbitan monostearate in place of the corresponding monolaurate.
• Example VIII Sucrose octakis [Z-methylethyl poly(oxyethyl) methanesulfonate] in which the oxyethylene groups of each molecule have a total molecular weight of 1320.
• Example IX vacuum on the steam bath until only a viscous oil remained, It was dissolved in m1. of methanol and the 55 oil precipitated outwith 50ml. of anhydrous ether. The ether was decanted from the oil and the precipitation repeated until no pyridine odor remained. Traces of ether were removed on the steam bath under vacuum leaving 9.1 grams of an orange-colored, viscous, water-soluble oil.
• Example X Sucrose octakis-[2-mezhylethyl poly(oxyethyl)triethylammonium methanesuljonate], in which the oxyethylene groups of each molecule have a total molecular weight of 1320.
• Example XI Surcrose octakis-[Z-methylethyl poly(oxyethyl)metlzane-sulfonate] in which the oxyethylene groups of each molecule have a total molecular Weight of 3080.
• This compound was prepared by the same procedure as was described in Example Vill excepting that process of adding ethylene oxide and catalyst described in paragraph 1 (Example VH1) was continued until a total of 70 molar equivalents of ethylene oxide had reacted with the octakis (2-hydroxypropy-l)sucrose to produce sucrose octakis-[Z-rnethylethyl poly(oxyethyl)] having oxyethylene groups with a total molecular weight of 3080 per molecule before the process of paragraph 2 (Example VII-I) was performed.
• Example XII was used in Example IX by using the molar equivalent amount of the corresponding sucrose octakis derivative in which the oxyethylene groups of each molecule had a total molecular weight of 3080 instead of 1320.
• Example XIII Sucrose oczakis-[Z-methylezhyl poly(oxyethyl)oxy-2- hydroxy-propyl-3-pylidinium perchlorate], in which the oxyethylene groups of each molecule have a total molecular weight of 1320.
• the dark syrup was dissolved in methanol, treated with activated carbon powder (Darco) and diatomaceous earth (Hyflo) and heated for 1 hour on a steam bath. The mixture was allowed to stand overnight, heated, filtered through a diatomaceous earth (Hyflo) filter cake and the orange-yellow solution concentrated. A yield of 17.3 grams of sucrose octakis-[2-methylethyl poly (oxyethyl)oxy-2-hydroxy-3-chloropropane)], a viscous, yellow oil was obtained.
• the above pyridinium salt was dissolved in 50 ml. of ethanol and added to a solution of 3.4 grams of sodium perchlorate monohydrate (no excess) in 50 ml. of acetone. The solution began precipitating sodium chloride immediately. After concentrating the solution continuously on the steam bath (bumping) the precipitated salt was filtered. The concentrated solution was then concentrated to dryness, leaving a turbid orange syrup. The syrup was redissolved in 30 ml. of dry acetone, gravity filtered and concentrated under vacuum, giving 11.1 grams (90%) of a dark orange-colored, viscous syrup.
• sucrose salt probably consists of a mixture ofv sugar pyridinium salts in which the oxyethylene chains may vary in size in each hydroxyl group, and where not all the chains may have been converted to pyridinium salt derivatives, giving for exmple, 5, 6 or 7 quaternary groups per sucrose unit.
• Example X1 Sucrose oczakis-[Z-methylethyl ply(oxyethyl)0xy-2- hydr0xy-pr0pyl-3-pyridinium perchl0mte)], in which the oxyethylene groups of each molecule hav a total molecular Weight of 3080.
• This compound was prepared by the same procedure as was used in Example XIII by using the corresponding sucrose octakis-[Z-methylethoxy poly(ethoxy)ethyl alcohol] in which the oxyethyleue groups of each molecule had a total molecular weight of 3080 instead of 1320.
• the compounds of my invention are added to ordinary photographic silver halide emulsions for the purpose of increasing the sensitivity thereof as has been indicate above.
• the preparation of photographic silver halide emulsions involves three separate operations:.
• the sensitizers of my invention can be added to the emul- .sion before the final digestion or after-ripening or they can be added immediately prior to coating.
• My new photographic sensitizers are characterized by not requiring any final digestion or after-ripening in order to obtain optimum sensitivity.
• the particular quantity of the sulfonic acid esters or quaternary salts of tertiary amine derivatives of the con densation products of allrylene ox de and pyranose ring products of my invention 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. I have found that generally from about 50 mg. to about 5 g. of my compound per mole of silver halide are quite adequate to accomplish the desired sensitization.
• My sensitizer can be added to photographic emulsions using any of the well known techniques in emulsion making. Generally these compounds are soluble enough in water so that the concentration needed may be readily obtained. Most of the compounds are water soluble viscous oils. The compounds can be dissolved in a suitable solvent other than water if necessary and added to 10 the silver halide emulsion or they can be added to the emulsion in the form of a dispersion by techniques similar to those used to incorporate certain types of color f rming 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.
• the solvent should be selected so that it has no harmful efiect upon the emulsion.
• solvents or diluents which are miscible with water are to be preferred.
• solvents such as ethanol, acetone, pyridine, N,N-dimethyl formamide, etc. can be used and this solution added to the emulsion.
• certain of my compounds can be prepared in finely divided form by dispersion in water alone or in the presence of a suitable dispersing agent and added to the emulsion in this form.
• the compounds of my invention should be dispersed suliiciently in water so thatthey can be adsorbed on the grains of the silver halide present in the emulsion in suflicient amount to sensitize the emulsion. It is apparent that the optimum amount for each of the compounds 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 making a series of tests in which the quantity or" my sensitizer-is varied over a given range.
• 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 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 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.
• the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum.
• Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used fog 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.
• 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 descfibed in Damschroder U.S. Patent 2,597,856,
• Suitable comounds are potassium chloroaurite, potassium aurithio- ,anate, potassium chloroaurate, auric trichloride and urosulfobenzothiazole 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 diethyl triaznine (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(;3-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 diethyl triaznine (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
• the emulsions can also be optically sensitized with ll 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. Patent2,493,748, 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 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. 47, 1952, pages 2-28; the disulfides of Kodak Belgian Patent 569,317, issued July 31, 1958; the
• 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;
• 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 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 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. 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,
• 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,
• a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-LS-disulfonyl chloride as described in Allen and Carroll U.S. Patents 2,725,294, and 2,725,295, both issued November 29, 1955; a cyclic 1,2-diketone such as cyclopentane-l,2-dione as described in Allen and Byers U.S.
• Patent 2,725,305 issued November 29, 1955; a bisester of methane-sulfonic acid such as 1,2-di-(methanesulfonoxy) -ethane as described in Allen and Laakso U.S. 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 2-3 carbon atoms, such as fi-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness U.S. patent application Serial No.
• the emulsions may contain a coating aid such as sapomin; 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 sapomin
• 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
• 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 watersoluble 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. 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, now U.S. Patent 2,992,108, issued July 11, 1961.
• a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypentaethoxy) glutamate as described in Knox and Wilson U.S.
• 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 13 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 2,327,808 of Lowe and Clark, issued August 24, 1943; a water-soluble ethanolamine cellulose acetate as described in Yutzy U.S. Patent 2,322,085, is-
• 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. 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.
• An ordinary high speed bromoiodide emulsion contain- 14 ing a sensitizing dye, sulfur sensitized as described in Sheppard U.S. Patent 1,623,499 and gold sensitized in the manner illustrated in U.S. Patent 2,448,060 for example Was divided into several portions.
• Sulfonic acid esters and quaternary salts of tertiary amine derivatives of condensation products of alkylene oxide and certain pyranose ring products and sugar derivatives, the sensitizing compounds of my invention were then added directly to the emulsion in the amounts indicated, in Table III.
• the various portions of emulsions were then coated on a transparent support such as cellulose acetate and dried. The dried coatings were exposed in an Eastman Type IB sensitorneter for A of a second and then processed for five minutes at 68 F. with good agitation in a developer of the following composition:
• a photographic silver halide emulsion containing a condensation product of alkylene oxides and products containing the pyranose ring system selected from the class consisting of the sulfonic acid esters, pyridinium salts, and quaternary ammonium salts of the said condensation products of alkylene oxides and products containing the pyranose ring system.
• X is a member selected from the class consisting of sulfonic ester radicals, pyridinium radicals and ammonium radicals; n I2 and 21 each represent a positive integer of at least 1 such that the sum of n +n +n is an integer of from 8 to 680; m and m are each positive integers of from 1 to 18 such that the sum of m-l-m is an integer of from 4 to 20; and d is a positive integer of 1 to 2.
• Zs represent a 2 2) n' d1' m-1 member selected from the class consisting of lower alkyl sulfonate radicals having from 1 to 4 carbon atoms, an arene sulfonate radical, a pyridinium radical and an ammonium group;
• Y is an anion selected from the class consisting of lower alkyl sulfonate ions having from 1 to 4 carbon atoms, an arene sulfonate ion, a perchlorate ion and a halide ion;
• m is the integer of l and 2 such that when X is a sulfonate group, m is 1 and when X is a pyridinium radical or an ammonium radical m is 2.

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  • BE BE597144D patent/BE597144A/xx unknown
• 1959
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