USOO651.8007B1 (12) United States Patent (10) Patent No.: US 6,518,007 B1 Reed et al. (45) Date of Patent: Feb. 11, 2003 (54) SILVER HALIDE ELEMENTS CONTAINING Bruce B. Jarvis et al., J. Org. Chem., vol. 40, No. 25, 1975, SOLUBILIZED ANTIFOGGANTS AND LOW pp. 3778-3780. FOGGING TABULAR SILVER HALIDE Dieter Scholz, Neue Synthesemethoden, 10, Liebigs Ann. GRAINS Chem., 1984, pp. 264-272. Udo Rheude et al., “Uber Reaktionen halogenierter Meth (75) Inventors: Kenneth J. Reed, Rochester, NY (US); anSulfonylchloride mit Trimethylamin und ein inverses George J. Burgmaier, Pittsford, NY Sulfen-Amin-Addukt", Chem. Ber. 118, 1985, pp. (US); John E. Keevert, Rochester, NY 2208-2219. (US); Roger L. Klaus, Victor, NY (US) George J. Burgmaier et al U.S. application Ser. No. 10/014961 “Photothermographic Materials Containing (73) Assignee: Eastman Kodak Company, Rochester, Solubilized Antifoggants” (Docket 81832/JLT). NY (US) Roger L. Klaus et al U.S. application Ser. No. 10/014990 “Silver Halide Photographic Materials Containing Solubi (*) Notice: Subject to any disclaimer, the term of this lized Antifoggants” (Docket 82700/SMR). patent is extended or adjusted under 35 George J. Burgmaier et al U.S. application Ser. No. U.S.C. 154(b) by 0 days. 10/14223 “Water Soluble Halogen Containing Compounds” (21) Appl. No.: 10/014,704 (Docket 83636/SMR). (22) Filed: Dec. 11, 2001 * cited by examiner (51) Int. Cl." ............................ G03C 1/34; GO3C 1/04; Primary Examiner Richard L. Schilling G03C 1/035; G03C 7/392 (74) Attorney, Agent, or Firm-Sarah Meeks Roberts (52) U.S. Cl. ....................... 430/545; 430/551; 430/567; (57) ABSTRACT 430/569; 430/607; 430/610; 430/617; 430/639 (58) Field of Search ................................. 430/607, 610, This invention relates to a multicolor silver halide photo 430/611, 617, 551, 545, 567,569, 639 graphic element comprising a Support and at least one high bromide Silver halide emulsion layer comprising low fog (56) References Cited ging tabular Silver halide grains, Said element further com prising an antifoggant represented by the following Struc U.S. PATENT DOCUMENTS ture I: 3,874,946 A 4/1975 Costa et al. ................ 430/617 3,946,007 A 3/1976 Goralski et al. 5,958,688 A * 9/1999 Matsumoto et al. ........ 430/611 6,074,813 A 6/2000 Asanuma et al. ........... 430/607 wherein R is an aliphatic or cyclic group, R and R are 6,350,569 B1 * 2/2002 Watanabe et al............ 430/611 independently hydrogen or bromine as long as at least one of them is bromine, L is a divalent linking group, m and in OTHER PUBLICATIONS are independently 0 or 1, and SG is a Solubilizing group that Hans Pritzkow et al, Darstellung perhalogenierter Mesyl has a pKa of 8 or less. Sulfene, XC-SO-C(X)=SO, und ihre Stabilisierung durch Chinuchlidin, Feb. 1990, pp. 1187–1192. 21 Claims, No Drawings US 6,518,007 B1 1 2 SILVER HALDE ELEMENTS CONTAINING Ser. No. 09/731,454 “PREPARATION OF HIGH BRO SOLUBILIZED ANTIFOGGANTS AND LOW MIDE PHOTOGRAPHIC EMULSIONS WITH STARCH FOGGING TABULAR SILVER HALIDE PEPTIZER AND OXIDIZING AGENT, and Ser. No. GRAINS 09/731,446 “PREPARATION OF HIGH BROMIDE PHO TOGRAPHIC EMULSIONS WITH STARCH PEPTIZER of Maskasky, all filed Dec. 7, 2000). Oxidized cationic FIELD OF THE INVENTION Starches are advantageous in exhibiting lower levels of Viscosity than gelatino-peptizers. This facilitates mixing. This invention relates to Silver halide elements containing Under comparable levels of chemical Sensitization higher Solubilized antifoggants. More specifically it relates to Silver photographic Speeds can be realized using cationic Starch halide elements containing Solubilized antifoggants and a peptizers. Alternatively, Speeds equal to those obtained using high bromide emulsion containing low fogging tabular Sil gelatino-peptizers can be achieved at lower precipitation Verhalide grains. In one embodiment the Silver halide grains and/or Sensitization temperatures, thereby avoiding are precipitated in a low pH environment. unwanted grain ripening. The Starch peptized emulsions, BACKGROUND OF THE INVENTION 15 when precipitated under certain conditions, also exhibit low Dmins, presumably as a consequence of either the removal Problems with fogging have plagued the photographic of or the prevention of metallic silver center formation industry from its inception. Fog is a deposit of Silver or dye which gives rise to primitive emulsion fog. The use of that is not directly related to the image-forming exposure, cationic Starch as a peptizer for the precipitation of high i.e., when a developer acts upon an emulsion layer, Some bromide 111 tabular grain emulsions is taught by reduced Silver is formed in areas that have not been exposed Maskasky in U.S. Pat. Nos. 5,604,085; 5,620,840; 5,667, to light. Fog can be defined as a developed density that is not 955, 5,691,131; and 5,733,718. asSociated with the action of the image-forming exposure, Starch peptized emulsions precipitated either at low pH or and is usually expressed as "D-min', the density obtained in else in the presence of bromine or a bromine precursor the unexposed portions of the emulsion. Density, as nor 25 appear particularly well Suited for use with very active mally measured, includes both that produced by fog and that chemistries Such as fragmental electron donors, FEDs (J. E. produced as a function of exposure to light. It is known in Maskasky et. al U.S. Pat. No. 6,090,536), one equivalent the art that the appearance of photographic fog related to yellow couplers (J. E. Maskasky et. al U.S. Pat. No. 6,225, intentional or unintentional reduction of silver ion (reduction 036), light scattering particles (J. E. Maskasky et. al U.S. Sensitization) can occur during many stages of preparation Pat. No. 6,027,869), and combinations of these chemistries. of the photographic element including Silver halide emulsion These active chemistries, however, tend to amplify image preparation, spectral/chemical Sensitization of the Silver and fog. While the use of the Starch peptized emulsions may halide emulsion, melting and holding of the liquid Silver provide a good initial Dmin position, further fog reduction halide emulsion melts, Subsequent coating of Silver halide is necessary to in order to obtain the maximum imaging emulsions, and prolonged natural and artificial aging of 35 coated Silver halide emulsions. The chemicals used for performance. preventing fog growth as a result of aging or Storage are SUMMARY OF THE INVENTION generally known as emulsion Stabilizers. The control of fog, whether occurring during the forma This invention provides a multicolor silver halide photo tion of the light-Sensitive Silver halide emulsion, during the 40 graphic element comprising a Support and at least one high Spectral/chemical Sensitization of those emulsions, during bromide Silver halide emulsion layer comprising low fog the preparation of Silver halide compositions prior to coating ging tabular Silver halide grains, Said element further com on an appropriate Support, or during the aging of Such coated prising an antifoggant represented by the following Struc Silver halide compositions, has been attempted by a variety ture I: of means. Mercury-containing compounds Such as those 45 described in U.S. Pat. Nos. 2,728,663; 2,728,664; and 2,728, 665 have been used as additives to control fog. Thiosul wherein R is an aliphatic or cyclic group, R and R are fonates and thiosulfonate esterS Such as those described in independently hydrogen or bromine as long as at least one U.S. Pat. Nos. 2.440,206; 2,934,198, 3,047,393, and 4,960, of them is bromine, L is a divalent linking group, m and in 689 have also been employed. Organic dichalcogenides, for 50 are independently 0 or 1 and SG is a Solubilizing group that example, the disulfide compounds described in U.S. Pat. has a pKa of 8 or less. Nos. 1962,133; 2465,149; 2,756,145, 2,935,404; 3,184, This invention further provides silver halide elements 313; 3,318,701; 3,409.437; 3,447,925; 4,243,748; 4,463, with an unexpected improvement in the fog position of 082, and 4,788,132 have been used not only to prevent already quite clean or low fog emulsions, particularly Starch formation of fog, but also as desensitizers and as agents in 55 precipitated emulsions. These improvements translate to processing baths and as additives in diffusion transfer SyS Substantial imaging advances as measured by Speed and temS image structure (granularity) metrics. Recently there has appeared in the patent literature art that describes the precipitation of Silver halide photographic DETAILED DESCRIPTION OF THE emulsions in a peptizer, cationic waxy Starch, which departs 60 INVENTION Substantially from the traditionally used medium, gelatin. The silver halide photographic elements of this invention These Starch precipitated emulsions may be unique in their include one or more water-Soluble or water-dispersible anti ability to tolerate the use of powerful oxidants Such as foggants containing a Solubilizing group with a pKa of 8 or elemental bromine or else very low pH used during the leSS. These compounds are represented by the following precipitation (U.S. application Ser. No. 09/731,454 65 Structure I. “PREPARATION OF HIGH CHLORIDE PHOTO GRAPHIC EMULSIONS WITH STARCH PEPTIZER”, US 6,518,007 B1 3 4 wherein R is a Substituted or unsubstituted aliphatic or SG is a carboxy, phospho, Sulfo, or Sulfonamido group. cyclic group of any size as long as the antifoggant remains When SG is a sulfonamido group, it may be -SON soluble or readily dispersible in water. Substituted or unsub CORM", or -NSORM" with R being a substituted or Stituted aliphatic groups for R include monovalent groups unsubstituted aliphatic or cyclic group that is defined the having 1 to 20 carbon, nitrogen, Sulfur, and oxygen atoms in the chain including, but not limited to, chains that include Same as for R, although R and R can be the same or one or more Substituted or unsubstituted alkyl groups having different in a particular compound.