HYDROLYZED AZOLIUM SPEED ENHANCING/FOG-INHIBITING AGENTS FOR SILVER HALIDE PHOTOGRAPHY

Abstract: Radiation sensitive silver halide photographic elements are disclosed which are protected from fog by hydrolyzed quaternized chalcogenazolium salts of middle chalcogens, wherein the quaternizing substituent contains a - T(NH-T¹) m group in which T and T¹ are carbonyl or sulfonyl and m is from 1 to 3.

Description: This invention relates to photography. It relates more specifically to silver halide photographic elements. In the course of processing a photographic element containing an imagewise exposed silver halide emulsion layer, reduced silver can be formed either as a direct or inverse function of exposure. At the same time, at least a low level of reduced silver formation also occurs independently of imagewise exposure. The term "fog" is herein employed to indicate the density of the processed photographic element attributable to the latter, usually measured in minimum density areas. In color photography, fog is typically observed as image dye density rather than directly as silver density. A common disadvantage of fog-inhibiting agents is that they concurrently inhibit fog and reduce photographic speed to an increasing degree as they are increased in concentration in a silver halide emulsion. Thus, the choice of a particular fog inhibiting agent for use in a silver halide emulsion is based on both fog and photographic speed considerations, hereinafter referred to as speed/fog relationships. Over the years a variety of differing materials have been introduced into silver halide emulsions to inhibit the formation of fog. Research Disclosure , Vol. 176, December 1978, Item 17643, Section VI, lists the more commonly employed fog inhibiting agents. Research Disclosure is published by Kenneth Mason Publications, Ltd., The Old Harbourmaster's, 8 North Street, Emsworth, Hampshire P010 7DD, England. It has been generally recognized in the art that a particularly effective class of fog-inhibiting agents is comprised of quaternized thiazolium and selenazolium salts. By contrast quaternized oxazolium salts are not effective fog-inhibiting agents. U.S. Patent 2,131,038 discloses thiazolium salts, including a simple cyanine dye, to be useful fog-inhibiting agents. U.S. Patent 4,237,214 discloses benzothiazolum salts having quaternizing substituents that can contain a carbamoyl or sulfamoyl group. Published European Patent Applications 0,136,847 and 0,137,600 disclose the preparation of aromatic tellurazolium salts and their utility as antifoggants. In addition to the foregoing patents relating to fog-inhibiting agents, the following patents are of interest by reason of compound fragment similarities: U.S. Patent 3,282,933 discloses polymethine dyes having a quaternizing substituent containing a divalent -CO-HN-SO₂- group. U.S. Patents 4,374,196 and 4,423,140 teach hydrolyzed quaternized chalcogenazolium salts to be useful latent image stabilizers in silver halide emulsions where the nitrogen atom contained in the ring prior to hydrolysis is substituted with an allyl group which may in turn be optionally substituted with an alkyl, alkoxy, carboxy, alkoxycarbonyl, or aminocarbonyl group. The present invention seeks to provide photographic elements containing radiation sensitive silver halide emulsions capable of producing photographic images exhibiting low levels of fog. Further, the invention seeks to provide photographic elements which permit a speed/fog relationship to be realized that is superior to that of photographic elements containing known fog-inhibiting agents closely related in structural form. According to the present invention silver halide photographic elements are provided containing a photographically effective amount of a hydrolyzed quaternized chalcogenazolium salt of a middle chalcogen including a quaternizing substituent having a carbon chain interrupted by a divalent group of the formula: where: L is an optionally substituted divalent linking group; R is a substituted or unsubstituted hydrocarbon residue, an amino group, or -NHCoR₆; wherein R₆ is an alkyl group of from 1 to 8 carbon atoms or a primary amino group T and T¹ are independently at each occurrence carbonyl or sulfonyl and m is an integer of from 1 to 3. From observations of a variety of quaternized chalcogenazolium salts of middle chalcogens incorporated in silver halide emulsions it has been noted that some are effective fog-inhibiting agents while others are as ineffective as oxazolium salts. After some study it has been concluded that those of the above compounds which are effective as fog-inhibiting agents are capable of undergoing hydrolysis which opens the chalcogenazolium ring between the 1 and 2 ring positions-that is, between the ring chalcogen atom and the carbon atom which lies mediate the ring chalcogen and nitrogen atoms. To provide a specific illustration, it has been recognized that compounds of the following general formula can be employed as fog-inhibiting agents when hydrolyzed: wherein R¹ is hydrogen, alkyl of from 1 to 8 carbon atoms, or aryl of from 6 to 10 carbon atoms; R² and R³ are independently hydrogen or halogen atoms; aliphatic or aromatic hydrocarbon moieties optionally linked through a divalent oxygen or sulfur atom; or cyano, amino, amido, sulfonamido, sulfamoyl, ureido, thioureido, hydroxy, -C(O)M, or -S(O)₂M groups, wherein M is chosen to complete an aldehyde, ketone, acid, ester, thioester, amide, or salt; or R² and R³ together represent the atoms completing a fused ring; Q represents a quaternizing substituent; X is a middle chalcogen atom; Y represents a charge balancing counter ion; and n is the integer 0 or 1. Heretofore the art has found to be useful as fog-inhibiting agents only those quaternized chalcogenazolium salts of middle chalcogens which are herein recognized to undergo spontaneous hydrolysis when incorporated in the silver halide emulsion layer of a photographic element. Although sweeping characterizations of R¹ substituents are published, in fact the art has seldom successfully employed R¹ substituents other than hydrogen or methyl. By recognizing the importance of ring hydrolysis to fog-inhibiting activity, it is now possible to hydrolyze quaternized chalcogenazolium salts of middle chalcogens deliberately. Where R¹ is hydrogen and, in some instances methyl, ring opening occurs spontaneously after incorporating the compound of formula (I) in a silver halide emulsion. However, when the pH of silver halide emulsions is too low for ring opening hydrolysis, treatment with a base, such as an aqueous alkaline solution of an alkali hydroxide, alkaline earth hydroxide, or ammonium hydroxide can be employed prior to incorporation in the silver halide emulsion. Whether prehydrolyzed or spontaneously hydrolyzed in situ , the effective fog-inhibiting compounds which can be derived by hydrolysis of the compounds of formula (I) can be represented by formula (II): wherein R¹, R², R³, Q, X, and n are as previously defined and Y² is a charge balancing counter ion. An improved speed/fog relationship can be realized by modification of the quaternizing substituent of any quaternized chalcogenazolium salt of a middle chalcogen which is capable of undergoing hydrolysis in the manner indicated. Conventional quaternizing substituents are optionally substituted hydrocarbon substituents, sometimes including a carbon chain interrupting group, such as an oxy, carboxy, carbamoyl, or sulfonamido group. It is the specific recognition of this invention that an improved speed/fog relationship can be realized by including a quaternizing substituent having a divalent group satisfying formula (III): where: T and T¹ are independently carbonyl (CO) or sulfonyl (SO₂) and m is an integer of from 1 to 3. In a specific preferred form the quaternizing substituent, e.g. Q, can take the form represented by formula (IV): wherein T is carbony or sulfonyl; T¹ is independently in each occurrence carbonyl or sulfonyl; and L represents a divalent linking group, such as an optionally substituted divalent hydrocarbon group; R represents an optionally substituted hydrocarbon residue, an amino group or -NHCoR₆; wherein R₆ is an alkyl group of from 1 to 8 carbon atom or a primary amino group; and m is an integer of from 1 to 3. In preferred embodiments of the invention T is carbonyl and T¹ is sulfonyl. However, either or both of T and T¹ can be either carbonyl or sulfonyl. Further, where m is greater than 1, T¹ can in each occurrence be carbonyl or sulfonyl independently of other occurrences. L is preferably an alkylene (i.e., alkanediyl) group of from 1 to 8 carbon atoms. In specifically preferred forms of the invention L is either methylene (-CH₂-) or ethylene (-CH₂CH₂-). R is preferably a primary or secondary amino group, an alkyl group of from 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, i -propyl, n -butyl, i -butyl, t -butyl, neo -pentyl, or n -octyl), or an aryl group of from 6 to 10 carbon atoms (e.g., phenyl or naphthyl). When R completes a secondary amine, it can be substituted with an optionally substituted hydrocarbon residue, preferably an alkyl group of from 1 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms, as above described. It is also recognized that R can be chosen, if desired, to complete a bis compound. For example, R can take a form similar to L and the hydrolyzed chalcogenazolium ring linked to L, thereby incorporating a second hydrolyzed chalcogenazolium ring into the fog-inhibiting agent. m is in a preferred form of the invention the integer 1. Although preferred values of R¹ are described above in connection with formulae (I) and (II), it is appreciated that R¹ can take the form of any other substituent that is compatible with ring opening hydroylsis of the chalcogenazolium salt in the manner indicated. In general, as noted above, the simpler the form of R¹, the more easily hydrolysis is accomplished. Conversely, R¹ cannot complete a carbocyanine or hemicarbocyanine dye, since ring opening hydrolysis in the manner contemplated has not been achieved. It is specifically recognized that R¹ can embrace substituents that do not permit spontaneous hydrolysis of quaternized chalcogenazolium salts in silver halide emulsion coatings, since the salts are added to the emulsion already hydrolysed. X, R², and R³ can together complete any convenient chalcogenazolium nucleus or hydrolyzed chalcogenazolium nucleus, provided the chalcogen atom is a middle chalcogen atom. The middle chalcogen atoms are sulfur, selenium, and tellurium, being designated "middle" chalcogen atoms since they are the atoms in Group VI of the Periodic Table of Elements, except the highest and lowest in atomic number. When oxygen is employed instead of a middle chalcogen atom, fog-inhibiting activity is largely absent. When X is sulfur or selenium, R² and R³ can take any form found in known thiazolium and selenazolium ring containing nuclei. R² and R³ can individually take the form of hydrogen or halogen atoms; hydrocarbon moieties (e.g., alkyl, aryl, alkaryl, or aralkyl) optionally linked through a divalent oxygen or sulfur atom (e.g., an alkoxy, aryloxy, alkaryloxy, aralkoxy, alkylthio, arylthio, alkarylthio, or aralkylthio group); cyano; an amino group, including primary, secondary, and tertiary amino groups; an amido group (e.g., acetamido and butyramido); a sulfonamido group (e.g., an alkyl or arylsulfonamido group); a sulfamoyl group (e.g., an alkyl or arylsulfamoyl group); a ureido group (e.g., 1-ureido, 3-phenyl-1-ureido, or 3-methyl-1-ureido); a thioureido group (e.g., a thioureido group corresponding to the above exemplary ureido groups); hydroxy; or a -C(O)M or -S(O)₂M group, wherein M is chosen to complete an aldehyde, ketone, acid, ester, thioester, amide, or salt (e.g., -C(O)H, -C(O)CH₃, -C(O)OH, -C(O)SCH₃, -C(O)OCH₃, -C(O)NH₂, -C(O)ONa, -S(O)₂OH, -S(O)₂OCH₂C₆H₅. -S(O)₂NH₂, or -S(O)₂OLi). The alkyl groups and the alkyl moieties of other groups preferably contain from 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, amyl, hexyl, or octyl), and most preferably contain from 1 to 4 carbon atoms and may be further substituted by other groups, such as halogen, cyano, aryl, carboxy, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, and aminocarbonyl. The aryl groups and the aryl moieties of other groups preferably contain 6 to 10 carbon atoms (e.g., phenyl or naphthyl) and include substituted or unsubstituted groups. Useful substituents include halogen, cyano, alkyl, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, and aminocarbonyl. In a preferred form, R² and R³ together form one or more fused carbocyclic aromatic rings--e.g., a benzo or naphtho ring, either of which can be optionally substituted. When X is sulfur or selenium, the salt can be a benzothiazolium salt, a benzoselenazolium salt, an α or β-naphthothiazolium salt, or an α or β-naphthoselenazolium salt, such as the quaternized but otherwise unsubstituted salts or the salts in which the fused carbocyclic rings are substituted. Fused carbocyclic ring substituents, when present, can be chosen from among those identified above for R² and R³ as individual substituents. In general, the fused carbocyclic ring substituents, when present, can be chosen from among those present in comparable nuclei in cyanine, merocyanine, and hemicyanine dyes. When the middle chalcogen represented by X is tellurium, R² and R³ together form a carbocyclic aromatic ring, such as a fused benzo or α or β-naphtho ring. The fused carbocyclic aromatic rings can be unsubstituted or substituted with aliphatic or aromatic groups comprised of hydrocarbon moieties optionally linked through a divalent oxygen or sulfur atom, amino groups, amido groups, sulfonamido groups, sulfamoyl groups, ureido groups, thioureido groups, hydroxy groups, C(O)M groups, and SO₂M groups, wherein M is chosen to complete an acid, ester, thioester, or salt. Specifically preferred benzo or naphtho ring substituents are alkyl, alkoxy, alkylthio, and hydroxy substituents, where alkyl is preferably of from 1 to 8 carbon atoms and most preferably of from 1 to 4 carbon atoms. Y¹ and Y² are included in formulae (I) and (II) to provide electronically neutral compounds. Y¹ and Y² can be chosen from a wide range of known anions and cations known to be compatible with silver halide emulsions. When the chalcogenazolium salt or the hydrolyzed chalcogenazolium salt is a betaine, no charge balancing counter ion may be required, and n can be zero. In the absence of an ionized substituent, the quaternized chalcogenazolium salt of formula (I) has a single positive charge and Y¹ is an acid anion, such as a halide or p -toluenesulfonate. In the absence of an ionized substituent, the hydrolyzed quaternized chalcogenazolium salt of formula (II) has a single negative charge and Y² is a cation, such as that provided by the base employed to effect hydrolysis--e.g., an alkali, alkaline earth, or ammonium cation. The hydrolyzed quaternized chalcogenazolium salt fog-inhibiting agents are incorporated in the photographic element to be protected prior to exposure and processing--e.g., at the time of manufacture. It is essential that the hydrolyzed quaternized chalcogenazolium salt fog-inhibiting agent be incorporated in the silver halide emulsion layer or layers to be protected. The hydrolyzed quaternized chalcogenazolium salt can be conveniently introduced into the silver halide emulsion to be protected at any time after precipitation of the emulsion and before coating. Any amount of hydrolyzed quaternized chalcogenazolium salt effective to inhibit fog can be employed. Optimum amounts of fog-inhibiting agents for specific applications are usually determined empirically by varying concentrations. Such investigations are typically relied upon to identify optimum fog-inhibiting concentrations or an optimum balance between fog-inhibition and other effects, such as reduction in photographic speed. Based on the investigations reported below, the quaternized chalcogenazolium salt is incorporated in a silver halide emulsion prior to coating in concentrations of from 10.0 to 0.01 millimole per silver mole, preferably 2.0 to 0.015 millimole per silver mole. It is, of course, recognized that conventional fog-inhibiting agents, such as those illustrated by Research Disclosure , Item 17643, Section VI, cited above, can be employed in combination with hydrolyzed guaternized chalcogenazolium salts in the practice of this invention. Since it is recognized that fog-inhibiting agents operate by a variety of differing mechanisms, the effects produced by combinations of hydrolyzed quaternized chalcogenazolium salts and conventional fog-inhibiting agents will range from highly interdependent to independently additive, but in any case optimum concentrations are susceptible to empirical determination. In addition to the fog-inhibiting agent this invention additionally requires a photographic element containing a radiation sensitive silver halide emulsion. These silver halide emulsions can be comprised of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions can include silver halide grains of any conventional shape or size. Specifically, the emulsions can include coarse, medium or fine silver halide grains of either regular (e.g., cubic or octahedral) or irregular (e.g., multiply twinned or tabular) crystallographic form. Recently developed high aspect ratio tabular grain emulsions, such as those disclosed by U.S. Patents 4,434,226; 4,414,310; 4,399,215; 4,433,048; 4,386,156, 4,504,570; 4,400,463; 4,414,306; and 4,435,501 are specifically contemplated. Sensitizing compounds, such as compounds of copper, thallium, lead, bismuth, cadmium and Group VIII noble metals, can be present during precipitation of the silver halide emulsion, as illustrated by U.S. Patents 1,195,432; 1,951,933; 2,448,060; 2,628,167; 2,950,972; 3,488,709; and 3,737,313. The silver halide emulsions can be either monodispersed or polydispersed as precipitated. The grain size distribution of the emulsions can be controlled by silver halide grain separation techniques or by blending silver halide emulsions of differing grain sizes. The emulsions can include Lippmann emulsions and ammoniacal emulsions, as illustrated by Glafkides, Photographic Chemistry , Vol.1, Fountain Press, London, 1958, pp.365-368 and pp.301-304; excess halide ion ripened emulsions as described by G. F. Duffin, Photographic Emulsion Chemistry , Focal Press Ltd., London, 1966, pp.60-72; thiocyanate ripened emulsions, as illustrated by U.S. Patent 3,320,069; thioether ripened emulsions, as illustrated by U.S. Patents 3,271,157, 3,574,628; and 3,737,313 or emulsions containing weak silver halide solvents, such as ammonium salts, as illustrated by U.S. Patent 3,784,381 and Research Disclosure , Vol.134, June 1975, Item 13452. The emulsions can be surface-sensitive emulsions--i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains--or internal latent image-forming emulsions--i.e., emulsions that form latent images predominantly in the interior of the silver halide grains, as illustrated by U.S. Patents 2,456,953; 2,592,250; 3,206,313; 3,317,322; 3,447;927; 3,761,276; 3,917,485; 3,979,213; and 3,767,413. The emulsions can be negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent, as illustrated by U.S. Patents 2,563,785; 3,761,276; 2,456,953; and 3,511,662. Blends of surface sensitive emulsions and internally fogged, internal latent image-forming emulsions can be employed, as illustrated by U.S. Patents 2,996,382; 3,397,987; 3,705,858; and 3,695,881; and Research Disclosure , Vol.134, June 1975, Item 13452, Defensive Publication T-904017, April 21, 1972 and Research Disclosure , Vol.122, June 1974, Item 12233. The hydrolyzed quaternized chalcogenazolium salts are preferably employed to inhibit fog in negative working silver halide emulsions and most preferably those that contain silver halide grains which form surface latent images on exposure. The silver halide emulsions can be surface sensitized. Noble metal (e.g., gold), middle chalcogen (e.g., sulfur, selenium, or tellurium), and reduction sensitizers, employed individually or in combination are specifically contemplated. Typical chemical sensitizers are listed in Research Disclosure , Item 17643, cited above, Section III. The silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines. Illustrative spectral sensitizing dyes are disclosed in Research Disclosure , Item 17643, cited above, Section IV. The silver halide emulsions as well as other layers of the photographic elements of this invention can contain as vehicles hydrophilic colloids, employed alone or in combination with other polymeric materials (e.g., lattices). Suitable hydrophilic materials include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives―e.g., cellulose esters, gelatin―e.g., alkali treated gelatin (cattle, bone, or hide gelatin) or acid treated gelatin (pigskin gelatin), gelatin derivatives―e.g., acetylated gelatin, and phthalated gelatin, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot, and albumin. The vehicles can be hardened by conven tional procedures. Further details of the vehicles and hardeners are provided in Research Disclosure , Item 17643, cited above, Sections IX and X. The silver halide photographic elements of this invention can contain other addenda conventional in the photographic art. Useful addenda are described, for example, in Research Disclosure , Item 17643, cited above. Other conventional useful addenda include desensitizers, couplers (such as dye forming couplers, masking couplers and DIR couplers) DIR compounds, anti-stain agents, image dye stabilizers, absorbing materials such as filter dyes and UV absorbers, light scattering materials, antistatic agents, coating aids, plasticizers and lubricants. The photographic elements of the present invention can be simple black-and-white or monochrome elements comprising a support bearing a layer of the silver halide emulsion, or they can be multilayer and/or multicolor elements. The photographic elements produce images ranging from low contrast to very high contrast, such as those employed for producing half tone images in graphic arts. They can be designed for processing with separate solutions or for in-camera processing. In the latter instance the photographic elements can include conventional image transfer features, such as those illustrated by Research Disclosure , Item 17643, cited above, Section XXIII. Multicolor elements contain dye image forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsion or emulsions can be disposed as one or more segmented layers, e.g., as by the use of microvessels or microcells, as described in U.S. Patent 4,387,154. A preferred color photographic element according to this invention comprises a support bearing at least one blue sensitive silver halide emulsion layer having associated therewith a yellow dye forming coupler, at least one green sensitive silver halide emulsion layer having associated therewith a magenta dye forming coupler and at least one red sensitive silver halide emulsion layer having associated therewith a cyan dye forming coupler, at least one of the silver halide emulsion layers containing a hydrolyzed quaternized chalcogenazolium salt fog-inhibiting compound. The elements of the present invention can contain additional layers conventional in photographic elements, such as overcoat layers, spacer layers, filter layers, antihalation layers, scavenger layers and the like. The support can be any suitable support used with photographic elements. Typical supports include polymeric films, paper (including polymer-coated paper), glass and the like. Details regarding supports and other layers of the photographic elements of this invention are contained in Research Disclosure , Item 17643, cited above, Section XVII. The photographic elements can be imagewise exposed with various forms of energy, which encompass the ultraviolet, visible, and infrared regions of the electromagnetic spectrum as well as electron beam and beta radiation, gamma ray, X ray, alpha particle, neutron radiation, and other forms of corpuscular and wave-like radiant energy in either noncoherent (random phase) forms or coherent (in phase) forms, as produced by lasers. When the photographic elements are intended to be exposed by X rays, they can include features found in conventional radiographic elements, such as those illustrated by Research Disclosure , Vol. 184, August 1979, Item 18431. Processing of the imagewise exposed photographic elements can be accomplished in any convenient conventional manner. Processing procedures, developing agents, and development modifiers are illustrated by Research Disclosure , Item 17643, cited above, Sections XIX, XX, and XXI, respectively. Residual dye stain attributable to sensitizing or filter dyes can be removed by processing in an aqueous alkali nitrite bath buffered to a pH of 5. The quaternized thiazolium and selenazolium salts, such as those satisfying formula (I), can be prepared by first preparing the corresponding protonated thiazolium or selenazolium salt. The latter can be purchased or prepared by procedures well known in the art, as illustrated by Brooker et al U.S. Patent 2,131,038. Quaternization can be achieved by employing C1-Q or Br-Q, where Q is chosen to satisfy the requirements of the invention. Such compounds are disclosed by U.S. Patent 3,282,933. Successful preparations of protonated tellurazolium salts are taught by published European Patent Applications 0,136,847 and 0,137,600. Examples The following examples further illustrate the invention. The structures of the fog-inhibiting agents of the invention and of comparative fog-inhibiting agents are listed in Table I. The letter E is employed to indicate fog-inhibiting agents according to the invention, and the letter C is employed to indicate comparative fog-inhibiting agents. Compounds Satisfying the Invention : Example 1. Example 1 illustrates the superior speed/fog relationship of FIA-E1, a compound satisfying the requirements of the invention, when compared with N-alkyl, N-sulfoalkyl, N-phosphonoalkyl, or N-hydroxyalkylbenzothiazolium compounds. On a cellulose acetate support was coated a surface chemically sensitized surface latent image forming fast negative-working silver bromoiodide emulsion, 5.8 mole % iodide, of mean grain size 1.0 µm, at 4.89 g/m² Ag, 11.1 g/m² gelatin. The coating was hardened with bis(vinylsulfonylmethyl) ether at 0.27 % of the gelatin weight. Additions of fog-inhibiting agents were made as listed in Table II. Samples of the film were exposed for 1/25 sec through a graduated density tablet to a 5500°K tungsten source in an EASTMAN 1B Sensitometer, and developed in KODAK DK-50® developer for 5 min at 20°C. Samples were also incubated for two weeks at 49°C, 50% relative humidity (RH), then similarly exposed and processed. The relative speed and fog values are tabulated in Table II. The sensitometric results show that FIA-E1 satisfying the requirements of the invention is an active fresh and incubation fog-inhibiting agent. Moreover, the speed/fog relationship obtained with FIA-E1 on incubation was clearly superior to that obtained with its N-methyl, FIA-C1; N-sulfopropyl, FIA-C5; N-phosphonoethyl FIA-C10; N-phosphonopropyl, FIA-C11; or N-dihydroxypropyl, FIA-C12, analogs. Example 2. Example 2 illustrates the speed/fog relationship on incubation of FIA-E2, the 5,6-dimethoxy analog of FIA-E1 of Example 1. FIA-E2 shows superior incubation speed/fog relationship as compared to its N-alkyl and N-sulfoalkyl analogs. The coatings were prepared, exposed, and processed as described for Example 1, with the fog-inhibiting agent addition and sensitometric results listed in Table III. Example 3. Example 3 illustrates the fresh and incubation speed/fog relationship of FIA-E3 of the invention, the 2-methyl-5-chloro analog of FIA-E1 of the invention, as well as additional data for FIA-E1. Comparisons are made with N-alkyl and sulfoalkyl analogs. The coatings were prepared, exposed, and processed as for the previous examples, and the results are tabulated in Table IV. These results again show the superior speed/fog relationship of FIA-E1 and FIA-E3 satisfying the invention as compared to that obtainable with N-alkyl and sulfoalkyl analogs. Example 4. Example 4 again illustrates the superior speed/fog relationship of FIA-E3 of the invention, as well as that of the amino-substituted analog FIA-E4 and the acetamido-substituted analogs FIA-E5 and FIA-E6. The coatings of Example 4 were prepared, exposed and processed as described for the previous examples, except that the hardener level was raised to 1.75% of the gelatin weight. The fog-inhibiting agent additions and sensitometric results are listed in Table V. The results show FIA-E3, FIA-E4, FIA-E5, and FIA-E6 satisfying the invention to provide a superior speed/fog relationship to that provided by FIA-C4. Example 5. Example 5a. Example 5a shows the superior speed/fog relationship obtained with FIA-E1 satisfying the invention as compared to its N-methyl and N-sulfopropyl analogs, in this case in a spectrally sensitized, dye-forming coupler containing chlorobromide emulsion system. FIA-E1 also provides results superior to those obtained with an alternative fog-inhibiting agent combination used as the control for this emulsion system. On a resin-coated paper support was coated a gelatin pad at 1.08 g/m². Over this was coated an optimally sulfur-sensitized cubic grain surface latent image forming negative-working silver chlorobromide emulsion containing 15% chloride and of mean grain size 0.3 µm, spectrally sensitized with 240 mg/Ag mole of the green-sensitizing dye anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylamine salt. The emulsion was coated at 0.32 g/m² Ag and 1.66 g/m² gelatin, and also contained 0.43 g/m² of the magenta dye-forming coupler, 1-(2,4,6-trichlorophenyl)-3-{5-[α-(3- t -butyl-4-hydroxyphenoxy)tetradecaneamido]-2-chloroanilino -5-pyrazolone. Over the emulsion layer was coated a protective layer containing 1.08 g/m² gelatin. The coating was hardened with bis(vinylsulfonylmethyl) ether at 1.75% of the total weight of gelatin. Fog-inhibiting agents were added to the emulsion as indicated in Table VI. Samples of the coatings were exposed through a step wedge in an EASTMAN 1B® sensitometer for 0.1 second to a 3000°K source filtered with Wratten® W12 + 2C filters to provide a minus blue exposure. The samples were then processed in the KODAK EKTAPRINT® 2 process, with development for 3-1/2 min at 33°C. Samples were also incubated for two weeks at 49°C, 50% RH, then similarly exposed and processed. The resulting relative speeds and D-min values are shown in Table VI. Incubation ▵ D-min was determined by comparison with samples held at -18°C. Inspection of the data shows the superior fresh speed/fog relationship obtained with FIA-E1 satisfying the invention when compared with FIA-C1 (N-methyl analog), with FIA-C5 (N-sulfopropyl analog) or with the alternative fog-inhibiting agent combination of FIA-C15 + FIA-C16. The superior prevention of D-min growth on incubation by the fog-inhibiting agent satisfying the invention is also apparent. Example 5b . Example 5b illustrates the superior fog-inhibiting agent properties of FIA-E3, a 2-methyl-5-chloro compound of the invention, when compared with its N-methyl and N-sulfopropyl analogs. A comparison is also made with 5- and 6-sulfo substituted benzothiazolium compounds as additional control compounds. The coating preparation, exposure and processing were as described for Example 5a. Each of the fog-inhibiting agents (with the exception of FIA-C15 + FIA-C16) was dissolved in water containing one equivalent of sodium hydroxide, based on the amount of fog-inhibiting agent used. The fog-inhibiting agent addition and sensitometric results are listed In Table VII. These results show that the 2-methyl-5-chloro compound satisfying the invention, FIA-E3, provides a superior speed/fog relationship both fresh and incubated when compared to the N-methyl, FIA-C4, and N-sulfopropyl, FIA-C7, control compounds; FIA-C3 is also superior to the two benzene-ring sulfo-substituted compounds, FIA-C13, and FIA-C14. Once again, the compound satisfying the invention is superior in its speed/fog relationship to the alternative fog-inhibiting agent combination, FIA-C15 + FIA-C16. Example 6. Example 6 illustrates the superior speed/fog relationships obtained with FIA-E1 satisfying the invention when compared to its N-carbamoyl analogs. The coatings were prepared and tested as described in Example 5a. The fog-inhibiting agents were added as indicated in Table VIII. All fog-inhibiting agents were dissolved in water for addition to the emulsion with the following exceptions: FIA-C18 was hydrolyzed by the addition of 1 equivalent of NaOH/mole of fog-inhibiting agent; the control fog-inhibiting agent FIA-C15 was dissolved in methanol; and the control fog-inhibiting agent FIA-C16 was dissolved in water plus 1 equivalent/mole fog-inhibiting agent of NeOH added for solubilization. Coatings 1 and 2 contain a compound satisfying the invention, FIA-E1. Coatings 3 and 4 also contain FIA-E1 but with the addition of KI et 1 equivalent/mole FIA-E1 for comparison with the iodide counterions of FIA-C17 and FIA-C18. Coatings 5 and 6 contain FIA-C17, the N-carbamoylmethyl analog of FIA-E1. Coatings 7 and 8 contain FIA-C18, the 2-methyl analog of FIA-C17. Coatings 9 and 10 contain FIA-C19, where the iodide counterion of FIA-C17 is replaced with tetrafluoroborate. Finally coatings 11 and 12 contain the control fog-inhibiting agent combination FIA-C15 + FIA-C16, as included also in Examples 5a and 5b. The resulting relative speeds and D-min values are tabulated in Table VIII. The fresh speed of Coating 1, containing FIA-E1 satisfying the invention et 0.68 mmole/Ag mole, is taken as 100. Addition of KI in Coatings 3 and 4 resulted in increased speed. Comparison of Coatings 5-8 with Coatings 1-4 shows that FIA-E1 has a superior fresh and incubation speed/fog relationship to those of FIA-C17 end FIA-C18, particularly when coatings containing equivalent amounts of iodide are considered. FIA-C19 (BF₄ ϑ ) also is clearly poorer in its speed/fog relationship than FIA-E1. The control fog-inhibiting agents combination FIA-C15 + FIA-C16 is again inferior in its speed/fog relationships.

Claims: A photographic element containing a radiation sensitive silver halide emulsion characterized in that it contains a photographically effective amount of a hydrolyzed quaternized chalcogenazolium salt of a middle chalcogens sulphur, selenium, or tellurium including a quaternizing substituent having the formula: where: L is an optionally substituted divalent linking group; R is a substituted or unsubstituted hydrocarbon residue, an amino group or-NHCoR₆; wherein R₆ is an alkyl group of from 1 to 9 carbon atoms or a primary amino group T is carbonyl or sulfonyl; T¹ is independently in each occurrence carbonyl or sulfonyl and m is an integer of from 1 to 3. A photographic element according to claim 1 further characterized in that said hydrolyzed quaternized chalcogenazolium salt is comprised of a hydrolyzed chalcogenazolium ring fused with a carbocyclic aromatic nucleus. A photographic element according to claim 1 containing a hydrolyzed quaternized chalcogenazolium salt satisfying the formula: wherein R¹ is hydrogen, alkyl of from 1 to 8 carbon atoms, or aryl of from 6 to 10 carbon atoms; R² and R³ are independently hydrogen or halogen atoms; optionally substituted aliphatic or aromatic hydrocarbon moieties optionally linked through a divalent oxygen or sulfur atom; or cyano, amino, amido, sulfonamido, sulfamoyl, ureido, thioureido, hydroxy, -C(O)M, or -S(O)₂M groups, wherein M is chosen to complete an aldehyde, ketone, acid, ester, thioester, amide, or salt; or R² and R³ together represent the atoms completing a fused ring which may be substituted; Y² represents a charge balancing counter ion; n is the integer 0 or 1; X is S, Se, or Te; and Q is a quaternizing substituent satisfying the formula: wherein L represents an optionally substituted divalent hydrocarbon group; R represents an amino group, an optionally substituted hydrocarbon residue or -NHCoR₆; wherein R₆ is an alkyl group of from 1 to 8 carbon atoms or a primary amino group T is carbonyl or sulfonyl; T¹ is independently in each occurrence carbonyl or sulfonyl; and m is an integer of from 1 to 3. A photographic element according to any of claims 1 to 3 further characterized in that L is an alkylene group of from 1 to 8 carbon atoms. A photographic element according to any of claims 1 to 4 further characterized in that R is a primary or secondary amino group, an alkyl group of from 1 to 8 carbon atoms, or an aryl group of from 6 to 10 carbon atoms. A photographic element according to any of claims 1 to 5 further characterized in that T is carbonyl. A photographic element according to any of claims 1 to 6 further characterized that m is 1. a photographic element according to any of claims 2 to 7 further characterized in that R² and R=3 together complete a fused carbocyclic ring which may be substituted and X is tellurium. A photographic element according to claim 3 further characterized by the quaternized salt in its unhydrolyzed form satisfies the formula: wherein R¹ is hydrogen, alkyl of from 1 to 8 carbon atoms, or aryl of from 6 to 10 carbon atoms; R⁴ and R⁵ are independently hydrogen or halogen atoms; aliphatic or aromatic hydrocarbon moieties optionally linked through a divalent oxygen or sulfur atom; or cyano, amino, amido, sulfonamido, sulfamoyl, ureido, thioureido, hydroxy, -C(O)M, or -S(O)₂M groups, wherein M is chosen to complete an aldehyde, ketone, acid, ester, thioester, amide, or salt; Y¹ is a charge balancing counter ion; n is the integer 0 or 1; and Q is a quaternizing substituent of the formula -LCONHSO₂R₆ or -LCONHSO₂NHCOR₆ wherein L is an alkylene group of from 1 to 8 carbon atoms R₆ is an alkyl group of from 1 to 8 carbon atoms or or a primary amino group. A photographic element according to claim 9 in which R¹ is hydrogen or methyl; R⁴ and R⁵ are individually hydrogen, halogen, or alkyl or alkoxy groups of from 1 to 4 carbon atoms; and L is methylene or ethylene. A photographic element according to any of claims 1 to 10 further characterized in that said fog-inhibiting agent is present in a concentration of from 10.0 to 0.01 millimole, preferably 2.0 to 0.015 millimole, per silver mole. A photographic element according to any of claims 1 to 11 further characterized in that said silver halide emulsion contains surface latent image forming silver halide grains. A photographic element according to claim 12 further characterized in that said silver halide grains are surface chemically sensitized. A photographic element according to any of claims 1 through 13 further characterized in that said silver halide grains are spectrally sensitized.

Inventors: FREEMAN, JOHN PAUL, MACON, FRED MATHIS, MEE, JOHN DAVID
Applicants: EASTMAN KODAK COMPANY (A NEW JERSEY CORPORATION)
Application year: 1986
Main classification: G03C1
IPC codes: G03C1