Toner and developer compositions with charge enhancing additives

Abstract: A toner composition comprising a resin, a pigment or dye, and a quaternary ammonium bisulfate charge enhancing additive of the formula R′₂R″₂N⁺X- wherein R′ and R′ are independently selected from the group consisting of alkyl, aryl, and alkylaryl; and X- is a bisulfate anion.

Description: The invention is generally directed to toner and developer compositions, and more specifically, the present invention is directed to developer and toner compositions containing charge enhancing additives, which impart or assist in imparting a positive charge to the toner resin particles and enable toners with rapid admix characteristics. Developer compositions with charge enhancing additives, which impart a positive charge to the toner resin, are well known. Thus, for example, there is described in US-A-3,893,935 the use of quaternary ammonium salts as charge control agents for electrostatic toner compositions. In this patent, there are disclosed quaternary ammonium compounds with four R substituents on the nitrogen atom, which substituents represent an aliphatic hydrocarbon group having 7 or less, and preferably about 3 to about 7 carbon atoms, including straight and branch chain aliphatic hydrocarbon atoms, and wherein X represents an anionic function including, according to this patent, a variety of conventional anionic moieties such as halides, phosphates, acetates, nitrates, benzoates, methylsulfates, perchloride, tetrafluoroborate, benzene sulfonate, and the like; US-A-4,221,856 which discloses electrophotographic toners containing resin compatible quaternary ammonium compounds in which at least two R radicals are hydrocarbons having from 8 to about 22 carbon atoms, and each other R is a hydrogen or hydrocarbon radical with from 1 to about 8 carbon atoms, and A is an anion, for example, sulfate, sulfonate, nitrate, borate, chlorate, and the halogens such as iodide, chloride and bromide, reference the Abstract of the Disclosure and column 3; a similar teaching is presented in US-A-4,312,933 which is a division of US-A-4,291,111; and similar teachings are presented in US-A-4,291,112 wherein A is an anion including, for example, sulfate, sulfonate, nitrate, borate, chlorate, and the halogens. There are also described in US-A-2,986,521 reversal developer compositions comprised of toner resin particles coated with finely divided colloidal silica. According to the disclosure of this patent, the development of electrostatic latent images on negatively charged surfaces is accomplished by applying a developer composition having a positively charged triboelectric relationship with respect to the colloidal silica. Also, there is disclosed in US-A-4,338,390, developer compositions containing as charge enhancing additives organic sulfate and sulfonates, which additives can impart a positive charge to the toner composition. Further, there is disclosed in US-A-4,298,672, positively charged toner compositions with resin particles and pigment particles, and as charge enhancing additives alkyl pyridinium compounds. Additionally, other documents disclosing positively charged toner compositions with charge control additives include US-A-3,944,493; US-A-4,007,293; US-A-4,079,014 and US-A-4,394,430. A patentability search report recited the following prior art: US-A-4,812,381 relating to toners and developers with quaternary ammonium salts of the formula illustrated in column 3, the preparation thereof, see column 4, and also note the working examples, columns 7 and 8, wherein specific charge additives, such as octadecyl ammonium trifluoromethane sulfonate, are reported; US-A-4,675,118 which discloses certain quaternary salts as fabric softeners, see the Abstract of the Disclosure, and note column 1, for example, wherein X is as recited including OSO₃CH₃ and halide; US-A-4,752,550, directed to toners and developers with inner salt charge, see for example column 4; US Reissue 32,883 (a reissue of US-A-4,338,390) wherein toners with organic sulfonate and organic sulfate charge enhancing additives are illustrated, see columns 3,4, and 5 to 10 for example; and US-A-4,058,585 which discloses a process of extracting metals with organic solvent solutions of the salts of hydrogen ionic exchange agents, and quaternary ammonium compounds including some of the bisulfates of the present invention. Processes for preparing quaternary ammonium salts by an ion exchange, or ion pair extraction method with soluble quaternary compounds is known, reference for example Phase Transfer Catalysis , Principles and Techniques , Academic Press, N.Y., 1978, especially page 76, C.M. Starks, and C. Liotta, and "Preparative Ion Pair Extraction", Apotekarsocieteten/Hassle, Lakemidel , pages 139 to 148, Sweden, 1974, which illustrates the preparation of certain bisulfates with water soluble ammonium salt reactants and a two-phase method wherein the product resides in the water phase. Moreover, toner compositions with negative charge enhancing additives are known, reference for example US-A-4,411,974 and US-A-4,206,064. The ′974 patent discloses negatively charged toner compositions comprised of resin particles, pigment particles, and as a charge enhancing additive ortho-halo phenyl carboxylic acids. Similarly, there are disclosed in the ′064 patent toner compositions with chromium, cobalt, and nickel complexes of salicylic acid as negative charge enhancing additives. There is illustrated in US-A-4,404,271 a complex system for developing electrostatic images with a toner which contains a metal complex represented by the formula in column 2, for example, and wherein ME can be chromium, cobalt or iron. Additionally, other patents disclosing various metal containing azo dyestuff structures wherein the metal is chromium or cobalt include US-A-2,891,939; 2,871,233; 2,891,938; 2,933,489; 4,053,462 and 4,314,937. Also, in US-A-4,433,040, there are illustrated toner compositions with chromium and cobalt complexes of azo dyes as negative charge enhancing additives. Other prior art includes Japanese Patent Publication No. 54-145542 which illustrates a negatively chargeable toner consisting of a resin, a colorant, and the charge control agent pyridoxine aliphatic acid ester; East German Patent Publication 218697 relating to liquid developers with charge control additives with structural units of Formulas (I), (II) and (III), and which contains olefinically polymerizable bonds; US-A-3,850,642 relating to multilayer sensitive elements with ionizable salts, acids, esters, and surfactants as charge control agents; US-A-2,970,802 illustrating a composition for the control of hypercholestermia, which composition consists of a nontoxic gelatin containing aluminum nicotinate; and US-A-3,072,659 which discloses a method of preparing aluminum salts of nicotinic acid. Although many charge enhancing additives are known, there continues to be a need for toners with additives, which toners possess many of the advantages illustrated herein. Additionally, there is a need for positive charge enhancing additives which are useful for incorporation into black, and/or colored toner compositions. Moreover, there is a need for colored toner compositions containing certain charge enhancing additives. There is also a need for toner compositions with certain charge enhancing additives, which toners possess acceptable substantially stable triboelectric charging characteristics, and excellent admixing properties. Moreover, there continues to be a need for positively charged toner and developer compositions. Further, there is a need for toners with certain charge enhancing additives which can be easily and permanently dispersed into toner resin particles. There also is a need for positively charged black, and colored toner compositions that are useful for incorporation into various imaging processes, inclusive of color xerography, as illustrated in US-A-4,078,929; in laser printers; and additionally a need for toner compositions useful in imaging apparatuses having incorporated therein layered photoresponsive imaging members, such as the members illustrated in US-A-4,265,990. Also, there is a need for toner compositions which have the desired triboelectric charge level, for example, from about 10 to about 40 microcoulombs per gram, and preferably from about 10 to about 20 microcoulombs per gram, and admix charging rates of from about 5 to about 60 seconds, and preferably less than about 15 seconds, as determined by the charge spectrograph, preferably for example at low concentrations, that is for example less than 1 percent, and preferably less than about 0.5 percent of the charge enhancing additive of the present invention. It is an object of the present invention to provide toner and developer compositions with charge enhancing additives which meet many of these needs. According to the present invention there is provided a toner composition comprising resin particles, a pigment or dye, and a quaternary ammonium salt as a charge enhancing additive, characterised in that said salt is a bisulfate. More specifically, the present invention is directed to toner compositions comprised of resin, pigment, or dye, and tetraalkyl, wherein alkyl, for example, contains from 1 to about 30 carbon atoms, ammonium bisulfate charge enhancing additives such as distearyl dimethyl ammonium bisulfate, tetramethyl ammonium bisulfate, tetraethyl ammonium bisulfate, tetrabutyl ammonium bisulfate, and preferably dimethyl dialkyl ammonium bisulfate compounds where the dialkyl radicals contain from about 10 to about 30 carbon atoms, and more preferably dialkyl radicals with from about 14 to about 22 carbon atoms, and the like. The aforementioned charge additives can be incorporated into the toner or may be present on the toner surface. Advantages of rapid admix, appropriate triboelectric characteristics, and the like are achieved with many of the toners of the present invention. In one embodiment, there are provided in accordance with the present invention toner compositions comprised of resin particles, pigment particles, and quaternary ammonium bisulfates, including preferably tetraalkyl ammonium bisulfate charge enhancing additives, which additives enable, for example, toners with rapid admix of less than about 15 seconds in some embodiments, extended developer life, stable electrical properties, high image print quality with substantially no background deposits, and compatibility with fuser rolls including Viton fuser rolls. The aforementioned toner compositions usually contain pigment particles comprised of, for example, carbon black, magnetites, or mixtures thereof, cyan, magenta, yellow, blue, green, red, or brown components, or mixtures thereof thereby providing for the development and generation of black and/or colored images. The toner compositions of the present invention possess excellent admix characteristics as indicated herein, and maintain their triboelectric charging characteristics for an extended number of imaging cycles, exceeding for example 1,000,000 in many embodiments. The toner and developer compositions of the present invention can be selected for electrophotographic, especially xerographic imaging and printing processes, including color processes. The toners of the present invention enable the making of positively charged toner compositions useful for the development of electrostatic latent images including color images. The toners of the invention are humidity insensitive, from about, for example, 20 to 80 percent relative humity at temperatures of from 15.5 to 26.7°C as determined in a relative humidity testing chamber, with desirable admix properties of 5 seconds to 60 seconds as determined by the charge spectrograph, and preferably less than 15 seconds for example, and more preferably from about 1 to about 14 seconds, and acceptable triboelectric charging characteristics of from about 10 to about 40 microcoulombs per gram. Additionally, there may be provided positively charged magnetic toner compositions, and positively charged colored toner compositions containing therein, or thereon quaternary ammonium bisulfate charge additives. The toners of the invention include thermally stable tetraalkyl ammonium bisulfate charge enhancing additives, that is for example additives which do not decompose at high temperatures, for example, of from about 130 to about 160°C. The toners will enable the development of images in electrophotographic imaging apparatuses, which images have substantially no background deposits thereon, are substantially smudge proof or smudge resistant, and therefore are of excellent resolution; and further, such toner compositions can be selected for high speed electrophotographic apparatuses, that is those exceeding 70 copies per minute. Preferred quaternary ammonium bisulfates are of the formula R′₂R″₂N⁺X⁻ or (R₄N)+X⁻ wherein R′ or R is aryl, substituted aryl such as alkylaryl, alkyl, preferably with 1 to about 30 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, heptyl, and preferably dimethyl dialkyl ammonium bisulfate compounds where the dialkyl radicals are from about 10 to about 30 carbon atoms, and more preferably dialkyl radicals with from about 14 to about 22 carbon atoms); R″ is aryl, substituted aryl such as alkylaryl, alkyl, preferably containing from 1 to about 18 carbon atoms; and X- is a bisulfate (HSO₄) anion. The charge control additives of the present invention may be prepared by ionic exchange reactions from a variety of tetrasubstituted ammonium salts, especially those of the formula R′₂R″₂N⁺X⁻ where X⁻ is selected from the group consisting of halide, alkyl or aryl sulfate, alkoxide, hydroxide, acetate, benzoate and phosphate; and R′ and R″ are as defined herein. The tetrasubstituted ammonium salt selected can be heated in an appropriate solvent or solvents, such as water, in the presence of a stoichiometric amount of sulfuric acid. One typical process of preparation involves heating at an effective temperature of, for example, from about 40 to about 100°C for an appropriate period of time, such as from about 5 to about 15 hours, the insoluble tetrasubstituted ammonium chloride, or other halide, such as distearyl dimethyl ammonium chloride (DDACl), or the corresponding methyl sulfate salt, distearyl dimethyl ammonium methyl sulfate (DDAMS) in aqueous solution, about one molar equivalent in 85 molar equivalents of water and 10 molar equivalents of sulfuric acid in 56 molar equivalents of water. The crude product resulting after cooling to room temperature can be collected by filtration, and then purified by washing with various solvents such as acetone, followed by recrystallization from, for example, an appropriate solvent such as acetone or methanol, and the like. The resulting products can be identified by a number of techniques including melting point information, differential scanning calorimetry, infrared spectra, carbon, and proton nuclear magnetic resonance, ion chromotography, elemental analysis, and the like. Toner compositions comprising a mixture of charge enhancing additives wherein one of the additives can be the bisulfate of the present invention and processes thereof are illustrated in our corresponding European Patent Application which claims priority from US Patent Application Serial No. 396,510. Process embodiments illustrated in the aforementioned copending applications for the preparation of the bisulfate charge additives of the present invention include the reaction of water insoluble quaternary ammonium salts, such as distearyl dimethyl ammonium methyl sulfate; distearyl dialkyl ammonium halides, such as distearyl dimethyl ammonium halide, especially the chloride or bromide; dialkyl distearyl ammonium hydroxides, wherein alkyl contains from 10 to about 30 carbon atoms, such as dimethyl distearyl ammonium hydroxide, and diethyl distearyl ammonium hydroxide; distearyl ammonium tosylate, such as dimethyl distearyl ammonium tosylate; distearyl dialkyl, wherein alkyl, for example, contains from 1 to about 30 carbon atoms; ammonium alkyl, wherein alkyl, for example, contains from 1 to about 20 carbon atoms; sulfonate; and the like with a sulfuric acid in the presence of heat. Usually a solvent for the acid, such as water, is selected. The acid is selected in effective amounts of, for example, from about 1 to about 10 molar equivalents, and preferably from about 5 to about 8 molar equivalents to about 1 molar equivalent of the quaternary ammonium salt reactant. Heating of the reaction mixture can be accomplished at various temperatures depending, for example, on the reactants selected, preferably the reaction, however, is accomplished at a temperature of from about 40 to about 100°C. Distearyl dimethyl ammonium methyl sulfate can be heated in an appropriate solvent or solvent mixture in the presence of stoichiometric amount or sulfuric acid. The solvent system comprised, for example, of water, water and alcohol mixtures, water and tetrahydrofuran mixtures, water and acetone mixtures, and water and halogenated, especially chlorinated solvent mixtures may be selected permitting a single phase or two phase system to facilitate the speed thereof by, for example, from days to hours of the reaction and enabling the isolation and purification of the desired quaternary ammonium product. In the one phase method, for example, there is dissolved the DDAMS quaternary ammonium salt reactant and the concentrated sulfuric acid, water, a water miscible organic cosolvent including acetone, dioxane, glycol ethers, tetrahydrofuran, or an aqueous alcohol, preferably methanol or tetrahydrofuran. Thereafter, the resulting solution can be heated, followed by cooling whereby a precipitate of the desired bisulfate product is obtained subsequent to isolation by filteration. The product may be purified by, for example, known recrystallization methods. With a two-phase process the appropriate quaternary ammonium salt in a solvent such as methylene chloride or chloroform is mixed and heated with an aqueous sulfuric acid solution. One preferred two-phase method comprises, as illustrated herein, heating the appropriate powdered DDAMS quaternary ammonium salt reactant in suspension with excess aqueous sulfuric acid. In the aforementioned two-phase methods, the desired bisulfate product can be isolated directly by filtration, and thereafter purified by recrystallization, or other similar methods when desirable. The resulting products obtained with the process of the present invention can be identified by a number of techniques including melting point information, differential scanning calorimetry, infrared spectra, carbon, and proton nuclear magnetic resonance, ion chromotography, elemental analysis, and the like. Preferred process embodiments comprise the addition of the appropriate insoluble quaternary ammonium salt, such as distearyl dimethyl ammonium methyl sulfate DDAMS, and water, followed by dissolving sulfuric acid in the aforementioned mixture, and thereafter separating the desired bisulfate product therefrom wherein water is selected in a sufficient amount to suspend the quaternary ammonium salt reactant, that is for example for one-half part of water to one part of reactant; the addition of a cosolvent to the water, acid, DDAMS reactants, which cosolvent includes tetrahydrofuran, aliphatic alcohols, such as methanol, ethanol, propanol, butanol; dioxane, glycol ethers, acetone, and the like; and then separating the desired product from the reaction mixture whereby there is enabled the DDAMS reactant to be substantially more soluble, for example, and thereby enabling a scale up in manufacturing processes in an effective manner wherein the mixture, for example, comprises from 1 part of water to 0.1 part of a second solvent such as acetone, dioxane, glycol ethers, preferably 0.1: 1.0 to about 20:10 of second cosolvent to water, tetrahydrofuran, alcohols, and the like; a two-phase system wherein there is formed a first water layer and a second solvent, such as chloroform or toluene layer, thus the DDAMS reactant is dissolved in chloroform and the water layer containing the acid wherein reaction is accomplished at the water interface, and the product is present in the organic phase containing the chloroform and the toluene. Generally, in the aforementioned two-phase reaction from about 1 part of water to 0.1 to 20 parts by weight of the second solvent, such as chloroform or alcohol, is selected. The two-phase system process generally comprises the preparation of quaternary ammonium compounds R₄N+X- wherein a quaternary ammonium salt is dissolved in a water immiscible organic solvent and added to a mixture comprised of an acid and water, thereafter heating whereby a reaction occurs at the interface between the organic solvent layer and the water layer, cooling, separating the organic layer from the water layer, and obtaining the product from the organic layer. Other embodiments for the preparation of the bisulfate salts of the present invention, which embodiments are illustrated in the aforementioned copending applications, include a process for the preparation of quaternary ammonium compounds of the formula R′₂R″₂N⁺X- wherein R′ and R″ are independently selected from the group consisting of alkyl, aryl, and alkylaryl; and X- is an anion, which comprises the reaction by heating of water insoluble quaternary ammonium salts with an acid; a process for the preparation of quaternary ammonium compounds wherein a quaternary ammonium salt is dissolved in a water immiscible organic solvent and added to a mixture comprised of an acid and water, thereafter heating whereby a reaction occurs at the interface between the organic solvent layer and the water layer, cooling, separating the organic layer from the water layer, and obtaining the product from the organic layer; and wherein the quaternary salt reactant is preferably distearyl dimethyl ammonium methyl sulfate (DDAMS), and the acid is sulfuric acid. The toner compositions of the present invention can be prepared by a number of known methods such as admixing and heating resin particles such as styrene butadiene copolymers, pigment particles such as magnetite, carbon black, or mixtures thereof, and preferably from about 0.5 percent to about 5 percent of the aforementioned charge enhancing additives in a toner extrusion device, such as the ZSK53 available from Werner Pfleiderer, and removing the formed toner composition from the device. Subsequent to cooling, the toner composition is subjected to grinding utilizing, for example, a Sturtevant micronizer for the purpose of achieving toner particles with a volume median diameter of less than about 25 µm, and preferably of from about 8 to about 12 µm, which diameters are determined by a Coulter Counter. Subsequently, the toner compositions can be classified utilizing, for example, a Donaldson Model B classifier for the purpose of removing fines, that is toner particles less than about 4 µm volume median diameter. Illustrative examples of suitable toner resins selected for the toner and developer compositions of the present invention include polyamides, polyolefins, epoxies, polyurethanes, vinyl resins, including homopolymers or copolymers of two or more vinyl monomers; and polymeric esterification products of a dicarboxylic acid and a diol comprising a diphenol. Vinyl monomers include styrene, p-chlorostyrene, unsaturated mono-olefins such as ethylene, propylene, butylene, isobutylene and the like; saturated mono-olefins such as vinyl acetate, vinyl propionate, and vinyl butyrate; vinyl esters like esters of monocarboxylic acids including methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; acrylonitrile, methacrylonitrile, acrylamide; styrene butadiene copolymers; mixtures thereof; and the like, reference the U.S. patents mentioned herein. As one preferred toner resin, there are selected the esterification products of a dicarboxylic acid and a diol comprising a diphenol. These resins are illustrated in US-A-3,590,000. Other preferred toner resins include styrene/methacrylate copolymers, and styrene/butadiene copolymers; Pliolites; suspension polymerized styrene butadienes, reference US-A-4,558,108; polyester resins obtained from the reaction of bisphenol A and propylene oxide; followed by the reaction of the resulting product with fumaric acid, and branched polyester resins resulting from the reaction of dimethylterephthalate, 1,3-butanediol, 1,2-propanediol, and pentaerythritol, styrene acrylates, and mixtures thereof. Also, waxes with a molecular weight of from about 1,000 to about 6,000 such as polyethylene, polypropylene, and paraffin waxes can be included in, or on the toner compositions as fuser roll release agents. The resin particles are present in a sufficient, but effective amount, for example from about 70 to about 90 weight percent. Thus, when 1 percent by weight of the charge enhancing additive is present, and 10 percent by weight of pigment or colorant, such as carbon black, is contained therein, about 89 percent by weight of resin is selected. Also, the charge enhancing additive of the present invention may be coated on the pigment particle. When used as a coating, the charge enhancing additive of the present invention is present in an amount of from about 0. 1 weight percent to about 5 weight percent, and preferably from about 0.3 weight percent to about 1 weight percent. Numerous well known suitable pigments or dyes can be selected as the colorant for the toner particles including, for example, carbon black, nigrosine dye, aniline blue, magnetite, or mixtures thereof. The pigment, which is preferably carbon black, should be present in a sufficient amount to render the toner composition highly colored. Generally, the pigment particles are present in amounts of from about 1 percent by weight to about 20 percent by weight, and preferably from about 2 to about 10 weight percent based on the total weight of the toner composition; however, lesser or greater amounts of pigment particles can be selected providing the objectives of the present invention are achieved. When the pigment particles are comprised of magnetites, thereby enabling single component toners in some instances, which magnetites are a mixture of iron oxides (FeO·Fe₂O₃) including those commercially available as Mapico Black, they are present in the toner composition in an amount of from about 10 percent by weight to about 70 percent by weight, and preferably in an amount of from about 10 percent by weight to about 50 percent by weight. Mixtures of carbon black and magnetite with from about 1 to about 15 weight percent of carbon black, and preferably from about 2 to about 6 weight percent of carbon black, and magnetite, such as Mapico Black, in an amount of, for example, from about 5 to about 60, and preferably from about 10 to about 50 weight percent can be selected. There can also be blended with the toner compositions of the present invention external additive particles including flow aid additives, which additives are usually present on the surface thereof. Examples of these additives include colloidal silicas such as Aerosil, metal salts and metal salts of fatty acids inclusive of zinc stearate, aluminum oxides, cerium oxides, and mixtures thereof, which additives are generally present in an amount of from about 0.1 percent by weight to about 5 percent by weight, and preferably in an amount of from about 0.1 percent by weight to about 1 percent by weight. Several of the aforementioned additives are illustrated in US-A-3,590,000 and US-A-3,800,588. With further respect to the present invention, colloidal silicas such as Aerosil can be surface treated with the charge additives of the present invention illustrated herein in an amount of from about 1 to about 30 weight percent and preferably 10 weight percent followed by the addition thereof to the toner in an amount of from 0.1 to 10 and preferably 0.1 to 1 weight percent. Also, there can be included in the toner compositions of the present invention low molecular weight waxes, such as polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation, Epolene N-15 commercially available from Eastman Chemical Products, Inc., Viscol 550-P, a low weight average molecular weight polypropylene available from Sanyo Kasei K.K., and similar materials. The commercially available polyethylenes selected have a molecular weight of from about 1,000 to about 1,500, while the commercially available polypropylenes utilized for the toner compositions of the present invention are believed to have a molecular weight of from about 4,000 to about 5,000. Many of the polyethylene and polypropylene compositions useful in the present invention are illustrated in GB-A-1,442,835. The low molecular weight wax materials are present in the toner composition of the present invention in various amounts, however, generally these waxes are present in the toner composition in an amount of from about 1 percent by weight to about 15 percent by weight, and preferably in an amount of from about 2 percent by weight to about 10 percent by weight. Encompassed within the scope of the present invention are colored toner and developer compositions comprised of toner resin particles, carrier particles, the charge enhancing additives illustrated herein, and as pigments or colorants red, blue, green, brown, magenta, cyan and/or yellow particles, as well as mixtures thereof. More specifically, with regard to the generation of color images utilizing a developer composition with the charge enhancing additives of the present invention, illustrative examples of magenta materials that may be selected as pigments include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like. Illustrative examples of cyan materials that may be used as pigments include copper tetra-4-(octadecyl sulfonamido) phthalocyanine, X-copper phthalocyanine pigment listed in the Color Index as Cl 74160, CI Pigment Blue, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like; while illustrative examples of yellow pigments that may be selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxy aceto-acetanilide, and Permanent Yellow FGL. The aforementioned pigments are incorporated into the toner composition in various suitable effective amounts providing the objectives of the present invention are achieved. In one embodiment, these colored pigment particles are present in the toner composition in an amount of from about 2 percent by weight to about 15 percent by weight calculated on the weight of the toner resin particles. For the formulation of developer compositions, there are mixed with the toner particles carrier components, particularly those that are capable of triboelectrically assuming an opposite polarity to that of the toner composition. Accordingly, the carrier particles of the present invention are selected to be of a negative polarity enabling the toner particles, which are positively charged, to adhere to and surround the carrier particles. Illustrative examples of carrier particles include iron powder, steel, nickel, iron, ferrites, including copper zinc ferrites, and the like. Additionally, there can be selected as carrier particles nickel berry carriers as illustrated in US-A-3,847,604. The selected carrier particles can be used with or without a coating, the coating generally containing terpolymers of styrene, methylmethacrylate, and a silane, such as triethoxy silane, reference US-A-3,526,533 and US-A-3,467,634; polymethyl methacrylates; other known coatings; and the like. The carrier particles may also include in the coating, which coating can be present in one embodiment in an amount of from about 0.1 to about 3 weight percent, conductive substances such as carbon black in an amount of from about 5 to about 30 percent by weight. Polymer coatings not in close proximity in the triboelectric series can also be selected, including for example Kynar and polymethylmethacrylate mixtures (40/60). Coating weights can vary as indicated herein; generally, however, from about 0.3 to about 2, and preferably from about 0.5 to about 1.5 weight percent coating weight is selected. Furthermore, the diameter of the carrier particles, preferably spherical in shape, is generally from about 50 µm to about 1,000 µm thereby permitting them to possess sufficient density and inertia to avoid adherence to the electrostatic images during the development process. The carrier component can be mixed with the toner composition in various suitable combinations, however, best results are obtained when about 1 to 5 parts per toner to about 10 parts to about 200 parts by weight of carrier are selected. The toner composition of the present invention can be prepared by a number of known methods including extrusion melt blending the toner resin particles, pigment particles or colorants, and the charge enhancing additive of the present invention as indicated herein, followed by mechanical attrition. Other methods include those well known in the art such as spray drying, melt dispersion, extrusion processing, dispersion polymerization, and suspension polymerization. Also, as indicated herein the toner composition without the charge enhancing additive can be prepared, followed by the addition of surface treated with charge additive colloidal silicas. Further, other methods of preparation for the toner are as illustrated herein. The toner and developer compositions of the present invention may be selected for use in electrostatographic imaging apparatuses containing therein conventional photoreceptors providing that they are capable of being charged negatively. Thus, the toner and developer compositions of the present invention can be used with layered photoreceptors that are capable of being charged negatively, such as those described in US-A-4,265,990. Illustrative examples of inorganic photoreceptors that may be selected for imaging and printing processes include selenium; selenium alloys, such as selenium arsenic, selenium tellurium and the like; halogen doped selenium substances; and halogen doped selenium alloys. Other similar photoreceptors can be selected providing the objectives of the present invention are achievable. The toner compositions are usually jetted and classified subsequent to preparation to enable toner particles with a preferred average diameter of from about 5 to about 25 µm, and more preferably from about 8 to about 12 µm. Also, the toner compositions of the present invention preferably possess a triboelectric charge of from about 0.1 to about 2 femtocoulombs per micron as determined by the known charge spectograph. Admix time for the toners of the present invention are preferably from about 5 seconds to 1 minute, and more specifically from about 5 to about 15 seconds as determined by the known charge spectograph. These toner compositions with rapid admix characteristics enable, for example, the development of images in electrophotographic imaging apparatuses, which images have substantially no background deposits thereon, even at high toner dispensing rates in some instances, for instance exceeding 20 grams per minute; and further, such toner compositions can be selected for high speed electrophotographic apparatuses, that is those exceeding 70 copies per minute. With further respect to the present invention, a preferred developer composition is comprised of a toner composition containing the quaternary ammonium bisulfate charge enhancing additive, and more preferably distearyl dimethyl ammonium bisulfate, pigment particles such as carbon black, resin particles, and carrier particles comprised of a core containing thereover a plurality and preferably two polymeric coatings, namely a first polymeric coating and a second polymeric coating, which coatings are not in close proximity in the triboelectric series. With the aforementioned carriers, in some embodiments from about 0.1 to about 0.5 weight percent of the charge enhancing additive can be selected. Accordingly, for example, small amounts of charge enhancing additives can be selected for developers with carrier particles containing a double polymeric coating thereover. With some charge enhancing additives, and particularly the known distearyl dimethyl ammonium methyl sulfate as mentioned herein, this additive is usually present in the toner components, which components are placed in an extruder, and during heating in the extrusion device this charge additive may decompose, which disadvantage is avoided with the present invention wherein a bisulfate charge enhancing additive can be incorporated into the toner and during extrusion decomposition thereof is avoided and/or substantially eliminated. Moreover, the charge enhancing bisulfate additives of the present invention, and in particular the distearyl dimethyl ammonium methyl bisulfate is thermally stable at high temperatures as indicated herein as is not the situation with some of the prior art charge enhancing additives. Also, the toner compositions of the present invention possess desirable narrow charge distributions, optimal charging triboelectric values, preferably of from 10 to about 40, and more preferably from about 10 to about 35 microcoulombs per gram with from about 0.1 to about 5 weight percent in one embodiment of the charge enhancing additive; and rapid admix charging times as determined in the charge spectrograph of less than 15 seconds, and more preferably in some embodiments from about 1 to about 14 seconds. The following examples are being supplied to further define various species of the present invention, it being noted that these examples are intended to illustrate and not limit the scope of the present invention. Parts and percentages are by weight unless otherwise indicated. EXAMPLE I Chemical Synthesis of Distearyl Dimethyl Ammonium Bisulfate (DDABS) by Ionic Exchange : Reaction of distearyl dimethyl ammonium methyl sulfate (DDAMS): to a suspension of 300 grams (0.45 mol) of DDAMS in 1,500 milliliters of water (3 liter Buchner filter flask) was cautiously added a solution of 250 milliliters of concentrated sulfuric acid (H₂SO₄, 4.5 mol, 10 equivalents) in 1,000 milliliters of ice water. The resulting stirred mixture was heated to about 70°C for four hours then cooled to room temperature overnight (18 hours) followed by filtration under reduced pressure for 24 hours with Whatman #4 paper. The resultant tan semigelatinous product filter cake was then suspended in 1,500 milliliters of water and heated to from about 50 to about 60°C for about 30 minutes, cooled to room temperature, then filtered under reduced pressure. The product filter cake (216 grams) was recrystallized (reconstituted) from an acetone, 1,500 milliliters/water, 100 milliliters, mixture and a second time from methanol 1,000 milliliters/water, 100 milliliters, to separate on cooling, filtering, and vacuum drying 187.8 grams of an off-white powder product DDABS, mp 96° to 100°C. A second, 22.5 grams, and third, 6.2 grams, fraction of less pure material was isolated from the mother liquor and these fractions can be further purified by recrystallization to improve the overall yield. Total isolated yield of the above product DDABS (all fractions) of the formula C₃₈H₈₁NSO₄ was 74 percent. H NMR (CDC1₃) for the first 187.8 gram fraction was δ6.43 (broad m, 1H, HSO₄), 3.21 to 3.29 (multiplet containing a singlet, 10H, (CH₃)₂N and (CH₂)₂N, 1.66 (broad m, 4H, beta CH₂), 1.20 to 1.32 (m 30H, aliphatic CH₂), and 0.86 to 0.89 (t, 6H, aliphatic CH₃); IR(KBr) 1,011, 1,185, 1,471, 1,490 (shoulder), 2,918. EXAMPLE II The product of Example I, DDABS, was also prepared as follows. To 1,200 milliliters of ice water was cautiously added 250 milliliters of concentrated sulfuric acid (H₂SO₄), then the resulting mixture was stirred and allowed to thermally equilibrate at ambient temperature for about 2 hours. The aforementioned prepared aqueous N₂SO₄ solution was added to a suspension of 500 grams of DDAMS (0.76 mol) in 1,000 milliliters water. The resulting suspension was mechanically stirred and heated on a hot plate (70 to 80°C) in a 3 liter Buchner filter flask for 4 hours. The suspension was cooled to room temperature then filtered under reduced pressure overnight (18 hours) to remove the aqueous H₂SO₄. The water filtrate, aqueous H₂SO₄, was carefully neutralized with NaOH to a pH of about 7 before disposal. The retentate, an off-white tan colored solid paste, was suspended in 2 liters of acetone with vigorous mixing then filtered under reduced pressure to remove additional water, H₂SO₄ and acetone soluble impurities. This filter cake was then suspended in 2 liters of hot acetone with vigorous mechanical stirring for about 30 minutes. The acetone suspension was cooled in an ice bath then filtered under reduced pressure to separate after drying about 450 grams of an off-white solid. The infrared spectrum of this material indicated a slight contamination was present. The material was again suspended in 2 liters of hot acetone with mechanical stirring for 30 minutes then cooled and filtered to separate 407 grams (0.628 mol, 83 percent yield) of an off-white solid powder, mp 90°C (softening), 110°C (liquid) of the above product DDABS of analytically pure material, about 99.5 percent pure. This procedure has the particular advantage that it avoids having to hot filter/recrystallize the crude product as in Example I. Instead, this is accomplished by the acetone washing and reprecipitation steps. EXAMPLE III A solution of 25 grams (0.0378) of DDAMS in 200 milliliters of CHCl₃ was mixed with a solution of 15 milliliters of concentrated H₂SO₄ in 15 milliliters of water and the mixture was heated with stirring for 3 hours. The reaction mixture was cooled to zero (0)°C in an ice bath to separate a white precipitate which was collected by filtration. The crude material was recrystallized from acetone to afford 21 grams of the DDABS product, identified in accordance with the procedure of Example I, as a white powder, mp 91 to 106°C (yield 86 percent of theory). Also, the compounds prepared by the processes of Examples II and III were further identified by ¹H NMR analysis and infrared (IR) analysis. EXAMPLE IV There was prepared in an extrusion device, available as ZSK28 from Werner Pfleiderer, a toner composition by adding thereto 80.13 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 16.4 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; and 0.32 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate obtained from Example II. The toner product which was extruded at a rate of 6.8 Kg per hour reached a melting temperature of 210°C. The strands of melt mixed product exiting from the extruder were cooled by immersing them in a water bath maintained at room temperature, about 25°C Subsequent to air drying, the resulting toner was subjected to grinding in a Sturtevant micronizer enabling particles with a volume median diameter of from 8 to 12 µm as measured by a Coulter Counter. Thereafter, the aforementioned toner particles were classified in a Donaldson Model B classifier for the purpose of removing fine particles, that is those with a volume median diameter of less than 4 µm. Subsequently, the above formulated toner, 3 parts by weight, was mixed with 97 parts by weight of a carrier containing a steel core with a polymer mixture thereof, 0.70 percent by weight, which polymer mixture contained 40 parts by weight of polyvinylidene fluoride, and 60 parts by weight of polymethyl methacrylate, and wherein mixing was accomplished in a paint shaker for 10 minutes. There resulted on the toner composition, as determined in the known Faraday Cage apparatus, a positive triboelectric charge of 19 microcoulombs per gram. There was then added to the above prepared developer composition 1 part by weight of an uncharged toner comprised of 80.13 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 16.4 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; 0.32 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate of Example II. Thereafter, the charge distribution of the resulting developer was measured as a function of the mixing time, and it was determined by a charge spectrograph that the admixing time was less than 15 seconds, which was the shortest time that was measured on the known charge spectrograph for this added uncharged toner, that is this was the fastest admix that could be measured in this situation. This is also applicable to the examples that follow. EXAMPLE V There was prepared in an extrusion device, available as ZSK28 from Werner Pfleiderer, a toner composition by adding thereto 80.13 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 16.4 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; and 0.32 percent by weight of the charge enhancing additive distearyl dimethyl bisulfate obtained from Example II. The toner was extruded at a rate of 2.7 Kg per hour and reached a temperature of 149°C. The toner strands of melt mixed product exiting from the extruder was cooled by immersion in a water bath by repeating the procedure of Example IV. Subsequently, the resulting toner was subjected to grinding in a Sturtevant micronizer enabling particles with a volume median diameter of from 8 to 12 µm as measured by a Coulter Counter. Thereafter, the aforementioned toner particles were classified in a Donaldson Model B classifier for the purpose of removing fine particles, that is those with a volume median diameter of less than 4 µm. Subsequently, the above formulated toner, 3 parts by weight, was mixed with 97 parts by weight of a carrier containing a steel core with a polymer mixture thereof, 0.70 percent by weight, which polymer mixture contained 40 parts by weight of polyvinylidene fluoride and 60 parts by weight of polymethyl methacrylate, and wherein mixing was accomplished in a paint shaker for 10 minutes. There resulted on the toner composition, as determined in the known Faraday Cage apparatus, a positive triboelectric charge of 17 microcoulombs per gram. There was then added to the above prepared developer composition 1 part by weight of an uncharged toner comprised of 80.13 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 16.4 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; and 0.32 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate of Example II that is obtained by the process of Example II. Thereafter, the charge distribution of the resulting developer was measured as a function of the mixing time, and it was determined by a charge spectrograph that the admixing time was less than 15 seconds for the uncharged added toner determined in accordance with the procedure of Example IV. EXAMPLE VI There was prepared in an extrusion device, available as ZSK53 from Werner Pfleiderer, a toner composition by adding thereto 79.53 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 17.0 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; and 0.32 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate obtained from Example II. The toner was extruded at a rate of 125 Kg per hour with a temperature setting to achieve a melt temperature of 186°C. Thereafter, the toner product was cut into pellets with a knife, and cooled in a water bath by repeating the procedure of Example IV. Subsequently, the resulting toner was subjected to grinding in a Sturtevant micronizer enabling toner particles with a volume median diameter of from 8 to 12 µm as measured by a Coulter Counter. Thereafter, the aforementioned toner particles were classified in a Donaldson Model B classifier for the purpose of removing fine particles, that is those with a volume median diameter of less than 4 µm. Subsequently, the above formulated toner, 3 parts by weight, was mixed with 97 parts by weight of a carrier containing a steel core with a polymer mixture thereof, 0.70 percent by weight, which polymer mixture contained 40 parts by weight of polyvinylidene fluoride and 60 parts by weight of polymethyl methacrylate, and wherein mixing was accomplished in a paint shaker for 10 minutes. There resulted on the toner composition, as determined in the known Faraday Cage apparatus, a positive triboelectric charge of 19 microcoulombs per gram. There was then added to the above prepared developer composition 1 part by weight of a substantially uncharged toner comprised of 79.53 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 17.0 percent by weight of the magnetite Mapico Black; 3.15 percent by weight of Regal 330® carbon black; and 0.32 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate obtained by the process of Example II. Thereafter, the charge distribution of the resulting developer was measured as a function of the mixing time, and it was determined by a charge spectrograph that the admixing time was less than 15 seconds for the added uncharged toner determined in accordance with the procedure of Example IV. When a toner composition and developer composition are prepared by repeating the above procedures, and there is selected in place of the bisulfate charge enhancing additive, the charge enhancing additive distearyl dimethyl ammonium methyl sulfate, the admix time was about 60 seconds. EXAMPLE VII There was prepared in an extrusion device, available as ZSK53 from Werner Pfleiderer, a toner composition by adding thereto 79.85 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 17.0 percent by weight of the magnetite Mapico Black; 3.0 percent by weight of Regal 330® carbon black; and 0.15 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate by the process of Example 1. The toner was extruded at a rate of 100 Kg per hour with temperature settings to achieve a melt temperature of 206°C. On exiting the extruder, the toner product was cut into pellets and cooled by repeating the procedure of Example IV. Subsequently, the toner was subjected to grinding in a Sturtevant micronizer enabling toner particles with a volume median diameter of from 8 to 12 µm as measured by a Coulter Counter. Thereafter, the aforementioned loner particles were classified in a Donaldson Model B classifier for the purpose of removing fine particles, that is those with a volume median diameter of less than 4 µm. Subsequently, the above formulated toner, 3 parts by weight, was mixed with 97 parts by weight of a carrier containing a steel core with a polymer mixture thereof, 0.70 percent by weight, which polymer mixture contained 50 parts by weight of polyvinylidene fluoride, and 50 parts by weight of polymethyl methacrylate, and wherein mixing was accomplished in a paint shaker for 10 minutes. There resulted on the toner composition, as determined in the known Faraday Cage apparatus, a positive triboelectric charge of 17 microcoulombs per gram. There was then added to the above prepared developer composition 1 part by weight of a toner comprised of 79.85 percent by weight of suspension polymerized styrene butadiene copolymer resin particles (87/13), reference US-A-4,558,108; 17.0 percent by weight of the magnetite Mapico Black; 3.0 percent by weight of Regal 330® carbon black; and 0.15 percent by weight of the charge enhancing additive distearyl dimethyl ammonium bisulfate of Example I. Thereafter, the charge distribution of the resulting developer was measured as a function of the mixing time, and it was determined by a charge spectrograph that the admixing time was less than 15 seconds for the added uncharged toner determined in accordance with the procedure of Example IV. EXAMPLE VIII About 4.5 Kg of the 23 Kg of the toner prepared in Example VII, subsequent to cooling, was subjected to grinding in an Alpine Fluid Bed Jet Model 200 AFG, available from Hosokawa Micron International, enabling toner particles with a median diameter size of from 8 to 12 µm as measured by a Coulter Counter. Thereafter, the aforementioned toner particles were classified in a Donaldson Model B classified for the purpose of removing fine particles, that is those with a volume median diameter of less than 4 µm. Subsequently, the above formulated toner, 3 parts by weight, was mixed with 97 parts by weight of a carrier containing a steel core with a polymer mixture thereof, 0.70 percent by weight, which polymer mixture contained 50 parts by weight of polyvinylidene fluoride and 50 parts by weight of polymethyl methacrylate, and wherein mixing was accomplished in a paint shaker for 10 minutes. There resulted on the toner composition, as determined in the known Faraday Cage apparatus, a positive triboelectric charge of 15 microcoulombs per gram. This developer was then placed in a high speed electrostatic imaging machine available from Xerox Corporation as the 5090™ and subsequent to engagement and development produced copies of high resolution with excellent solid areas of coverage, and substantially no background deposits under conditions of a toner dispense rate of about 30 grams per minute. The admixing charging time of uncharged added toner was substantially similar to that of Example VI, which admix time was determined by repeating the procedure of Example VI. EXAMPLE IX A slurry of 5.0 grams of Aerosil R972 (Degussa) in about 250 milliliters of the organic solvent methylene chloride were mixed thoroughly for 15 minutes in an explosion proof blender. The charge-enhancing additive compound obtained by the process of Example II, namely dimethyl distearyl ammonium bisulfate (0.5 gram) was dissolved in 150 milliliters of additional methylene chloride solvent, followed by adding the resulting mixture to the aforementioned slurry of the Aerosil and methylene chloride. Mixing was accomplished for about 10 minutes. The resulting mixture was then transferred to a round-bottom flask surrounded by a water bath, which water bath was heated to about 40°C, and thereafter the mixture resulting in the flask was evaporated to dryness on a rotoevaporator. The residual solvent was then dried in a vacuum oven for 4 hours, then placed in a blender equipped with a 4 blade agitator, and fluffed to a powdery consistency. There resulted a fine powder comprised of Aerosil particles coated with the charge enhancing additive, dimethyl distearyl ammonium disulfate salt, with an average diameter of about 0.5 µm as determined by scanning electron microscopy. EXAMPLE X A black toner and developer composition was prepared by repeating the procedure of Example V with the exception that in place of the charge enhancing additive in the bulk there was selected 0.5 weight percent of the treated Aerosil articles of Example IX. More specifically, 50 grams, 99.5 weight percent, of the aforementioned toner, and 0.5 weight percent of the treated Aerosil articles of Example IX were placed in a paint shaker for 10 minutes and removed therefrom. A developer composition was then prepared by repeating the procedure of Example IV. The toner had a measured triboelectric charge of 25 microcoulombs per gram, and an admix time of 60 seconds, which admix was determined by the procedure of Example IV. EXAMPLE XI Cyan Developer : A cyan developer composition was prepared as follows: 45 parts by weight of a styrene butadiene resin (91/9), 45 parts by weight of styrene-n-butylmethacrylate resin and 7.5 parts by weight of Sudan Blue OS from BASF were melt blended at approximately 80 to 120°C in an extruder, followed by micronization and air classification to yield toner particles of a size of 9 µm in volume average diameter and 7 µm in number average diameter. The toner particles were then treated with the above prepared Aerosil treated charge control agent of Example IX by the addition thereof, 0.5 weight percent, and 99.5 weight percent of the above prepared cyan toner to a container with steel balls, and mixing thereof was accomplished for 30 minutes. Subsequently, carrier particles were prepared by powder coating a Toniolo core, available from Toniolo Company, with a particle diameter range of from 80 to 150 µm with 0.7 parts by weight of a coating blend of 40 parts of Kynar and 60 parts of PMMA (polymethyl methacrylate) at 375 to 400°C. The magenta developer was then prepared by blending 97 parts by weight of the resulting coated carrier particles with 3 parts by weight of the above prepared toner in a lab blender for 10 minutes resulting in a developer composition. The above prepared toner had a triboelectric charge of 42 microcoulombs per gram, and an admix time of 60 seconds, which characteristics were determined by the procedure of Example IV. EXAMPLE XII Magenta Developer : A magenta developer composition was prepared as follows: 90 parts by weight of a styrene butadiene resin (91/9), and 10 parts of a mixture of 5 parts Hostaperm Pink, available from American Hoechst, and 5 parts of styrene-n-butylmethacrylate were melt blended at approximately 80 to 120°C in an extruder, followed by micronization and air classification to yield toner particles of an average particle diameter size of 9 µm in volume average diameter and 7 µm in number average diameter. The toner particles were then admixed with the Aerosil treated charge control agent of Example IX by repeating the procedure of Example XI. Subsequently, carrier particles were prepared by powder coating a Toniolo core, available from Toniolo Company, with a particle diameter range of from 80 to 150 µm with 0.7 parts by weight of a coating blend of 40 parts of Kynar and 60 parts of PMMA (polymethyl methacrylate) at 375 to 400°C. The magenta developer was then prepared by blending 97 parts by weight of the aforementioned coated carrier particles with 3 parts by weight of the above prepared toner in a lab blender for 10 minutes resulting in a developer composition. The above prepared toner had a triboelectric charge of 59 microcoulombs per gram, and an admix time of 0.5 minute, which characteristics were determined by the procedure of Example IV. Other modifications of the present invention may occur to those skilled in the art subsequent to a review of the present application, and these modifications, including equivalents thereof, are intended to be included within the scope of the claims of the present invention.

Claims: A toner composition comprising resin particles, a pigment or dye, and a quaternary ammonium salt as a charge enhancing additive, characterised in that said salt is a bisulfate. A toner composition in accordance with claim 1 wherein the quaternary ammonium bisulfate is of the formula R′₂R″₂N⁺X⁻ wherein R′ and R″ are independently selected from alkyl, aryl, and alkylaryl; and X- is a bisulfate anion. A toner composition in accordance with claim 2 wherein each R′ and R″ contains from 1 to about 30 carbon atoms. A toner composition in accordance with claim 2 wherein the charge enhancing additive is a dimethyl dialkyl ammonium bisulfate such as distearyl dimethyl ammonium bisulfate. A toner composition in accordance with claim 1 wherein the quaternary ammonium bisulfate is a tetraalkyl ammonium bisulfate such as tetramethyl ammonium bisulfate, tetraethyl ammonium bisulfate, or tetrabutyl ammonium bisulfate. A toner composition in accordance with any one of claims 1 to 5 wherein the charge additive is present in an amount of from about 0.05 to about 5 weight percent. A toner composition in accordance with any one of claims 1 to 6 wherein the charge additive is incorporated into the toner. A toner composition in accordance with any one of claims 1 to 6 wherein the charge additive is present on the surface of the toner composition. A toner composition in accordance with any one of claims 1 to 6 wherein the charge additive is contained on colloidal silica particles. A toner composition in accordance with any one of claims 1 to 9 wherein the resin particles are comprised of styrene polymers, polyesters, or mixtures thereof.

Inventors: HAACK JOHN L, LAING JOHN R, SMITH MICHAEL, HAACK, JOHN L., LAING, JOHN R., SMITH, MICHAEL
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 1990
Main classification: G03G9
IPC codes: G03G9