Abstract:
The disclosure describes a one reaction process for making a bio-based polyester resin. The resultant polyester resin retains thermal properties as compared to a similar resin but made using previous multi-step processes conducted in separate vessels.

Description:
FIELD 
     Bio-based resins are prepared by a simplified process that reduces the complexity, process time and cost of the procedure, by forming a bio-based organic diol in a reactor and adding thereto other components to make a bio-based polyester resin which can be used to make toner. 
     BACKGROUND 
     The vast majority of polymeric materials are based on processing of fossil fuels, a limited resource, and result in accumulation of non-degradable materials in the environment. Using bio-based monomers in polymeric materials reduces dependency on fossil fuels and renders the polymeric materials more sustainable. Recently, the USDA proposed that all toners/ink have a bio content of at least 20%. Bio-based resins are being developed but integration of such reagents into toner and ink remains to be resolved. 
     A bio-based resin that can be used in toner made by a one-pot process that reduces complexity, materials and process time is described. 
     SUMMARY 
     The instant disclosure describes a one-pot process for preparing a bio-based polyester resin which reduces the overall process time, materials and cost. Reagents are added to a reactor under conditions that enable sequential condensation reactions producing a polyester with a bio-based content of at least about 45% by weight. 
     Hence, disclosed herein is a process for making a bio-based polyester polymer comprising the steps of (i) preparing a rosin derivative comprising plural alcohol groups in a reactor; (ii) reacting said rosin derivative with dimethyl terephthalate or terephthalic acid, succinic acid and 1,2-propanediol in said reactor to form said polyester polymer; and (iii) recovering said polyester polymer. 
    
    
     DETAILED DESCRIPTION 
     Currently, a process for making a bio-based resin requires a first bioreactor where a bio-based organic diol is obtained by reacting, for example, a bio-based organic acid, such as, a rosin acid, with a bis-organo-epoxide material to result with an organic diol such as a bis-(epoxy-propyl)-neopentylene glycol to result in a bio-based organic diol. 
     
       
                 
         
             
             
         
      
     
     The rosin diol above is a suitable reagent for a polyester toner because of the hydrophobicity of the resulting resin. 
     In another reactor, a polyester is obtained by reacting, for example, an acid or an ester, such as, for example, terephthalic acid or a terephthalate, such as, bis-1,2-hydroxypropyl-terephthalate, with a polyol in a transesterification reaction. For example, dimethyl terephthalate can be reacted with, for example, propanediol. Generally, in such reactions, an excess of polyol is used, for example, about 2.5 equivalents 1,2-propanediol are used as reactant, wherein an about 0.5 equivalents of excess 1,2-propanediol are used. 
     In a third reactor, another polyester reactant is produced, for example, a polyacid can be reacted with a polyol as described above to provide another reagent for the resulting polyester. Thus, a polyacid, such as, fumaric acid, succinic acid, and so on can be reacted with a polyol, again, in polyol excess to provide a diester reagent. 
     The three components are then combined in different proportions in a fourth reactor to make a polyester resin, such as, one comprising a terephthalate or a terephthalic acid, a rosin acid and a succinic acid as original reagents, producing a bio-based polyester resin. 
     The process disclosed herein enables a particular bio-based resin to be produced in a simplified 1-pot procedure, accomplished by, using the example above, first making the rosin-diol, followed by adding the other monomers, such as, dimethyl terephthalate or terephthalic acid, 1,2-propanediol and succinic acid to make the polyester resin. Furthermore, the 0.5 equivalent of excess 1,2-propanediol is avoided because the ratio of diol to diacid is maintained in the 1-pot process. The thermal properties of the resulting one-pot resin are the same as that of polyester produced by the four reactor mechanism. 
     Unless otherwise indicated, all numbers expressing quantities and conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term, “about.” “About,” is meant to indicate a variation of no more than 10% from the stated value. Also used herein is the term, “equivalent,” “similar,” “essentially,” “substantially,” “approximating” and “matching,” or grammatical variations thereof, have generally acceptable definitions or at the least, are understood to have the same meaning as, “about.” 
     As used herein, a polymer is defined by the monomer(s) from which the polymer is made. Thus, for example, while in a polymer a terephthalic acid per se does not exist, as used herein, that polymer is said to comprise a terephthalic acid. Thus, a biopolymer made by the one-pot process disclosed herein can comprise terephthalate/terephthalic acid; succinic acid; and dehydroabietic acid. That bio-polymer also can be said to comprise 1,2-propanediol as that diol is used with the terephthalate/terephthalic acid and succinic acid. 
     As used herein, “bio-based,” or use of the prefix, “bio,” refers to a reagent or to a product that is composed, in whole or in part, of a biological product, including plant, animal and marine materials, or derivatives thereof. Generally, a bio-based or biomaterial is biodegradable, that is, substantially or completely biodegradable, by substantially is meant greater than 50%, greater than 60%, greater than 70% or more of the material is degraded from the original molecule to another form by a biological or environmental mechanism, such as, action thereon by bacteria, animals, plants, light, temperature, oxygen and so on in a matter of days, matter of weeks, a year or more, but generally no longer than two years. A, “bio-resin,” is a resin, such as, a polyester, which contains or is composed of a bio-based material in whole or in part. 
     As used herein, a “rosin,” or, “rosin product,” is intended to encompass a rosin, a rosin acid, a rosin ester and so on, as well as a rosin derivative which is a rosin that is treated, for example, disproportionated or hydrogenated. As known in the art, rosin is a blend of at least eight monocarboxylic acids. Abietic acid can be a primary species, and the other seven acids are isomers thereof. Because of the composition of a rosin, often the synonym, “rosin acid,” is used to describe various rosin-derived products. As known, rosin is not a polymer but essentially a varying blend of the eight species of carboxylic acids. A rosin product includes, as known in the art, chemically modified rosin, such as, partially or fully hydrogenated rosin acids, partially or fully dimerized rosin acids, esterified rosin acids, functionalized rosin acids, disproportionated or combinations thereof. Rosin is available commercially in a number of forms, for example, as a rosin acid, as a rosin ester and so on. For example, rosin acids, rosin ester and dimerized rosin are available from Eastman Chemicals under the product lines, Poly-Pale™, Dymerex™, Staybelite-E™, Foral™ Ax-E, Lewisol™ and Pentalyn™; Arizona Chemicals under the product lines, Sylvalite™ and Sylvatac™; and Arakawa-USA under the product lines, Pensel and Hypal. Disproportionated rosins are available commercially, for example, KR-614 and Rondis™ available from Arakawa-USA, and hydrogenated rosin is available commercially, for example, Foral AX™ available from Pinova Chemicals. 
     A rosin acid can be reacted with an organic bis-epoxide, which during a ring-opening reaction of the epoxy group, combines at the carboxylic acid group of a rosin acid to form a joined molecule, a bis-rosin ester. Such a reaction is known in the art and is compatible with the one-pot reaction conditions disclosed herein for producing a bioresin. A catalyst can be included in the reaction mixture to form the rosin ester. Suitable catalysts include tetra-alkyl ammonium halides, such as, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetraethyl ammonium chloride, tetra-alkyl phosphonium halides and so on. The reaction can be conducted under anaerobic conditions, for example, under a nitrogen atmosphere. The reaction can be conducted at an elevated temperature, such as, from about 100° C. to about 200° C., from about 105° C. to about 175° C., from about 110° C. to about 170° C. and so on, although temperatures outside of those ranges can be used as a design choice. The progress of this reaction can be monitored by evaluating the acid value of the reaction product, and when all or most of the rosin acid has reacted the overall acid value of the product is less than about 4 meq of KOH/g, less than about 1 meq of KOH/g, about 0 meq of KOH/g. The acid value of a resin can be manipulated by adding an excess of bis-epoxide monomer. The aforementioned rosin-diol is then reacted with terephthalic acid (or dimethyl terephthalate), and succinic acid and an excess of excess 1,2-propane-diol to form the bio-based polyester resin by polycondensation process with removal of the water (and/or methanol) byproduct and some of the excess 1,2-propanediol. Furthermore, at the end of the polycondensation step, suitable acids include biopolycarboxylic acids, such as, organic acids, such as, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, maleic acid can be added to control the acid value of the bio-based resin such that an acid value of from about 8 to about 16 meq of KOH/g is obtained. 
     Toner Particles 
     The toner particle can include other optional reagents, such as, a surfactant, a wax, a shell and so on. The toner composition optionally can comprise inert particles, which can serve as toner particle carriers, which can comprise the resin taught herein. 
     The discussion below is directed to polyester resins. 
     A. Components 
     1. Resin 
     Toner particles of the instant disclosure include an optional one or more colorants of a toner, other optional reagents, such as, a wax, for use in certain imaging devices. The bio-polyester of interest is used alone or in combination with one or more other known resins such as, a crystalline resin, used in toner. 
     For example, a toner can comprise two forms of amorphous polyester resins, one of which is a biopolymer of interest, and a crystalline resin in relative amounts as a design choice. 
     The biopolymer may be present in an amount of from about 25 to about 85% by weight, from about 55 to about 80% by weight of toner particles on a solid basis. 
     a. Polyester Resins 
     Suitable polyester resins include, for example, those which are crystalline and amorphous, combinations thereof and the like. The polyester resins may be linear, branched, crosslinked, combinations thereof and the like. 
     When a mixture is used, such as, amorphous and crystalline polyester resins, the ratio of crystalline polyester resin to amorphous polyester resin can be in the range from about 1:99 to about 30:70; from about 5:95 to about 25:75. 
     A polyester resin may be obtained synthetically, for example, in an esterification reaction involving a reagent comprising a carboxylic acid or ester group and another reagent comprising an alcohol. The alcohol reagent can comprise two or more hydroxyl groups, three or more hydroxyl groups. The acid can comprise two or more carboxylic acid or ester groups, three or more carboxylic acid or ester groups. Reagents comprising three or more functional groups enable, promote or enable and promote polymer branching and crosslinking. A polymer backbone or a polymer branch can comprise at least one monomer unit comprising at least one pendant group or side group, that is, the monomer reactant from which the unit was obtained can comprise at least three functional groups. 
     Examples of polyacids or polyesters, which may be a bio-acid or a bio-ester, that can be used for preparing an amorphous polyester resin include rosin acid, terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, diethyl fumarate, dimethyl itaconate, cis-1,4-diacetoxy-2-butene, dimethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic acid, cyclohexanoic acid, succinic anhydride, dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, dimethyl naphthalenedicarboxylate, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, naphthalene dicarboxylic acid, dimer diacid, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate and combinations thereof. The polyacid or polyester reagent may be present, for example, in an amount from about 40 to about 60 mole % of the resin, from about 42 to about 52 mole % of the resin, from about 45 to about 50 mole % of the resin, irrespective of the number of species of acid or ester monomers used. 
     Examples of polyols which may be used in generating an amorphous polyester resin include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, heptanediol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene glycol and combinations thereof. The amount of polyol can vary, and may be present, for example, in an amount from about 40 to about 60 mole % of the resin, from about 42 to about 55 mole %, from about 45 to about 53 mole % of the resin, and a second polyol, can be used in an amount from about 0.1 to about 10 mole %, from about 1 to about 4 mole % of the resin. 
     For forming a crystalline polyester resin, suitable polyols include aliphatic polyols with from about 2 to about 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like; alkali sulfo-aliphatic diols such as sodio 2-sulfo-1,2-ethanediol, lithio 2-sulfo-1,2-ethanediol, potassio 2-sulfo-1,2-ethanediol, sodio 2-sulfo-1,3-propanediol, lithio 2-sulfo-1,3-propanediol, potassio 2-sulfo-1,3-propanediol, mixture thereof and the like, including their structural isomers. The polyol may be selected in an amount from about 40 to about 60 mole %, from about 42 to about 55 mole %, from about 45 to about 53 mole %, and a second polyol, can be used in an amount from about 0.1 to about 10 mole %, from about 1 to about 4 mole % of the resin. 
     Examples of polyacid or polyester reagents for preparing a crystalline resin include a rosin acid, oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethyl itaconate, cis, 1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid (sometimes referred to herein as cyclohexanedioic acid), malonic acid and mesaconic acid, a polyester or anhydride thereof. The polyacid may be selected in an amount of from about 40 to about 60 mole %, from about 42 to about 52 mole %, from about 45 to about 50 mole % of the resin, and optionally, a second polyacid can be selected in an amount from about 0.1 to about 10 mole % of the resin. 
     Specific crystalline resins that can be used include poly(ethylene-adipate), poly(propylene-adipate), poly(butylene-adipate), poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate), poly(ethylene-succinate), poly(propylene-succinate), poly(butylene-succinate), poly(pentylene-succinate), poly(hexylene-succinate), poly(octylene-succinate), poly(ethylene-sebacate), poly(propylene-sebacate), poly(butylene-sebacate), poly(pentylene-sebacate), poly(hexylene-sebacate), poly(octylene-sebacate), poly(decylene-sebacate), poly(decylene-decanoate), poly(ethylene-decanoate), poly(ethylene dodecanoate), poly(nonylene-sebacate), poly(nonylene-decanoate), copoly(ethylene-fumarate)-copoly(ethylene-sebacate), copoly(ethylene-fumarate)-copoly(ethylene-decanoate), copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate), copoly(2,2-dimethylpropane-1,3-diol-decanoate)-copoly(ethylene-adipate), alkali copoly(5-sulfoisophthaloyl)-copoly(propylene-adipate) and so on. 
     Suitable crystalline resins include those disclosed in U.S. Pub. No. 2006/0222991, the disclosure of which is hereby incorporated by reference in entirety. 
     A suitable crystalline resin may include a resin formed of nonanediol and dodecanedioic acid comonomers. 
     The crystalline resin may be present, for example, in an amount from about 1 to about 85%, from about 2 to about 50%, from about 5 to about 15% by weight of the toner components. The crystalline resin can possess a melting points of from about 30° C. to about 120° C., from about 50° C. to about 90° C., from about 60° C. to about 80° C. The crystalline resin may have a number average molecular weight (M n ), as measured by gel permeation chromatography (GPC) of from about 1,000 to about 50,000, from about 2,000 to about 25,000, and a weight average molecular weight (M w ) of, for example, from about 2,000 to about 100,000, from about 3,000 to about 80,000, as determined by GPC. The molecular weight distribution (M w /M n ) of the crystalline resin may be, for example, from about 2 to about 6, from about 3 to about 4. 
     b. Esterification Catalyst 
     Condensation catalysts may be used in the polyester reaction and include tetraalkyl titanates; dialkyltin oxides; tetraalkyltins; dibutyltin diacetate; dibutyltin oxide; dialkyltin oxide hydroxides; aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, stannous chloride, butylstannoic acid or combinations thereof. 
     Such catalysts may be used in amounts of from about 0.01 mole % to about 5 mole % based on the amount of starting polyacid, polyol or polyester reagent in the reaction mixture. 
     c. Branching/Crosslinking 
     Branching agents can be used, and include, for example, a multivalent polyacid, such as, 1,2,4-benzene-tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane, tetra(methylene-carboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, acid anhydrides thereof, lower alkyl esters thereof and so on. The branching agent can be used in an amount from about 0.01 to about 10 mole % of the resin, from about 0.05 to about 8 mole %, from about 0.1 to about 5 mole % of the resin. 
     Generally, as known in the art, the polyacid/polyester and polyols reagents, are mixed together, optionally with a catalyst, and incubated at an elevated temperature, such as, from about 130° C. or more, from about 140° C. or more, from about 150° C. or more, and so on, although temperatures outside of those ranges can be used, which can be conducted anaerobically, to enable esterification to occur until equilibrium, which generally yields water or an alcohol, such as, methanol, arising from forming the ester bonds in esterification reactions. The reaction can be conducted under vacuum to promote polymerization. 
     Accordingly, disclosed herein is one-pot reaction for producing a bio-polyester resin suitable for use in an imaging toner. A bio-polyester resin can be processed to form a polymer reagent, which can be dried and formed into flowable particles, such as, a pellet, a powder and the like. The polymer reagent then can be incorporated with, for example, other reagents suitable for making a toner particle, such as, a colorant and/or a wax, and processed to a known manner to produce toner particles. 
     Polyester resins can carry one or more properties, such as, a T g (onset) of at least about 40° C., at least about 45° C., at least about 50° C.; a T g  of at least about 110° C., at least about 115° C., at least about 120° C.; an acid value (AV) of at least about 10, at least about 12.5, at least about 15; and an M w  of at least about 5000, at least about 15,000, at least about 20,000. 
     2. Colorants 
     Suitable colorants include those comprising carbon black, such as, REGAL 330® and Nipex 35; magnetites, such as, Mobay magnetites, MO8029™ and MO8060™; Columbian magnetites, MAPICO® BLACK; surface-treated magnetites; Pfizer magnetites, CB4799™, CB5300™, CB5600™ and MCX6369™; Bayer magnetites, BAYFERROX 8600™ and 8610™; Northern Pigments magnetites, NP-604™ and NP-608™; Magnox magnetites, TMB-100™ or TMB-104™; and the like. 
     Colored pigments, such as, cyan, magenta, yellow, red, orange, green, brown, blue or mixtures thereof can be used. The additional pigment or pigments can be used as water-based pigment dispersions. 
     Examples of pigments include SUNSPERSE 6000, FLEXIVERSE and AQUATONE, water-based pigment dispersions from SUN Chemicals; HELIOGEN BLUE L6900™, D6840™, D7080™, D7020™, PYLAM OIL BLUE™, PYLAM OIL YELLOW™ and PIGMENT BLUE 1™ available from Paul Uhlich &amp; Company, Inc.; PIGMENT VIOLET 1™, PIGMENT RED 48™, LEMON CHROME YELLOW DCC IO26™, TOLUIDINE RED™ and BON RED C™ available from Dominion Color Corporation, Ltd., Toronto, Ontario; NOVAPERM YELLOW FGL™ and HOSTAPERM PINK E™ from Hoechst; CINQUASIA MAGENTA™ available from E.I. DuPont de Nemours &amp; Co., and the like. 
     Examples of magenta pigments include 2,9-dimethyl-substituted quinacridone, an anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, a diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19 and the like. 
     Illustrative examples of cyan pigments include copper Tetra(octadecylsulfonamido) phthalocyanine, a copper phthalocyanine pigment listed in the Color Index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, Pigment Blue 15:4, an Anthrazine Blue identified in the Color Index as CI 69810, Special Blue X-2137 and the like. 
     Illustrative examples of yellow pigments are diarylide yellow 3,3-dichlorobenzidene acetoacetanilide, 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 Disperse Yellow 3, 2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide and Permanent Yellow FGL. 
     Other known colorants can be used, such as, Levanyl Black A-SF (Miles, Bayer) and Sunsperse Carbon Black LHD 9303 (Sun Chemicals), and colored dyes, such as, Neopen Blue (BASF), Sudan Blue OS (BASF), PV Fast Blue B2G 01 (American Hoechst), Sunsperse Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA (CibaGeigy), Paliogen Blue 6470 (BASF), Sudan III (Matheson, Coleman, Bell), Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman, Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (Hoechst), Permanent Yellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), Suco-Gelb L1250 (BASF), SUCD-Yellow D1355 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (DuPont), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), E.D. Toluidine Red (Aldrich), Lithol Rubine Toner (Paul Uhlich), Lithol Scarlet 4440 (BASF), Bon Red C (Dominion Color Company), Royal Brilliant Red RD-8192 (Paul Uhlich), Oracet Pink RF (Ciba-Geigy), Paliogen Red 3871K (BASF), Paliogen Red 3340 (BASF), Lithol Fast Scarlet L4300 (BASF), combinations of the foregoing and the like. Other pigments that can be used, and which are commercially available include various pigments in the color classes, Pigment Yellow 74, Pigment Yellow 14, Pigment Yellow 83, Pigment Orange 34, Pigment Red 238, Pigment Red 122, Pigment Red 48:1, Pigment Red 269, Pigment Red 53:1, Pigment Red 57:1, Pigment Red 83:1, Pigment Violet 23, Pigment Green 7 and so on, and combinations thereof. 
     The colorant, for example carbon black, cyan, magenta and/or yellow colorant, may be incorporated in an amount sufficient to impart the desired color to the toner. In general, pigment or dye, may be employed in an amount ranging from 0% to about 35% by weight of the toner particles on a solids basis, from about 5% to about 25% by weight, from about 5% to about 15% by weight. 
     More than one colorant may be present in a toner particle. For Example, two colorants may be present in a toner particle, such as, a first colorant of pigment blue, may be present in an amount ranging from about 2% to about 10% by weight of the toner particle on a solids basis, from about 3% to about 8% by weight, from about 5% to about 10% by weight; with a second colorant of pigment yellow that may be present in an amount ranging from about 5% to about 20% by weight of the toner particle on a solids basis, from about 6% to about 15% by weight, from about 10% to about 20% by weight and so on. 
     3. Optional Components 
     a. Surfactants 
     Toner compositions or reagents therefore may be in dispersions including a surfactant. Emulsion aggregation methods where the polymer and other components of the toner are in combination can employ one or more surfactants to form an emulsion. 
     One, two or more surfactants may be used. The surfactants may be selected from ionic surfactants and nonionic surfactants, or combinations thereof. Anionic surfactants and cationic surfactants are encompassed by the term, “ionic surfactants.” 
     The surfactant or the total amount of surfactants may be used in an amount of from about 0.01% to about 5% by weight of the toner-forming composition, from about 0.75% to about 4%, from about 1% to about 3% by weight of the toner-forming composition. 
     Examples of nonionic surfactants include, for example, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether and dialkylphenoxy poly(ethyleneoxy) ethanol, for example, available from Rhone-Poulenc as IGEPAL CA-210™, IGEPAL CA-520™, IGEPAL CA-720™, IGEPAL CO-890™, IGEPAL CO-720™, IGEPAL CO-290™, IGEPAL CA-210™, ANTAROX 890™ and ANTAROX 897™. Other examples of suitable nonionic surfactants include a block copolymer of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC® PR/F, in embodiments, SYNPERONIC® PR/F 108; and a DOWFAX, available from The Dow Chemical Corp. 
     Anionic surfactants include sulfates and sulfonates, such as, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate and so on; dialkyl benzenealkyl sulfates; acids, such as, palmitic acid, and NEOGEN or NEOGEN SC obtained from Daiichi Kogyo Seiyaku, and so on, combinations thereof and the like. Other suitable anionic surfactants include, in embodiments, alkyldiphenyloxide disulfonates or TAYCA POWER BN2060 from Tayca Corporation (Japan), which is a branched sodium dodecyl benzene sulfonate. Combinations of those surfactants and any of the foregoing nonionic surfactants may be used in embodiments. 
     Examples of cationic surfactants include, for example, alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, trimethyl ammonium bromides, halide salts of quarternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chlorides, MIRAPOL® and ALKAQUAT® available from Alkaril Chemical Company, SANISOL® (benzalkonium chloride) available from Kao Chemicals and the like, and mixtures thereof, including, for example, a nonionic surfactant as known in the art or provided hereinabove. 
     b. Waxes 
     The toners of the instant disclosure, optionally, may contain a wax, which can be either a single type of wax or a mixture of two or more different types of waxes (hereinafter identified as, “a wax”). A combination of waxes can be added to provide multiple properties to a toner or a developer composition. 
     When included, the wax may be present in an amount of, for example, from about 1 wt % to about 25 wt % of the toner particles, from about 5 wt % to about 20 wt % of the toner particles. 
     Waxes that may be selected include waxes having, for example, a weight average molecular weight of from about 500 to about 20,000, in embodiments, from about 1,000 to about 10,000. Waxes that may be used include, for example, polyolefins, such as, polyethylene, polypropylene and polybutene waxes, such as, those that are commercially available, for example, POLYWAX™ polyethylene waxes from Baker Petrolite, wax emulsions available from Michaelman, Inc. or Daniels Products Co., EPOLENE N15™ which is commercially available from Eastman Chemical Products, Inc., VISCOL 550-P™, a low weight average molecular weight polypropylene available from Sanyo Kasei K.K.; plant-based waxes, such as carnauba wax, rice wax, candelilla wax, sumac wax and jojoba oil; animal-based waxes, such as beeswax; mineral-based waxes and petroleum-based waxes, such as montan wax, ozokerite, ceresin wax, paraffin wax, microcrystalline wax and Fischer-Tropsch waxes; ester waxes obtained from higher fatty acids and higher alcohols, such as stearyl stearate and behenyl behenate; ester waxes obtained from higher fatty acids and monovalent or multivalent lower alcohols, such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate and pentaerythritol tetrabehenate; ester waxes obtained from higher fatty acids and multivalent alcohol multimers, such as diethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryl distearate and triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, such as sorbitan monostearate; cholesterol higher fatty acid ester waxes, such as, cholesteryl stearate, and so on. 
     Examples of functionalized waxes that may be used include, for example, amines and amides, for example, AQUA SUPERSLIP 6550™ and SUPERSLIP 6530™ available from Micro Powder Inc.; fluorinated waxes, for example, POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™ and POLYSILK 14™ available from Micro Powder Inc.; mixed flourinated amide waxes, for example, MICROSPERSION 19™ also available from Micro Powder Inc.; imides, esters, quaternary amines, carboxylic acids, acrylic polymer emulsions, for example, JONCRYL 74™, 89™, 130™, 537™ and 538™ available from SC Johnson Wax; and chlorinated polypropylenes and polyethylenes available from Allied Chemical, Petrolite Corp. and SC Johnson. Mixtures and combinations of the foregoing waxes also may be used in embodiments. 
     c. Aggregating Factor 
     An aggregating factor (or coagulant) may be used to facilitate growth of the nascent toner particles and may be an inorganic cationic coagulant, such as, for example, polyaluminum chloride (PAC), polyaluminum sulfosilicate (PASS), aluminum sulfate, zinc sulfate, magnesium sulfate, chlorides of magnesium, calcium, zinc, beryllium, aluminum, sodium, other metal halides including monovalent and divalent halides. 
     The aggregating factor may also contain minor amounts of other components, for example, nitric acid. 
     The aggregating factor may be present in an emulsion in an amount of from, for example, from about 0 to about 10 wt %, or from about 0.05 to about 5 wt % based on the total solids in the toner. 
     A sequestering agent or chelating agent may be introduced after aggregation to contribute to pH adjustment and/or to sequester or to extract a metal complexing ion, such as, aluminum, from the aggregation process. Thus, the sequestering, chelating or complexing agent used after aggregation may comprise an organic complexing component, such as, ethylenediamine tetraacetic acid (EDTA), gluconal, hydroxyl-2,2′iminodisuccinic acid (HIDS), dicarboxylmethyl glutamic acid (GLDA), methyl glycidyl diacetic acid (MGDA), hydroxydiethyliminodiacetic acid (HIDA), sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate salt, humic acid, fulvic acid; salts of EDTA, such as, alkali metal salts of EDTA, tartaric acid, gluconic acid, oxalic acid, polyacrylates, sugar acrylates, citric acid, polyaspartic acid, diethylenetriamine pentaacetate, 3-hydroxy-4-pyridinone, dopamine, eucalyptus, iminodisuccinic acid, ethylenediaminedisuccinate, polysaccharide, sodium ethylenedinitrilotetraacetate, thiamine pyrophosphate, farnesyl pyrophosphate, 2-aminoethylpyrophosphate, hydroxyl ethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, diethylene triaminepentamethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid and mixtures thereof. 
     d. Surface Additive 
     The toner particles can be mixed with one or more of silicon dioxide or silica (SiO 2 ), titania or titanium dioxide (TiO 2 ) and/or cerium oxide, among other additives. Silica may be a first silica and a second silica. The second silica may have a larger average size (diameter) than the first silica. The titania may have an average primary particle size in the range of from about 5 nm to about 50 nm, from about 5 nm to about 20 nm, from about 10 nm to about 50 nm. The cerium oxide may have an average primary particle size in the range of, for example, about 5 nm to about 50 nm, from about 5 nm to about 20 nm, from about 10 nm to about 50 nm. 
     Zinc stearate also may be used as an external additive. Calcium stearate and magnesium stearate may provide similar functions. Zinc stearate may have an average primary particle size in the range of from about 500 nm to about 700 nm, from about 500 nm to about 600 nm, from about 550 nm to about 650 nm. 
     B. Toner Particle Preparation 
     The toner particles may be prepared by any method within the purview of one skilled in the art, for example, any of the emulsion/aggregation methods can be used with a polyester resin. However, any suitable method of preparing toner particles may be used, including chemical processes, such as, suspension and encapsulation processes disclosed, for example, in U.S. Pat. Nos. 5,290,654 and 5,302,486, the disclosure of each of which hereby is incorporated by reference in entirety; by conventional granulation methods, such as, jet milling; pelletizing slabs of material; other mechanical processes; any process for producing nanoparticles or microparticles; and so on. 
     In embodiments relating to an emulsification/aggregation process, a resin, for example, made as described above, can be dissolved in a solvent, and can be mixed into an emulsion medium, for example water, such as, deionized water (DIW), optionally containing a stabilizer, and optionally a surfactant. Examples of suitable stabilizers include water-soluble alkali metal hydroxides, such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide or barium hydroxide; ammonium hydroxide; alkali metal carbonates, such as, sodium bicarbonate, lithium bicarbonate, potassium bicarbonate, lithium carbonate, potassium carbonate, sodium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, barium carbonate or cesium carbonate; or mixtures thereof. When a stabilizer is used, the stabilizer can be present in amounts of from about 0.1% to about 5%, from about 0.5% to about 3% by weight of the resin. 
     Following emulsification, toner compositions may be prepared by aggregating a mixture of a resin, an optional colorant, an optional wax and any other desired additives in an emulsion, optionally, with surfactants as described above, and then optionally coalescing the aggregated particles in the mixture. A mixture may be prepared by adding an optional wax or other materials, which optionally also may be in a dispersion, including a surfactant, to the emulsion comprising a resin-forming material or a resin. The pH of the resulting mixture may be adjusted with an acid, such as, for example, acetic acid, nitric acid or the like. The pH of the mixture may be adjusted to from about 2 to about 4.5. 
     Additionally, the mixture may be homogenized. If the mixture is homogenized, mixing can be at from about 600 to about 4,000 rpm. Homogenization may be by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer. 
     Following preparation of the above mixture, larger particles or aggregates, often sized in micrometers, of the smaller particles from the initial polymerization reaction, often sized in nanometers, are obtained. An aggregating agent may be added to the mixture to facilitate the process. 
     The aggregating factor may be added to the mixture at a temperature that is below the glass transition temperature (T g ) of the resin or of a polymer. 
     The aggregating factor may be added to the mixture components to form a toner in an amount of, for example, from about 0.1 part per hundred (pph) to about 1 pph, from about 0.25 pph to about 0.75 pph. 
     To control aggregation of the particles, the aggregating factor may be metered into the mixture over time. For example, the factor may be added incrementally into the mixture over a period of from about 5 to about 240 minutes, from about 30 to about 200 minutes. 
     Addition of the aggregating factor also may be done while the mixture is maintained under stirred conditions, from about 50 rpm to about 1,000 rpm, from about 100 rpm to about 500 rpm; and at a temperature that is below the T g  of the resin or polymer, from about 30° C. to about 90° C., from about 35° C. to about 70° C. The growth and shaping of the particles following addition of the aggregation factor may be accomplished under any suitable condition(s). 
     The particles may be permitted to aggregate until a predetermined desired particle size is obtained. Particle size is monitored during the growth process, for example, with a COULTER COUNTER, for average particle size. 
     Once the desired final size of the toner particles or aggregates is achieved, the pH of the mixture may be adjusted with base to a value of from about 5 to about 10, from about 6 to about 8. The adjustment of pH may be used to freeze, that is, to stop, toner particle growth. The base used to stop toner particle growth may be, for example, an alkali metal hydroxide, such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof and the like. A chelator, such as, EDTA, may be added to assist adjusting the pH to the desired value. 
     After aggregation, but prior to coalescence, a resin coating may be applied to the aggregated particles to form a shell thereover. The shell can comprise any resin described herein or as known in the art. A polyester amorphous resin latex as described herein may be included in the shell. A polyester amorphous resin latex described herein may be combined with a different resin, and then added to the particles as a resin coating to form a shell. 
     A shell resin may be applied to the aggregated particles by any method within the purview of those skilled in the art. The emulsion possessing the resins may be combined with the aggregated particles so that the shell forms over the aggregated particles. 
     The formation of the shell over the aggregated particles may occur while heating to a temperature from about 30° C. to about 80° C., from about 35° C. to about 70° C. The formation of the shell may take place for a period of time from about 5 minutes to about 10 hours, from about 10 minutes to about 5 hours. 
     The shell may be present in an amount from about 1% by weight to about 80% by weight of the toner components, from about 10% by weight to about 40%, from about 20% by weight to about 35%. 
     Following aggregation to a desired particle size and application of any optional shell, the particles then may be coalesced to a desired final shape, such as, a circular shape, for example, to correct for irregularities in shape and size, the coalescence being achieved by, for example, heating the mixture to a temperature from about 45° C. to about 100° C., from about 55° C. to about 99° C., which may be at or above the T g  of the resins used to form the toner particles, and/or reducing the stirring, for example, from about 1000 rpm to about 100 rpm, from about 800 rpm to about 200 rpm. Coalescence may be conducted over a period from about 0.01 to about 9 hours, in embodiments from about 0.1 to about 4 hours, see, for example, U.S. Pat. No. 7,736,831. 
     Optionally, a coalescing agent can be used. Examples of suitable coalescence agents include, but are not limited to, benzoic acid alkyl esters, ester alcohols, glycol/ether-type solvents, long chain aliphatic alcohols, aromatic alcohols, mixtures thereof and the like. 
     The coalescence agent (or coalescing agent or coalescence aid agent) can evaporate during later stages of the emulsion/aggregation process, such as, during a second heating step, that is, generally above the T g  of the resin or a polymer. The final toner particles are thus, free of, or essentially or substantially free of any remaining coalescence agent. To the extent that any remaining coalescence agent may be present in a final toner particle, the amount of remaining coalescence agent is such that presence thereof does not affect any properties or the performance of the toner or developer. 
     The coalescence agent can be added prior to the coalescence or fusing step in any desired or suitable amount. For example, the coalescence agent can be added in an amount of from about 0.01 to about 10% by weight, based on the solids content in the reaction medium, on from about 0.05, or from about 0.1%, to about 0.5 or to about 3.0% by weight, based on the solids content in the reaction medium. Of course, amounts outside those ranges can be used, as desired. 
     After coalescence, the mixture may be cooled to room temperature, such as, from about 20° C. to about 25° C. The cooling may be rapid or slow, as desired. A suitable cooling method may include introducing cold water in a jacket around the reactor. After cooling, the toner particles optionally may be washed with water and then dried. Drying may be accomplished by any suitable method for drying including, for example, freeze drying. 
     In embodiments, the toner particles also may contain other optional additives. 
     The toner may include any known charge additives in amounts of from about 0.1 to about 10 weight %, from about 0.5 to about 7 weight % of the toner. Examples of such charge additives include alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430; and 4,560,035, the disclosure of each of which hereby is incorporated by reference in entirety, negative charge enhancing additives, such as, aluminum complexes, and the like. 
     Charge enhancing molecules can be used to impart either a positive or a negative charge on a toner particle. Examples include quaternary ammonium compounds, see, for example, U.S. Pat. No. 4,298,672, organic sulfate and sulfonate compounds, see for example, U.S. Pat. No. 4,338,390, cetyl pyridinium tetrafluoroborates, distearyl dimethyl ammonium methyl sulfate, aluminum salts and so on. 
     Surface additives can be added to the toner compositions of the present disclosure, for example, after washing or drying. Examples of such surface additives include, for example, one or more of a metal salt, a metal salt of a fatty acid, a colloidal silica, a metal oxide, such as, TiO 2  (for example, for improved RH stability, tribo control and improved development and transfer stability), an aluminum oxide, a cerium oxide, a strontium titanate, SiO 2 , mixtures thereof and the like. Examples of such additives include those disclosed in U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374; and 3,983,045, the disclosure of each of which hereby is incorporated by reference in entirety. 
     Surface additives may be used in an amount of from about 0.1 to about 10 wt %, from about 0.5 to about 7 wt % of the toner. 
     Other surface additives include lubricants, such as, a metal salt of a fatty acid (e.g., zinc or calcium stearate) or long chain alcohols, such as, UNILIN 700 available from Baker Petrolite and AEROSIL R972® available from Degussa. The coated silicas of U.S. Pat. Nos. 6,190,815 and 6,004,714, the disclosure of each of which hereby is incorporated by reference in entirety, also can be present. The additive can be present in an amount of from about 0.05 to about 5%, and in embodiments, of from about 0.1 to about 2% of the toner, which additives can be added during the aggregation or blended into the formed toner product. 
     The gloss of a toner may be influenced by the amount of retained metal ion, such as, Al 3+ , in a particle. The amounted of retained metal ion may be adjusted by the addition of a chelator, such as, EDTA. The amount of retained catalyst, for example, Al 3+ , in toner particles may be from about 0.1 pph to about 1 pph, from about 0.25 pph to about 0.8 pph. The gloss level of a toner of the instant disclosure may have a gloss, as measured by Gardner gloss units (gu), of from about 20 gu to about 100 gu, from about 50 gu to about 95 gu, from about 60 gu to about 90 gu. 
     Hence, a particle can contain at the surface one or more silicas, one or more metal oxides, such as, a titanium oxide and a cerium oxide, a lubricant, such as, a zinc stearate and so on. In some embodiments, a particle surface can comprise two silicas, two metal oxides, such as, titanium oxide and cerium oxide, and a lubricant, such as, a zinc stearate. All of those surface components can comprise about 5% by weight of a toner particle weight. There can also be blended with the toner compositions, external additive particles including flow aid additives, which additives may be present on the surface of the toner particles. Examples of these additives include metal oxides like titanium oxide, tin oxide, mixtures thereof, and the like; colloidal silicas, such as AEROSIL®, metal salts and metal salts of fatty acids, including zinc stearate, aluminum oxides, cerium oxides, and mixtures thereof. Each of the external additives may be present in embodiments in amounts of from about 0.1 to about 5 wt %, or from about 0.1 to about 1 wt %, of the toner. Several of the aforementioned additives are illustrated in U.S. Pat. Nos. 3,590,000, 3,800,588, and 6,214,507, the disclosure of each of which is incorporated herein by reference. 
     Toners may possess suitable charge characteristics when exposed to extreme relative humidity (RH) conditions. The low humidity zone (C zone) may be about 10° C. and 15% RH, while the high humidity zone (A zone) may be about 28° C. and 85% RH. 
     Toners of the instant disclosure also may possess a parent toner charge per mass ratio (q/m) of from about −5 μC/g to about −90 μC/g, and a final toner charge after surface additive blending of from about −15 μC/g to about −80 μC/g. 
     Other desirable characteristics of a toner include storage stability, particle size integrity, high rate of fusing to the substrate or receiving member, sufficient release of the image from the photoreceptor, nondocument offset, use of smaller-sized particles and so on, and such characteristics can be obtained by including suitable reagents, suitable additives or both, and/or preparing the toner with particular protocols. 
     The characteristics of the toner particles may be determined by any suitable technique and apparatus. Volume average particle diameter and geometric standard deviation may be measured using an instrument, such as, a Beckman Coulter MULTISIZER 3, operated in accordance with the instructions of the manufacturer. 
     The dry toner particles, exclusive of external surface additives, may have the following characteristics: (1) volume average diameter (also referred to as “volume average particle diameter”) of from about 2.5 to about 20 μm, from about 2.75 to about 10 μm, from about 3 to about 7.5 μm; (2) number average geometric standard deviation (GSDn) and/or volume average geometric standard deviation (GSDv) of from about 1.18 to about 1.30, from about 1.21 to about 1.24; and (3) circularity of from about 0.9 to about 1.0 (measured with, for example, a Sysmex FPIA 2100 analyzer), from about 0.95 to about 0.985, from about 0.96 to about 0.98. 
     Developers 
     The toner particles thus formed may be formulated into a developer composition. For example, the toner particles may be mixed with carrier particles to achieve a two component developer composition. The toner concentration in the developer may be from about 1% to about 25% by weight of the total weight of the developer, from about 2% to about 15% by weight of the total weight of the developer, with the remainder of the developer composition being the carrier. However, different toner and carrier percentages may be used to achieve a developer composition with desired characteristics. 
     1. Carrier 
     Examples of carrier particles for mixing with the toner particles include those particles that are capable of triboelectrically obtaining a charge of polarity opposite to that of the toner particles. Illustrative examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrites, iron ferrites, silicon dioxide, one or more polymers and the like. Other carriers include those disclosed in U.S. Pat. Nos. 3,847,604; 4,937,166; and 4,935,326. 
     The carrier particles may include a core with a coating thereover, which may be formed from a polymer or a mixture of polymers that are not in close proximity thereto in the triboelectric series, such as, those as taught herein or as known in the art. The coating may include fluoropolymers, such as polyvinylidene fluorides, terpolymers of styrene, methyl methacrylates, silanes, such as triethoxy silanes, tetrafluoroethylenes, other known coatings and the like. For example, coatings containing polyvinylidenefluoride, available, for example, as KYNAR 301F™, and/or polymethylmethacrylate (PMMA), for example, having a weight average molecular weight of about 300,000 to about 350,000, such as, commercially available from Soken, may be used. In embodiments, PMMA and polyvinylidenefluoride may be mixed in proportions of from about 30 to about 70 wt % to about 70 to about 30 wt %, in embodiments, from about 40 to about 60 wt % to about 60 to about 40 wt %. The coating may have a coating weight of, for example, from about 0.1 to about 5% by weight of the carrier, from about 0.5 to about 2% by weight of the carrier. 
     Various effective suitable means can be used to apply the polymer to the surface of the carrier core, for example, cascade roll mixing, tumbling, milling, shaking, electrostatic powder cloud spraying, fluidized bed mixing, electrostatic disc processing, electrostatic curtain processing, combinations thereof and the like. The mixture of carrier core particles and polymer then may be heated to enable the polymer to melt and to fuse to the carrier core. The coated carrier particles then may be cooled and thereafter classified to a desired particle size. 
     The carrier particles may be prepared by mixing the carrier core with polymer in an amount from about 0.05 to about 10% by weight, from about 0.01 to about 3% by weight, based on the weight of the coated carrier particle, until adherence thereof to the carrier core is obtained, for example, by mechanical impaction and/or electrostatic attraction. 
     In embodiments, suitable carriers may include a steel core, for example, of from about 25 to about 100 μm in size, from about 50 to about 75 μm in size, coated with about 0.5% to about 10% by weight, from about 0.7% to about 5% by weight of a polymer mixture including, for example, methylacrylate and carbon black, using the process described, for example, in U.S. Pat. Nos. 5,236,629 and 5,330,874. 
     Devices Comprising a Toner Particle 
     Toners and developers can be combined with a number of devices ranging from enclosures or vessels, such as, a vial, a bottle, a flexible container, such as a bag or a package, and so on, to devices that serve more than a storage function. 
     A. Imaging Device Components 
     The toner compositions and developers of interest can be incorporated into devices dedicated, for example, to delivering same for a purpose, such as, forming an image. Hence, particularized toner delivery devices are known, see, for example, U.S. Pat. No. 7,822,370, and can contain a toner preparation or developer of interest. Such devices include cartridges, tanks, reservoirs and the like, and can be replaceable, disposable or reusable. Such a device can comprise a storage portion; a dispensing or delivery portion; and so on; along with various ports or openings to enable toner or developer addition to and removal from the device; an optional portion for monitoring amount of toner or developer in the device; formed or shaped portions to enable sitting and seating of the device in, for example, an imaging device; and so on. 
     B. Toner or Developer Delivery Device 
     A toner or developer of interest may be included in a device dedicated to delivery thereof, for example, for recharging or refilling toner or developer in an imaging device component, such as, a cartridge, in need of toner or developer, see, for example, U.S. Pat. No 7,817,944, wherein the imaging device component may be replaceable or reusable. 
     Imaging Devices 
     The toners or developers can be used for electrostatographic or electrophotographic processes, including those disclosed in U.S. Pat. No. 4,295,990, the disclosure of which hereby is incorporated by reference in entirety. In embodiments, any known type of image development system may be used in an image developing device, including, for example, magnetic brush development, jumping single component development, hybrid scavengeless development (HSD) and the like. Those and similar development systems are within the purview of those skilled in the art. 
     Imaging processes include, for example, preparing an image with an electrophotographic device including, for example, one or more of a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, a fusing component and so on. The electrophotographic device may include a high speed printer, a color printer and the like. 
     Once the image is formed with toners/developers via a suitable image development method, such as any of the aforementioned methods, the image then may be transferred to an image receiving medium or substrate, such as, a paper and the like. In embodiments, the fusing member or component, which can be of any desired or suitable configuration, such as, a drum or roller, a belt or web, a flat surface or platen, or the like, may be used to set the toner image on the substrate. Optionally, a layer of a liquid, such as, a fuser oil can be applied to the fuser member prior to fusing. 
     Color printers commonly use four housings carrying different colors to generate full color images based on black plus the standard printing colors, cyan, magenta and yellow. However, in embodiments, additional housings may be desirable, including image generating devices possessing five housings, six housings or more, thereby providing the ability to carry additional toner colors to print an extended range of colors (extended gamut). 
     The following Examples illustrate embodiments of the instant disclosure. The Examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. Parts and percentages are by weight unless otherwise indicated. As used herein, “room temperature,” (RT) refers to a temperature of from about 20° C. to about 30° C. 
     EXAMPLES 
     Example 1 
     Synthesis of Bio-Based Resins 
     To a 1-L Parr reactor were added a rosin (Arakawa KR614) comprised primarily of disproportionated dehydro-abietic acid (180 g), bis-(epoxy-propyl)-neopentylene glycol (76 g) and tetraethyl ammonium bromide catalyst (0.35 g). The mixture was heated from 105° C. to 160° C. over a four-hour period with stirring under nitrogen bleed. To that mixture then were added 1,2-propanediol (183 g), dimethyl terephthalate (231 g), succinic acid (19.2 g) and FASCAT 4100 catalyst (1.5 g). The mixture was heated from 160° C. to 195° C. over a 6 hour period, followed by increasing the temperature to 210° C. over a 2 hour period, followed by reducing the pressure to 10 mm-Hg. The mixture was then heated to 225° C. until the desired softening point was obtained (Table 1). During the polycondensation process, water, methanol and glycol were distilled. The resin then was discharged through a bottom drain valve and left undisturbed to cool to RT. Two resins were made, Resins A and B of differing molecular weight. The thermal properties are listed in Table 1 below. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Resin 
                 Tg 
                 Ts 
                 AV 
                 Mn/Mw 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 A 
                 59.5 
                 121 
                 16.8 
                 3.05/40.9 
               
               
                 B 
                 55.4 
                 114.1 
                 21.5 
                 2.5/50  
               
               
                   
               
             
          
         
       
     
     Example 2 
     Toner Made with Resin A, 9% Wax and 6.8% Crystalline Resin 
     Into a 2 liter glass reactor equipped with an overhead mixer were added 312.96 g emulsion of resin A (19.19 wt %) prepared by a standard phase inversion emulsion (PIE) process (particle size of 126.5 nm), 23.38 g crystalline resin emulsion (35.60 wt %), 36.94 g wax dispersion (29.97 wt %) and 44.30 g cyan pigment PB15:3 (16.24 wt %). Separately 1.35 g Al 2 (SO 4 ) 3  (27.85 wt %) were added as the flocculent (aggregating agent) under homogenization. The mixture was heated to 46.9° C. to aggregate the particles while stirring at 300 rpm. The particle size was monitored with a COULTER COUNTER until the core particles reached a volume average particle size of 4.13 μm with a GSD volume of 1.23, and then 175.09 g of above mentioned resin A emulsion were added as shell material, resulting in core-shell structured particles with an average particle size of 5.48 μm, GSD volume 1.20. Thereafter, the pH of the reaction slurry was increased to 7.7 using a 4 wt % NaOH solution followed by 2.77 g EDTA (39 wt %) to freeze toner particle growth. After freezing, the reaction mixture was heated to 85° C. and pH was reduced to 7.00 using a pH 5.7 acetic acid/sodium acetate (HAc/NaAc) buffer solution for coalescence. The toner slurry then was cooled to RT, separated by sieving (25 μm), filtered, and followed by washing and freeze drying. 
     Example 3 
     Toner Made with Resin B, 9% Wax and 6.8% Crystalline Resin 
     Into a 2 liter glass reactor equipped with an overhead mixer were added 331.91 g emulsion of resin B (18.33 wt %) prepared by a standard phase inversion emulsification process (particle size of 217.1 nm), 23.38 g crystalline resin emulsion (35.60 wt %), 36.94 g wax dispersion (29.97 wt %) and 44.3 g cyan pigment PB15:3 (16.24 wt %). Separately 2.15 g Al 2 (SO 4 ) 3  (27.85 wt %) were added in as the flocculent under homogenization. The mixture was heated to 38.9° C. to aggregate the particles while stirring at 300 rpm. The particle size was monitored with a COULTER COUNTER until the core particles reached a volume average particle size of 4.40 μm with a GSD volume of 1.22, and then 183.31 g of above mentioned resin B emulsion were added as shell material, resulting in core-shell structured particles with an average size of 6.15 μm, GSD volume of 1.21. Thereafter, the pH of the reaction slurry was then increased to 7.67 using a 4 wt % NaOH solution followed by 4.62 g EDTA (39 wt %) to freeze the toner particle growth. After freezing, the reaction mixture was heated to 85° C., and pH was reduced to 6.73 using pH 5.7 acetic acid/sodium acetate (HAc/NaAc) buffer solution for coalescence. The toner slurry was then cooled to RT, separated by sieving (25 μm), filtered, followed by washing and freeze dried. 
     
       
         
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 Toner 
                 Resin 
                 Size 
                 GSDv/n 
                 Circularity 
               
               
                   
               
             
             
               
                 A 
                 A 
                 5.54 
                 1.25/1.36 
                 0.972 
               
               
                 B 
                 B 
                 6.02 
                 1.25/1.34 
                 0.953 
               
               
                   
               
             
          
         
       
     
     Example 4 
     Fusing 
     All unfused images were generated using a DC12 copier (Xerox). A TMA (toner mass per unit area) of 1.00 mg/cm 2  was used for the amount of toner placed onto CXS paper (Color Xpressions Select, 90 gsm, uncoated, Xerox No. 3R11540) and used for gloss, crease and hot offset measurements. Gloss/crease targets were a square image placed in the centre of the page as known in the art. In general, two passes through the DC12 while adjusting developer bias voltage were required to achieve the desired TMA. Samples then were fused with a Xerox DocuColor™ copier/printer). Fusing properties are listed in Table 3. The fusing results of both bio-based toners indicated similar performance to a DocuColor™ toner containing an amorphous resin. 
     
       
         
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Toner 
                 Resin 
                 Cold Offset 
                 MFT 
                 Hot Offset 
               
               
                   
               
             
             
               
                 Control 
                 Control 
                 120 
                 113 
                 165 
               
               
                 A 
                 A 
                 113 
                 112 
                 155 
               
               
                 B 
                 B 
                 113 
                 115 
                 175 
               
               
                   
               
             
          
         
       
     
     Example 5 
     Heat Cohesion Measurement 
     Five grams of toner were placed into an open dish and conditioned in an environmental chamber at 55° C. and 50% relative humidity. After 24 hours, the samples were removed and acclimated to ambient conditions for 30 minutes. Each re-acclimated sample was then poured into a stack of two preweighed mesh sieves, which were stacked as follows, 1,000 μm on top and 106 μm on bottom. The sieves were vibrated for 90 seconds at 1 millimeter amplitude with a Hosokawa flow tester. After the vibration was completed, the sieves were reweighed and toner heat cohesion was calculated from the total amount of toner remaining on both sieves as a percentage of the starting weight. 
     The toner derived from resin A has good blocking performance. 
     Example 6 
     Electrical Properties 
     Tribocharge and RH sensitivity were tested. 
     Developer samples were prepared in a 60 ml glass bottle by weighing 0.5 gram of toner onto 10 grams of carrier comprised of a steel core and a coating of a polymer mixture of polymethylmethacrylate (PMMA, 60 wt %) and polyvinylidene fluoride (40 wt %). Developer samples were prepared in duplicate as above for each toner that was being evaluated. One sample of the pair was conditioned in the A zone environment of 28° C./85% RH and the other was conditioned in the C-zone environment of 10° C./15% RH. The samples were kept in the respective environments overnight, about 18 to about 21 hours, to fully equilibrate. The following day, the developer samples were mixed for 1 hour using a Turbula mixer, after which the charge on the toner particles was measured using a charge spectrograph. The toner charge was calculated as the midpoint of the toner charge distribution. The charge was in millimeters of displacement from the zero line for both the parent particles and particles with additives. The relative humidity (RH) ratio was calculated as the A-zone charge at 85% humidity (in ml) over the C-zone charge at 15% humidity (in ml). 
     Compared to the DocuColor control, the A-zone charge was slightly lower for parent charge, and in the J-zone, slightly higher with additives. Considering that the acid value of the resins was higher than that of the control toner, and acid value is manipulable, charge performance can be optimized. The charge maintenance was similar to that of the control toner after 24 hrs. 
     Overall, the thermal properties of the bio-resins as well as the bench test fusing, blocking and electrical performance of the bio-based toners of interest are similar to the commercial Xerox DocuColor™ DC 12 toner. 
     Example 7 
     Synthesis of Bio-Based Resin (1-Pot) 
     To a 2 liter Hoppes reactor were added rosin acid (Rondis R, Arakawa Chemical, Chicago, Ill.) comprised primarily of dehydro-abietic acid (527.1 g), bis-(epoxy-propyl)-neopentylene glycol (BNG, 222.8 g) and tetraethyl ammonium bromide catalyst (TAB, 0.68 g). The mixture was heated from 105° C. to over 165° C. over a four-hour period with stirring under nitrogen bleed and the mixture was held at that temperature for 2-4 hours until the acid value was less than 5. The mixture was cooled and then were added 1,2-propanediol (PD, 461 g), terephthalic acid (477.4 g), succinic acid (SA, 38.8 g) and FASCAT 4100 catalyst (3 g). The mixture was heated from 160° C. to 195° C. over a 2.5 hour period, followed by increasing the temperature to 210° C. over a 20 minute period. The reactor was pressurized to 200 kPa once the internal temperature reached 185° C. The reaction was maintained from about 8 hours or until the acid value was ≦10. The reaction pressure was then reduced to about 10 mm-Hg. The propylene glycol and any residual water were distilled out. The mixture was then heated to 210° C. until the desired softening point was obtained (Table 4). The resin then was discharged through a bottom drain valve and left undisturbed to cool to room temperature. Three resins were made (Resins C-E). 
     Example 8 
     Synthesis of Bio-Based Resin with Fumaric Acid (FA) to Adjust AV 
     The same materials and methods as that of Example 7 for Resin E were practiced except that the resulting resin mixture was heated until a softening point of 122° C. was obtained. The reactor temperature was reduced to 175° C. and 24 g of fumaric acid were added. The mixture was heated for an additional hour, discharged through a bottom drain valve and cooled to RT (Resin F). 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
               
                   
                   
                   
                 Av (mg 
                 GPC (×10 3 ) 
               
               
                 Resin 
                 Tg 
                 Ts 
                 KOH/g) 
                 Mn/Mw 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 C 
                 59.5 
                 11.5 
                 11.2 
                  3.89/13.51 
               
               
                 D 
                 64.5 
                 121.3 
                 13.3 
                 3.85/18.5 
               
               
                 E 
                 60.9 
                 122.7 
                 7.5 
                 3.83/63.5 
               
               
                 F 
                 59.1 
                 123 
                 12.9 
                 3.63/63.6 
               
               
                   
               
             
          
         
       
     
     As noted in comparing Resins E and F, the acid value of the resin was altered by including fumaric acid in the reaction without altering the remaining thermal properties of the resin. 
     Example 9 
     Scale-Up Synthesis of Bio-Based Resin (1-Pot) with FA 
     To a 5 gallon reactor were added Rondis R rosin (5.27 kg), 2.33 kg BNG and 68 g or TAB. The mixture was heated from 105° C. to over 165° C. over a four-hour period with stirring under nitrogen bleed and the mixture was held at that temperature for 2-4 hours until the acid value was less than 5. The mixture was cooled and then were added 461 g of PD, terephthalic acid (TA, 477.4 g), 38.8 g of SA and 3 g of FASCAT 4100. The mixture was heated from 160° C. to 195° C. over a 2.5 hour period, followed by increasing the temperature to 199° C. over a 20 minute period. The reactor was pressurized to 200 kPa once the internal temperature reached 185° C. The reaction was maintained from about 8 hours or until the acid value was ≦10. The reaction pressure was then reduced to about 10 mm-Hg. The propylene glycol and any residual water were distilled out. The mixture was then heated to 195° C. until the desired softening point (Resin G, 113.5° C.; Resin H, 117.5° C.) was obtained (Table 5). The reactor temperature was reduced to 175° C. and 208 g of FA and 0.24 g hydroquinone to serve as an inhibitor to avoid crosslinking of fumaric with oxygen. The mixture was heated for an additional 5-6 hours and then discharged through a bottom drain valve and left undisturbed to cool to room temperature. 
     Example 10 
     The process of Example 9 was practiced but using 165 g of FA to yield Resin H. 
     Example 11 
     The process of Example 9 was practiced except that 2.38 kg of BNG and 165 g of FA were added to yield Resin 1. 
     
       
         
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 Resin 
                 Tg 
                 Ts 
                 AV 
                 Mn/Mw 
               
               
                   
               
             
             
               
                 G 
                 57.8 
                 114.9 
                 12.9 
                 3.12/37.2  
               
               
                 H 
                 58.6 
                 119.5 
                 11.3 
                 3.51/104.7 
               
               
                 I 
                 55.6 
                 116.3 
                 11.1 
               
               
                   
               
             
          
         
       
     
     Example 12 
     Toner C Made with Resin G 
     Into a 2 liter glass reactor equipped with an overhead mixer was added 328.16 g emulsion of resin G (18.54 wt %) prepared by a standard PIE process (particle size of 186.3 nm), 23.38 g crystalline resin emulsion (35.60 wt %), 36.94 g wax dispersion (29.97 wt %) and 46.12 g cyan pigment PB15:3 (15.60 wt %). Separately, 2.15 g Al 2 (SO 4 ) 3  (27.85 wt %) were added in as flocculent under homogenization. The mixture was heated to 41° C. to aggregate the particles while stirring at 300 rpm. The particle size was monitored with a COULTER COUNTER until the core particles reached a volume average particle size of 4.68 μm with a GSD volume of 1.23, and then 181.23 g of resin G emulsion were added as shell material, resulting in core-shell structured particles with an average particle size of 5.83 μm, GSD volume 1.22. Thereafter, the pH of the reaction slurry was increased to 8.1 using a 4 wt % NaOH solution followed by 6.92 g EDTA (39 wt %) to freeze toner particle growth. After freezing, the reaction mixture was heated to 75° C. and pH was increased to 9.05. After 2 hours of coalescence, pH was reduced stepwise from 8.52 to 8.32 using a pH 5.7 acetic acid/sodium acetate (HAc/NaAc) buffer solution. The toner was quenched after coalescence, resulting in a final particle size of 6.41 μm, GSD volume of 1.23, GSD number 1.26 and circularity 0.967 (Sysmex FPIA 2100 analyzer). The toner slurry was then cooled to RT, separated by sieving (25 μm), filtration, followed by washing and freeze drying. 
     Example 13 
     Toner D Made with Resin H 
     Into a 2 liter glass reactor equipped with an overhead mixer were added 286.41 g emulsion of resin H (21.72 wt %) prepared by standard PIE process (particle size of 100.1 nm), 23.91 g crystalline resin emulsion (35.60 wt %), 36.94 g wax dispersion (29.97 wt %) and 47.15 g cyan pigment PB15:3 (15.60 wt %). Separately 1.32 g Al 2 (SO 4 ) 3  (37.67 wt %) were added as flocculent under homogenization. The mixture was heated to 46.9° C. to aggregate the particles while stirring at 300 rpm. The particle size was monitored with a COULTER COUNTER until the core particles reached a volume average particle size of 4.05 μm with a GSD volume of 1.25, and then 158.18 g of above mentioned resin H emulsion were added as shell material, resulting in core-shell structured particles with an average particle size of 5.42 μm, GSD volume 1.24. Thereafter, the pH of the reaction slurry was then increased to 7.87 using a 4 wt % NaOH solution followed by 4.72 g EDTA (39 wt %) to freeze toner particle growth. After freezing, the reaction mixture was heated to 75° C. and pH was increased to 9.05. After 2 hours of coalescence, pH was reduced stepwise from 8.45 to 8.1 using a pH 5.7 acetic acid/sodium acetate (HAc/NaAc) buffer solution. The toner was quenched after coalescence, resulting in a final particle size of 6.41 μm, GSD volume of 1.25, GSD number 1.29 and circularity 0.955. The toner slurry was then cooled to RT, separated by sieving (25 μm), filtered, followed by washing and freeze drying. 
     Example 14 
     Toner E Made with Resin I 
     Into a 2 liter grass reactor equipped with an overhead mixer were added 274.67 g emulsion of resin I (22.15 wt %) prepared by a standard PIE process (particle size of 178.6 nm), 23.38 g crystalline resin emulsion (35.60 wt %), 36.84 g wax dispersion (30.05 wt %) and 46.12 g cyan pigment PB15:3 (15.60 wt %). Separately 2.15 g Al 2 (SO 4 ) 3  (27.85 wt %) were added as flocculent. The mixture was heated to 43.9° C. to aggregate the particles while stirring at 300 rpm. The particle size was monitored with a COULTER COUNTER until the core particles reached a volume average particle size of 4.49 μm with a GSD volume of 1.24, and then 151.69 g of the above mentioned resin I emulsion were added as shell material, resulting in core-shell structured particles with an average particle size of 5.37 μm, GSD volume 1.22. Thereafter, the pH of the reaction slurry was increased to 8.03 using a 4 wt % NaOH solution followed by 4.62 g EDTA (39 wt %) to freeze the toner growth. After freezing, the reaction mixture was heated to 75° C. and pH was increased to 9.52. After 2 hours of coalescence, pH was reduced stepwise from 8.79 to 8.66 using a pH 5.7 acetic acid/sodium acetate (HAc/NaAc) buffer solution. The toner was quenched after coalescence, resulting in a final particle size of 5.71 μm, GSD volume of 1.22, GSD number 1.28 and circularity of 0.957. The toner slurry was then cooled to RT, separated by sieving (25 mm), filtered, followed by washing and freeze drying. 
     Example 15 
     Toner F was made with 50:50 mixture of resins G and H. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 Resin 
                 Toner 
                 D50 
                 Mn/Mw 
                 Circ 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 G 
                 C 
                 6.41 
                 1.23/1.26 
                 .967 
               
               
                 H 
                 D 
                 5.83 
                 1.25/1.29 
                 .955 
               
               
                 I 
                 E 
                 5.71 
                 1.22/1.28 
                 .957 
               
               
                 G/H 
                 F 
                 5.9 
                 1.23/1.25 
                 .956 
               
               
                   
               
             
          
         
       
     
     It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art, which are also intended to be encompassed by the following claims. Unless specifically recited in a claim, steps or components of claims should not be implied or imported from the specification or any other claims as to any particular order, number, position, size, shape, angle, color or material. 
     All references cited herein are herein incorporated by reference in entirety.