Dual wax toner composition

Abstract

To provide improved toners having acceptable properties including storage, gloss, fusing latitude and hot offset characteristics.SOLUTION: A toner composition includes: a first wax, and a second wax different from the first wax, where the first wax comprises a paraffin wax, and the second wax comprises a polymethylene wax; at least one polyester; and an optional colorant.SELECTED DRAWING: None

Description

[Background technology]

[0001] Disclosed herein is a toner composition comprising a first wax, a second wax different from the first wax, at least one polyester, and an optional colorant, wherein the first wax comprises a paraffin wax and the second wax comprises a polymethylene wax.

[0002] Polyester toner compositions are desirable for toners and toner / developers. It is desirable for the toner to meet several requirements of the intended machine, including high temperature offset or release properties. High temperature offset can be controlled by the addition of release agents such as wax or gel latex. Alternatively, the release properties can be modified by increasing the molecular weight of the toner binder resin. However, this can affect other rheological properties and adversely affect the quality of the final printed image.

[0003] Currently available toners are suitable for their intended purposes, however, there is a need for improved toners that have acceptable properties including storage characteristics, gloss characteristics, fixing latitude characteristics, and high temperature offset characteristics.

[0004] The appropriate components and process aspects of each of the above U.S. patents and published patent applications may be selected for the present disclosure in its embodiments. Additionally, throughout this application, various publications, patents, and published patent applications are referenced by specific citations. The disclosures of the publications, patents, and published patent applications referenced in this application are hereby incorporated by reference into this disclosure in order to more fully describe the state of the art to which this invention pertains. Summary of the Invention

[0005] A toner composition is described that includes a first wax, a second wax different from the first wax, where the first wax includes a paraffin wax and the second wax includes a polymethylene wax, at least one polyester, and an optional colorant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] An emulsion aggregation toner is provided that includes a dual wax. The toner provides acceptable storage, gloss, fix latitude, and hot offset characteristics. The dual wax toner includes a paraffin wax and a polymethylene wax.

[0007] In an embodiment, a toner composition is provided that includes a first wax, a second wax different from the first wax, where the first wax includes a paraffin wax and the second wax includes a polymethylene wax, at least one polyester, and an optional colorant.

[0008] Two types of wax.

[0009] The toner compositions herein include a first wax and a second wax different from the first wax, hi embodiments, the first wax is a paraffin wax and the second wax is a polymethylene wax.

[0010] In an embodiment, the first wax is a paraffin wax, in an embodiment, having a low onset melting point of greater than about 50° C. or greater than about 60° C. In an embodiment, the first wax is a paraffin wax having a peak melting temperature of about 60 to about 80° C., or about 70 to about 80° C., or about 65 to about 75° C. In certain embodiments, the first wax is a paraffin wax having a low onset melting point of about 70 to about 75° C. In certain embodiments, the first wax is a paraffin wax having an onset melting temperature of greater than about 55° C.

[0011] Any suitable or desired paraffin wax can be selected for the embodiments herein, in embodiments, the paraffin wax has a peak melting temperature, a low onset melting point characteristic, or a combination thereof, as described herein. In embodiments, the paraffin wax may be BW-422 and BW-436 from Blended Waxes, Inc.; IGI 1245A, IGI 1250A, IGI 1297A, IGI 1266A from the International Group, Inc.; Indrawax 6062-F, Indrawax 6264-F, Indrawax 6466-F, Indrawax 6668-F, Indrawax 6870-F, Indrawax 7072-F, Indrawax 8070, Indrawax 6062-S 140-144, Indrawax 6062-S from Industrial Raw Materials LLC; Sell Sarawax SX70 from Alpha Wax; Strahl & Pitsch 434 and 674 paraffin waxes; dispersions of paraffin waxes including CHEMBEAD® 30, CHEMBEAD® 30-AM, PARAFINE 30, PARAFFIN 60, PARAFFIN EMULSION 135-45FDA, PARAFFIN EMULSION 150-45 FDA (all from BYK Additives & Instruments); and combinations thereof.

[0012] In an embodiment, the first wax is a paraffin wax having a carbon to oxygen ratio (C / O ratio) of about 100 to about 200, or about 50 to about 150, or about 100 to about 200. In an embodiment, the first wax is a paraffin wax having a carbon to oxygen ratio of greater than about 50.

[0013] In certain embodiments, the first wax is a paraffin wax having a number average molecular weight of about 400 grams / mole to about 600 grams / mole, or about 500 grams / mole to about 600 grams / mole, or about 500 grams / mole to about 530 grams / mole.

[0014] In an embodiment, the second wax is a distilled synthetic polymethylene wax (Fischer-Tropsch) wax having a melting point of about 92°C.

[0015] In certain embodiments, the polymethylene wax has a number average molecular weight of about 600 grams / mole to about 800 grams / mole, or about 600 grams / mole to about 700 grams / mole, or about 670 grams / mole to about 700 grams / mole.

[0016] In embodiments, the toner comprises a total amount of waxes, including both paraffin wax and polymethylene wax, in an amount of from about 7 to about 14, or from about 7 to about 10, or from about 9 to about 10 weight percent, based on the total weight of the toner composition. In certain embodiments, the toner composition comprises a total amount of waxes, including the first wax and the second wax, in an amount of from about 9 to about 12 weight percent, based on the total weight of the toner composition.

[0017] In embodiments, the paraffin wax is present in an amount of about 3 to about 10, or about 5 to about 9, or about 6 to about 8 weight percent, based on the total weight of the paraffin wax and the polymethylene wax. In certain embodiments, the paraffin wax is present in an amount of about 25 to about 75 weight percent, based on the total weight of the paraffin wax and the polymethylene wax.

[0018] In certain embodiments, the paraffin wax and polymethylene wax are present in a ratio of 3:1 paraffin:polymethylene.

[0019] Crystalline resin.

[0020] The toner herein comprises a crystalline polyester. The crystalline resin herein may be a crystalline polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst. Suitable organic diols for forming the crystalline polyester include aliphatic diols having 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, combinations thereof, including structural isomers. The aliphatic diol can be selected in an amount of, for example, from about 40 to about 60 mole percent of the resin, from about 42 to about 55 mole percent of the resin, from about 45 to about 53 mole percent of the resin, and the second diol can be selected in an amount of from about 0 to about 10 mole percent of the resin, or from about 1 to 4 mole percent of the resin.

[0021] Examples of organic diacids or diesters, including vinyl diacids or vinyl diesters, selected for the preparation of crystalline resins include 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, aphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid, and mesaconic acid, diesters or anhydrides thereof. The organic diacid may be selected in an amount of, for example, about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, about 45 to about 50 mole percent of the resin, and the second diacid may be selected in an amount of about 0 to about 10 mole percent of the resin.

[0022] Polycondensation catalysts that may be utilized to form crystalline (as well as amorphous) polyesters include tetraalkyl titanates, dialkyl tin oxides such as dibutyltin oxide, tetraalkyl tins such as dibutyltin dilaurate, and dialkyl tin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxides, stannous oxides, or combinations thereof. Such catalysts may be utilized, for example, in amounts of about 0.01 mole percent to about 5 mole percent based on the starting diacid or diester used to produce the polyester resin.

[0023] Examples of crystalline resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, mixtures thereof, and the like. Specific crystalline resins 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 ...ethylene sebacate), poly(propylene sebacate), poly(butylene sebacate), poly(pentylene sebacate), poly(hexylene sebacate), poly(octylene sebacate), poly(ethylene sebacate), poly(ethylene sebacate), poly(ethylene sebacate), poly(propylene sebacate), poly(butylene sebacate), poly(pentylene sebacate), poly( The polyolefin may be based on polyesters such as poly(ethylene-decanoate), 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(nonylene-decanoate), poly(octylene-adipate), and mixtures thereof. Examples of polyamides include poly(ethylene-adipamide), poly(propylene-adipamide), poly(butylene-adipamide), poly(pentylene-adipamide), poly(hexylene-adipamide), poly(octylene-adipamide), poly(ethylene-succinimide), poly(propylene-sebacamide), and mixtures thereof.Examples of polyimides include poly(ethylene-adipimide), poly(propylene-adipimide), poly(butylene-adipimide), poly(pentylene-adipimide), poly(hexylene-adipimide), poly(octylene-adipimide), poly(ethylene-succinimide), poly(propylene-succinimide), poly(butylene-succinimide), and mixtures thereof.

[0024] In an embodiment, the crystalline polyester is of the formula: [ka]

[0025] Each of a and b may range from 1 to 12, 2 to 12, or 4 to 12, and further, p may range from 10 to 100, 20 to 80, or 30 to 60. In an embodiment, the crystalline polyester is poly(1,6-hexylene-1,12-dodecanoate), which may be produced by the reaction of dodecanedioic acid with 1,6-hexanediol.

[0026] The designations "CX:CY", "CX:Y", "X:Y" and forms thereof, as used herein, refer to crystalline resins, where C is carbon, X is a positive non-zero integer that specifies the number of methylene groups of the acid / ester monomers used to produce the crystalline polyester (CPE), and Y is a positive non-zero integer that specifies the number of methylene groups of the alcohol monomers used to produce the CPE. Thus, for example, C10 can represent, for example, dodecanedioic acid, and C6 can represent, for example, hexanediol. X and Y are each equal to or less than 10. In embodiments, the sum of X and Y is equal to or less than 16. In certain embodiments, the sum of X and Y is equal to or less than 14.

[0027] In an embodiment, the crystalline polyester is a C10:9 resin, which comprises a polyester made from dodecanedioic acid (C10) and 1,9-nonanediol (C9).

[0028] As mentioned above, the crystalline polyester can be prepared by a polycondensation process by reacting a suitable organic diol with a suitable organic diacid in the presence of a polycondensation catalyst. A stoichiometric equimolar ratio of the organic diol and the organic diacid can be utilized, but when the boiling point of the organic diol is about 180°C to about 230°C, an excess amount of diol, such as about 0.2 to 1 molar equivalent of ethylene glycol or propylene glycol, can be utilized and removed during the polycondensation process by distillation. The amount of catalyst utilized can vary and can be selected, for example, in an amount of about 0.01 to about 1 or about 0.1 to about 0.75 mole percent of the crystalline polyester resin.

[0029] The crystalline resin may be present in the toner in any suitable or desired amount. In embodiments, the crystalline resin may be present in an amount of, for example, from about 1 to about 85 weight percent of the toner, from about 5 to about 50 weight percent of the toner, or from about 10 to about 35 weight percent of the toner. In certain embodiments, the crystalline polyester is present in an amount of from about 6 to about 7 weight percent, based on the total weight of the toner composition. In certain embodiments, the crystalline polyester is a C10:9 resin present in the toner in an amount of from about 6 to about 7 weight percent, based on the total weight of the toner composition.

[0030] The crystalline resin may have various melting points, for example, about 30°C to about 120°C, about 50°C to about 90°C, or about 60°C to about 80°C. The crystalline resin may have a number average molecular weight (Mn) of, for example, about 1,000 to about 50,000, about 2,000 to about 25,000, or about 5,000 to about 20,000 when measured by gel permeation chromatography (GPC), and a weight average molecular weight (Mw) of, for example, about 2,000 to about 100,000, about 3,000 to about 80,000, or about 10,000 to about 30,000 when determined by GPC. The molecular weight distribution (Mw / Mn) of the crystalline resin may be, for example, about 2 to about 6, about 3 to about 15 about 5, or about 2 to about 4.

[0031] Amorphous resin.

[0032] In embodiments, the toner composition comprises at least one amorphous polyester. In embodiments, the toner composition comprises at least one amorphous polyester and at least one crystalline polyester. In certain embodiments, the at least one polyester comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester. In further embodiments, the at least one polyester in the toner comprises a first amorphous polyester, a second amorphous polyester different from the first amorphous polyester, and a crystalline polyester.

[0033] The amorphous resin may be an amorphous polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst. Examples of diacids or diesters, including vinyl diacids or vinyl diesters, that may be utilized to prepare the amorphous polyester include terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, dimethyl fumarate, dimethyl itaconate, cis-1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, glutaric acid, glutaric anhydride, Included are dicarboxylic acids or diesters such as adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl phthalate, phthalic anhydride, diethyl phthalate, dimethyl succinate, dimethyl fumarate, dimethyl maleate, dimethyl glutarate, dimethyl adipate, dimethyl dodecyl succinate, and combinations thereof. The organic dibasic acid or diester may be present in an amount of, for example, about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, or about 45 to about 50 mole percent of the resin.

[0034] Examples of diols that may be utilized in the production of amorphous polyesters 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, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(2-hydroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylylene dimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene, and combinations thereof. The amount of organic diol selected may vary, and the organic diol may be present in an amount of, for example, about 40 to about 60 mole percent of the resin, about 42 to about 55 mole percent of the resin, or about 45 to about 53 mole percent of the resin.

[0035] Examples of suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, and the like, and mixtures thereof.

[0036] Unsaturated amorphous polyester resins may be utilized as the resin. Examples of such resins include those disclosed in U.S. Pat. No. 6,063,827, the disclosure of which is incorporated herein by reference in its entirety. Exemplary unsaturated amorphous polyester resins include poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(copropoxylated bisphenol co-ethoxylated bisphenol co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyl ... Poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(copropoxylated bisphenol co-ethoxylated bisphenol co-itaconate), poly(1,2-propylene itaconate), and combinations thereof.

[0037] Suitable polyester resins may be amorphous polyesters such as poly(propoxylated bisphenol A co-fumarate) resins. Examples of such resins and processes for their manufacture include those disclosed in U.S. Patent No. 6,063,827, the disclosure of which is incorporated herein by reference in its entirety.

[0038] Suitable polyester resins include amorphous acid polyester resins.Amorphous acid polyester resins may be any combination of propoxylated bisphenol A, ethoxylated bisphenol A, terephthalic acid, fumaric acid, and dodecenyl succinic anhydride, such as poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate).Another amorphous acid polyester resin that can be used is poly(propoxylate-ethoxylated bisphenol-co-terephthalate-dodecenyl succinic acid-trimellitic anhydride).

[0039] An example of a linear propoxylated bisphenol A fumarate resin that can be utilized as the resin is available under the trade name SPAM II from Resana S / A Industrias Quimicas, Sao Paulo, Brazil. Other commercially available propoxylated bisphenol A fumarate resins that can be utilized include GTUF and FPESL-2 from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, NC.

[0040] The combination of crystalline or amorphous resins may be present in an amount of, for example, from about 5 to about 95% by weight of the toner, from about 30 to about 90% by weight of the toner, or from about 35 to about 85% by weight of the toner.

[0041] In embodiments, the toner composition comprises an amorphous polyester in an amount of from about 73 to about 78 weight percent, based on the total weight of the toner composition. In a particular embodiment, the toner composition comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester, and the total amount of amorphous polyester, including both the first and second amorphous polyesters, is from about 73 to about 78 weight percent, based on the total weight of the toner composition.

[0042] The amorphous resin or combination of amorphous resins may have a glass transition temperature of about 30° C. to about 80° C., about 35° C. to about 70° C., or about 40° C. to about 65° C. The glass transition temperature may be measured using differential scanning calorimetry (DSC). The amorphous resin may have, for example, an Mn of about 1,000 to about 50,000, about 2,000 to about 25,000, or about 1,000 to about 10,000 when measured by GPC, and may have, for example, an Mw of about 2,000 to about 100,000, about 5,000 to about 90,000, about 10,000 to about 90,000, about 10,000 to about 30,000, or about 70,000 to about 100,000 when determined by GPC.

[0043] In embodiments, one, two, or more resins may be used. When two or more resins are used, the resins may be in any suitable ratio (e.g., weight ratio), such as, for example, about 1% (first resin) / 99% (second resin) to about 99% (first resin) / 1% (second resin), about 10% (first resin) / 90% (second resin) to about 90% (first resin) / 10% (second resin). When the resin includes a combination of an amorphous resin and a crystalline resin, the resin may be in a weight ratio, for example, about 1% (crystalline resin) / 99% (amorphous resin) to about 99% (crystalline resin) / 1% (amorphous resin), or about 10% (crystalline resin) / 90% (amorphous resin) to about 90% (crystalline resin) / 10% (amorphous resin). In some embodiments, the weight ratio of the resins is about 80% to about 60% amorphous resin and about 20% to about 40% crystalline resin, in such embodiments, the amorphous resin may be an amorphous resin, for example, a combination of two amorphous resins.

[0044] In embodiments, the toner comprises a core-shell configuration, the core comprises at least one amorphous polyester and at least one crystalline polyester, and the shell comprises at least one amorphous polyester.

[0045] In other embodiments, the toner comprises a core-shell configuration, the core comprises at least one amorphous polyester and at least one crystalline polyester, and the shell comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester.

[0046] In another embodiment, the toner comprises a first amorphous polyester comprising poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and a second amorphous polyester comprising poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0047] In embodiments, the toner core further comprises a third amorphous polyester and a fourth amorphous polyester. In embodiments, the third and fourth amorphous polyester resins are different. In embodiments, the third amorphous polyester resin is present in an amount of from about 1 to about 20, or from about 3 to about 18, or from about 5 to about 15 weight percent, based on the total weight of the toner. In embodiments, the fourth amorphous polyester resin is present in an amount of from about 1 to about 20, or from about 3 to about 18, or from about 5 to about 15 weight percent, based on the total weight of the toner. In certain embodiments, the third amorphous polyester is poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and the fourth amorphous polyester is poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0048] In embodiments, the third amorphous polyester resin and the fourth amorphous polyester resin are present in the toner core in equal amounts.

[0049] In a particular embodiment, the toner comprises a core-shell configuration, the shell comprises a resin, and the shell resin comprises about 28 weight percent of the toner composition, based on the total weight of the toner composition including the core and shell. The shell resin or resins comprising 28 percent of the toner can be selected from any of the resins described herein. In an embodiment, the shell resin comprises 28 percent of the toner particle mass, and in an embodiment, the shell resin comprises a combination of two different amorphous polyesters, and in an embodiment, the shell comprises a combination of a low molecular weight amorphous polyester and a high molecular weight amorphous polyester.

[0050] In an embodiment, the amorphous resin may include at least one low molecular weight amorphous polyester resin. Low molecular weight amorphous polyester resins available from a number of sources may have a variety of melting points, for example, from about 30°C to about 120°C, in embodiments, from about 75°C to about 115°C, in embodiments, from about 100°C to about 110°C, or in embodiments, from about 104°C to about 108°C. As used herein, low molecular weight amorphous polyester resins have a number average molecular weight (Mn), for example, as measured by gel permeation chromatography (GPC), of about 1,000 to about 10,000, in embodiments, about 2,000 to about 8,000, in embodiments, about 3,000 to about 7,000, and in embodiments, about 4,000 to about 6,000. The weight average molecular weight (Mw) of the resin, as determined by GPC using a polystyrene standard, is 50,000 or less, for example, in an embodiment, about 2,000 to about 50,000, in an embodiment, about 3,000 to about 40,000, in an embodiment, about 10,000 to about 30,000, and in an embodiment, about 18,000 to about 21,000. The molecular weight distribution (Mw / Mn) of the low molecular weight amorphous resin is, for example, about 2 to about 6, and in an embodiment, about 3 to about 4. The low molecular weight amorphous polyester resin may have an acid value of about 8 to about 20 mg KOH / g, in an embodiment, about 9 to about 16 mg KOH / g, and in an embodiment, about 10 to about 14 mg KOH / g.

[0051] In embodiments, the toner of the present disclosure may also include at least one high molecular weight branched or crosslinked amorphous polyester resin. The high molecular weight resin may, in embodiments, include, for example, a branched amorphous resin or amorphous polyester, a crosslinked amorphous resin or amorphous polyester, or a mixture thereof, or a crosslinked non-crosslinked amorphous polyester resin. In accordance with the present disclosure, from about 1% to about 100% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked, and in embodiments, from about 2% to about 50% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0052] As used herein, the high molecular weight amorphous polyester resin may have, for example, a number average molecular weight (Mn) as measured by gel permeation chromatography (GPC) of, for example, about 1,000 to about 10,000, in embodiments, about 2,000 to about 9,000, in embodiments, about 3,000 to about 8,000, and in embodiments, about 6,000 to about 7,000. The weight average molecular weight (Mw) of the resin is greater than 55,000, for example, about 55,000 to about 150,000, in embodiments, about 60,000 to about 100,000, in embodiments, about 63,000 to about 94,000, and in embodiments, about 68,000 to about 85,000, as determined by GPC using polystyrene standards. The polydispersity index (PD), as measured by GPC against standard polystyrene resin standards, is greater than about 4, such as, for example, greater than about 4, in embodiments from about 4 to about 20, in embodiments from about 5 to about 10, and in embodiments from about 6 to about 8. The PD index is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Low molecular weight amorphous polyester resins can have an acid number of about 8 to about 20 mg KOH / g, in embodiments from about 9 to about 16 mg KOH / g, and in embodiments from about 11 to about 15 mg KOH / g. High molecular weight amorphous polyester resins available from a number of sources can have a variety of melting points, for example, from about 30°C to about 140°C, in embodiments from about 75°C to about 130°C, in embodiments from about 100°C to about 125°C, and in embodiments from about 115°C to about 121°C.

[0053] High molecular weight amorphous resins available from a number of sources can have a variety of onset glass transition temperatures (Tg), as measured by differential scanning calorimetry (DSC), for example, from about 40° C. to about 80° C., in embodiments from about 50° C. to about 70° C., and in embodiments, from about 54° C. to about 68° C. In embodiments, the linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0054] High molecular weight amorphous polyester resins can be prepared by branching or crosslinking linear polyester resins. Branching agents such as trifunctional or polyfunctional monomers can be utilized, which typically increase the molecular weight and polydispersity of the polyester. Suitable branching agents include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, diglycerol, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, combinations thereof, and the like. These branching agents can be utilized in effective amounts of about 0.1 mole % to about 20 mole %, based on the starting diacid or diester used to make the resin.

[0055] Compositions containing modified polyester resins having polybasic carboxylic acids that may be utilized to form high molecular weight polyester resins include those disclosed in U.S. Pat. No. 3,681,106, as well as branched or crosslinked polyesters derived from polyacids or alcohols as exemplified in U.S. Pat. Nos. 4,863,825, 4,863,824, 4,845,006, 5,143,809, 5,057,596, 4,988,794, 4,981,939, 4,980,448, 4,933,252, 4,931,370, 4,917,983, and 4,973,539, the disclosures of each of which are incorporated herein by reference in their entirety.

[0056] In embodiments, crosslinked polyester resin can be made from linear amorphous polyester resin, which contains unsaturated sites that can react under free radical conditions.Examples of such resins include those disclosed in U.S. Patent Nos. 5,227,460, 5,376,494, 5,480,756, 5,500,324, 5,601,960, 5,629,121, 5,650,484, 5,750,909, 6,326,119, 6,358,657, 6,359,105 and 6,593,053, the disclosures of each of which are incorporated herein by reference in their entirety. In embodiments, suitable unsaturated polyester-based resins can be prepared from diacids and / or anhydrides such as, for example, maleic anhydride, terephthalic acid, trimellitic acid, fumaric acid, and the like, and combinations thereof, and diols such as, for example, bisphenol A ethylene oxide adducts, bisphenol A propylene oxide adducts, and the like, and combinations thereof. In embodiments, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0057] In an embodiment, the crosslinked branched polyester may be utilized as a high molecular weight amorphous polyester resin. Such a polyester resin may be formed from at least two pregel compositions comprising at least one polyol having two or more hydroxyl groups or esters thereof, at least one aliphatic or aromatic polyfunctional acid or esters thereof or mixtures thereof having at least three functional groups, and optionally at least one long chain aliphatic carboxylic acid or esters thereof, or aromatic monocarboxylic acid or esters thereof, or mixtures thereof. The two components may be reacted to substantially completion in separate vessels to produce a first composition comprising a pregel having carboxyl end groups in a first reactor, and a second composition comprising a pregel having hydroxyl end groups in a second reactor. The two compositions may then be mixed to produce a crosslinked branched polyester high molecular weight resin. Examples of such polyesters and methods for their synthesis include those disclosed in U.S. Pat. No. 6,592,913, the disclosure of which is incorporated herein in its entirety by reference.

[0058] Suitable polyols may contain from about 2 to about 100 carbon atoms and contain at least two or more hydroxyl groups, or esters thereof. The polyols may include glycerol, pentaerythritol, polyglycols, polyglycerols, and the like, or mixtures thereof. The polyols may include glycerol. Suitable esters of glycerol include glycerol palmitate, glycerol sebacate, glycerol adipate, triacetin tripropionin, and the like. The polyol may be present in an amount of from about 20% to about 30% by weight of the reaction mixture, in embodiments from about 22% to about 26% by weight of the reaction mixture.

[0059] Aliphatic polyfunctional acids having at least two functional groups may include saturated and unsaturated acids or esters thereof containing from about 2 to about 100 carbon atoms, in some embodiments from about 4 to about 20 carbon atoms. Other aliphatic polyfunctional acids include malonic acid, succinic acid, tartaric acid, malic acid, citric acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, sebacic acid, and the like, or mixtures thereof. Other aliphatic polyfunctional acids that may be utilized include dicarboxylic acids containing C3-C6 cyclic structures and positional isomers thereof, including cyclohexane dicarboxylic acid, cyclobutane dicarboxylic acid, or cyclopropane dicarboxylic acid.

[0060] Aromatic polyfunctional acids having at least two functional groups that may be utilized include terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and naphthalene 1,4-, 2,3-, and 2,6-dicarboxylic acids.

[0061] The aliphatic or aromatic polyfunctional acid may be present in an amount from about 40% to about 65% by weight of the reaction mixture, in embodiments from about 44% to about 60% by weight of the reaction mixture.

[0062] Long chain aliphatic carboxylic acids or aromatic monocarboxylic acids may include those containing from about 12 to about 26 carbon atoms, in embodiments from about 14 to about 18 carbon atoms, or esters thereof. Long chain aliphatic carboxylic acids may be saturated or unsaturated. Suitable saturated long chain aliphatic carboxylic acids may include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cerotic acid, and the like, or combinations thereof. Suitable unsaturated long chain aliphatic carboxylic acids may include dodecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, and the like, or combinations thereof. Aromatic monocarboxylic acids may include benzoic acid, naphthoic acid, and substituted naphthoic acids. Suitable substituted naphthoic acids may include naphthoic acids substituted with linear or branched alkyl groups containing from about 1 to about 6 carbon atoms, such as 1-methyl-2 naphthoic acid and / or 2-isopropyl-1-naphthoic acid. The long chain aliphatic carboxylic acid or aromatic monocarboxylic acid may be present in an amount from about 0% to about 70% by weight of the reaction mixture, in embodiments from about 15% to about 30% by weight of the reaction mixture.

[0063] If desired, additional polyols, ionic species, oligomers, or derivatives thereof may be used. These additional glycols or polyols may be present in an amount of about 0% to about 50% by weight of the reaction mixture. Additional polyols or derivatives thereof may include propylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, triacetin, trimethylolpropane, pentaerythritol, cellulose ethers, cellulose acetate, cellulose esters such as sucrose isobutyl acetate, and the like.

[0064] In embodiments, the crosslinked branched polyester of the high molecular weight amorphous polyester resin may include that resulting from the reaction of dimethyl terephthalate, 1,3-butanediol, 1,2-propanediol, and pentaerythritol.

[0065] In embodiments, a high molecular weight resin, such as a branched polyester, may be present on the surface of the toner particles of the present disclosure. The high molecular weight resin on the surface of the toner particles may also be particulate in nature, and may be high molecular weight resin particles having diameters of from about 100 nanometers to about 300 nanometers, in embodiments from about 110 nanometers to about 150 nanometers.

[0066] The amount of high molecular weight amorphous polyester resin in the toner particles of the present disclosure, in any core, any shell, or both, may be from about 25% to about 50% by weight of the toner, in embodiments from about 30% to about 45% by weight, and in other embodiments, alternatively from about 40% to about 43% by weight of the toner (i.e., toner particles excluding external additives and water).

[0067] The ratio of crystalline resin to low molecular weight amorphous resin to high molecular weight amorphous polyester resin may range from about 1:1:98 to about 98:1:1 to about 1:98:1, in embodiments from about 1:5:5 to about 1:9:9, and in embodiments from about 1:6:6 to about 1:8:8.

[0068] The resin(s) in the toner may have acid groups that may be present at the end of the resin. Possible acid groups include carboxylic acid groups. The number of carboxylic acid groups may be controlled by adjusting the materials and reaction conditions utilized to form the resin. In embodiments, the resin may be a polyester resin having an acid value of about 2 mg KOH / g resin to about 200 mg KOH / g, about 5 mg KOH / g resin to about 50 mg KOH / g resin, or about 5 mg KOH / g resin to about 15 mg KOH / g resin. The acid-containing resin may be dissolved in a tetrahydrofuran solution. The acid value may be detected by titration with a KOH / methanol solution containing phenolphthalein as an indicator. The acid value may then be calculated based on the equivalent amount of KOH / methanol required to neutralize all the acid groups on the resin identified as the titration endpoint.

[0069] Coloring agent.

[0070] The toner may optionally contain a colorant. Any suitable or desired surfactant may be selected. In embodiments, the colorant may be a pigment, a dye, a mixture of pigment and dye, a mixture of pigments, a mixture of dyes, or the like. For brevity, as used herein, the term "colorant" is meant to encompass such colorants, dyes, pigments, and mixtures unless specified as a particular pigment or other colorant component. In embodiments, the colorant comprises a pigment, a dye, a mixture thereof, in embodiments, carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, or a mixture thereof, in an amount of about 1 weight percent to about 25 weight percent based on the total weight of the toner composition. In embodiments, the colorant is selected from cyan, magenta, yellow, black, or a combination thereof. In certain embodiments, the colorant comprises a combination of carbon black and cyan. It is understood that other useful colorants will be readily apparent based on this disclosure.

[0071] In certain embodiments, the colorant comprises a pigment present in an amount of from about 5 to about 8 weight percent, based on the total weight of the toner composition.

[0072] Useful colorants include Paliogen® Violet 5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Uhlrich), Permanent Violet VT2645 (Paul Uhlrich), Heliogen® Green L8730 (BASF), Argyle Green XP-111-S (Paul Uhlrich), Brilliant Green Toner GR 0991 (Paul Uhlrich), Lithol® Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD Red (Aldrich), Lithol® Rubine Toner (Paul Uhlrich), Lithol® Scarlet 4440, NBD3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Uhlrich), Uhlrich), Oracet® Pink RF (Ciba Geigy), Paliogen® Red 3340 and 3871K (BASF), Lithol® Fast Scarlet L4300 (BASF), Heliogen® Blue D6840, D7080, K7090, K6910, and L7020 (BASF), Sudan Blue OS (BASF), Neopen® Blue FF4012 (BASF), PV Fast Blue B2G01 (American Hoechst), Irgalite® Blue BCA (Ciba Geigy), Paliogen® Blue 6470 (BASF), Sudan II, III, and IV (Matheson, Coleman, Bell), Sudan Orange (Aldrich), Sudan Orane 220 (BASF), Paliogen® Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlrich), Paliogen® Yellow 152 and 1560 (BASF), Lithol® FastYellow 0991K (BASF), Paliotol® Yellow 1840 (BASF), Novaperm® Yellow FGL (Hoechst), Permanent Yellow YE 0305 (Paul Uhlrich), Lumogen® Yellow 00790 (BASF), Suco-Gelb 1250 (BASF), Suco-Yellow D1355 (BASF), Suco Fast Yellow D1165, D1355, and D1351 (BASF), Hostaperm® Pink E (Hoechst), Fanal® Pink D4830 (BASF), Cinquasia® Magenta (DuPont), Paliogen® Black L9984 (BASF), Pigment Black K801 (BASF), and in particular carbon blacks such as REGAL® 330 (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals), or mixtures thereof.

[0073] Additional useful colorants include pigments in aqueous dispersions, such as those commercially available from Sun Chemical, e.g., SUNSPERSE® BHD 6011X (Blue 15 Type), SUNSPERSE® BHD9312X (Pigment Blue 15 74160), SUNSPERSE® BHD6000X (Pigment Blue 15:3 74160), SUNSPERSE® GHD9600X and GHD6004X (Pigment Green7 74260), SUNSPERSE® QHD6040X (Pigment Red122 73915), SUNSPERSE® RHD 9668X (Pigment Red185 12516), SUNSPERSE® RHD9365X and 9504X (Pigment Red57 15850:1), SUNSPERSE® YHD 6005X (Pigment Yellow 83 21108), FLEXIVERSE® YFD 4249 (Pigment Yellow 17 21105), SUNSPERSE® YHD 6020X and 6045X (Pigment Yellow 74 11741), SUNSPERSE® YHD 600X and 9604X (Pigment Yellow 14 21095), FLEXIVERSE® LFD 4343 and LFD 9736 (Pigment Black 7 77226), and the like, or mixtures thereof. Other useful water-based colorant dispersions include those commercially available from Clariant, such as HOSTAFINE® Yellow GR, HOSTAFINE® Black T and Black TS, HOSTAFINE® Blue B2G, HOSTAFINE® Rubine F6B, and magenta dry pigments such as Toner Magenta 6BVP2213 and Toner Magenta EO2, which can be dispersed in water and / or surfactants prior to use.

[0074] Other useful colorants include magnetites such as Mobay magnetite M08029, M98960, Columbian magnetite, MAPICO® BLACKS, and surface treated magnetites; Pfizer magnetite CB4799, CB5300, CB5600, MXC6369, Bayer magnetite, BAYFERROX® 8600, 8610; Northern Pigments magnetite, NP-604, NP-608; Magnox magnetite TMB-100 or TMB-104, or mixtures thereof. Additional examples of pigments include the phthalocyanines HELIOGEN® BLUE L6900, D6840, D7080, D7020, PYLAM® OIL BLUE, PYLAM® OIL YELLOW, PIGMENT BLUE 1, PIGMENT VIOLET 1, PIGMENT RED 48, LEMON CHROME YELLOW DCC 1026, ED. TOLUIDINE RED, and BON RED C, all available from Paul Uhlrich & Company, Inc., NOVAPERM® YELLOW FGL, HOSTAPERM® PINK E, and CINQUASIA® MAGENTA from Hoechst (DuPont), and the like. Examples of magenta include 2,9-dimethyl-substituted quinacridone and anthraquinone dyes identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dyes identified in the Color Index as CI 26050, CI Solvent Red 19, and the like, and mixtures thereof. Examples of cyan include copper tetra(octadecylsulfonamido)phthalocyanine, x-copper phthalocyanine pigments listed in the Color Index as CI 74160, DI 69810, Cl Pigment Blue, Anthrathrene Blue, identified in the Color Index as Special Blue X-2137, and the like, or mixtures thereof.Illustrative examples of yellows that may be selected include diarylide yellow 3,3-dichlorobenzideneacetoacetanilide, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, nitrophenylamine sulfonamide identified in the Color Index as Foron Yellow SE / GLN, CI Dispersed Yellow 33, 2,5-dimethoxy-4 sulfonanilide phenylazo-4'-chloro-2,4-dimethoxyacetoacetanilide, and Permanent Yellow FGL. Colored magnetites such as MAPICO® BLACK and mixtures of cyan components may also be selected as pigments.

[0075] Colorants, such as carbon black, cyan, magenta, and / or yellow colorants, are incorporated in an amount sufficient to impart the desired color to the toner. Generally, pigments or dyes are used in an amount of from about 1 weight percent to about 35 weight percent, or from about 5 weight percent to about 25 weight percent, or from about 5 weight percent to about 15 weight percent of the toner particles on a solids basis. However, amounts outside these ranges can be used in embodiments.

[0076] In an embodiment, the toner includes a carbon black colorant. Certain emulsion aggregation toners include NIPex® 35 non-oxidized low structure furnace black, while other emulsion aggregation toners use Regal® 330. A low conductivity carbon black, such as NIPex® 35, is selected to obtain the lowest possible dielectric loss. Carbon black is a semiconductor, so it is desirable to keep the carbon black as pure as possible. Heteroatoms such as oxygen and sulfur dope the carbon black semiconductor and increase the electrical conductivity. NIPex® 35 has a very high carbon content on the surface, greater than 99.5%, as determined by XPS, and a very low At% of O and S, less than 0.5% overall. The carbon black is very pure, with very little of the very strong dopants oxygen and sulfur on the surface, making it very low conductive. This provides a lower dielectric loss than a lower purity carbon black, such as Regal® 330, which has more than 1% oxygen and sulfur. The difference in purity is most dramatically shown by the carbon. The carbon black oxygen ratio is 499:1 in NIPex® 35 compared to 139:1 in Regal® 330.

[0077] In embodiments, the colorant comprises a combination of carbon black and cyan, in embodiments cyan PB 15:3.

[0078] In embodiments, the toner comprises 5-8 weight percent pigment. In a particular embodiment, the toner comprises 5-8 weight percent pigment, where the pigment is a combination of carbon black and cyan, 73-78 weight percent amorphous polyester, where the amorphous polyester comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester, and 6-7 weight percent crystalline polyester, where in an embodiment the crystalline polyester is a C10:C9 crystalline polyester, the weight percentages being based on the total weight of the toner composition. In an embodiment, the toner comprises a cyan pigment present at about 1 weight percent and a carbon black pigment present in an amount of about 6.9 weight percent, based on the total weight of the toner composition.

[0079] In other embodiments, the toner comprises a colorant comprising a combination of two or more of cyan, in embodiments, cyan PB15:3, magenta, in embodiments, one or both of magenta PR269 and magenta RE05, yellow, in embodiments, yellow PY74, and carbon black. In other embodiments, the toner comprises 5 to 8 percent pigment comprising a combination of two or more of cyan, in embodiments, cyan PB15:3, magenta, in embodiments, one or both of magenta PR269 and magenta RE05, yellow, in embodiments, yellow PY74, and carbon black.

[0080] Optional Additives.

[0081] If desired, the toner particles may contain other optional additives. For example, the toner may contain a positive or negative charge control agent in any desired or effective amount, in one embodiment at least about 0.1 weight percent of the toner, in another embodiment at least about 1 weight percent of the toner, in one embodiment up to about 10 weight percent of the toner, in another embodiment up to about 3 weight percent of the toner. Examples of suitable charge control agents include, but are not limited to, quaternary ammonium compounds such as alkylpyridinium halides, bisulfates, alkylpyridinium compounds, including those disclosed in U.S. Pat. No. 4,298,672, which is incorporated herein by reference in its entirety; organic sulfate and sulfonate compositions, including those disclosed in U.S. Pat. No. 4,338,390, which is incorporated herein by reference in its entirety; cetylpyridinium tetrafluoroborate; aluminum salts such as distearyl dimethyl ammonium methyl sulfate, BONTRON E84™ or E88™ (Hodogaya Chemical); and the like, and mixtures thereof. Such charge control agents may be applied simultaneously with the shell resin or after application of the shell resin.

[0082] The toner particles may also be blended with external additive particles, including flow aid additives, which may be present on the surface of the toner particles. Examples of these additives include, but are not limited to, metal oxides, such as titanium oxide, silicon oxide, tin oxide, and mixtures thereof; colloidal and amorphous silicas, such as AEROSIL®, metal salts, and fatty acid metal salts, including zinc stearate, aluminum oxide, cerium oxide, and mixtures thereof. Each of these external additives may be present in any desired or effective amount, in embodiments at least about 0.1 weight percent of the toner, or at least about 0.25 weight percent of the toner, or up to about 5 weight percent of the toner, or up to about 3 weight percent of the toner. Suitable additives include, but are not limited to, those disclosed in U.S. Pat. Nos. 3,590,000 and 6,214,507, each of which is incorporated herein by reference. Such additives may be applied simultaneously with the shell resin or after application of the shell resin.

[0083] Emulsion aggregation polyester toners typically use about 7.2 parts per hundred (pph) of TaycaPower B2060 surfactant, a sodium salt of dodecylbenzenesulfonate, as a dispersing agent for dispersing NIPex® carbon black in the toner.

[0084] In embodiments, the amount of TaycaPower surfactant can be reduced to only 2 pph in the pigment dispersion with the addition of 3.2 pph of DEMOL SN-B, a polymeric surfactant of butyl naphthalene sulfonic acid / 2-naphthalene sulfonic acid / formaldehyde, sodium salt (Kao Corporation). The dispersion can then be used to make a toner.

[0085] Similar products can be used to reduce dielectric loss, such as DEMOL M, sodium allylsulfonate formaldehyde condensate powder, DEMOL SS-L, sodium allylsulfonate formaldehyde condensate, DEMOL N, DEMOL RN, DEMOL T and DEMOL T-45 sodium naphthalenesulfonate formaldehyde condensate powder, DEMOL NL sodium naphthalenesulfonate formaldehyde condensate liquid. Other manufacturers offer similar sulfonate formaldehyde condensates, such as 1-Naphthalenesulfonic Acid, Formaldehyde Polymer, Sodium Salt CAS NO. 32844-36-3 available from Anyang Double Circle Auxiliary Co., LTD (China) and Sodium Naphthalenesulfonate Formaldehyde CAS NO. 9084-06-4 available from Chemtrade International (China).

[0086] Coagulant.

[0087] The toner herein may also contain a coagulant, such as a monovalent metal coagulant, a divalent metal coagulant, a polyionic coagulant, etc. A variety of coagulants are known in the art. As used herein, "polyionic coagulant" refers to a coagulant that is a salt or oxide, such as a metal salt or metal oxide, formed from a metal species having a valence of at least 3, preferably at least 4 or 5. Suitable coagulants therefore include, for example, aluminum-based coagulants, such as aluminum polyhalides, such as aluminum fluoride and polyaluminum chloride (PAC), polyaluminum silicates, such as polyaluminum sulfosilicate (PASS), polyaluminum hydroxide, and polyaluminum phosphate. Other suitable coagulants include, but are not limited to, tetraalkyl titanates, dialkyl tin oxides, tetraalkyl tin oxide hydroxides, dialkyl tin oxide hydroxides, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxides, tin oxides, dibutyl tin oxides, dibutyl tin oxide hydroxides, tetraalkyl tins, combinations thereof, and the like. When the coagulant is a polyion coagulant, the coagulant can have any desired number of polyion atoms present. For example, in embodiments, suitable polyaluminum compounds can have from about 2 to about 13, or from about 3 to about 8 aluminum ions present in the compound.

[0088] Such coagulants can be incorporated into the toner particles during particle aggregation. Thus, the coagulant can be present in the toner particles in an amount of from about 0 to about 5 percent by weight, or from about 0 to about 3 percent by weight, of the toner particles, excluding external additives, on a dry weight basis.

[0089] Surfactant.

[0090] When preparing toner by emulsion aggregation procedure, one or more surfactants may be used in the process. Suitable surfactants include anionic, cationic, and nonionic surfactants. In embodiments, the use of anionic and nonionic surfactants helps to stabilize the aggregation process in the presence of coagulants that may otherwise lead to aggregation instability.

[0091] Anionic surfactants include sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzene alkyl sulfates and sulfonates, abietic acid, and NEOGEN® brand anionic surfactants. Examples of suitable anionic surfactants are NEOGEN® RK available from Daiichi Kogyo Seiyaku Co. Ltd., or TAYCA POWER BN2060 from Tayca Corporation (Japan), which is composed mainly of branched sodium dodecylbenzenesulfonate.

[0092] Examples of cationic surfactants include dialkylbenzene alkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkyl benzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, ethyl pyridinium bromide, C12, C15, C17 trimethyl ammonium bromide, halide salts of quaternized polyoxyethyl alkyl amines, dodecyl benzyl triethyl ammonium chloride. MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, SANISOL (benzalkonium chloride) available from Kao Chemicals, etc. An example of a suitable cationic surfactant is SANISOL B-50 available from Kao Corp., which is mainly composed of benzyl dimethyl alkonium chloride.

[0093] Examples of nonionic surfactants include polyvinyl alcohol, polyacrylic acid, methalose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol available from Rhone-Poulenc Inc. 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. An example of a suitable nonionic surfactant is ANTAROX® 897 available from Rhone-Poulenc Inc. which consists primarily of alkylphenol ethoxylates.

[0094] Examples of bases used to raise the pH and thus ionize the aggregated particles and provide stability, thereby preventing size growth of the aggregates, can be selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, cesium hydroxide, etc., among others.

[0095] Examples of acids that can be used include, for example, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, trifluoroacetic acid, succinic acid, salicylic acid, and the like, which, in embodiments, are used in diluted form in the range of about 0.5 to about 10 weight percent water, or in the range of about 0.7 to about 5 weight percent water.

[0096] In an embodiment, a naphthalene sulfonic acid polymer surfactant is selected.

[0097] Toner Preparation.

[0098] In embodiments, the toner of the present invention is prepared by an emulsion aggregation (EA) process, for example, by a process comprising agglomerating a mixture of one or more emulsions, in embodiments each emulsion comprising a resin, in embodiments the emulsion comprising a combination of resins, in embodiments the emulsion comprising a first amorphous polyester, the emulsion comprising a second amorphous polyester, the emulsion comprising a crystalline polyester, the emulsion comprising a paraffin wax, and the emulsion comprising a polymethylene wax, with a pigment dispersion, and then combining the mixture. In embodiments, the crystalline polyester is provided in a separate emulsion. In embodiments, the crystalline polyester is a C10:C9 polyester. The first and second amorphous polyesters may be utilized as separate aqueous dispersions. In embodiments, a latex comprising the first amorphous polyester, the second amorphous polyester, and the crystalline polyester is used.

[0099] In embodiments, the process herein includes combining a first wax, a second wax different from the first wax, where the first wax comprises a paraffin wax and the second wax comprises a polymethylene wax, at least one polyester, and an optional colorant, agglomerating to form aggregate particles, optionally adding a shell resin to form core-shell particles, and coalescing to form coalesced toner particles.

[0100] In an embodiment, the process herein includes combining a first amorphous polyester, a second amorphous polyester, where the first amorphous polyester and the second amorphous polyester are different, water, a paraffin wax, a polymethylene wax, a crystalline polyester, and a colorant to prepare a latex, optionally adding an aggregating agent to the latex, heating the latex to form aggregated particles, adding a shell resin to the aggregated toner particles, where the shell comprises at least one amorphous polyester, heating to coalesce the particles to form coalesced toner particles, and collecting the coalesced toner particles.

[0101] In an embodiment, the process herein further comprises adding a third amorphous polyester and a fourth amorphous polyester before the coalescence, and the third amorphous polyester, the third amorphous polyester and the fourth amorphous polyester are different. In an embodiment, the third amorphous polyester is poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and the fourth amorphous polyester is poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0102] The mixture may be homogenized, which may be accomplished by any suitable or desired process, such as by mixing at about 600 to about 6,000 revolutions per minute. Homogenization may be accomplished by any suitable means, including, for example, using an IKA ULTRA TURRAX TSO probe homogenizer.

[0103] Following preparation of the mixture, a flocculant may be added to the mixture. Alternatively, a crystalline polyester may be added to one or both of the amorphous polyester-containing latexes. Any suitable flocculant may be utilized. Suitable flocculants include, for example, aqueous solutions of divalent agents, such as inorganic cationic flocculants, such as polyaluminum halides, such as polyaluminum chloride (PAC), or the corresponding bromides, fluorides, or iodides, polyaluminum silicates, such as polyaluminum sulfosilicate (PASS), or water-soluble metal salts, including aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxyacid, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, and copper sulfate, or combinations thereof. The flocculant may be added to the mixture at a temperature below the glass-transition temperature (Tg) of the resin(s). The flocculant may be added to the mixture under homogenization.

[0104] The flocculant may be added to the mixture in any suitable or desired amount, in embodiments, for example, from about 0% to about 10% by weight of the resin, from about 0.2% to about 8% by weight of the resin, or from about 0.5% to about 5% by weight of the resin.

[0105] The particles of the mixture may be aggregated until a predetermined desired particle size is obtained. The predetermined desired size refers to the desired particle size obtained as determined prior to formation, and the particle size is monitored during the growth process until such particle size is reached. Samples may be taken during the growth process and analyzed for volume average particle size, for example, with a Coulter Counter. Thus, aggregation may proceed by maintaining an elevated temperature, or maintaining the temperature, for example, in embodiments, from about 30° C. to about 100° C., in embodiments, from about 30° C. to about 80° C., or in embodiments, from about 30° C. to about 50° C. The temperature may be maintained for a period of about 0.5 hours to about 6 hours, or in embodiments, from about 1 hour to about 5 hours, with stirring, to provide aggregated particles. Once the predetermined desired particle size is reached, a shell may be added. The volume average particle size of the particles prior to application of the shell may be, for example, from about 3 micrometers (μm) to about 10 μm, in embodiments, from about 4 μm to about 9 μm, or from about 6 μm to about 8 μm.

[0106] Shell resin.

[0107] As described herein, the toner may include a core-shell configuration. In embodiments, after aggregation but before coalescence, a resin coating may be applied to the aggregated particles to form a shell thereon. Any of the resins described above may be utilized in the shell. In embodiments, an amorphous polyester resin is utilized in the shell. In embodiments, the shell includes a first amorphous polyester and a second amorphous polyester. In embodiments, the shell includes a first amorphous polyester and a second amorphous polyester, and does not include any other resin. In embodiments, the two amorphous polyester resins are utilized in the shell, for example, in substantially equal amounts. In embodiments, a crystalline polyester resin and two different types of amorphous polyester resins are utilized in the core, and the same two types of amorphous polyester resins are utilized in the shell.

[0108] In certain embodiments, the toner compositions herein comprise polyester toner compositions and do not include other types of resins, in embodiments, do not include styrene, acrylate, or other resins.

[0109] In certain embodiments, the shell comprises a first amorphous polyester comprising poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and a second amorphous polyester comprising poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0110] The shell may be applied to the aggregated particles by using a shell resin in the form of an emulsion(s) as described above. Such an emulsion may be combined with the aggregated particles under conditions sufficient to form a coating on the aggregated particles. For example, formation of the shell on the aggregated particles may occur upon heating to a temperature of from about 30° C. to about 80° C., or from about 35° C. to about 70° C. Formation of the shell may occur over a period of from about 5 minutes to about 10 hours, or from about 10 minutes to about 5 hours.

[0111] Once the desired size of the toner particles is achieved, the pH of the mixture may be adjusted with a pH control agent, using a base, to a value of from about 3 to about 10, or in embodiments from about 5 to about 9. The pH adjustment may be utilized to freeze to stop toner growth. The base utilized to stop toner growth may include any suitable base, such as, for example, an alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, etc. In embodiments, a chelating agent, such as ethylene diamine tetraacetic acid (EDTA), may be added to assist in adjusting the pH to the desired value above. Other chelating agents may be used.

[0112] In embodiments, the size of the core-shell toner particles (before coalescence) may be from about 3 μm to about 10 μm, from about 4 μm to about 10 μm, or from about 6 μm to about 9 μm.

[0113] Merge.

[0114] Following aggregation to the desired particle size and optional application of a shell, the particles may then be coalesced to the desired final shape, for example by heating the mixture to a temperature of about 45°C to about 150°C, about 55°C to about 99°C, or about 60°C to about 90°C (which may be equal to or higher than the glass transition temperature of the resin utilized to form the toner particles). Heating may be continued, or the pH of the mixture may be adjusted (e.g., reduced) over a period of time to reach the desired circularity. The period may be from about 1 hour to about 5 hours, or from about 2 hours to about 4 hours. Various buffers may be used during coalescence. The total period of coalescence may be from about 1 hour to about 9 hours, from about 1 hour to about 8 hours, or from about 1 hour to about 5 hours. Agitation may be utilized during coalescence, for example, from about 20 rpm to about 1000 rpm, or from about 30 rpm to about 800 rpm.

[0115] After aggregation and / or coalescence, the mixture may be cooled to room temperature. Cooling may be rapid or slow, as desired. A suitable cooling process may include introducing cold water into a jacket around the reactor. After cooling, the toner particles may be sieved through a sieve of the desired size, filtered, washed with water, and then dried. Drying may be accomplished by any suitable drying process, including, for example, freeze drying.

[0116] Toner characteristics.

[0117] In embodiments, the dry toner particles, excluding external surface additives, exhibit one or more of the following characteristics:

[0118] (1) A volume average particle size of about 5.0 μm to about 10.0 μm, about 5.0 μm to about 9.0 μm, or about 5.0 μm to about 7.0 μm.

[0119] (2) a mean geometric size distribution (GSDn) and / or a volume mean geometric size distribution (GSDv) of about 1.05 to about 1.55, about 1.10 to about 1.40, or about 1.10 to about 1.35.

[0120] (3) A circularity of about 0.90 to about 1.00, or about 0.92 to about 0.99, or about 0.95 to about 0.98.

[0121] These properties may be measured according to the techniques described in the examples below, or according to techniques known to those skilled in the art.

[0122] The toners of the present invention may have excellent charging properties under various relative humidity (RH) conditions, for example, in the low humidity zone (J-zone) of 21.1° C. / 10% RH and in the high humidity zone (A-zone) of about 28° C. / 85% RH. Similarly, the toners of the present invention may have excellent flow and blocking properties. In embodiments, the toner particles, excluding external surface additives, exhibit one or more of the following properties:

[0123] (4) An A-zone charge-to-mass ratio (Q / M) of about 1 μC / g to about 20 μC / g, about 5 μC / g to about 15 μC / g, or about 10 μC / g to about 15 C / g.

[0124] (5) A J-zone charge-to-mass ratio (Q / M) of about 40 μC / g to about 80 μC / g, about 40 μC / g to about 70 μC / g, or about 50 μC / g to about 70 μC / g.

[0125] In embodiments, the toner particles containing the external surface additives exhibit one or more of the following characteristics.

[0126] (6) A dielectric loss (x1000) in the range of about 20 to about 40, about 22 to about 38, or about 23 to about 35.

[0127] Toners of the present invention may have excellent fixing properties as reflected by one or more of a gloss value of 40, peak gloss, low temperature offset temperature, high temperature offset temperature, and gloss temperature at which the minimum fixation temperature (MFT) is reached. In embodiments, the toner particles including the external surface additives exhibit an MFT of about 130° C. or less, about 128° C. or less, about 127° C. or less, or an MFT in the range of about 120° C. to about 130° C.

[0128] Developers and carriers.

[0129] The toner of the present invention may be formulated into a developer composition. The developer composition can be prepared by mixing the toner of the present disclosure with known carrier particles, including coated carriers such as steel, ferrite, etc. Such carriers include those disclosed in U.S. Pat. Nos. 4,937,166 and 4,935,326, the entire disclosures of each of which are incorporated herein by reference.

[0130] The toner may be present in the carrier in an amount of about 1% to about 15% by weight, about 2% to about 8% by weight, or about 4% to about 6% by weight. The carrier particles may also include a core having a polymer coating, such as polymethylmethacrylate (PMMA), in which a conductive component, such as conductive carbon black, is dispersed. Carrier coatings include silicone resins, such as methylsilsesquioxane, fluoropolymers, such as polyvinylidene fluoride, mixtures of resins that are not adjacent in the triboelectric series, such as polyvinylidene fluoride and acrylic, thermosetting resins, such as acrylic, combinations thereof, and other known components.

[0131] Apply.

[0132] The toner of the present invention may be used in a variety of electrophotographic processes and with a variety of electrophotographic printers. The electrophotographic imaging process includes, for example, preparing an image in an electrophotographic printer that includes a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fusing component. In embodiments, the developing component may include a developer prepared by mixing a carrier with any of the toners described herein. The electrophotographic printer may include a high speed printer, a black and white high speed printer, a color printer, and the like. Once an image is formed with the toner / developer, the image may then be transferred to an image receiving medium, such as paper. A fuser roll member may be used to fuse the toner to the image receiving medium by using heat and pressure. The use of the toner of the present invention in an electrophotographic printing process can provide printed images having the properties described herein and other desirable properties.

[0133] Toners of the present invention find use in other applications such as powder coating applications in which a powder spray gun (eg, a tribo gun) containing any of the toners of the present invention is used to deliver the toner to a substrate.

[0134] In embodiments, the process herein includes forming an image with the toner described herein using an electrophotographic printer, transferring the image including the toner to an image receiving medium, and fusing the toner to the image receiving medium to form a toner image. EXAMPLES

[0135] The following examples are presented to further define the various species of the present disclosure. These examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. Also, unless otherwise stated, parts and percentages are by weight.

[0136] Toner particles were prepared using an emulsion aggregation coalescence process as follows.

[0137] The core polyester latex, pigment, wax, and deionized water were mixed in a reactor. The pH was adjusted to 4.2 using a nitric acid solution.

[0138] The flocculant was added and the slurry was homogenized.

[0139] The mixture was heated to 45-50°C for agglomeration. Particle size (D50v) was monitored using a Coulter Multisizer-3 instrument.

[0140] With a D50v of about 4.9 to 5.1 μm (micrometers) μm, the shell latex was added to the mixture using a metering pump to achieve a D50v of about 5.8 to 6.0 μm.

[0141] The reaction was quenched by adding sodium hydroxide solution and a chelating agent to raise the pH to about 7.8-8.2.

[0142] The mixture was heated to 85-90° C. for coalescence. Sodium hydroxide solution was slowly added to the slurry during the rise to maintain a pH of 7.8-8.2.

[0143] The mixture was coalesced and held, and the circularity was monitored using an FPIA Sysmex 3000 instrument. In some embodiments, during coalescence, the pH was lowered by adding an acid, such as a nitric acid solution, to increase the rate of coalescence.

[0144] Once a circularity of about 0.972 was achieved, the mixture was passed through a heat exchanger to quickly reduce the temperature below the Tg of the toner.

[0145] The toner was then filtered, washed and dried using typical methods.

[0146] Five runs were performed to quantify the properties of the different wax formulations, as shown in Table 1. [Table 1]

[0147] The results show that hot offset was significantly affected by the total amount of wax, and to a lesser extent, by the type of wax used. Compared to Comparative Toner A, each of the Example toners showed improvement in hot offset.

[0148] Thus, the toner composition of the present invention using dual waxes including paraffin wax and polymethylene wax provided improved high temperature offset over conventional toners. The toner of the present invention also meets ultra-fine particle (UFP) emission targets. Examples 6 to 9

[0149] Examples 6, 7, 8, and 9, containing cyan, magenta, yellow, and black toners, respectively, were prepared according to the process of Examples 1-5 above, except that they had the compositions shown in Table 2. [Table 2] Examples 10 to 11

[0150] Examples 10 and 11, which include yellow toners, were prepared according to the process of Examples 1-5 above, except that they had the compositions shown in Table 3. [Table 3]

[0151] Toner data was obtained by wet deposition of the toner and then analyzed using an X-Rite Spectrodensitometer.

[0152] Comparative Toner A was prepared having the same ingredients as Example 1, except that it contained only polymethylene wax in an amount of 9%.

[0153] Table 4 shows the hot offset temperature results for Comparative Toner A and Examples 1-5. [Table 4] [Table 5]

[0154] It will be understood that various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into other different systems or applications. Also, various presently unanticipated or unprecedented alternatives, modifications, variations, or improvements may occur to those skilled in the art, which are also intended to be encompassed by the following "claims." Unless specifically recited in the claims, no particular order, number, position, size, shape, angle, color, or material of the steps or components of the claims should be implied or implied from this specification or any other claims. Yet another aspect of the present invention may be as follows. [1] a first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; A toner composition wherein said second wax comprises a polymethylene wax. [2] The toner composition according to [1], wherein the toner composition contains a total amount of wax, including the first wax and the second wax, in an amount of about 9 to about 12 weight percent based on the total weight of the toner composition. [3] The toner composition according to [1], wherein the paraffin wax is present in an amount of about 25 to about 75 weight percent based on the total weight of the paraffin wax and the polymethylene wax. [4] The toner composition according to [1] above, wherein the first wax comprises a paraffin wax having a peak melting point of about 60 to about 80°C. [5] The toner composition according to [1], wherein the first wax is a paraffin wax having a carbon / oxygen ratio of greater than about 50. [6] The toner composition according to [1] above, wherein the first wax is a paraffin wax having a number average molecular weight of about 400 g / mole to 600 g / mole. [7] The toner composition according to [1] above, wherein the second wax is a polymethylene wax having a number average molecular weight of about 600 g / mole to 800 g / mole. [8] The toner composition according to [1] above, wherein the at least one polyester comprises at least one amorphous polyester and at least one crystalline polyester. [9] The toner composition according to [1], wherein the at least one polyester comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester.

[10] The toner composition according to [1], wherein the toner composition comprises an amorphous polyester present in an amount of about 73 to about 78 weight percent based on the total weight of the toner composition.

[11] The toner composition according to [1], wherein the at least one polyester comprises a first amorphous polyester, a second amorphous polyester different from the first amorphous polyester, and a crystalline polyester.

[12] The toner composition according to [1], wherein the toner composition comprises a crystalline polyester present in an amount of about 6 to about 7 weight percent based on the total weight of the toner composition.

[13] Further comprising a core-shell structure, the core comprises at least one amorphous polyester and at least one crystalline polyester; The toner composition according to claim 1, wherein the shell comprises at least one amorphous polyester.

[14] Further comprising a core-shell structure, the core comprises at least one amorphous polyester and at least one crystalline polyester; The toner composition according to claim 1, wherein the shell comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester.

[15] Further comprising a core-shell structure, The toner composition according to claim 1, wherein the core comprises a first amorphous polyester comprising poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and a second amorphous polyester comprising poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[16] Further comprising a core-shell structure, The core comprises a crystalline polyester of the formula:

change

[17] The toner composition according to [1], wherein the optional colorant is present and is selected from cyan, magenta, yellow, black, or combinations thereof.

[18] The toner composition according to [1], wherein the optional colorant is present, and the colorant comprises a pigment present in an amount of about 5 to about 8 weight percent, based on the total weight of the toner composition.

[19] The toner composition according to [1], wherein the optional colorant is present and the colorant comprises a combination of carbon black and cyan.

[20] Further comprising a core-shell structure, 2. The toner composition of claim 1, wherein the shell comprises a resin, the shell resin comprising approximately 28 weight percent of the toner composition, based on the total weight of the toner composition including the core and shell.

Claims

1. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; A toner composition, wherein said at least one polyester comprises at least one amorphous polyester and at least one crystalline polyester.

2. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; The toner composition, wherein the at least one polyester comprises a first amorphous polyester, a second amorphous polyester different from the first amorphous polyester, and a crystalline polyester.

3. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; A toner composition, wherein said toner composition comprises a crystalline polyester present in an amount of from 6 to 7 weight percent, based on the total weight of said toner composition.

4. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; Further comprising a core-shell configuration, the core comprises at least one amorphous polyester and at least one crystalline polyester; A toner composition, wherein the shell comprises at least one amorphous polyester.

5. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; Further comprising a core-shell configuration, the core comprises at least one amorphous polyester and at least one crystalline polyester; A toner composition, wherein the shell comprises a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester.

6. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; Further comprising a core-shell configuration, A toner composition, wherein the core comprises a first amorphous polyester comprising poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and a second amorphous polyester comprising poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

7. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; Further comprising a core-shell configuration, The core comprises a crystalline polyester of the formula: 【Chemistry 1】 wherein a and b each range from 1 to 12, and p ranges from 10 to 100.

8. A first wax; a second wax different from the first wax; At least one polyester; and an optional colorant, the first wax comprises a paraffin wax; The second wax comprises a polymethylene wax. the toner composition is free of styrene and acrylate; Further comprising a core-shell configuration, A toner composition, wherein said shell comprises a resin, said shell resin comprising 28 weight percent of said toner composition, based on the total weight of said toner composition including the core and shell.

9. 9. The toner composition of claim 1, wherein the toner composition comprises a total amount of waxes, including the first wax and the second wax, in an amount of 9 to 12 weight percent, based on the total weight of the toner composition.

10. The toner composition of any one of claims 1 to 8, wherein said paraffin wax is present in an amount of from 25 to 75 weight percent, based on the total weight of said paraffin wax and said polymethylene wax.

11. The toner composition of any one of claims 1 to 8, wherein the first wax comprises a paraffin wax having a peak melting point of 60 to 80°C.

12. The toner composition of any one of claims 1 to 8, wherein said first wax is a paraffin wax having a carbon / oxygen ratio of greater than 50.

13. The toner composition of any one of claims 1 to 8, wherein the first wax is a paraffin wax having a number average molecular weight of 400 grams / mole to 600 grams / mole.

14. The toner composition of any one of claims 1 to 8, wherein the second wax is a polymethylene wax having a number average molecular weight of 600 grams / mole to 800 grams / mole.

15. The toner composition of any one of claims 1 to 8, wherein the toner composition comprises an amorphous polyester present in an amount of from 73 to 78 weight percent, based on the total weight of the toner composition.

16. The toner composition of any one of claims 1 to 8, wherein said optional colorant is present and said colorant is selected from cyan, magenta, yellow, black, or combinations thereof.

17. 9. The toner composition of claim 1, wherein said optional colorant is present and comprises a pigment present in an amount of from 5 to 8 weight percent, based on the total weight of the toner composition.

18. The toner composition of any one of claims 1 to 8, wherein said optional colorant is present and said colorant comprises a combination of carbon black and cyan.

19. The toner composition of any one of claims 1 to 8, wherein the second wax is a Fischer-Tropsch wax.

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