Toner

Abstract

Toner, comprising particles, comprising: a core comprising 8 wt.% to 15 wt.% of at least one first amorphous resin having a glass transition temperature of 58.5°C to 66°C in combination with 36 wt.% to 43 wt.% of at least one amorphous resin having a glass transition temperature of 53°C to 58°C, and at least one crystalline resin; and a shell comprising 25 wt.% to 35 wt.% of-% comprising at least one second amorphous resin with a glass transition temperature of 58.5°C to 66°C, wherein the at least one first and second amorphous resin with a glass transition temperature of 58.5°C to 66°C and the at least one amorphous resin with a glass transition temperature of 53°C to 58°C comprise a polyester resin of the following formula (I): in which R is hydrogen or a methyl group and m and n represent random units of the copolymer, where m is from 2 to 10 and n is from 2 to 10, and wherein the at least one crystalline resin comprises a crystalline polyester resin of the following formula (II): in which b is from 5 to 2000 and d is from 5 to 2000.

Description

STATE OF THE ART This disclosure relates generally to toner processes and, more specifically, emulsion aggregation and coalescence processes, toner compositions formed by such processes, and development processes using such toners for use in electrophotographic copying or printing devices. Emulsion aggregation / coalescence processes for the manufacture of toner are described in a number of patents, such as U.S. Patents Nos. 5,290,654, 5,278,020, 5,308,734, 5,370,963, 5,344,738, 5,403,693, 5,418,108, 5,364,729, and 5,346,797; and also perhaps of interest are U.S. Patents Nos. 5,348,832. 5,405,728 ; 5,366,841 ; 5,496,676 ; 5,427,658 ; 5,585,215 ; 5,650,255 ; 5,650,256 ; 5,501,935 ; 5,723,253 ; 5,744,520 ; 5,763,133 ; 5,766,818 ; 5,747,215 ; 5,827,633 ; 5,853,944 ; 5,804,349 ; 5,840,462 ; 5,869,215 ; 5,902,710 ; 5,910,387 ; 5,916,725; 5,919,595; 5,925,488 and 5,977,210.Other patents disclosing exemplary emulsion aggregation / coalescence processes include, for example, US patents Nos. 6,730,450, 6,743,559, 6,756,176, 6,780,500, 6,830,860, and 7,029,817. JP 2008-165017 A describes a toner comprising a polyester resin A, a polyester resin B and a crystalline polyester resin C, as well as a colorant and a release agent. US 2009 / 0,305,159 A1 discloses a toner composition comprising toner particles that include a core comprising at least one crystalline resin and one or more optional components selected from the group consisting of dyes, optional waxes and combinations thereof; and a shell comprising a high molecular weight amorphous polyester resin having a weight-average molecular weight of about 10,000 to about 5,000,000. US 2009 / 0,286,176 A1 relates to a set consisting of a yellow toner, a magenta toner, a cyan toner, and a black toner. Each of the colored toners contains a colored particle and cerium oxide particles, wherein the colored particle contains an amorphous polyester resin, a crystalline polyester resin, a colorant, and a release agent. US 2009 / 0,047,593 A1 discloses a process for forming particles, comprising the steps of producing a first emulsion containing an amorphous polyester resin and wax; producing a second emulsion consisting of a crystalline polyester resin; aggregating the first and second emulsions and the dye to form nuclei; adding an additional amount of the first emulsion to the nuclei and forming a shell on the nuclei; and coalescing the particles. US 2009 / 0,155,707 A1 relates to a toner for the development of electrostatic charge images, comprising a binder resin containing a non-crystalline polyester resin and a crystalline polyester resin, and a colorant. EP 2 259 145 A2 discloses a process comprising contacting at least one resin with at least one surfactant to form an emulsion; contacting the emulsion with an optional wax, an optional dye, and at least one rheology modifier comprising a polyol of the formula H(HCHO)n+1H, wherein n is 1 to 20, to form a primary slurry; aggregating the at least one resin with an aggregating agent to form aggregated particles; coalescing the aggregated particles to form toner particles; and recovering the toner particles, wherein the emulsion has a solids content of about 5 to about 35 wt.%.

[0002] Improved toners and processes for their preparation remain desirable. SUMMARY This disclosure relates to toners and methods for their production. In embodiments, a toner of this disclosure comprises particles comprising a core comprising 8 wt.% to 15 wt.% of at least one first amorphous resin having a glass transition temperature of 58.5°C to 66°C in combination with 36 wt.% to 43 wt.% of at least one amorphous resin having a glass transition temperature of 53°C to 58°C, at least one crystalline resin, and a shell comprising 25 wt.% to 35 wt.% of at least one second amorphous resin having a glass transition temperature of 58.5°C to 66°C, wherein the at least one first and second amorphous resin having a glass transition temperature of 58.5°C to 66°C and the at least one amorphous resin having a glass transition temperature of 53°C to 58°C comprise a polyester resin of the following formula (I): where R is hydrogen or a methyl group and m and n represent random units of the copolymer, where m is from 2 to 10 and n is from 2 to 10, and wherein the at least one crystalline resin comprises a crystalline polyester resin of the following formula (II): where b is from 5 to 2000 and d is from 5 to 2000. DETAILED DESCRIPTION According to the present disclosure, low-melting EA toners are created comprising a low molecular weight resin, optionally a high molecular weight resin, a crystalline resin, a pigment, and a wax. The toners of the present disclosure exhibit good fixing properties. In embodiments, the toners of the present disclosure have a core-shell configuration with a mixture of two amorphous resins in the shell. In embodiments, the two amorphous resins in the shell can comprise one having a high glass transition temperature (Tg) in combination with one having a low glass transition temperature (Tg). The toners of the present disclosure may comprise any latex resin suitable for forming a toner. Such resins may, in turn, be prepared from any suitable monomer. Suitable monomers useful for forming the resin include, but are not limited to, acrylonitriles, diols, diacids, diamines, diesters, diisocyanates, combinations thereof, and the like. Depending on the specific polymer to be used, any suitable monomer may be selected. Any toner resin can be used in the processes of the present disclosure. Such resins can, in turn, be produced from any suitable monomer or monomers by suitable polymerization processes. In embodiments, the resin can be produced by a process other than emulsion polymerization. In further embodiments, the resin can be produced by condensation polymerization. In embodiments, the polymer used to form the resin can be a polyester resin. Suitable polyester resins include, for example, sulfonated, non-sulfonated, crystalline, amorphous resins, and combinations thereof, and the like. The polyester resins can be linear, branched, combinations thereof, and the like. In embodiments, the polyester resins can include those described in U.S. Patents 6,593,049 and 6,756,176. Suitable resins can also include a mixture of an amorphous polyester resin and a crystalline polyester resin, as described in U.S. Patent 6,830,860. In embodiments, a resin used to form a toner can comprise an amorphous polyester resin. In embodiments, the resin can be a polyester resin formed by reacting a diol with a dicarboxylic acid or a diester in the presence of an optional catalyst. Examples of organic diols selected for the production of amorphous resins include aliphatic diols with 2 to 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like, as well as aliphatic alkali sulfodiols such as... Examples include sodium 2-sulfo-1,2-ethanediol, lithium 2-sulfo-1,2-ethanediol, potassium 2-sulfo-1,2-ethanediol, sodium 2-sulfo-1,3-propanediol, lithium 2-sulfo-1,3-propanediol, potassium 2-sulfo-1,3-propanediol, mixtures thereof, and the like. The aliphatic diol, for example, is selected in an amount of 45 to 50 mol percent of the resin, and the aliphatic alkali sulfodiol can be selected in an amount of about 1 to about 10 mol percent of the resin. Examples of dicarboxylic acids or dicarboxylic acid esters selected for the production of the amorphous polyester include dicarboxylic acids or diesters selected from the group consisting of terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, dodecenyl succinic acid, dodecenyl succinic anhydride, glutaric acid, glutaric anhydride, 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, dimethyl dodecenyl succinate, and mixtures thereof. The organic dicarboxylic acid or the diester is selected, for example, from 45 to 52 mol percent of the resin. Examples of suitable polycondensation catalysts for one of the amorphous polyester resins include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltin compounds such as dibutyltin dilaurate, and dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkylzinc, dialkylzinc, zinc oxide, tin(II) oxide, or mixtures thereof. These catalysts are selected in amounts ranging from, for example, 0.01 mol% to 5 mol%, based on the starting dicarboxylic acid or diester used to produce the polyester resin. In embodiments, suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, combinations thereof, and the like. Examples of amorphous resins that may be used include:These include amorphous polyester resins. Examples of amorphous polyester resins include poly(propoxylated bisphenol-co-fumarate), poly(ethoxylated bisphenol-co-fumarate), poly(butyloxylated bisphenol-co-fumarate), poly(co-propoxylated bisphenol-co-ethoxylated bisphenol-co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol-co-maleate), poly(ethoxylated bisphenol-co-maleate), poly(butyloxylated bisphenol-co-ethoxylated bisphenol-co-maleate), poly(co-propoxylated bisphenol-co-ethoxylated bisphenol-co-malestede), poly(1,2-propylene maleate), poly(propoxylated bisphenol-co-itaconate), poly(ethoxylated bisphenol-co-itaconate), poly(butyloxylated bisphenol-co-itaconate), and poly(co-propoxylated bisphenol-co-ethoxylated bisphenol-co-itaconate). Poly(1,2-propylene itaconate), a copoly(propoxylated bisphenol A-co-fumarate)-copoly(propoxylated bisphenol A-co-terephthalate),a terpoly(propoxylated bisphenol-A-co-fumarate)-terpoly(propoxylated bisphenol-A-co-terephthalate)-terpoly(propoxylated bisphenol-A-cododecylsuccinate) and combinations thereof, but are not limited to these. In embodiments, the amorphous resin used in the core can be linear. In embodiments, a suitable amorphous polyester resin may be a copoly(propoxylated bisphenol-A-co-fumarate)-copoly(propoxylated bisphenol-A-co-terephthalate) resin with the following formula (I): where R is hydrogen or a methyl group and m and n represent random units of the copolymer, with m ranging from 2 to 10 and n ranging from 2 to 10. An example of a linear copoly(propoxylated bisphenol A fumarate)-copoly(propoxylated bisphenol A co-terephthalate) that can be used as a latex resin is available under the trade name SPARII from Resana S / A Industrias Quimicas, Sao Paulo, Brazil. Other propoxylated bisphenol A fumarate resins that can be used and are commercially available include GTUF and FPESL-2 from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, North Carolina, USA, and the like. In embodiments, the amorphous polyester resin can be a saturated or unsaturated amorphous polyester resin. Illustrative examples of saturated and unsaturated amorphous polyester resins that can be selected for the process and particles of the present disclosure include any of the various amorphous polyesters, such as... B. polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypentylene terephthalate, polyhexalene terephthalate, polyheptadene terephthalate, polyoctalene terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polypentylene isophthalate, polyhexalene isophthalate, polyheptadene isophthalate, polyoctalene isophthalate, Polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polypentylene adipate, polyhexalene adipate, polyheptadene adipate, polyoctalene adipate, polyethylene glutarate, polypropylene glutarate, polybutylene glutarate, polypentylene glutarate,Polyhexalenglutarat, Polyheptadenglutarat, Polyoctalenglutarat Polyethylenpimelat, Polypropylenpimelat, Polybutylenpimelat, Polypentylenpimelat, Polyhexalenpimelat, Polyheptadenpimelat, Poly(ethoxyliertes Bisphenol-A-fumarat), Poly(ethoxyliertes Bisphenol-A-succinat), Poly(ethoxyliertes Bisphenol-A-adipat), Poly(ethoxyliertes Bisphenol-A-glutarat), Poly(ethoxyliertes Bisphenol-A-terephthalat), Poly(ethoxyliertes Bisphenol-A-isophthalat), Poly(ethoxyliertes Bisphenol-A-dodecenylsuccinat), Poly(propoxyliertes Bisphenol-A-fumarat), Poly(propoxyliertes Bisphenol-A-succinat), Poly(propoxyliertes Bisphenol-A-adipat), Poly(propoxyliertes Bisphenol-A-glutarat), Poly(propoxyliertes Bisphenol-A-terephthalat), Poly(propoxyliertes Bisphenol-A-isophthalat), Poly(propoxyliertes Bisphenol-A-dodecenylsuccinat), SPAR (Dixie Chemicals), BECKOSOL (Reichhold Inc), ARAKOTE (Ciba-Geigy Corporation), HETRON (Ashland Chemical), PARAPLEX (Rohm & Haas), POLYLITE (Reichhold Inc), PLASTHALL (Rohm & Haas),CYGAL (American Cyanamide), ARMCO (Armco Composites), ARPOL (Ashland Chemical), CELANEX (Celanese Engineering), RYNITE (DuPont), STYPOL (Freeman Chemical Corporation), and combinations thereof. The resins can also be functionalized, if desired, such as carboxylated, sulfonated, or the like, and in particular sodium sulfonated. The amorphous polyester resin may be a branched resin. As used herein, the terms "branched" or "branching" include branched resins and / or cross-linked resins. Branching agents for use in the formation of these branched resins include, for example, a polyhydric polycarboxylic acid such as 1,2,4-benzenetricarboxylic 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-methylenecarboxylic propane, tetra(methylenecarboxylic)methane, and 1,2,7,8-octanetetracarboxylic acid, their acid anhydrides, and their lower alkyl esters with 1 to 6 carbon atoms; a polyhydric polyol such as... B. Sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, mixtures thereof and the like.The amount of branching agent is selected, for example, from 0.1 to 5 mol percent of the resin. Linear or branched unsaturated polyesters selected for reactions include both saturated and unsaturated dicarboxylic acids (or anhydrides) and dihydric alcohols (glycols or diols). The resulting unsaturated polyesters are reactive (e.g., crosslinkable) on two fronts: (i) at the unsaturated sites (double bonds) along the polyester chain, and (ii) at the functional groups such as carboxyl, hydroxyl, and the like, which are accessible for acid-base reactions. Typical unsaturated polyester resins can be prepared by melt polycondensation or other polymerization processes using dicarboxylic acids and / or anhydrides and diols. In embodiments, a suitable amorphous resin used in a toner of the present disclosure may be a low molecular weight amorphous resin, which in embodiments is occasionally referred to as an oligomer, with a weight-averaged molecular weight (Mw) of 500 Daltons to 10,000 Daltons, in embodiments of 1,000 Daltons to 5,000 Daltons, and in further embodiments of 1,500 Daltons to 4,000 Daltons. The low molecular weight amorphous resin can have a glass transition temperature of 58.5°C to 66°C, and in embodiments of 60°C to 62°C. The low molecular weight amorphous resin can have a softening point of 105°C to 118°C, and in embodiments of 107°C to 109°C. In further embodiments, the combined resins can have a melt viscosity at 130°C of 10 to 1,000,000 Pa·S, and in embodiments of 50 to 100,000 Pa·S. The monomers used to produce the selected amorphous polyester resins are not restricted, and the molecules employed can comprise one or more of any type, such as ethylene, propylene, and the like. Known chain transfer agents, such as dodecanethiol or carbon tetrabromide, can be used to control the molecular weight properties of the polyester. Any suitable method for forming the amorphous or crystalline polyester from the monomers can be used without restriction. In further embodiments, the amorphous resin used for the formation of a toner of the present disclosure can be a high molecular weight amorphous resin. As used herein, the high molecular weight amorphous polyester resin can have a number-averaged molecular weight (Mn) measured by gel permeation chromatography (GPC) of, for example, 1,000 to 10,000, in embodiments of 2,000 to 9,000, in embodiments of 3,000 to 8,000, and in embodiments of 6,000 to 7,000. The weight-averaged molecular weight (Mw) of the resin, determined by GPC using polystyrene standards, is higher than 45,000, for example from 45,000 to 150,000, in embodiments from 50,000 to 100,000, in embodiments from 63,000 to 94,000 and in embodiments from 68,000 to 85,000.The polydispersity index (PD) measured by GPC against standard polystyrene reference resins is greater than 4, for example, more than 4 in embodiments of 4 to 20, in embodiments of 5 to 10, and in embodiments of 6 to 8. The PD index is the ratio of the weight-averaged molecular weight (Mw) to the number-averaged molecular weight (Mn). The low molecular weight amorphous polyester resins can have an acid number of 8 to 20 mg KOH / g, in embodiments of 9 to 16 mg KOH / g, and in embodiments of 11 to 15 mg KOH / g. The amorphous high molecular weight polyester resins, which are available from a variety of sources, can have different melting points, for example from 30°C to 140°C, in embodiments from 75°C to 130°C, in embodiments from 100°C to 125°C and in embodiments from 115°C to 124°C. The amorphous high molecular weight resins can have a glass transition temperature of 53°C to 58°C, and in embodiments of 54.5°C to 57°C. The amorphous polyester resin is generally present in the toner composition in various suitable amounts, such as 60 to 90 percent by weight, or in embodiments 50 to 65 percent by weight of the toner or solids. The toner composition may, in embodiments, comprise at least one crystalline resin. As used herein, "crystalline" refers to a polyester with three-dimensional order. "Semi-crystalline resins," as used herein, refer to resins with a crystalline content of, for example, 10 to 90%, or, in embodiments, 12 to 70%. Furthermore, "crystalline polyester resins" and "crystalline resins" hereafter include both crystalline and semi-crystalline resins unless otherwise specified. In embodiments, the crystalline polyester resin is either a saturated or an unsaturated crystalline polyester resin. Suitable organic diols for forming a crystalline polyester include aliphatic diols with 2 to 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, ethylene glycol, combinations thereof, and the like. The aliphatic diol can be selected, for example, in an amount of 40 to 60 mol percent, in embodiments of 42 to 55 mol percent, and in embodiments of 45 to 53 mol percent of the resin.Examples of organic dicarboxylic acids or diesters selected for the production of the crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, dodecanedioic acid, sebacenic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, and mesaconic acid, a diester or an anhydride thereof, and combinations thereof. The organic dicarboxylic acid may be selected in an amount of, for example, 40 to 60 mol percent in some embodiments, 42 to 55 mol percent in others, and 45 to 53 mol percent in still others. 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 can be polyester-based, such as...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), alkalicopoly(5-sulfoisophthaloyl)-copoly(ethylene adipate), poly(decylene sebacate), poly(decylene decanoate), polydecylene decanoate), poly(ethylene decanoate), Poly(ethylene endodecanoate), poly(nonylene sebacate), poly(nonyl decanoate), copoly(ethylene fumarate)-copoly(ethylene sebacate), Copoly(ethylene fumarate)-copoly(ethylene decanoate), copoly(ethylene fumarate)-copoly(ethylene endodecanoate), and combinations thereof. The crystalline resin can be present, for example, in an amount of 5 to 50 percent by weight of the toner components, or in embodiments, in an amount of 10 to 35 percent by weight of the toner components. The crystalline polyester resins, available from a variety of sources, can have different melting points, for example, from 30°C to 120°C, and in some embodiments from 50°C to 90°C. The crystalline resins can have a number-averaged molecular weight (Mn), measured by gel permeation chromatography (GPC), of, for example, 1,000 to 50,000, in some embodiments from 2,000 to 25,000, in others from 3,000 to 15,000, and in others from 6,000 to 12,000. The weight-averaged molecular weight (Mw) of the resin, determined by GPC using polystyrene standards, is 50,000 or less, for example, from 2,000 to 50,000, in embodiments from 3,000 to 40,000, in embodiments from 10,000 to 30,000, and in embodiments from 21,000 to 24,000. The molecular weight distribution (Mw / Mn) of the crystalline resin is, for example, from 2 to 6, in embodiments from 3 to 4.The crystalline polyester resins can have an acid number of 2 to 20 mg KOH / g, in embodiments of 5 to 15 mg KOH / g, and in embodiments of 8 to 13 mg KOH / g. The acid number (or neutralization number) is the amount of potassium hydroxide (KOH) in milligrams required to neutralize one gram of the crystalline polyester resin. Suitable crystalline polyester resins include those disclosed in U.S. Patent No. 7,329,476 and pending U.S. Patent Applications Nos. 2006 / 0216626, 2008 / 0107990, 2008 / 0236446, and 2009 / 0047593. In embodiments, a suitable crystalline resin may comprise a resin composed of ethylene glycol or nonanediol and a mixture of dodecanedioic and fumaric acid comonomers having the following formula (II): where b is from 5 to 2000 and d is from 5 to 2000. Werden hierin halbkristalline Polyesterharze eingesetzt, kann das halbkristalline Harz Poly(3-methyl-1-buten), Poly(hexamethylencarbonat), Poly(ethylen-p-carboxyphenoxybutyrat), Poly(ethylenvinylacetat), Poly(docosylacrylat), Poly(dodecylacrylat), Poly(octadecylacrylat), Poly(octadecylmethacrylat), Poly(behenylpolyethoxyethylmethacrylat), Poly(ethylenadipat), Poly(decamethylenadipat), Poly(decamethylenazelaat), Poly(hexamethylenoxalat), Poly(decamethylenoxalat), Poly(ethylenoxid), Poly(propylenoxid), Poly(butadienoxid), Poly(decamethylenoxid), Poly(decamethylensulfid), Poly(decamethylendisulfid), Poly(ethylensebacat), Poly(decamethylensebacat), Poly(ethylensuberat), Poly(decamethylensuccinat), Poly(eicosamethylenmalonat), Polyethylen-p-carboxyphenoxyundecanoat), Poly(ethylendithionisophthalat), Poly(methylethylenterephthalat), Poly(ethylen-p-carboxyphenoxyvalerat), Poly(hexamethylen-4,4'-oxydibenzoat), Poly(10-hydroxycaprinsäure), Poly(isophthalaldehyd), Poly(octamethylendodecandioat),Poly(dimethylsiloxane), poly(dipropylsiloxane), poly(tetramethylenephenylene diacetate), poly(tetramethylenetrithiodicarboxylate), poly(trimethylenedodecanedioate), poly(m-xylene), poly(p-xylylenepimelamide) and combinations thereof. A crystalline polyester resin in a toner particle of the present disclosure can be present in an amount of 1 to 15 percent by weight, in embodiments of 5 to 10 percent by weight and in embodiments of 6 to 8 percent by weight of the toner particles (that is, toner particles without external additives and water). As mentioned above, a toner according to the present disclosure may also comprise at least one branched or crosslinked high molecular weight amorphous polyester resin. In embodiments, this high molecular weight resin may, for example, comprise a branched amorphous resin or a branched amorphous polyester, a crosslinked amorphous resin or a crosslinked amorphous polyester, or mixtures thereof, or a non-crosslinked amorphous polyester resin that has undergone crosslinking. According to the present disclosure, from 1 wt.% to 100 wt.% of the high molecular weight amorphous polyester resin may be branched or crosslinked; in embodiments, from 2 wt.% to 50 wt.% of the high molecular weight amorphous polyester resin may be branched or crosslinked. According to the present disclosure, it was surprisingly found that the blocking performance can be improved by about 50% while maintaining good operating behavior during toner charging and melt fixing. In embodiments, such improvements can be achieved by forming toner particles comprising a core of 8 wt.% to 15 wt.% of a low molecular weight, high Tg amorphous resin, in embodiments 9 wt.% to 12 wt.% of a low molecular weight, high Tg amorphous resin, in embodiments 10.85 wt.% of a low molecular weight, high Tg resin in combination with 36 wt.% to 43 wt.% of a high molecular weight, low Tg amorphous resin, in embodiments 37 wt.% to 41 wt.% of a high molecular weight, low Tg amorphous resin, in embodiments 38.85 wt.% of a high molecular weight, low Tg resin.Such toner particles can also comprise a shell containing 25 wt.% to 35 wt.% of a low molecular weight, high Tg amorphous resin, in embodiments 26 wt.% to 30 wt.% of a low molecular weight, high Tg amorphous resin, in embodiments 28 wt.% of a low molecular weight, high Tg resin. The ratio of crystalline resin to low molecular weight amorphous resin to high molecular weight amorphous polyester resin can range from 1:1:98 to 98:1:1 to 1:98:1, in embodiments from 1:5:5 to 1:9:9, in embodiments from 1:6:6 to 1:8:8. As mentioned above, the resin can be produced in embodiments by means of an emulsion aggregation process. When using such processes, the resin can be present in a resin emulsion, which can then be combined with the other components and additives to form a toner of the present disclosure. The resins described above, in embodiments a combination of polyester resins, for example a low molecular weight resin, a high molecular weight resin, and a crystalline resin, can be used to form toner compositions. Such toner compositions can optionally include colorants, waxes, and other additives. Toners can be formed by any process within the scope of application of a person skilled in the art, including, but not limited to, emulsion aggregation processes. surfactants In embodiments, colorants, waxes, and other additives used to form toner compositions can be present in dispersions containing surfactants. Furthermore, toner particles can be formed by means of an emulsion aggregation process in which the resin and other components of the toner are added to one or more surfactants and an emulsion is formed, and the toner particles are aggregated, coalesced, optionally washed, dried, and isolated. One, two, or more surfactants can be used. The surfactants can be selected from ionic and non-ionic surfactants. The term "ionic surfactants" includes anionic and cationic surfactants. In some embodiments, the surfactant can be used in an amount of 0.01% to 5% by weight of the toner composition, for example, 0.75% to 4% by weight of the toner composition, or in other embodiments, 1% to 3% by weight of the toner composition. Examples of non-ionic surfactants that can be used include, for example, polyacrylic acid, methalose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene encetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, and dialkylphenoxy-poly(ethyleneoxy)ethanol, 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 may include a block copolymer of polyethylene oxide and polypropylene oxide, including that commercially available as SYN-PERONIC PE / F, in embodiments SYN-PERONIC PE / F 108. Anionic surfactants that may be used include sulfates and sulfonates, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl sulfates and sulfonates, acids such as abietic acid (available from Aldrich), NEOGEN RTM, NEOGEN SCTM (obtained from Daiichi Kogyo Seiyaku), combinations thereof, and the like. Other suitable anionic surfactants include, in embodiments, DOWFAXTM2A1, an alkyl diphenyl oxide disulfonate from The Dow Chemical Company, and / or TAYCA POWER BN2060 from Tayca Corporation (Japan), which is a branched sodium dodecylbenzenesulfonate. In embodiments, combinations of these surfactants and any of the preceding anionic surfactants may be used. Examples of cationic surfactants that are typically positively charged include, for example, alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide, C12-, C15-, C17-trimethylammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL™ and ALKAQUATT™, available from Alkaril Chemical Company, SANIZOL™ (benzalkonium chloride), available from Kao Chemicals and the like, as well as mixtures thereof. colorant Various well-known colorants, such as dyes, pigments, dye mixtures, pigment mixtures, pigment and dye mixtures, and the like, can be added to the toner. The colorant may be present in the toner in a quantity of, for example, 0.1 to 35 percent by weight, or 1 to 15 percent by weight, or 3 to 10 percent by weight. Examples of suitable colorants include carbon black such as REGAL 330® (Cabot), magnetites such as Mobay magnetite MO8029™, MO8060™; Colombian magnetites; MAPICO BLACKS™ and surface-treated magnetites; Pfizer magnetites CB4799™, CB5300™, CB5600™, MCX6369™; Bayer magnetites BAYFERROX 8600™, 8610™; Northern Pigments magnetites NP-604™, NP-608™; Magnox magnetites TMB-100™ or TMB-104™; and similar materials. Colored pigments such as cyan, magenta, yellow, red, green, brown, blue, or mixtures thereof can be selected. Generally, cyan, magenta, or yellow pigments or dyes, or mixtures thereof, are used. The pigment or pigments are generally used as water-based pigment dispersions. Specific examples of pigments include the water-based pigment dispersions SUNSPERSE 6000, FLEXIVERSE and AQUATONE from SUN Chemicals, HELIOGEN BLUE L6900TM, D6840TM, D7080TM, D7020TM, PYLAM OIL BLUETM, PYLAM OIL YELLOWTM, PIGMENT BLUE 1TM, available from Paul Uhlich & Company, Inc., PIGMENT VIOLET 1TM, PIGMENT RED 48TM, LEMON CHROMS YELLOW DCC 1026TM, ED TOLUIDINE REDTM and BON RED CTM, available from Dominion Color Corporation, Ltd., Toronto, Ontario, Canada, NOVAPERM YELLOW FGLTM, HOSTAPERM PINK ETM from Hoechst, and CINQUASIA MAGENTATM, available from E.I. DuPont de Nemours & Company, and the like. Generally, the colors that can be selected are black, cyan, magenta, or yellow, or mixtures thereof.Examples of magenta colors include 2,9-dimethyl-substituted quinacridone and anthraquinone dye, identified in the Color Index as CI 60710, CI Dispersed Red 15; diazo dye, identified in the Color Index as CI 26050, CI Solvent Red 19; and similar dyes. Illustrative examples of cyan dyes include copper tetra(octadecylsulfonamido)phthalocyanine, x-copper phthalocyanine pigment, listed in the Color Index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, Pigment Blue 15:4; and anthrathrene blue, identified in the Color Index as CI 69810, Special Blue X-2137; and similar dyes. Illustrative examples of yellow include Diarylide Yellow 3,3-Dichlorobenzideneacetoacetanilide, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenylamine sulfonamide identified in the Color Index as Foron Yellow SE / GLN, Cl Dispersed Yellow 33, 2,5-Dimethoxy-4-sulfonanilide-phenylazo-4'-chloro-2,5-dimethoxyacetoacetanilide, Yellow 180 and Permanent Yellow FGL.Colorants can also include colored magnetites, such as mixtures of MAPICO BLACK™, and cyan components. Other well-known colorants can also be selected, such as Levanyl Black A-SF (Miles, Bayer) and Sunsperse Carbon Klack LHD 9303 (Sun Chemicals), as well as colored dyes such as...Neogen blue (BASF), Sudan blue OS (BASF), PV real blue B2G01 (American Hoechst), Sunsperse blue BHD 6000 (Sun Chemicals), Irgalite blue BCA (Ciba-Geigy), Paliogen blue 6470 (BASF), Sudan III (Matheson, Coleman, Bell), Sudan II (Matheson, Coleman, Bell), Sudan IV (Matheson, Coleman, Bell), Sudanorange G (Aldrich), Sudanorange 220 (BASF), Paliogen-Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlich), Paliogen-Yellow 152, 1560 (BASF), Lithol Real Yellow 0991K (BASF), Paliotol-Yellow 1840 (BASF), Neogen-Yellow (BASF), Novoperm-Yellow FG 1 (Hoechst), permanent yellow YE 0305 (Paul Uhlich), Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), Suco Yellow L1250 (BASF), Suco Yellow D1355 (BASF), Hostaperm Pink E (American Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (DuPont), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplastics NSD PS PA (Ugine Kuhlmann of Canada), EDToluidine 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 True Scarlet L4300 (BASF), combinations of the foregoing and the like. wax In addition to the polymer binder resin and the photoinitiator, the toners of this disclosure may optionally also contain a wax, which may be either a single type of wax or a mixture of two or more different waxes. A single wax may be added to toner formulations to improve, for example, certain toner properties, such as toner particle shape, presence and amount of wax on the toner particle surface, charge-setting and / or melt-fixing properties, gloss, release, offset properties, and the like. Alternatively, a combination of waxes may be added to endow the toner composition with multiple properties. If used, the wax can combine with the resin during the formation of the toner particles. If present, the wax can be in an amount ranging from, for example, 1% to 25% by weight of the toner particles, or in some embodiments, from 3% to 20% by weight of the toner particles. Waxes that can be selected include waxes with, for example, a weight-averaged molecular weight of 500 to 20,000, in embodiments of 1,000 to 10,000. Waxes that can be used include, for example, polyolefins such as polyethylene, polypropylene, and polybutene waxes, such as those commercially available from Allied Chemical and Petrolite Corp., for example, POLYWAX™ polyethylene waxes from Baker Petrolite, wax emulsions available from Michelman Inc. and the Daniels Products Company, EPOLENE N-15 commercially available from Eastman Chemical Products, Inc., and VISCOL 550-P, a low-mass-averaged molecular weight polypropylene available from Sanyo Kasel KK, plant-based waxes such as carnauba wax, rice wax, candelilla wax, Japan wax, and jojoba oil, and animal waxes such as... B. beeswax, mineral-based waxes and petroleum-based waxes such as e.g.Montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; 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 monohydric or polyhydric lower alcohols, such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetrabehenate; ester waxes obtained from higher fatty acids and polyhydric alcohol multimers, such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate, and triglyceryl tetrastearate; higher fatty acid ester waxes containing sorbitan, such as sorbitan monostearate; and higher fatty acid ester waxes containing cholesterol, such as... B. Cholesteryl stearate. Examples of functionalized waxes that can be used include, for example, amines and amides, such as AQUA SUPERSLIP 6550TM and SUPERSLIP 6530TM, available from Micro Powder Inc.Fluorinated waxes, for example POLYFLUG 190™, POLYFLUG 200™, POLYSILK 19™, POLYSILK 14™, available from Micro Powder Inc.; mixed fluorinated amide waxes, for example MICROSPERSION 19™, also available from Micro Powder Inc.; imides, esters, quaternary amines, carboxylic acids, or acrylic polymer emulsions, for example JONCRYL 74™, 89™, 130™, 537™, and 538™, all available from SC Johnson Wax; and chlorinated polypropylenes and polyethylenes, available from Allied Chemical and Petrolite Corporation and SC Johnson Wax. In embodiments, mixtures and combinations of the above waxes may also be used. Waxes may, for example, be included as fixer roller release agents. Toner production The toner particles can be produced by any method within the scope of application of a person skilled in the art. Although embodiments relating to the production of toner particles are described below with regard to emulsion aggregation processes, any suitable method for producing toner particles can be used, including chemical processes such as the suspension and encapsulation processes described in U.S. Patents Nos. 5,290,654 and 5,302,486. In embodiments, toner compositions and toner particles can be produced by aggregation and coalescence processes in which small-sized resin particles are aggregated to the appropriate toner particle size and subsequently coalesced to achieve the final toner particle shape and morphology. In embodiments, the toner compositions can be prepared by means of an emulsion aggregation process, such as a process comprising aggregating a mixture of an optional wax and any other desired or required additives, as well as the emulsions comprising the resins described above, optionally with surfactants as described above, and subsequently coalescing the aggregated mixture. A mixture can be prepared by adding an optional wax or other materials, which may also optionally be present in a dispersion comprising a surfactant, to the emulsion, which may be a mixture of two or more resin-containing emulsions. The pH of the resulting mixture can be adjusted using an acid such as acetic acid, nitric acid, or the like.In some embodiments, the pH of the mixture can be adjusted to approximately 2 to approximately 4.5. Furthermore, in some embodiments, the mixture can be homogenized. If homogenization is desired, it can be achieved by mixing at approximately 600 to approximately 4,000 revolutions per minute. Homogenization can be achieved by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer. Following the preparation of the aforementioned mixture, an aggregating agent may be added. Any suitable aggregating agent may be used to form the toner. Suitable aggregating agents include, for example, aqueous solutions of a divalent cation or a polyvalent cation material. The aggregating agent may include, for example, polyaluminum halides such as polyaluminum chloride (PAC), or the corresponding bromide, fluoride, or iodide; polyaluminum silicates such as polyaluminum sulfosilicate (PASS); and water-soluble metal salts, including aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, and combinations thereof.In embodiments, the aggregating agent can be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin. The aggregating agent can be added to the mixture to form a toner in an amount ranging from, for example, 0.1 parts per hundred (pph) to 1 pph, in embodiments from 0.25 pph to 0.75 pph, and in further embodiments from 0.5 pph. This ensures a sufficient quantity of aggregating agent. The gloss of a toner can be influenced by the amount of metal ion, such as Al3+, retained in the particle. The amount of retained metal ion can be further adjusted by the addition of EDTA. The amount of crosslinking agent, for example Al3+, retained in the toner particles of the present disclosure can be from 0.1 pph to 1 pph in embodiments, from 0.25 pph to 0.8 pph in embodiments, and from 0.5 pph in further embodiments. To control particle aggregation and coalescence, the aggregating agent can be dosed into the mixture over a period of time in certain embodiments. For example, the agent can be dosed over a period of 5 to 240 minutes, or in other embodiments, from 30 to 200 minutes. The agent can also be added while the mixture is stirred, in some embodiments at a speed of 50 to 1,000 rpm, and in other embodiments at a temperature below the glass transition temperature of the resin, as discussed above, from 30°C to 90°C in some embodiments, and from 35°C to 70°C in others. The particles can be aggregated until a predetermined, desired particle size is obtained. A predetermined, desired size refers to the desired particle size to be obtained, which is set prior to formation. The particle size is monitored during the growth process until this size is reached. During the growth process, samples can be taken and analyzed, for example, using a Coulter counter to determine the mean particle size. Aggregation can be continued by maintaining an elevated temperature or by slowly increasing the temperature to, for example, 40°C to 100°C and holding the mixture at this temperature for a period of 0.5 to 6 hours, or in some embodiments, 1 to 5 hours, with continuous stirring, to yield the aggregated particles. Once the predetermined, desired particle size is reached, the growth process is stopped.In embodiments, the predetermined, desired particle size lies within the toner particle size ranges listed above. The growth and shaping of the particles after the addition of aggregating agent can be achieved under any suitable conditions. For example, growth and shaping can be carried out under conditions in which aggregation occurs separately from coalescence. With separate aggregation and coalescence stages, the aggregation process can be carried out under shear conditions at an elevated temperature, which may be below the glass transition temperature of the resin, as discussed above, for example, from 40°C to 90°C, or in embodiments from 45°C to 80°C. The aggregate particles can have a size of less than 3 micrometers in some embodiments, from 2 micrometers to 3 micrometers in others, and from 2.5 micrometers to 2.9 micrometers in still others. Schalenharz In embodiments, an optional shell can be formed on the aggregated toner particles. Any resin described above as suitable for the core resin can be used as the shell resin. The shell resin can be applied to the aggregated particles by any method within the scope of application by those skilled in the art. In embodiments, the shell resin can be present in an emulsion comprising the surfactants described above. The aggregated particles described above can be combined with said emulsion, so that the resin forms a shell over the aggregates. In embodiments, an amorphous polyester can be used to form the shell over the aggregates to create toner particles with a core-shell configuration.In some embodiments, the amorphous resin with a high glass transition temperature can be used to form a shell over the aggregates formed. The shell latex can be present in an amount of 5 to 40 percent by weight of the toner particles, or in embodiments, in an amount of 24 to 30 percent by weight of the toner particles. Once the desired final toner particle size is reached, the pH of the mixture can be adjusted with a base to a value of 5 to 10, or in some embodiments, 6 to 8. Adjusting the pH can be used to freeze, or stop, toner growth. The base used to stop toner growth can be any suitable base, such as alkali metal hydroxides like sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, and the like. In some embodiments, ethylenediaminetetraacetic acid (EDTA) can be added to aid in adjusting the pH to the desired values ​​specified above. The base can be added in an amount of 2 to 25 percent by weight of the mixture, and in some embodiments, 4 to 10 percent by weight. Coalescence After aggregation to the desired particle size, forming an optional shell as described above, the particles can then be coalesced to the desired final shape. Coalescence is achieved, for example, by heating to a temperature of 55°C to 100°C, in some embodiments 65°C to 90°C, and in others 85°C. The temperature may be below the melting point of the crystalline resin to prevent softening. Higher or lower temperatures may be used, and it is understood that the temperature depends on the resins used for the binder. Coalescence can take place and be carried out over a period of 0.1 to 9 hours, and in embodiments from 0.5 to 4 hours. After coalescence, the mixture can be cooled to a lower temperature, such as from 20°C to 40°C. Cooling can be rapid or slow, as desired. A suitable cooling method may involve introducing cold water into a jacket surrounding the reactor. After cooling, the toner particles can be washed with water, if necessary, and then dried. Drying can be carried out using any suitable drying method, including, for example, freeze-drying. In certain embodiments, the toner particles may also contain other optional additives, depending on the desired outcome or requirement. For example, the toner may include any known charge additives in amounts of, say, 0.1 to 10 percent by weight, and in other embodiments, 0.5 to 5 percent by weight of the toner. Examples of such charge additives include alkylpyridinium halides, bisulfates, the charge-control additives of U.S. Patents Nos. 3,944,493, 4,007,293, 4,079,014, 4,394,430, and 4,560,635, negative charge-enhancing additives such as aluminum complexes, and the like. Surface additives may be added to the toner compositions of the present disclosure after washing or drying. Examples of such surface additives include, for example, metal salts, metal salts of fatty acids, colloidal silicas, metal oxides, strontium titanates, mixtures thereof, and the like. Surface additives may be present in an amount of about 0.1 to about 10 percent by weight and, in embodiments, about 0.5 to about 7 percent by weight of the toner. Examples of such additives include those described in U.S. Patents Nos. 3,590,000, 3,720,617, 3,655,374, and 3,983,045. Other additives include zinc stearate and AEROSIL R972®, available from Degussa. The coated silicon dioxides of U.S. Patents Nos.6,190,815 and 6,004,714 may also be present in amounts of about 0.05 to about 5 percent and in embodiments of about 0.1 to about 2 percent of the toner, wherein the additives may be added during aggregation or mixed into the toner product formed. The properties of the toner particles can be determined using any suitable technique and apparatus. Volume-averaged particle diameters D50v, GSDv, and GSDn can be measured using an instrument such as a Beckman Coulter Multisizer 3, operated according to the manufacturer's instructions. A typical sampling procedure is as follows: A small amount of toner sample, approximately 1 gram, can be obtained and filtered through a 25-micrometer sieve and then added to an isotonic solution to obtain a 10% concentration, with the sample then being analyzed in a Beckman Coulter Multisizer 3. Toners produced according to the present disclosure can exhibit excellent charge properties when exposed to conditions of extreme relative humidity (RH).The low-humidity zone (C-zone) can have a relative humidity of 15% at 10°C, while the high-humidity zone (A-zone) can have a relative humidity of 85% at 28°C. Toners of the present disclosure can also have an original toner charge / mass ratio (Q / M) of -3 µC / g to -35 µC / g and a charge of the final toner after mixing with surface additive of -10 µC / g to -45 µC / g. Desirable gloss levels can be obtained using the methods of the present disclosure. For example, the gloss level of a toner of the present disclosure can have a gloss level of 20 ggu to 100 ggu, measured in Gardner gloss units (ggu), in embodiments of 50 ggu to 95 ggu, and in embodiments of 60 ggu to 90 ggu. In embodiments, toners of the present disclosure can be used as ultra-low melt (ULM) toners. In embodiments, the dry toner particles, apart from external surface additives, can have the following properties: (1) A volume-averaged diameter (also referred to as "volume-averaged particle diameter") of 2.5 to 20 micrometers, in embodiments of 2.75 to 18 micrometers, in further embodiments of about 3 to about 15 micrometers. (2) A number-averaged geometric standard deviation (GSDn) and / or volume-averaged geometric standard deviation (GSDv) of 1.18 to 1.30, in embodiments of 1.21 to 1.24. (3) A roundness of 0.9 to 1 (measured, for example, by means of a Sysmex FPIA 2100 analyzer), in embodiments of 0.95 to 0.985, in further embodiments of 0.96 to 0.98. developer The toner particles thus formed can be formulated into a developer composition. The toner particles can be mixed with carrier particles to produce a two-component developer composition. The toner concentration in the developer can range from 1% to 25% by weight of the total developer weight, or in some embodiments, from 2% to 15% by weight of the total developer weight. carrier Examples of carrier particles that can be used for mixing with the toner include particles that can triboelectrically acquire a charge of opposite polarity to that of the toner particles. Illustrative examples of suitable carrier particles include granulated zirconium, granulated silicon, glass, steel, nickel, ferrites, iron ferrites, silicon dioxide, and the like. Other carriers include those described in U.S. Patents Nos. 3,847,604, 4,937,166, and 4,935,326. The selected carrier particles can be used with or without a coating. In embodiments, the carrier particles can comprise a core with a coating on it, which can be formed from a mixture of polymers that are not particularly close to each other in the triboelectric series. The coating can comprise fluoropolymers, such as polyvinylidene fluoride resins, terpolymers of styrene, methyl methacrylate, and / or silanes, such as triethoxysilane, tetrafluoroethylene, or other known coatings, and the like. For example, coatings containing polyvinylidene fluoride, for example, available as KYNAR 301FTM, and / or polymethyl methacrylate, for example, with a mass-averaged molecular weight of about 300,000 to about 350,000, such as commercially available from Soken, can be used. In embodiments, polyvinylidene fluoride and polymethyl methacrylate (PMMA) can be present in proportions of 30 to 70 wt.% up to 70 to 30 wt.%.-%, in embodiments ranging from 40 to 60 wt.% to 60 to 40 wt.%. The coating can have a coating weight of, for example, 0.1 to 5 wt.% of the substrate, in embodiments ranging from 0.5 to 2 wt.% of the substrate. In some embodiments, PMMA can optionally be copolymerized with any desired comonomer, provided that the resulting copolymer maintains a suitable particle size. Suitable comonomers can include monoalkyl or dialkylamines, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, or tert-butylaminoethyl methacrylate, and the like. The carrier particles can be mixed by blending the carrier core with polymer in an amount of 0.05 to 10% by weight, or in some embodiments, 0.01 to 3% by weight, based on the weight of the coated carrier particles, until the polymer adheres to the carrier core by mechanical impact and / or electrostatic attraction. Various effective and suitable methods can be used to apply the polymer to the surface of the carrier core particles, for example, cascade roll mixing, drum coating, milling, shaking, electrostatic powder coating, fluidized bed, electrostatic disc atomization, electrostatic curtain, combinations thereof, and the like. The mixture of carrier core particles and polymer can then be heated so that the polymer melts and fuses with the carrier core particles. The coated carrier particles can then be cooled and subsequently classified to the desired particle size. Suitable carriers may, in embodiments, comprise a steel core, for example in a size of 25 to 100 µm, in embodiments in a size of 50 to 75 µm, which has been coated with 0.5% to 10 wt.%, in embodiments 0.7% to 5 wt.%, of a conductive polymer mixture comprising, for example, methyl acrylate and carbon black, using the process described in US patents Nos. 5,236,629 and 5,330,874. The carrier particles can be mixed with the toner particles in various suitable combinations. The concentrations can range from 1% by weight to 20% by weight of the toner composition. However, different toner and carrier proportions can be used to obtain a developer composition with the desired properties. Image generation The toners can be used for electrophotographic processes, including those disclosed in U.S. Patent No. 4,295,990. In embodiments, any known type of image development system can be used in an image development device, including, for example, magnetic brush development, jumping single-component development, hybrid scavengerless (HSD) development, and the like. These and similar development systems are within the scope of application for a person skilled in the art. Image generation processes include, for example, the production of an image using an electrophotographic device comprising a charging component, an image generation component, a photoconductive component, a developing component, a transfer component, and a fusion-fixing component. In embodiments, the developing component may include a developer prepared by mixing a carrier with a toner composition described herein. The electrophotographic device may include a high-speed printer, a high-speed black-and-white printer, a color printer, and the like. Once the image has been produced with toners / developers using a suitable image development process, such as one of the aforementioned methods, the image can be transferred to an image-receiving medium, such as paper or the like. In some embodiments, the toners can be used in the development of an image on the image development device using a fusible fixer. The fusible fixer can have any desired or suitable configuration, such as a drum or roller, a belt or web, a flat surface or plate, or the like. The fusible fixer can be applied to the image by any desired or suitable method, such as passing the final recording substrate through a roller gap formed by a fusible fixer and a backing element, which can have any desired or suitable configuration, such as...A drum or roller, a belt or web, a flat surface or plate, or the like. In some embodiments, a fuser roller may be used. Fuser roller elements are contact fixing devices that are within the scope of application for a person skilled in the art and in which pressure from the roller, optionally with the application of heat, can be used to fix the toner to the image-receiving medium. Optionally, a liquid layer, such as a fixing oil, may be applied to the fusible fixing element before fixing. In embodiments, the toner image can be fixed by cold melt fixing under pressure, i.e., without the application of heat. The melt fixing can be performed at any desired or effective pressure, in embodiments from about 1000 pounds per square inch (psi, about 69 bar) to 10,000 pounds per square inch (about 689 bar), and in embodiments from 1,500 pounds per square inch (about 103 bar) to 5,000 pounds per square inch (about 345 bar). An advantage of cold melt fixing under pressure is that little energy is required and, unlike hot roller processes, no standby power is needed. Thus, the toners of the present disclosure can be used in systems that are more environmentally friendly and have lower energy requirements. Furthermore, the toners do not melt because no heat is transferred to them, and therefore no offset occurs during fixing. Toners of the present disclosure may exhibit excellent blocking; that is, the ability of the toner to resist sticking together during shipping and / or storage. The following examples are provided to illustrate the embodiments of the present disclosure. These examples are intended to be illustrative only; there is no intention to limit the scope of the present disclosure. Furthermore, unless otherwise stated, all parts and percentages refer to weight. As used herein, "room temperature" refers to a temperature of 20°C to 30°C. EXAMPLES COMPARISON EXAMPLE 1 A yellow emulsion aggregation toner was prepared using a nominal amount (about 14 wt%) of a high Tg amorphous resin in the tray. A yellow polyester toner was prepared on a laboratory scale of 2 liters (about 150 grams of dry, theoretical toner). The core toner slurry comprised two emulsions (in a 50:50 ratio). Both emulsions comprised amorphous resins containing alkoxylated bisphenol A with terephthalic, fumaric, and dodecenyl succinic acid comonomers. One had a high Tg of about 64°C, and the other had a low Tg of about 59°C. To these, about 29.8 grams of a crystalline resin of the following formula were added: in which b is from about 5 to about 2000 and d is from about 5 to about 2000, in an emulsion (about 6.8 percent by weight), about 1.7 grams of DOWFAX TM 2A1, an alkyldiphenyl oxide disulfonate from The Dow Chemical Company, and about 53.2 grams of a yellow pigment, Yellow 74, in a dispersion, and about 46.2 grams of a polyethylene wax (from IGI) in a dispersion. The components were mixed, and then the pH was adjusted to 4.2 using 0.3 M nitric acid. The slurry was then homogenized for approximately 10 minutes at about 3000 rpm to about 6000 rpm, during the addition of approximately 0.5 ppm aluminum sulfate as a coagulant. The toner slurry was then transferred to the 2-liter Büchi reactor and heated to initiate aggregation. The toner slurry aggregated at a temperature of approximately 45°C. During aggregation, the toner particle size was closely monitored. At a size of approximately 4.8 micrometers, a tray containing the same amorphous emulsions (50:50 ratio) as in the core was added to achieve the final target particle size of approximately 5.8 micrometers. The pH of the slurry was adjusted to 7.5 using sodium hydroxide (NaOH) and Versene-100 from The Dow Chemical Company. set to freeze, i.e., stop, the aggregation step. The process was continued, with the reactor temperature (Tr) being increased to reach 85°C while maintaining a pH ≥ approximately 7.5 until Tr reached approximately 85°C. Once Tr reached 85°C, the pH of the toner slurry was reduced to 7 by adding dilute nitric acid and maintained there until the roundness reached approximately ≥ 0.960. The final toner particles had a particle size (D50), particle distribution by volume and roundness of 5.74 micrometers, 1.21 and 0.968 respectively. REFERENCE EXAMPLE 1 A yellow toner was prepared as in Comparative Example 1, but with twice the amount (28%) of high Tg amorphous resin in the tray. The core toner slurry comprised two amorphous emulsions as described above in Comparative Example 1, including the high Tg amorphous resin and the low Tg amorphous resin, in a ratio of 22:78. The particles were formed as described above in Comparative Example 1. At a size of approximately 4.8 micrometers, a shell containing 100% of the high Tg amorphous resin was added to achieve the final, target particle size of approximately 5.8 micrometers. The pH of the slurry was adjusted to 7.5 using sodium hydroxide (NaOH) and VERSENE-100 from The Dow Chemical Company to freeze, i.e., stop, the aggregation step. As in Comparative Example 1, the process was continued, with the reactor temperature (Tr) being increased to reach 85°C while maintaining a pH ≥ approximately 7.5 until the Tr reached approximately 85°C. Once the Tr reached 85°C, the pH of the toner slurry was reduced to 7 by adding dilute nitric acid and maintained there until the roundness reached approximately ≥ 0.960. The final toner particles had a particle size (D50), particle distribution by volume and roundness of 6 micrometers, 1.21 and 0.968 respectively. blocking The blocking behavior of the toners from Comparative Example 1 and Reference Example 1 was obtained by performing a procedure in which 2 grams of the toner with additives were weighed into an open dish and climate-controlled in an environmental chamber at a predetermined temperature and approximately 50% relative humidity. After approximately 17 hours, the samples were removed and acclimatized to ambient conditions for 30 minutes. The amount of blocked toner was quantified by sieving the climate-controlled samples through a stack of two pre-weighed mesh sieves stacked as follows: 1000 µm on top and 106 µm on the bottom. The sieves were shaken for approximately 90 seconds at an amplitude of 1 mm using a Hosokawa flow tester.After the shaking process was completed, the sieves were weighed again and the toner blockage was calculated from the total amount of toner remaining on both sieves as a proportion of the initial weight. Table 1 below shows the toner blocking behavior from comparison example 1 and reference example 1, as well as the toner charging characteristics in zone A and zone C at 60 minutes (60') and 2 minutes (2'). Table 1: Charging data with blocking improved by 50% <row> <cell>A-Zone 60' q / d< / cell> <cell> 7,5< / cell> <cell> 7,9< / cell> < / row> <row> <cell> Zone A 60' sq m< / cell> <cell> 32< / cell> <cell> 36< / cell> < / row> <row> <cell> Zone A 2' sq m< / cell> <cell> 42< / cell> <cell> 46,1< / cell> < / row> <row> <cell> C-Zone 60' q / d< / cell> <cell> 13,4< / cell> <cell> 16,7< / cell> < / row> <row> <cell> C-Zone 60' sq m< / cell> <cell> 57< / cell> <cell> 72< / cell> < / row> <row> <cell> Charge retention 24 h< / cell> <cell> 77< / cell> <cell> 82< / cell> < / row> <row> <cell> Charge retention 7 days< / cell> <cell> 57< / cell> <cell> 56< / cell> < / row> <row> <cell> Blocking @ 53°C< / cell> <cell> 26< / cell> <cell / > < / row> <row> <cell> Blocking @ 54°C< / cell> <cell> 89,2< / cell> <cell> 44,4< / cell> < / row> <p xml:id="_2f558b0248" n="0094"> In general, toner blockage causes print quality problems such as background or streaking, and in severe cases, blockage can create toner clumps that inhibit toner development from the developer chamber. For example, at a temperature of 54°C, toner agglomeration could impair print quality. In a severe case, the agglomerated toner might not be fed to the printer or transferred to the developer chamber during machine operation. As shown in Table 1 above, improved blockage was observed at temperatures up to 54°C, meaning that the experimental toner exhibited less toner agglomeration during shipping and / or in the printers. Fix <p xml:id="_2f558b0250" n="0095">The toners from comparison example 1 and reference example 1 were subjected to a fixing test. The fixing behavior (gloss, wrinkling, and hot offset measurements) of the particles was compiled. <p xml:id="_2f558b0251" n="0096">All unfixed images were produced using a modified Xerox Corporation DC 12 copier. A toner density (TMA) of 1.00 mg / cm² was achieved on Color Xpressions+ paper (90 gsm, uncoated) (occasionally referred to as CX+ paper) using a commercially available hot-fusing device. <hi rend="superscript"> 2< / hi> Produced by each toner. The targets for gloss / crease were a square image positioned in the center of the page. <p xml:id="_2f558b0253" n="0097"> The process speed of the melt fixer was set to 220 mm / second (holding time in the roller gap of approximately 34 milliseconds), and the fixing roller temperature was varied from cold offset to hot offset or up to 210°C for gloss and wrinkling measurements. <p xml:id="_2f558b0254" n="0098">Wrinkle area measurements were performed using an image analysis system. Gloss as a function of the fuser roller temperature was measured with a BYK Gardner 75° gloss meter. A summary of the fixer results is given in Table 2 below. It lists gloss at 185°C, the fixing tolerance, and the minimum fixing temperature (MFT). Table 2 <title desc="title"> Table 2< / title> Cold offset on CX+120123 Gloss at 185°C to CX+66,068.5 Maximum gloss on CX+69,468.6 ΔMFT-30-27 Spotting / Hot Offset CX+ 220mm / second 185 / 195 200 / 210 As can be seen from Table 2, the gloss data measured at 185°C on CX+ paper were very similar when comparing toner from Reference Example 1 with toner from Comparison Example 1 and were within the experimental accuracy of the measurement. The temperature at which hot offset occurred was at a slightly higher fuser roller temperature. No shift towards higher fuser roller temperatures was measured in the MFT crease test. The changes in the particle formulation to improve blocking behavior had, if any, only a very minor adverse effect on the melt fusing properties.

Claims

Toner comprising particles, comprising: a core comprising 8 wt.% to 15 wt.% of at least one first amorphous resin having a glass transition temperature of 58.5°C to 66°C in combination with 36 wt.% to 43 wt.% of at least one amorphous resin having a glass transition temperature of 53°C to 58°C, and at least one crystalline resin; and a shell comprising 25 wt.% to 35 wt.% of at least one second amorphous resin having a glass transition temperature of 58.5°C to 66°C, wherein the at least one first and second amorphous resin having a glass transition temperature of 58.5°C to 66°C and the at least one amorphous resin having a glass transition temperature of 53°C to 58°C comprise a polyester resin of the following formula (I): where R is hydrogen or a methyl group and m and n represent random units of the copolymer, where m is from 2 to 10 and n is from 2 to 10, and wherein the at least one crystalline resin comprises a crystalline polyester resin of the following formula (II): where b is from 5 to 2000 and d is from 5 to 2000. Toner according to claim 1, wherein the toner further comprises a wax, and wherein the wax is selected from the group consisting of polyethylene wax, polypropylene wax, polybutene wax, Japan wax, jojoba oil, beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, stearyl stearate, behenyl behenate, butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, pentaerythritol tetrabehenate; diethylene glycol monostearate, dipropylene glycol distearate and combinations thereof. Toner according to claim 1 or 2, wherein the core comprises 9 wt.% to 12 wt.% of the at least one first amorphous resin having a glass transition temperature of 58.5°C to 66°C and 37 wt.% to 41 wt.% of the at least one amorphous resin having a glass transition temperature of 53°C to 58°C. Toner according to one of claims 1 to 3, wherein the shell comprises 26 wt.% to 30 wt.% of the at least one second amorphous resin having a glass transition temperature of 58.5°C to 66°C.