Toner containing charge control agent

Abstract

To provide an improved toner, in particular an emulsion aggregation toner that can be prepared with a reduced amount of TiO2, or can be free of TiO2 altogether, and offers stable charging performance in all environmental extremes.SOLUTION: An emulsion aggregation toner is provided, comprising toner particles, each containing at least one type of resin, an optional colorant, an optional wax, and a charge control agent disposed on a surface of the toner particle, the charge control agent comprising a phenyl siloxane, and a complex formed from a metal ion donor and at least one ligand selected from a group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone, or a combination thereof.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] Cross - reference to Related Applications U.S. Patent Application No. 17 / 697,783 (Attorney Docket No. 20210493US01 titled "Toner Comprising Charge Control Agent") filed by the same applicant simultaneously with this specification and incorporated herein by reference in its entirety describes an emulsion aggregation toner comprising toner particles containing at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the charge control agent comprising a complex formed from at least one member selected from the group consisting of a metal ion donor and a ligand selected from polyaromatic acids containing humic acid, pyranone - based ligands, furanone - based ligands, or combinations thereof.

[0002] Filing concurrently with this Specified and incorporated herein in its entirety by reference, U.S. Patent Application No. 17 / 697,809 ("Toner Comprising Reactive Charge Control Agent," Agent Reference Number 20210498US01) by the same applicant provides an emulsion-aggregated toner comprising toner particles comprising at least one resin, an optional colorant, an optional wax, and a reactive charge control agent disposed on the surface of the toner particles, wherein the reactive charge control agent comprises at least one positively charged compound, comprising a member selected from the group consisting of amine compounds having at least three carbon atoms, ammonium compounds having at least three carbon atoms, phosphonium compounds having at least three carbon atoms, polonium compounds having at least three carbon atoms, and combinations thereof. The following emulsion agglomeration toner is described, comprising at least one positively charged compound and at least one reactive anchor compound comprising a member selected from the group consisting of amino, epoxy, carboxylic acid, hydroxyl, silanol, cyanide, anhydride, aldehyde, ketone, vinyl, and combinations thereof, and further comprising a charge control agent optionally comprising a negatively charged compound comprising a member selected from the group consisting of aromatic carboxylic acid, silanol, phenol, pyranone, furanone, and combinations thereof. [Background technology]

[0003] This specification discloses an emulsion-aggregated toner comprising toner particles containing at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0004] Also disclosed is a developer comprising emulsion-aggregated toner particles and a toner carrier, wherein the emulsion-aggregated toner particles comprise at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the charge control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid including humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0005] Furthermore, an emulsion agglomeration toner process comprising: obtaining a latex of at least one resin; optionally obtaining an aqueous dispersion of an optionally selected colorant; optionally obtaining an aqueous dispersion of an optionally selected wax; forming a mixture of the latex of at least one resin, an aqueous dispersion of an optionally selected colorant, and an aqueous dispersion of an optionally selected wax; heating the mixture to a first temperature; maintaining the first temperature to form agglomerated toner particles; adding a shell resin latex to form a shell on the agglomerated particles; optionally adding a chelating agent solution; stopping further agglomeration; raising the temperature to a second temperature higher than the first temperature to fuse the agglomerated particles; and cooling the emulsion agglomerated toner particles, optionally washing, optionally washing An emulsion agglomeration toner process is disclosed, comprising: selectively drying and recovering the emulsion agglomeration toner particles; introducing a charge control agent to the emulsion agglomeration toner particles by adding a metal ion donor and at least one ligand selected from the group consisting of a humic acid-containing polyaromatic acid, a pyranone ligand, a furanone ligand, or a combination thereof, wherein the metal ion donor and the polyaromatic acid ligand, pyranone ligand, furanone ligand, or a combination thereof form a charge control agent, and thus form emulsion agglomeration toner particles containing a charge control agent; adding a phenyl siloxane to the emulsion agglomeration toner particles; and subsequently cooling, optionally washing, and recovering the emulsion agglomeration toner particles.

[0006] The emergence of chemically generated toner particles has enabled significant improvements in print quality and transfer efficiency over many years. However, the chemicals involved in the formulation of these particles can create significant interactions during the manufacturing process, potentially leading to suboptimal customer performance. In particular, the chemicals and raw materials used in emulsion aggregation (EA) processes can produce particles with compromised environmental stability in both charging rate and average charge. Under low humidity conditions, typical polyester and / or styrene acrylate particles become very highly charged, requiring long mixing times with the carrier for a stable and uniform charge distribution when new toner is combined with aged toner in the developer. Conversely, the average charge peak of these particles can be very low under high humidity conditions. This presents a challenge in ensuring good print performance under all environmental extremes. In the era of conventional particle processes (extrusion / grinding), charge control agents (CCAs) were incorporated into the molten resin mixture to provide improved environmental stability of the final toner. In EA processes, it has been shown to be difficult to incorporate similar charge control agents into the particles without adversely impacting the particle process. The suspension polymerization method for particle formulations allows for the easy incorporation of internal CCA into particles using a solvent in the process. One way to address environmental instability in EA particles is to use titanium dioxide (TiO2) as an external additive in toner formulations. This additive tends to reduce average charge under low humidity conditions and improve charging rate (mixing) without seriously affecting high humidity charging performance, thereby greatly improving environmental stability. However, because TiO2 is considered a potential health risk to humans, recent regulations have been implemented or are expected to be implemented regarding TiO2, such as limiting the amount of TiO2 that can be used in toner formulations to less than 1% by weight. In addition, most charge control agents are complexes of molecular aromatic hydroxycarboxylic acid ligands with metal ions selected from calcium, zinc, aluminum, iron, chromium atoms, boron, zirconium, and titanium.The manufacture and application of these charge control agents raise environmental and health concerns due to the high toxicity of molecular aromatic hydroxycarboxylic acid ligands. It is highly desirable to develop more sustainable charge control agents using less hazardous alternative ligands.

[0007] Currently available toners are suitable for their intended purposes. However, improved toners are still needed. Furthermore, there is still a need for improved toners, in embodiments such as emulsion-aggregated toners, that can be prepared with reduced amounts of TiO2, or even without any TiO2 at all, while still providing stable charging performance under all environmental extremes.

[0008] Appropriate components and processes of the aforementioned U.S. patents and patent application publications may be selected for this disclosure in their respective embodiments. Furthermore, various publications, patents, and published patent applications are referenced by specific citations throughout this application. The disclosures of publications, patents, and published patent applications referenced in this application are incorporated by reference to more fully illustrate the current technology to which the present invention relates. [Overview of the project]

[0009] The following emulsion agglutinated toner is described, comprising toner particles containing at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0010] The developer also includes emulsion-aggregated toner particles and a toner carrier, wherein the emulsion-aggregated toner particles comprise at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the charge control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid including humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0011] Furthermore, an emulsion agglomeration toner process comprising: obtaining a latex of at least one resin; optionally obtaining an aqueous dispersion of an optionally selected colorant; optionally obtaining an aqueous dispersion of an optionally selected wax; forming a mixture of the latex of at least one resin, an aqueous dispersion of an optionally selected colorant, and an aqueous dispersion of an optionally selected wax; heating the mixture to a first temperature; maintaining the first temperature to form agglomerated toner particles; adding a shell resin latex to form a shell on the agglomerated particles; optionally adding a chelating agent solution; stopping further agglomeration; raising the temperature to a second temperature higher than the first temperature to fuse the agglomerated particles; and cooling the emulsion agglomerated toner particles, optionally washing, optionally washing An emulsion agglomeration toner process is described, comprising: selectively drying and recovering the emulsion agglomeration toner particles; introducing a charge control agent to the emulsion agglomeration toner particles by adding a metal ion donor and at least one ligand selected from the group consisting of a humic acid-containing polyaromatic acid, a pyranone ligand, a furanone ligand, or a combination thereof, wherein the metal ion donor and the polyaromatic acid ligand, pyranone ligand, furanone ligand, or a combination thereof form a charge control agent, and thus form emulsion agglomeration toner particles containing a charge control agent; adding a phenyl siloxane to the emulsion agglomeration toner particles; and subsequently cooling, optionally washing, and recovering the emulsion agglomeration toner particles. [Brief explanation of the drawing]

[0012] [Figure 1] This is a charge spectrograph showing data for comparison particles in low humidity (J zone). [Figure 2] This is a charge spectrograph showing data for comparison particles in high humidity (Zone A). [Figure 3]This is a charge spectrograph showing data for particles containing an Al3+ / dehydroacetic acid / phenylsiloxane charge control agent according to this embodiment in low humidity (J zone). [Figure 4] This is a charge spectrograph showing data for particles containing an Al3+ / dehydroacetic acid / phenylsiloxane charge control agent according to this embodiment in high humidity (Zone A). [Modes for carrying out the invention]

[0013] The embodiments describe a method for incorporating a charge control agent, in embodiments an internal charge control agent (CCA), by arranging, in embodiments an internal charge control agent (CCA), CCA molecules on the surface of particles during or after an emulsion aggregation (EA) manufacturing process, by deposition.

[0014] In the embodiments, the emulsion agglomeration toner process includes forming a latex, agglomerating it to form agglomerated particles, adhering the agglomerated particles, and preparing the emulsion agglomerated toner particles by cooling, optionally washing, and optionally drying. In the embodiments herein, the charge control agent is placed on the surface of the emulsion agglomerated toner particles after the cooling step, or deposited in the embodiments. In the embodiments, the charge control agent is placed on the surface of the emulsion agglomerated toner particles between the cooling step and the washing step. In other embodiments, the charge control agent is placed on the surface of the emulsion agglomerated toner particles after the drying step.

[0015] In the embodiments herein, the charge control agent is an internal charge control agent. As used herein, an internal charge control agent means a charge control agent incorporated into the wet portion of the toner process. This is in contrast to external additives added to the toner after it has dried.

[0016] CCA ligands, such as dehydroacetic acid or humic acid, contain an aromatic nucleus motif having a phenol substituent and a carboxylic acid substituent linked together. 3+ Ionic Zn 2+ Metal ions, such as ions, are added to form a dehydroacetic acid complex or humic acid complex that can be deposited on the surface of the toner particles. In combination with a hydrophobized product, in an embodiment phenylsilane, for example phenylsiloxane, this process allows the charge control agent to be incorporated into the EA process after the prepared emulsion-aggregated toner particles are cooled in an embodiment, cooled and washed in another embodiment, and cooled, washed and dried in a preferred embodiment. In an embodiment, the CCA is placed on the emulsion-aggregated toner particles using a redispersion process to obtain prepared emulsion-aggregated toner particles, which are dispersed in a slurry, and then the CCA is placed on the redispersed toner particles. The CCA provides improved charging performance in the form of an increased charging rate (mixing rate) and improved environmental stability over a wide range of humidity.

[0017] In the embodiments, the charge control agent is deposited on the emulsion agglomerated toner particles after cooling but before washing and drying, or after drying. In preferred embodiments, the deposition process occurs after cooling, washing, and drying via an additional redispersion process. Thus, in embodiments, the process described herein includes forming emulsion agglomerated toner particles via agglomeration, bonding, cooling, washing, and drying to obtain dried emulsion agglomerated toner particles; redispersing the dried emulsion agglomerated toner particles, such as by redispersing them in water, to form a slurry of emulsion agglomerated toner particles; then depositing a charge control agent on the surface of the redispersed emulsion agglomerated toner particles; and adding a hydrophobic treatment.

[0018] In the embodiment, the charge control ligand and metal ions are added to the emulsion-aggregated toner batch while the toner particles are still being formed. Therefore, in the embodiment, the charge control agent of the present invention is referred to as an internal charge control agent, in contrast to external additives added after the toner particles have been formed. The addition of metal ions forms a charge control agent complex or molecule that can be deposited on the surface of the particles before washing and drying.

[0019] In embodiments, an emulsion agglutinating toner is described, comprising toner particles containing at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0020] In further embodiments, a developer comprising emulsion-aggregated toner particles and a toner carrier is described, wherein the emulsion-aggregated toner particles comprise at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the charge control agent comprising a complex formed from a phenyl siloxane, a metal ion donor, and at least one ligand selected from the group consisting of a polyaromatic acid including humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0021] In a further embodiment, an emulsion aggregation toner process comprising obtaining a latex of at least one resin, optionally obtaining an aqueous dispersion of an optional colorant, optionally obtaining an aqueous dispersion of an optional wax, forming a mixture of the latex of at least one resin, the aqueous dispersion of the optional colorant, and the aqueous dispersion of the optional wax, heating the mixture to a first temperature, maintaining the first temperature to form aggregated toner particles, adding a latex of a shell resin to form a shell on the aggregated particles, optionally adding a solution of a chelating agent, stopping further aggregation and raising the temperature to a second temperature higher than the first temperature to coalesce the aggregated particles, cooling, optionally washing, optionally drying, and recovering the emulsion aggregation toner particles, and introducing a charge control agent into the emulsion aggregation toner particles by adding at least one member selected from the group consisting of a metal ion donor, and a polyaromatic acid, a pyranone ligand, a furanone ligand, or a combination thereof containing humic acid, wherein the metal ion donor and the polyaromatic acid ligand, pyranone ligand, furanone ligand, or combination thereof form a charge control agent, and thus forming emulsion aggregation toner particles containing the charge control agent, introducing, adding a phenyl-based siloxane to the emulsion aggregation toner particles, and subsequently cooling, optionally washing, and recovering the emulsion aggregation toner particles is described.

[0022] Thus, the charge control agent herein includes a phenyl-based siloxane combined with a complex formed from a ligand and an ion donor. The ligand and the ion donor together form a complex that deposits on the surface of the toner particles. The phenyl-based siloxane also deposits on the surface of the toner particles.

[0023] In some embodiments, the toner particles comprise a core-shell structure, and a charge control agent comprising a phenyl-based siloxane and a complex formed from a member of the group consisting of a metal ion donor, and a polyaromatic acid, a pyranone ligand, a furanone ligand, or a combination thereof, containing humic acid, is disposed on the surface of the toner particle shell.

[0024] The toner particles of the present invention include a hydrophobic silane-treated product provided as a charge control agent. The silane-treated product improves the charging speed. The complex enables adjustment of the A / J ratio, that is, controls the charge amount in humid conditions and dry conditions, and minimizes the difference therebetween.

[0025] The hydrophobized product can be any suitable or desired phenyl siloxane. In embodiments, the phenyl-based siloxane is selected from members of the group consisting of phenyl siloxane, alkylphenyl siloxane having an alkyl group of 1 to about 50 carbon atoms, diphenyl siloxane, and combinations thereof.

[0026] The charge control agent also includes a complex formed from a metal ion donor and a ligand in combination with a phenyl-based siloxane. Any suitable or desired metal ion donor can be selected. In embodiments, the metal ion donor of the charge control agent complex is selected from members of the group consisting of a divalent calcium ion donor, a divalent magnesium ion donor, a divalent barium ion donor, a divalent zinc ion donor, a trivalent aluminum ion donor, a trivalent iron ion donor, a tetravalent titanium ion donor, a tetravalent zirconium ion donor, and combinations thereof. In certain embodiments, the metal ion donor of the charge control agent complex is selected from members of the group consisting of a divalent zinc ion donor, a trivalent aluminum ion donor, a tetravalent titanium ion donor, a tetravalent zirconium ion donor, and combinations thereof.

[0027] In the embodiment, the metal ion donor of the charge control agent complex is selected from members of the group consisting of zinc nitrate, zinc acetate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, aluminum chloride, and combinations thereof. In a particular embodiment, the metal ion donor of the charge control agent complex is selected from members of the group consisting of zinc nitrate hexahydrate, aluminum nitrate notahydrate, and combinations thereof.

[0028] In the embodiment, the charge control agent comprises a complex formed from a metal ion donor and at least one ligand selected from the group consisting of a polyaromatic acid including humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0029] Any suitable or desired ligand can be selected. In embodiments, the ligand is selected from members of the group consisting of polyaromatic acids, humic acids, pyranone ligands, furanone ligands, and combinations thereof.

[0030] In certain embodiments, the ligand is selected from the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

[0031] In the embodiment, the ligand includes a pyranone and / or furanone having a conjugated structure in which electrons are readily delocalized within the molecule.

[0032] Examples of pyrones include hydroxypyrone, hydroxy(thio)pyrone, maltol, tert-butylmaltol, coumaric acid, tetraacetate lactone, and chelidonic acid.

[0033] Examples of furanones include 5-hydroxy-2(5H)-furanone, 5-ethyl-4-hydroxy-2-methyl-3(2H)-furanone, 2-methyl-3-furanchiol, and tetronic acid.

[0034] In a particular embodiment, the ligand is selected from the group consisting of hydroxypyranone, thiopyranone, pyranone carboxylic acid, hydroxyfuranone, thiofuranone, furanone carboxylic acid, and combinations thereof.

[0035] Any toner resin can be used when forming the toner of the present disclosure. Such a resin may then be prepared from any preferred one or more monomers via any preferred polymerization method. In embodiments, the resin is prepared by emulsion polymerization. In embodiments, the resin may be prepared by methods other than emulsion polymerization. In further embodiments, the resin may be prepared by condensation polymerization.

[0036] In the embodiment, the emulsion-aggregated toner comprises toner particles having a core-shell structure. The toner particle core and shell may contain any suitable or desired resin, including the resins described herein. In a particular embodiment, the particle core comprises at least one amorphous polyester, at least one crystalline polyester, an optional colorant, and an optional wax, and the particle shell comprises at least one amorphous polyester.

[0037] The toner compositions of this disclosure, in embodiments, include an amorphous resin. The amorphous resin may be linear or branched. In embodiments, the amorphous resin may include at least one low molecular weight amorphous polyester resin. Low molecular weight amorphous polyester resins, available from numerous sources, may have a variety of melting points, for example, about 30°C to about 120°C, in embodiments about 75°C to about 115°C, in embodiments about 100°C to about 110°C, or in embodiments about 104°C to about 108°C. When used herein, the low molecular weight amorphous polyester resin has a number average molecular weight (Mn), for example, about 1,000 to about 10,000, in embodiments about 2,000 to about 8,000, in some embodiments about 3,000 to about 7,000, and in embodiments about 4,000 to about 6,000, as measured by gel permeation chromatography (GPC). The weight-average molecular weight (Mw) of the resin, when determined by GPC using polystyrene standards, is 50,000 or less, for example, about 2,000 to about 50,000 in embodiments, about 3,000 to about 40,000 in embodiments, about 10,000 to about 30,000 in some embodiments, and about 18,000 to about 21,000 in embodiments. The molecular weight distribution (Mw / Mn) of low molecular weight amorphous resins is, for example, about 2 to about 6, and about 3 to about 4 in embodiments. Low molecular weight amorphous polyester resins may have an acid value of about 8 to about 20 mg KOH / g, about 9 to about 16 mg KOH / g in embodiments, and about 10 to about 14 mg KOH / g in embodiments.

[0038] Examples of linear amorphous polyester resins that can be used include poly(propoxylated bisphenol A cofmarate), poly(ethoxylated bisphenol A cofmarate), poly(butyl oxidized bisphenol A cofmarate), poly(copropoxylated bisphenol A coethoxylated bisphenol A cofmarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol A comareate), poly(ethoxylated bisphenol A comareate), and poly(butyl oxidized bisphenol A cofmarate). Examples include poly(biphenol A comaleate), poly(copropoxylated bisphenol A coethoxylated bisphenol A comaleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol A coitaconate), poly(ethoxylated bisphenol A coitaconate), poly(butylene bisphenol A coitaconate), poly(copropoxylated bisphenol A coethoxylated bisphenol A coitaconate), poly(1,2-propylene itaconate), and combinations thereof.

[0039] In the embodiment, suitable amorphous resins include alkoxylated bisphenol A fumarate / terephthalate polyesters and copolyester resins. In the embodiment, a suitable amorphous polyester resin may be a copoly(propoxylated bisphenol A cofumarate)-copoly(propoxylated bisphenol A coterephthalate) resin having the following formula (I), [ka] In the formula, R may be hydrogen or a methyl group, and m and n represent random units of the copolymer, where m may be about 2 to 10 and n may be about 2 to 10. Examples of such resins and processes for producing them include those disclosed in U.S. Patent No. 6,063,827, the entire disclosure of which is incorporated herein by reference.

[0040] Examples of linear propoxylated bisphenol A fumarate resins that can be used as latex resins are available from Resana S / A Industrias Quimicas (Sao Paulo Brazil) under the trade name SPARII®. Other suitable linear resins are disclosed in U.S. Patents 4,533,614, 4,957,774, and 4,533,614, each of which is incorporated herein by reference in whole. These may be linear polyester resins containing alkyloxylated bisphenol A, such as terephthalic acid, dodecyl succinic acid, trimellitic acid, fumaric acid, and alkyloxylated bisphenol A, such as bisphenol A ethylene oxide adducts and bisphenol A propylene oxide adducts. Other commercially available propoxylated bisphenol A terephthalate resins that can be used include GTU-FC115, which is commercially available from Kao Corporation, Japan.

[0041] In embodiments, the low molecular weight amorphous polyester resin may be a saturated or unsaturated amorphous polyester resin. Exemplary examples of saturated and unsaturated amorphous polyester resins selected for the processes and particles of this disclosure include 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-aziperte, polypropylene-aziperte, polybutylene-aziperte, polypentylene-aziperte, polyhexalene-aziperte, polyheptadene-aziperte, polyoctalene-aziperte, polyethylene-glutarate, polypropylene-glutarate, polybutylene-glutarate, polypentylene-glutarate, polyhexalene- Glutarate, polyheptadene-glutarate, polyoctalene-glutarate, polyethylene-pimelate, polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate, polyhexalene-pimelate, polyheptadene-pimelate, poly(ethoxylated bisphenol A-fumarate), poly(ethoxylated bisphenol A-succinate), poly(ethoxylated bisphenol A-azipart), poly(ethoxylated bisphenol A-glutarate), poly(ethoxylated bisphenol A-fumarate), Poly(ethoxylated bisphenol A-terephthalate), poly(ethoxylated bisphenol A-isophthalate), poly(ethoxylated bisphenol A-dodecenyl succinate), poly(propoxylated bisphenol A-fumarate), poly(propoxylated bisphenol A-succinate), poly(propoxylated bisphenol A-aziperte), poly(propoxylated bisphenol A-glutarate), poly(propoxylated bisphenol A-terephthalate), poly(propoxylated bisphenol A-isophthalate),Examples include any of the various amorphous polyesters, such as poly(propoxylated bisphenol A-dodecenyl succinate), SPAR (Dixie Chemicals), BECKOSOL® (Reichhold Inc.), ARAKOTE (Ciba-Geigy Corporation), HETRON® (Ashland Chemical), PARAPLEX® (Rohm & Haas), POLYLITE® (Reichhold Inc.), PLASTHALL® (Rohm & Haas), CELANEX® (Celanese Corporation), RYNITE® (DuPont®), STYPOL® (Polynt Composites, Inc.), and combinations thereof. The resin may also be functionalized, such as carboxylation or sulfonation, or, if particularly desired, sodium sulfonation.

[0042] Low molecular weight linear amorphous polyester resins are generally prepared by polycondensation of an organic diol, diacid, or diester with a polycondensation catalyst. Low molecular weight amorphous resins are generally present in toner compositions in various suitable amounts, such as about 60 to about 90% by weight of the toner or solid, and in embodiments, about 50 to about 65% by weight.

[0043] Examples of organic diols selected for the preparation of low molecular weight resins include aliphatic diols having approximately 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, and 1,12-dodecanediol; sodio 2-sulfo-1,2-ethanediol, lithio 2-sulfo-1,2-ethanediol, potasio 2-sulfo-1,2-ethanediol, sodio 2-sulfo-1,3-propanediol, lithio 2-sulfo-1,3-propanediol, potasio 2-sulfo-1,3-propanediol, and mixtures thereof. Aliphatic diols can be selected, for example, in an amount of about 45 to 50 mol% of the resin, while alkali sulfo-aliphatic diols can be selected in an amount of about 1 to 10 mol% of the resin.

[0044] Examples of diacids or diesters selected for the preparation of low molecular weight amorphous polyesters include dicarboxylic acids or diesters such as terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecenyl succinic acid, dodecenyl succinic acid, glutaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanediic 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 combinations thereof. Organic diacids or diesters are selected, for example, in an amount of about 45 to about 52 mol% of the resin.

[0045] Examples of suitable polycondensation catalysts for either low molecular weight amorphous polyester resins or crystalline resins (described below) include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkylzincs, dialkylzincs, zinc oxide, stannous oxide, or mixtures thereof. This catalyst can be used in amounts of, for example, about 0.01 mol% to about 5 mol%, based on the diacid or diester used as the starting material for producing the polyester resin.

[0046] Low molecular weight amorphous polyester resins may also be branched resins. As used herein, the terms “branched” or “branched” include branched resins and / or crosslinked resins. Examples of branching agents used in forming these branched resins include 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane, tetra(methylene-carboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, its acid anhydride, and its low molecular weight of 1 to about 6 carbon atoms. Examples include polyhydric polyacids such as quaternary alkyl esters, sorbitol, 1,2,3,6-hexanetetralol, 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, and mixtures thereof. The amount of branching agent selected is, for example, about 0.1 to about 5 mol% of the resin.

[0047] The resulting unsaturated polyester is reactive (e.g., crosslinkable) in two leading parts: (i) unsaturated sites (double bonds) along the polyester chain, and (ii) functional groups such as carboxyl groups and hydroxyl groups, groups suitable for acid-base reactions. In embodiments, the unsaturated polyester resin is prepared by melt polycondensation or other polymerization processes using diacids and / or anhydrides and diols.

[0048] In some embodiments, the low molecular weight amorphous polyester resin or combination of low molecular weight amorphous resins may have a glass transition temperature of about 30°C to about 80°C, and in some embodiments, about 35°C to about 70°C. In further embodiments, the combined amorphous resin may have a melt viscosity of about 10 to about 1,000,000 Pa*S at about 130°C, and in some embodiments, about 50 to about 100,000 Pa*S.

[0049] The amount of low molecular weight amorphous polyester resin in the toner particles of the present disclosure may be 25 to about 50% by weight, in embodiments about 30 to about 45% by weight, and in embodiments about 35 to about 43% by weight of toner particles (i.e., toner particles excluding external additives and water) in any core, any shell, or both.

[0050] In embodiments, the toner composition comprises at least one crystalline resin. As used herein, “crystalline” refers to polyester having a three-dimensional order. As used herein, “semi-crystalline resin” refers to a resin having a crystallinity of, for example, about 10 to about 90%, and in embodiments, about 12 to about 70%. Furthermore, as used below, “crystalline polyester resin” and “crystalline resin” encompass both crystalline and semi-crystalline resins unless otherwise specified.

[0051] In this embodiment, the crystalline polyester resin is either a saturated crystalline polyester resin or an unsaturated crystalline polyester resin.

[0052] Crystalline polyester resins, available from many sources, can have a variety of melting points, for example, from about 30°C to about 120°C, and in embodiments, from about 50°C to about 90°C. Crystalline resins can have number-average molecular weights (Mn) of, for example, about 1,000 to about 50,000, in embodiments, about 2,000 to about 25,000, in embodiments, about 3,000 to about 15,000, and in embodiments, about 6,000 to about 12,000, when measured by gel permeation chromatography (GPC). The weight-average molecular weight (Mw) of the resin, when determined by GPC using a polystyrene standard, is 50,000 or less, for example, from about 2,000 to about 50,000, in embodiments, about 3,000 to about 40,000, in embodiments, about 10,000 to about 30,000, and in embodiments, about 21,000 to about 24,000. The molecular weight distribution (Mw / Mn) of the crystalline resin is, for example, about 2 to about 6, and in embodiments, about 3 to about 4. The crystalline polyester resin may have an acid value of about 2 to about 20 mg KOH / g, in embodiments, about 5 to about 15 mg KOH / g, and in embodiments, about 8 to about 13 mg KOH / g.

[0053] Examples of crystalline polyester 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-sevacate), and poly(propylene-sevacate). Poly(butylene-sebacate), Poly(pentylene-sebacate), Poly(hexylene-sebacate), Poly(octylene-sebacate), Poly(nonylene-sebacate), Poly(decylene-sebacate), Poly(undecylene-sebacate), Poly(dodecylene-sebacate), Poly(ethylene-dodecanediote), Poly(propylene-dodecanediote), Poly(butylene-dodecanediote), Poly(pentylene-dodecanediote), Poly(hexylene-dodecanediote), Poly(octylene-dodecanediote) Poly(nonylene-dodecanediote), poly(decylene-dodecanediote), poly(undecylene-dodecanediote), poly(dodecylene-dodecanediote), poly(ethylene-fumarate), poly(propylene-fumarate), poly(butylene-fumarate), poly(pentylene-fumarate), poly(hexylene-fumarate), poly(octylene-fumarate), poly(nonylene-fumarate), poly(decylene-fumarate), copoli(5-sulfoisophthaloyl)-copoly(ethylene-aziparte), copoli( 5-Sulfoisophthaloyl)-copoly(propylene-adipate), copoly(5-sulfoisophthaloyl)-copoly(butylene-adipate), copoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), copoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), copoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), copoly(5-sulfo-isophthaloyl)-copoly(ethylene-adipate), copoly(5-sulfo-isophthaloyl)-copoly(propylene-adipate),Copoly(5-sulfo-isophthaloyl)-copoly(butylene-adipate), Copoly(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), Copoly(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), Copoly(5-sulfo-isophthaloyl)-copoly(octylene-adipate), Copoly(5-sulfoisophthaloyl)-copoly(ethylene-succinate), Copoly(5-sulfoisophthaloyl)-co Poly(propylene-succinate), copoli(5-sulfoisophthaloyl)-copoly(butylene-succinate), copoli(5-sulfoisophthaloyl)-copoly(pentylene-succinate), copoli(5-sulfoisophthaloyl)-copoly(hexylene-succinate), copoli(5-sulfoisophthaloyl)-copoly(octylene-succinate), copoli(5-sulfo-isophthaloyl)-copoly(ethylene-sevacate), copoli Li(5-sulfo-isophthaloyl)-copoly(propylene-sebacate), copoly(5-sulfo-isophthaloyl)-copoly(butylene-sebacate), copoly(5-sulfo-isophthaloyl)-copoly(pentylene-sebacate), copoly(5-sulfo-isophthaloyl)-copoly(hexylene-sebacate), copoly(5-sulfo-isophthaloyl)-copoly(octylene-sebacate), copoly(5-sulfo-isophthaloyl)-co Examples of various crystalline polyesters include poly(ethylene-adipate), copoli(5-sulfo-isophthaloyl)-copoly(propylene-adipate), copoli(5-sulfo-isophthaloyl)-copoly(butylene-adipate), copoli(5-sulfo-isophthaloyl)-copoly(pentylene-adipate), copoli(5-sulfo-isophthaloyl)-copoly(hexylene-adipate), and any combination thereof.

[0054] Crystalline resins can be prepared by a polycondensation process in which a suitable organic diol and a suitable organic diacid are reacted in the presence of a polycondensation catalyst. Generally, stoichiometric equimolar ratios of the organic diol and organic diacid are used, but in some cases, the boiling point of the organic diol is about 180°C to about 230°C, and an excess amount of diol can be used and removed during the polycondensation process. The amount of catalyst used varies and can be selected, for example, in an amount of about 0.01 to about 1 mol% of the resin. Furthermore, an organic diester can be selected instead of an organic diacid, resulting in the production of an alcohol byproduct. In a further embodiment, the crystalline polyester resin is poly(dodecanediol-cononanediol).

[0055] Examples of organic diols selected for the preparation of crystalline polyester resins include aliphatic diols having approximately 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, and 1,12-dodecanediol; sodio 2-sulfo-1,2-ethanediol, lithio 2-sulfo-1,2-ethanediol, potasio 2-sulfo-1,2-ethanediol, sodio 2-sulfo-1,3-propanediol, lithio 2-sulfo-1,3-propanediol, potasio 2-sulfo-1,3-propanediol, and mixtures thereof. Aliphatic diols can be selected, for example, in an amount of about 45 to 50 mol% of the resin, while alkali sulfo-aliphatic diols can be selected in an amount of about 1 to 10 mol% of the resin.

[0056] Examples of organic diacids or diesters selected for the preparation of crystalline polyester resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid and mesaconic acid, their diesters or anhydrides; and alkali sulfo-organic diacids, such as dimethyl-5-sulfo-isophthalate and dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride. Examples include 4-sulfophthalic acid, dimethyl-4-sulfophthalate, dialkyl-4-sulfophthalate, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid, dimethyl-sulfo-terephthalate, 5-sulfo-isophthalic acid, dialkyl-sulfo-terephthalate, sulfo-p-hydroxybenzoic acid, sodium, lithium, or potassium salts of N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, or mixtures thereof. Organic diacids may be selected in amounts of, for example, about 40 to about 50 mole percent of the resin, and alkali sulfoaliphatic diacids may be selected in amounts of about 1 to about 10 mole percent of the resin.

[0057] Suitable crystalline polyester resins include those disclosed in U.S. Patent No. 7,329,476 and U.S. Patent Publication Nos. 2006 / 0216626, 2008 / 0107990, 2008 / 0236446, and 2009 / 0047593, each of which is incorporated herein by reference in whole. In embodiments, suitable crystalline resins may include resins comprising ethylene glycol or nonanediol, and mixtures of dodecanediic acid and fumarate comonomer having the following formula (II): [ka] In the formula, b is approximately 5 to approximately 2000, and d is approximately 5 to approximately 2000.

[0058] When semicrystalline polyester resins are used herein, the semicrystalline resins include poly(3-methyl-1-butene), poly(hexamethylene carbonate), poly(ethylene-p-carboxyphenoxybutyrate), poly(ethylene vinyl acetate), poly(docosyl acrylate), poly(dodecyl acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), poly(behenyl polyethoxyethyl methacrylate), poly(ethylene adipate), poly(decamethylene adipate), poly(decamethylene azelaate), poly(hexamethylene oxalate), poly(decamethylene oxalate), poly(ethylene oxide), poly(propylene oxide), poly(butadiene oxide), poly(decamethylene oxide), poly(decamethylene sulfide), poly(decamethylene disulfide), and poly(ethylene seba Poly(decamethylene sebacate), poly(ethylene sverate), poly(decamethylene succinate), poly(eicosamethylene malonate), poly(ethylene-p-carboxyphenoxy undecanoate), poly(ethylenedithion ethophthalate), poly(methylethylene terephthalate), poly(ethylene-p-carboxyphenoxy valerate), poly(hexamethylene-4,4-oxydibenzoate), poly Possible examples include poly(10-hydroxycapric acid), poly(isophthalaldehyde), poly(octamethylene dodecanediate), poly(dimethylsiloxane), poly(dipropylsiloxane), poly(tetramethylenephenylenediacetate), poly(tetramethylene trithiodicarboxylate), poly(trimethylene dodecanediate), poly(m-xylene), poly(p-xylylenepimeramide), and combinations thereof.

[0059] The amount of crystalline polyester resin in the toner particles of this disclosure may be present in the core, shell, or both in amounts of 1 to about 15% by weight, in embodiments about 5 to about 10% by weight, and in embodiments about 6 to about 8% by weight of toner particles (i.e., toner particles excluding external additives and water).

[0060] In embodiments, the toner of the present disclosure may also contain at least one high molecular weight branched or crosslinked amorphous polyester resin. Examples of such high molecular weight resins in embodiments include branched amorphous resins or amorphous polyesters, crosslinked amorphous resins or amorphous polyesters, or mixtures thereof, or crosslinked non-crosslinked amorphous polyester resins. According to the present disclosure, about 1% to about 100% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked, and in embodiments, about 2% to about 50% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0061] When used herein, high molecular weight amorphous polyester resins may have a number-average molecular weight (Mn) 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, when measured by gel permeation chromatography (GPC). 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, when determined by GPC using a polystyrene standard. The polydispersity index (PD), when measured against standard polystyrene standard resins by GPC, is greater than approximately 4, for example, greater than approximately 4, approximately 4 to approximately 20 in embodiments, approximately 5 to approximately 10 in embodiments, and approximately 6 to approximately 8 in embodiments. The PD index is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). Low molecular weight amorphous polyester resins may have acid values ​​of approximately 8 to approximately 20 mg KOH / g, approximately 9 to approximately 16 mg KOH / g in embodiments, and approximately 11 to approximately 15 mg KOH / g in embodiments. High molecular weight amorphous polyester resins, available from numerous sources, may have a variety of melting points, for example, approximately 30°C to approximately 140°C, approximately 75°C to approximately 130°C in embodiments, approximately 100°C to approximately 125°C in embodiments, and approximately 115°C to approximately 121°C in embodiments.

[0062] High molecular weight amorphous resins, available from numerous sources, may have a variety of glass transition temperatures (Tg) when measured by differential scanning calorimetry (DSC), for example, about 40°C to about 80°C, in embodiments about 50°C to about 70°C, and in embodiments about 54°C to about 68°C. In embodiments, linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0063] 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 used, and these agents 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-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, and combinations thereof. These branching agents can be used in effective amounts of about 0.1 mol% to about 20 mol%, based on the diacid or diester used as the starting material for producing the resin.

[0064] Compositions containing modified polyester resins having polybasic carboxylic acids that can be used in forming high molecular weight polyester resins include those disclosed in U.S. Patent No. 3,681,106, and branched or crosslinked polyesters derived from polyhydric acids or alcohols, as exemplified in U.S. Patents No. 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 respective disclosures of which are incorporated herein by reference in their entirety.

[0065] In embodiments, the crosslinked polyester resin may be made from a linear amorphous polyester resin containing unsaturated moieties that can react under free radical conditions. Examples of such resins are disclosed in U.S. Patents 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, each of which is incorporated herein by reference in whole. In the embodiment, suitable unsaturated polyester resins can be prepared from diacids and / or anhydrides such as maleic anhydride, terephthalic acid, trimellitic acid, fumaric acid, and combinations thereof, and diols such as bisphenol A ethylene oxide adduct, bisphenol A-propylene oxide adduct, and combinations thereof. In the embodiment, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0066] In embodiments, crosslinked branched polyesters can be used as high molecular weight amorphous polyester resins. Such polyester resins 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 ester thereof or a mixture thereof having at least three functional groups, and optionally at least one long-chain aliphatic carboxylic acid or ester thereof, or an aromatic monocarboxylic acid or ester thereof, or a mixture thereof. The two components may be reacted and substantially completed in separate vessels to produce a first composition containing a pregel having carboxyl-terminated groups in a first reactor, and a second composition containing a pregel having hydroxyl-terminated 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 synthesizing them are disclosed in U.S. Patent No. 6,592,913, the entire disclosure of which is incorporated herein by reference.

[0067] Suitable polyols contain about 2 to about 100 carbon atoms and may have at least two or more hydroxyl groups, or esters thereof. Examples of polyols include glycerol, pentaerythritol, polyglycol, polyglycerol, or mixtures thereof. The polyol may also contain glycerol. Suitable esters of glycerol include glycerol palmitate, glycerol sebacate, glycerol azipart, and triacetin trippropionine. The polyol may be present in an amount of about 20% to about 30% by weight of the reaction mixture, and in embodiments, about 22% to about 26% by weight of the reaction mixture.

[0068] Examples of aliphatic polyfunctional acids having at least two functional groups include saturated and unsaturated acids, or esters thereof, containing about 2 to about 100 carbon atoms, and in some embodiments, about 4 to about 20 carbon atoms. Other examples of 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, or mixtures thereof. Other aliphatic polyfunctional acids that can be used include dicarboxylic acids containing C3-C6 cyclic structures and their positional isomers, such as cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, or cyclopropanedicarboxylic acid.

[0069] Aromatic polyfunctional acids having at least two functional groups that can be utilized include terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and naphthalene 1,4-, 2,3-, and 2,6-dicarboxylic acids.

[0070] Aliphatic polyfunctional acids or aromatic polyfunctional acids may be present in an amount of about 40% to about 65% by weight of the reaction mixture, and in embodiments, about 44% to about 60% by weight of the reaction mixture.

[0071] Examples of long-chain aliphatic carboxylic acids or aromatic monocarboxylic acids include those containing about 12 to about 26 carbon atoms, in embodiments, those containing 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 include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cerotic acid, etc., or combinations thereof. Suitable unsaturated long-chain aliphatic carboxylic acids include dodecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, etc., or combinations thereof. Examples of aromatic monocarboxylic acids include benzoic acid, naphthoic acid, and substituted naphthoic acid. Suitable substituted naphthoic acid includes naphthoic acid substituted with linear or branched alkyl groups containing about 1 to about 6 carbon atoms, such as 1-methyl-2-naphthoic acid and / or 2-isopropyl-1-naphthoic acid. Long-chain aliphatic carboxylic acids or aromatic monocarboxylic acids may be present in an amount of about 0% to about 70% by weight of the reaction mixture, and in embodiments, about 15% to about 30% by weight of the reaction mixture.

[0072] If desired, additional polyols, ionic species, oligomers, or derivatives thereof may be used. These additional glycols or polyols may be present in amounts of about 0% to about 50% by weight of the reaction mixture. Examples of additional polyols or derivatives thereof 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.

[0073] In embodiments, the crosslinked branched polyester of the high molecular weight amorphous polyester resin may include those resulting from the reaction of dimethyl terephthalate, 1,3-butanediol, 1,2-propanediol, and pentaerythritol.

[0074] 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, and may be high molecular weight resin particles having a diameter of about 100 nanometers to about 300 nanometers, and in embodiments, about 110 nanometers to about 150 nanometers.

[0075] The amount of high molecular weight amorphous polyester resin in the toner particles of the present disclosure may be about 25% to about 50% by weight of the toner (i.e., toner particles excluding external additives and water) in any core, any shell, or both; in embodiments, about 30% to about 45% by weight; and in other embodiments, about 40% to about 43% by weight of the toner.

[0076] The ratio of crystalline resin to low molecular weight amorphous resin to high molecular weight amorphous polyester resin may range from approximately 1:1:98 to approximately 98:1:1 to approximately 1:98:1, approximately 1:5:5 to approximately 1:9:9 in embodiments, and approximately 1:6:6 to approximately 1:8:8 in embodiments.

[0077] The toner as used herein, and the toner core as used herein in the embodiments, may comprise one or a combination of styrene-acrylate copolymers. In embodiments, the resin is selected from the group consisting of styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, and combinations thereof.

[0078] Examples of polymers that can be used in toner resins include styrene acrylate, styrene butadiene, styrene methacrylate, and more specifically, poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl Poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene) Examples include poly(styrene-propyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), and combinations thereof. The polymer may be a block, random, or alternating copolymer.

[0079] In certain embodiments, the resin is poly(styrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate The following are selected from the group consisting of to-isoprene, poly(propylacrylate-isoprene), poly(butylacrylate-isoprene), poly(styrene-butylacrylate), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butadiene-acrylic acid), poly(styrene-isoprene-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), and combinations thereof.

[0080] In embodiments, the resins, waxes, and other additives used to form the toner composition may be included and may be provided in the form of a dispersion containing a surfactant. Furthermore, toner particles may be formed by an emulsion agglomeration method, in which the resins and other components of the toner are placed in one or more surfactants to form an emulsion, the toner particles are agglomerated and adsorbed, the charge control agent of the present invention is deposited on the toner surface in a wet portion of the process, and the toner having the thus-placed charge control agent is optionally washed and dried and recovered. Accordingly, in embodiments, the toner particles of this specification include emulsion agglomerated toner particles.

[0081] One, two, or more surfactants may be used. The surfactants may be selected from ionic surfactants and nonionic surfactants. Anionic surfactants and cationic surfactants are included in the term "ionic surfactants". In embodiments, the surfactant may be used in an amount of about 0.01% to about 5% by weight of the toner composition, for example, about 0.75% to about 4% by weight of the toner composition, and in embodiments, about 1% to about 3% by weight of the toner composition.

[0082] Examples of nonionic surfactants include polyvinyl alcohol, polyacrylic acid, metalose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxytheylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, and IGEPAL CA-210(registered trademark), IGEPAL CA-520(registered trademark), IGEPAL CA-720(registered trademark), IGEPAL CO-890(registered trademark), IGEPAL CO-720(registered trademark), IGEPAL CO-290(registered trademark), IGEPAL CA-210(registered trademark), ANTAROX 890(registered trademark), and ANTAROX, all available from Rhone-Poulenc Inc. 897 (registered trademark) is one example. An example of a suitable nonionic surfactant is ANTAROX (registered trademark) 897, available from Rhone-Poulenc Inc., which mainly consists of alkylphenol ethoxylates. Other examples of suitable nonionic surfactants include block copolymers of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC PE / F, and in embodiments as SYNPERONIC PE / F 108.

[0083] Examples of anionic surfactants that can be used include sulfates and sulfonates, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl sulfates and sulfonates, for example, abietic acid available from Aldrich, and anionic surfactants of the NEOGEN® brand. Examples of preferred anionic surfactants include NEOGEN® R, NEOGEN® RK, and NEOGEN® SC available from Daiichi Kogyo Seiyaku Co. Ltd., or TAYCA POWER BN2060 from Tayca Corporation (Japan), which mainly consists of branched sodium dodecylbenzenesulfonate. Another preferred anionic surfactant, in this embodiment, is DOWFAX® 2A1, an alkyl diphenyl disulfonate available from The Dow Chemical Company. Combinations of these surfactants may be used. Combinations of these surfactants with any of the aforementioned anionic surfactants may be used in this embodiment.

[0084] Examples of cationic surfactants typically possess a positive charge and include alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide, C12, C15, and C17 trimethylammonium bromide, quaternary polyoxyethylalkylamine halide salts, dodecylbenzyltriethylammonium chloride, and mixtures thereof. Specific examples include MIRAPOL® and ALKAQUAT® available from Alkaril Chemical Company, and SANISOL® (benzalkonium chloride) available from Kao Chemicals. A preferred example of a cationic surfactant is SANISOL® B-50, available from Kao Corp., which mainly consists of benzyldimethylalkonium chloride. These surfactants and mixtures of other surfactants may be used in the embodiments.

[0085] The latex particles produced as described above can be added to a colorant to produce toner. In embodiments, the colorant may be in the form of a dispersion. The colorant dispersion may contain, for example, submicron colorant particles having a volume average diameter of about 50 to about 500 nanometers, and in embodiments, a volume average diameter of about 100 to about 400 nanometers. The colorant particles may be suspended in an aqueous phase containing an anionic surfactant, a nonionic surfactant, or a combination thereof. Suitable surfactants include any of the surfactants described above. In embodiments, the surfactant may be ionic and may be present in the dispersion in an amount of about 0.1 to about 25% by weight of the colorant, and in embodiments, about 1 to about 15% by weight of the colorant.

[0086] Colorants useful for toner formation according to this disclosure include pigments, dyes, mixtures of pigments and dyes, mixtures of pigments, and mixtures of dyes. The colorants may be, for example, carbon black, cyan, yellow, magenta, red, orange, brown, green, blue, violet, or mixtures thereof.

[0087] In embodiments where the coloring agent is a pigment, the pigment may be, for example, carbon black, phthalocyanine, quinacridone or RHODAMINE B(trademark) type, red, green, orange, brown, violet, yellow, a fluorescent coloring agent, etc.

[0088] Exemplary colorants include carbon black such as REGAL 330® magnetite, Mobay magnetite, Columbia magnetite, MAPICO BLACKS® and surface-treated magnetite including MO8029® and M08060®, Pfizer magnetite including CB4799®, CB5300®, CB5600® and MCX6369®, Bayer magnetite including BAYFERROX 8600® and 8610®, Northern Pigments magnetite including NP-604® and NP-608®, TMB-100® or TMB-104® available from Paul Uhlich and Company, Inc., and HELIOGEN BLUE. Examples include Magnox magnetites including L6900(trademark), D6840(trademark), D7080(trademark), D7020(trademark), PYLAM OIL BLUE(trademark), PYLAM OIL YELLOW(trademark), and PIGMENT BLUE 1(trademark); PIGMENT VIOLET 1(trademark), PIGMENT RED 48(trademark), LEMON CHROME YELLOW DCC 1026(trademark), EDTOLUIDINE RED(trademark), and BON RED C(trademark) available from Dominion Color Corporation, Ltd., Toronto, Ontario; NOVAPERM YELLOW FGL(trademark) and HOSTAPERM PINK E(trademark) available from Hoechst; and CINQUASIA MAGENTA(trademark) available from EIDuPont de Nemours and Company.Other colorants include 2,9-dimethyl-substituted quinacridone and anthraquinone dyes identified as CI 60710 in the Color Index, CI Dispersed Red 15, diazo dyes identified as CI 26050 in the Color Index, CI Solvent Red 19, copper tetra(octadecylsulfonamide) phthalocyanine, x-copper phthalocyanine pigment listed as CI 74160 in the Color Index, CI Pigment Blue, Anthrathrene Blue identified as CI 69810 in the Color Index, Special Blue X-2137, Diallylide Yellow 3,3-dichlorobenzydenacetoacetanilide, monoazo pigment identified as CI 12700 in the Color Index, CI Solvent Yellow 16, nitrophenylamine sulfonamide identified as Foron Yellow SE / GLN in the Color Index, CI Dispersed Yellow 33, and 2,5-dimethoxy-4-sulfonanilide. Examples include phenylazo-4'-chloro-2,5-dimethoxyacetoacetanilide, Yellow 180, and Permanent Yellow FGL. Examples of organic solvent-soluble dyes with high purity for the available color gamut include Neopen Yellow 075, Neopen Yellow 159, Neopen Orange 252, Neopen Red 336, Neopen Red 335, Neopen Red 366, Neopen Blue 808, Neopen Black X53, and Neopen Black X55, where the dye is selected in various suitable amounts, for example, about 0.5 to about 20% by weight of the toner, and in embodiments, about 5 to about 18% by weight of the toner.

[0089] In the embodiment, examples of colorants include Pigment Blue 15:3 with color index number 74160, Magenta Pigment Red 81:3 with color index number 45160:3, and Yellow 17 with color index number 21105, as well as known dyes such as food dyes, yellow, blue, green, red, and magenta dyes.

[0090] In other embodiments, magenta pigment, Pigment Red 122 (2,9-dimethylquinacridone), Pigment Red 185, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 235, Pigment Red 269, or combinations thereof may be used as colorants.

[0091] In certain embodiments, the colorant includes a black pigment, a cyan pigment, or a combination thereof.

[0092] Selectively stirring the resulting latex and colorant dispersion in the dispersion and heating it to a temperature of about 35°C to about 70°C, or in embodiments, about 40°C to about 65°C, may yield toner aggregates with a volume-average diameter of about 2 micrometers to about 10 micrometers, or in embodiments, about 5 micrometers to about 8 micrometers.

[0093] Optionally, wax may also be combined with resin to form toner particles. If included, the wax may be present in an amount of, for example, about 1% to about 25% by weight of the toner particles, and in embodiments, about 5% to about 20% by weight of the toner particles.

[0094] Examples of waxes that can be selected include waxes having a weight-average molecular weight of about 500 to about 20,000, and in embodiments, about 1,000 to about 10,000. Examples of waxes that can be used include polyolefins such as polyethylene, polypropylene, and polybutene wax, such as those commercially available from Allied Chemical and Petrolite Corporation, such as POLYWAX® polyethylene wax from Baker Petrolite, wax emulsions available from Michaelman, Inc. and Daniels Products Company, EPOLENE N-15® commercially available from Eastman Chemical Products, Inc., and VISCOL, a low weight-average molecular weight polypropylene available from Sanyo Kasei KK. Examples include 550-P (trademark), plant-based waxes such as carnauba wax, rice wax, candelilla wax, lacquer wax, and jojoba oil, animal-based waxes such as beeswax, mineral waxes such as montane wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax, and petroleum-based waxes, ester waxes obtained from higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate, ester waxes obtained from higher fatty acids and 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, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes such as cholesteryl stearate.Examples of functionalized waxes that may be used include, for example, amines, amides, e.g., AQUA SUPERSLIP 6550™ and SUPERSLIP 6530™ available from Micro Powder Inc.; fluorinated waxes, e.g., POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™, and POLYSILK 14™ available from Micro Powder Inc.; mixed fluorinated amide waxes (e.g., MICROSPERSION 19™ available from Micro Powder Inc.); imides, esters, quaternary amines, carboxylic acids, or acrylic polymer emulsions (e.g., JONCRYL 74™, 89™, 130™, 537™, and 538™, all available from SC Johnson Wax); and chlorinated polypropylene and polyethylene available from Allied Chemical, Petrolite Corporation, and SC Johnson Wax. The aforementioned wax mixtures and combinations may also be used in the embodiments. The wax may be included, for example, as a release agent for the fuser roll.

[0095] In embodiments, the toner composition may be prepared by an emulsion flocculation process, such as a process comprising flocculating an emulsion containing the resin in the surfactant with an optionally selected mixture of an optionally selected wax and any other desired or required additive, and then bonding the flocculated mixture. The mixture may also be prepared by adding an optionally selected wax or other material (which may also be optionally in a dispersion containing the surfactant) to an emulsion (which may be a mixture of two or more emulsions containing the resin). The pH of the resulting mixture can be adjusted with an acid, for example, acetic acid or nitric acid. In embodiments, the pH of the mixture can be adjusted to about 2 to about 4.5. In addition, in embodiments, the mixture may be homogenized. If the mixture is homogenized, homogenization can be achieved by mixing at 4,000 to about 6,000 revolutions per minute. Homogenization can be achieved by any preferred means, for example, an IKA ULTRA TURRAX® T50 probe homogenizer.

[0096] Following the preparation of the above mixture, a flocculant may be added to the mixture. Toner may be formed using any suitable flocculant. Suitable flocculants include, for example, aqueous solutions of divalent or polyvalent cationic materials. The flocculant may be, for example, a polyaluminum halide such as polyaluminum chloride (PAC), or a corresponding bromide, fluoride, or iodide, or an aluminum polysilicate such as polyaluminum sulfosilicate (PASS), and a water-soluble metal salt containing aluminum chloride, aluminum nitrite, aluminum sulfate, aluminum sulfate, calcium chloride, calcium nitrite, calcium oxyate, 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 the embodiment, the flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

[0097] The flocculant may be added to the mixture used to form the toner in an amount of about 0.1% to about 8% by weight of the resin in the mixture, about 0.2% to about 5% by weight in an embodiment, and about 0.5% to about 5% by weight in another embodiment. This provides a sufficient amount of the agent for flocculation.

[0098] To control particle aggregation and adhesion, in embodiments, the flocculant may be added to the mixture by weighing over time. For example, the agent may be added to the mixture by weighing over a period of about 5 to about 240 minutes, or in embodiments, about 30 to about 200 minutes. The addition of the agent may be carried out while the mixture is stirred at a rate of about 50 rpm to about 1,000 rpm in embodiments, or about 100 rpm to about 500 rpm in other embodiments, and while the temperature is maintained below the glass transition temperature of the resin, which is about 30°C to about 90°C in embodiments, or about 35°C to about 70°C in embodiments.

[0099] The particles may be aggregated until a predetermined desired particle size is obtained. The predetermined desired diameter refers to the desired particle size to be obtained when determined before formation, and the particle size is monitored during the growth process until such a particle size is reached. Samples may be taken during the growth process and analyzed for the average particle size, for example, with a Coulter Counter. Thus, aggregation may proceed by maintaining a high temperature, or by slowly raising the temperature, for example, from about 40°C to about 100°C, and holding the mixture at this temperature for about 0.5 hours to about 6 hours, in embodiments about 1 to about 5 hours, while maintaining stirring to provide aggregated particles. Once the predetermined desired particle size is reached, the growth process is stopped. In embodiments, the predetermined desired particle size is within the above-mentioned toner particle size range.

[0100] The growth and molding of particles after the addition of a flocculant can be achieved under any suitable conditions. For example, growth and molding may be carried out under conditions in which aggregation occurs separately from bonding. For the separate aggregation and bonding stages, the aggregation process may be carried out under shear conditions at a high temperature, for example, below the glass transition temperature of the resin, about 40°C to 90°C, and in embodiments about 45°C to 80°C.

[0101] In this embodiment, the shell may be applied to the aggregated particles after aggregation but before cementation.

[0102] Examples of resins that can be used to form the shell include, but are not limited to, the amorphous resins used for the core. Such amorphous resins may be low molecular weight resins, high molecular weight resins, or combinations thereof. In embodiments, an example of an amorphous resin that can be used to form the shell according to this disclosure is the amorphous polyester of formula I described above.

[0103] In some embodiments, the amorphous resin used to form the shell may be crosslinked. For example, crosslinking can be achieved by combining the amorphous resin with a crosslinking agent, sometimes referred to herein as a reaction initiator in embodiments. Examples of suitable crosslinking agents include, but are not limited to, the above-mentioned organic peroxides and azo compounds, which are suitable for forming a gel within the core, as free radicals or thermal reaction initiators.Suitable examples of organic peroxides include diacyl peroxides, such as decanoyl peroxide, lauroyl peroxide, and benzoyl peroxide; ketone peroxides, such as cyclohexanone peroxide and methyl ethyl ketone; and alkyl peroxyesters, such as t-butyl peroxyneodecanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-amyl peroxy 2-ethylhexanoate, and t-butyl peroxy 2-ethyl Alkyl peroxides such as hexanoates, t-butyl peroxyacetate, t-amyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, co-t-butyl o-isopropyl monoperoxycarbonate, 2,5-dimethyl 2,5-di(benzoyl peroxy)hexane, co-t-butyl o-(2-ethylhexyl) monoperoxycarbonate, and co-t-amyl o-(2-ethylhexyl) monoperoxycarbonate, for example, dicumyl peroxide. Alkyl hydroperoxides such as 2,5-dimethyl2,5-di(t-butylperoxy)hexane, t-butylcumylperoxide, α-α-bis(t-butylperoxy)diisopropylbenzene, di-t-butylperoxide, and 2,5-dimethyl2,5-di(t-butylperoxy)hexine-3, as well as alkyl hydroperoxides such as 2,5-dihydroperoxy2,5-dimethylhexane, cumene hydroperoxide, t-butyl hydroperoxide, and t-amyl hydroperoxide, and Alkyl peroxyketals include, for example, n-butyl 4,4-di(t-butylperoxy)valerate, 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, ethyl 3,3-di(t-butylperoxy)butyrate and ethyl 3,3-di(t-amylperoxy)butyrate, and combinations thereof.Suitable azo compounds include 2,2,'-azobis(2,4-dimethylpentanenitrile), azobis-isobutyronitrile, 2,2,-azobis(isobutyronitrile), 2,2,-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'-azobis(cyanocyclohexane), other similar known compounds, and combinations thereof.

[0104] The crosslinking agent and amorphous resin may be combined for a sufficient time and at a sufficient temperature to form a crosslinked polyester gel. In embodiments, the crosslinking agent and amorphous resin may be heated to a temperature of about 25°C to about 99°C, or in embodiments, about 30°C to about 95°C, for a period of about 1 minute to about 10 hours, or in embodiments, about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell.

[0105] When used, the crosslinking agent may be present in an amount of about 0.001% to about 5% by weight of the resin, and in embodiments, about 0.01% to about 1% by weight of the resin. The amount of CCA can be reduced in the presence of the crosslinking agent or reaction initiator.

[0106] A single polyester resin may be used as the shell, or, as described above, in the embodiment, the first polyester resin may be combined with other resins to form the shell. Multiple resins may be used in any suitable amount. In the embodiment, the first amorphous polyester resin, for example, the low molecular weight amorphous resin of formula I, may be present in an amount of about 20% to about 100% by weight of the total shell resin, and in the embodiment, about 30% to about 90% by weight of the total shell resin. Therefore, in the embodiment, the second resin, in the embodiment, the high molecular weight amorphous resin, may be present in the shell resin in an amount of about 0% to about 80% by weight of the shell resin, and in the embodiment, about 10% to about 70% by weight of the shell resin.

[0107] Following aggregation to a desired particle size and the application of an optional shell, the particles may then be cemented to a desired final shape, which is achieved by heating the mixture to a temperature of, for example, about 45°C to about 100°C, in embodiments about 55°C to about 99°C (this temperature may be above the glass transition temperature of the resin used to form the toner particles), and / or reducing the stirring speed to, for example, about 100 rpm to about 400 rpm, in embodiments about 200 rpm to about 300 rpm. The cemented particles can be measured for shape factor or roundness using an analyzer such as a SYSMEX FPIA 3000 until the desired shape is achieved.

[0108] Bonding may be achieved over a period of time of approximately 0.01 to 9 hours, or in an embodiment, approximately 0.1 to 4 hours.

[0109] In embodiments, after aggregation and / or bonding, the pH of the mixture may be lowered to about 3.5 to about 6, and in embodiments to about 3.7 to about 5.5, for example, with an acid, in order to further bond the toner aggregates. Suitable acids include, for example, nitric acid, sulfuric acid, hydrochloric acid, citric acid, and / or acetic acid. The amount of acid added may be about 0.1 to about 30% by weight of the mixture, and in embodiments to about 1 to about 20% by weight of the mixture.

[0110] The process described herein includes arranging a charge control agent as described. In embodiments, the emulsion agglomeration toner process described herein includes obtaining a latex of at least one resin; optionally, obtaining an aqueous dispersion of an optionally selected colorant; optionally, obtaining an aqueous dispersion of an optionally selected wax; forming a mixture of the latex of at least one resin, the aqueous dispersion of an optionally selected colorant, and the aqueous dispersion of an optionally selected wax; heating the mixture to a first temperature; maintaining the first temperature to form agglomerated toner particles; adding a latex of a shell resin to form a shell on the agglomerated particles; optionally, adding a solution of a chelating agent; stopping further agglomeration; raising the temperature to a second temperature higher than the first temperature to bond the agglomerated particles to form bonded toner particles; and cooling. The present invention provides a method for introducing a charge control agent into emulsion agglutinated toner particles by optionally washing and optionally drying the particles, and by adding a metal ion donor and at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone, or a combination thereof to the emulsion agglutinated toner particles, wherein the metal ion donor and the polyaromatic acid ligand, pyranone ligand, furanone ligand, or a combination thereof form a charge control agent, and thus form emulsion agglutinated toner particles containing a charge control agent, and by adding phenylsiloxane to the emulsion agglutinated toner particles.

[0111] The mixture may be cooled, washed, and dried. Cooling may take place at a temperature of about 20°C to about 40°C, or in embodiments, about 22°C to about 30°C, for about 1 hour to about 8 hours, or in embodiments, about 1.5 hours to about 5 hours.

[0112] In embodiments, the slurry may be passed through at least one heat exchanger to rapidly cool the slurry after cementation. After cementation, the mixture may be rapidly cooled to a temperature below the glass transition temperature of the resin, such as below about 40°C. Cooling may be rapid or slow as desired. A preferred cooling method may include rapidly cooling by introducing chilled water into a jacket around at least one heat exchanger.

[0113] Next, the toner slurry can be washed. Washing may be carried out at a pH of about 7 to about 12, or in embodiments, at a pH of about 9 to about 11. Washing may be carried out at a temperature of about 30°C to about 70°C, or in embodiments, at a temperature of about 40°C to about 67°C. Washing may include filtering and re-slurring the filtration cake containing toner particles in deionized water. The filtration cake may be washed once or more times with deionized water, or the pH of the slurry may be adjusted with acid to a pH of about 4 and washed once with deionized water, followed optionally by one or more more washes with deionized water.

[0114] Drying may be carried out at a temperature of approximately 35°C to approximately 75°C, and in embodiments, approximately 45°C to approximately 60°C. Drying may be continued until the moisture level of the particles falls below the set target of approximately 1% by weight, and in embodiments, below approximately 0.7% by weight.

[0115] In embodiments, the charge control agent according to this specification is placed on emulsion agglomerated toner particles after cooling, washing, and drying. In one embodiment, the charge control agent is deposited on the surface of the emulsion agglomerated toner particles after cooling. In a particular embodiment, the charge control agent is deposited on the surface of the emulsion agglomerated toner particles after drying. In a preferred embodiment, the prepared dried emulsion agglomerated toner particles are redispersed, such as by being dispersed in water, to form a toner slurry, and the charge control agent is deposited on the surface of the toner particles in the toner slurry. Thus, in embodiments, the emulsion agglomerated toner process according to this specification further includes dispersing dried emulsion agglomerated toner particles in water to form a slurry of emulsion agglomerated toner particles, placing a charge control agent on the surface of the dispersed emulsion agglomerated toner particles, and placing a hydrophobic treatment on the surface of the dispersed emulsion agglomerated toner particles.

[0116] In this embodiment, the process further includes combining emulsion-aggregated toner particles with a toner carrier to form a developer.

[0117] In embodiments, the toner particles described herein may, if desired or as needed, include optional additives in addition to the internal charge control agents described herein. For example, the toner may contain, for example, a positive or negative charge control agent in an amount of about 0.1 to about 10% by weight of the toner, and in embodiments, about 1 to about 3% by weight of the toner. Examples of suitable charge control agents include quaternary ammonium compounds containing alkylpyridinium halides, disulfates, alkylpyridinium compounds including those disclosed in U.S. Patent No. 4,298,672 (which is incorporated entirely herein by reference), organic sulfate and sulfonate compositions including those disclosed in U.S. Patent No. 4,338,390 (which is incorporated entirely herein by reference), cetylpyridinium tetrafluoroborate, distearyldimethylammonium methyl sulfate, aluminum salts such as BONTRON E84 (trademark) or E88 (trademark) (Orient Chemical Industries, Ltd.), and combinations thereof. Such charge control agents may be applied simultaneously with the shell resin or after the application of the shell resin.

[0118] Furthermore, external additive particles containing flow aid additives may be compounded with the toner particles after formation, and these additives may be present on the surface of the toner particles. Examples of these additives include metal oxides such as titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, tin oxide, and mixtures thereof; colloidal silica and amorphous silica such as AEROSIL®; metal salts and fatty acid metal salts including zinc stearate and calcium stearate; or long-chain alcohols such as UNILIN® 700, and mixtures thereof. In embodiments, the toner according to this specification further comprises cleaning additives selected from the group consisting of stearates, cerium oxide, strontium titanate, and combinations thereof.

[0119] Each of these external additives may be present in an amount of about 0% to about 3% by weight of the toner, and in embodiments, about 0.25% to about 2.5% by weight of the toner, although the amount of additives may be outside these ranges. In embodiments, the toner may contain, for example, about 0% to about 3% by weight of titania, about 0% to about 3% by weight of silica, and about 0% to about 3% by weight of zinc stearate.

[0120] In certain embodiments, the toner does not contain external TiO2 additives, i.e., it does not contain them.

[0121] In embodiments, the toner of the present disclosure may be used as an ultra-low melt (ULM) toner. In embodiments, dry toner particles having a core and / or shell may have one or more of the following properties, apart from external surface additives:

[0122] (1) A volume-average diameter (also called "volume-average particle size") of approximately 3 to approximately 25 micrometers (μm), approximately 4 to approximately 15 μm in some embodiments, and approximately 5 to approximately 12 μm in other embodiments.

[0123] (2) Number Average Geometric Size Distribution (GSDn) and Volume Average Geometric Size Distribution (GSDv): In embodiments, the toner particles described in (1) above may have a narrow particle size distribution with a low number ratio GSD of about 1.15 to about 1.38, and in other embodiments less than about 1.31. The toner particles of the present disclosure may also have a size such that the upper volume GSD is in the range of about 1.20 to about 3.20, and in other embodiments about 1.26 to about 3.11. The volume average particle sizes D50V, GSDv, and GSDn can be measured by measuring instruments such as a Beckman Coulter Multisizer 3 operated according to the manufacturer's instructions. Typical sampling may occur as follows: a small amount of toner sample, about 1 gram, is obtained, filtered through a 25-micrometer sieve, then placed in an isotonic solution to obtain a concentration of about 10%, and then the sample is measured with a Beckman Coulter Multisizer 3.

[0124] (3) Roundness of approximately 0.92 to approximately 0.99, and in other embodiments, approximately 0.94 to approximately 0.975. The instrument used to measure the roundness of the particles may be an FPIA-3000 manufactured by SYSMEX, in accordance with the manufacturer's instructions.

[0125] The properties of toner particles can be determined by any suitable technique and apparatus, and are not limited to those described above.

[0126] The toner particles formed in this way can be incorporated into a developer composition. By mixing the toner particles with carrier particles, a two-component developer composition can be obtained. The toner concentration in the developer may be about 1% to 25% by weight of the total weight of the developer, and in embodiments, about 2% to 15% by weight of the total weight of the developer.

[0127] Examples of carrier particles that can be used for mixing with toner include particles that can acquire a charge of opposite polarity to that of the toner particles through triboelectric means. Exemplary examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrite, iron ferrite, and silicon dioxide. Other carriers are disclosed in U.S. Patents No. 3,847,604, No. 4,937,166, and No. 4,935,326.

[0128] The selected carrier particles may be used with or without a coating. In embodiments, the carrier particles may comprise a core having a coating thereon, which may be formed from a mixture of polymers that are not in close proximity in the triboelectric system. The coating may include fluoropolymers, such as polyvinylidene fluoride resins, styrene terpolymers, methyl methacrylate, and / or silanes, such as triethoxysilane, tetrafluoroethylene, and other known coatings. For example, a coating containing polyvinylidene fluoride, available as KYNAR 301F®, and / or polymethyl methacrylate having a weight-average molecular weight of about 300,000 to about 350,000, such as that available from Soken, may be used. In embodiments, polyvinylidene fluoride and polymethyl methacrylate (PMMA) may be mixed in a ratio of about 30 to about 70% by weight to about 70 to about 30% by weight, and in embodiments, about 40 to about 60% by weight to about 60 to about 40% by weight. The coating may have a coating weight of, for example, about 0.1 to about 5% by weight of the carrier, and in embodiments, about 0.5 to about 2% by weight of the carrier.

[0129] In embodiments, PMMA may be optionally copolymerized with any desired comonomer, as long as the resulting copolymer maintains a suitable particle size. Suitable comonomers include monoalkyl or dialkylamines, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, or t-butylaminoethyl methacrylate. The carrier particles can be prepared by mixing the polymer with a carrier core in an amount of about 0.05 to about 10% by weight, or in embodiments, about 0.01 to about 3% by weight, based on the weight of the coated carrier particles, until the carrier core adheres to the carrier core by mechanical impact and / or electrostatic attraction.

[0130] The polymer can be applied to the surface of the carrier core particles using various effective and suitable means, such as cascade roll mixing, tumbling, milling, shaking, electrostatic powder cloud spraying, fluidized bed, electrostatic disk treatment, electrostatic curtain, or a combination thereof. The mixture of carrier core particles and polymer can then be heated to allow the polymer to melt and fuse to the carrier core particles. The coated carrier particles can then be cooled and subsequently sorted into the desired particle size.

[0131] In embodiments, a suitable carrier may include a steel core, for example, with a diameter of about 25 to about 100 μm, and in embodiments, about 50 to about 75 μm, coated with about 0.5% to about 10% by weight, and in embodiments, about 0.7% to about 5% by weight, of a conductive polymer mixture, including, for example, methyl acrylate and carbon black, using the processes described in U.S. Patents No. 5,236,629 and No. 5,330,874.

[0132] The carrier particles can be mixed with toner particles in various suitable combinations. The concentration may be about 1% to 20% by weight of the toner composition. However, by using different percentages of toner and carrier, a developer composition with desired properties can be obtained.

[0133] In embodiments, the developer as described herein comprises emulsion-aggregated toner particles and a toner carrier, wherein the emulsion-aggregated toner particles comprises at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles, the charge control agent comprising phenylsiloxane and a complex formed from the metal ion donor and ligand described herein.

[0134] The toner can be used in electrostatic or electrophotographic processes. In embodiments, any known type of developing system may be used in a developing apparatus, including, for example, magnetic brush developing, jumping single-component developing, and hybrid scavengeless developing (HSD). These and similar development systems are within the intent of those skilled in the art.

[0135] The imaging process includes, for example, preparing an image using an electrophotographic apparatus that includes a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fixing component. In embodiments, the developing component may include a developer prepared by mixing a carrier with a toner composition described herein. The electrophotographic apparatus may include a high-speed printer, a black-and-white high-speed printer, a color printer, and the like.

[0136] Once an image is formed with toner / developer via a preferred developing method such as one of the methods described above, the image can then be transferred to an image-receiving medium such as paper. In embodiments, toner may be used for development in a developing apparatus utilizing a fuser roll member. The fuser roll member is a contact fusing device within the intent of those skilled in the art, which can use heat and pressure from the roll to fuse the toner to the image-receiving medium. In embodiments, the fuser member may be heated to a temperature exceeding the toner fixing temperature, for example, about 70°C to about 160°C, about 80°C to about 150°C in embodiments, and about 90°C to about 140°C in other embodiments, after or during melting onto the image-receiving substrate.

[0137] In embodiments where the toner resin is crosslinkable, such crosslinking can be achieved by any preferred method. For example, the toner resin may be crosslinked to a substrate that is crosslinkable at the fixing temperature during toner fixing. Crosslinking can also be achieved by heating the fixed image to a temperature at which the toner resin is crosslinked, for example, in a post-fixing operation. In embodiments, crosslinking can be achieved at temperatures of about 160°C or less, about 70°C to about 160°C in embodiments, and about 80°C to about 140°C in other embodiments. [Examples]

[0138] The following embodiments are provided to further define the various types of this disclosure. These embodiments are for illustrative purposes only and are not intended to limit the scope of this disclosure. Unless otherwise stated, proportions and percentages are given by weight.

[0139] Polyester particle process. Emulsion-aggregated toner particles were synthesized using an agglomeration / coating method. Core polyester latex, pigment, wax, nitric acid, and flocculent were homogenized and then agglomerated while being mixed in a reaction vessel at a temperature of approximately 46°C. At a target particle size of approximately 5.3 micrometers (D50v), a mixture of shell polyester latex and nitric acid was added, and the batch was held for a sufficient time to allow the latex to completely adhere to the existing toner aggregates. Next, the pH was raised to approximately 7.8 using sodium hydroxide and ethylenediaminetetraacetic acid (EDTA) to stop the agglomeration reaction. Then, the batch temperature was raised to 85°C to bond the material to particles with a target roundness of 0.972. Finally, the batch was passed through a heat exchanger to rapidly cool the toner particles to below 40°C. The resulting slurry was then washed and dried to obtain toner matrix particles. [Table 1]

[0140] High MW (molecular weight) amorphous polyester was prepared from an amorphous polyester resin in emulsion containing terpoly-(propoxylated bisphenol A-terephthalate)terpoly-(propoxylated bisphenol A-dodecenyl succinate)terpoly-(propoxylated bisphenol A-fumarate) with an average molecular weight (Mw) of approximately 86,000, a number-average molecular weight (Mn) of approximately 5,600, a starting glass transition temperature (Tg start) of approximately 56°C, a particle size of approximately 70 nm (nanometers), and a solid content of approximately 35%.

[0141] Low MW (molecular weight) amorphous polyester was prepared from amorphous polyester resin in an emulsion containing terpoly-(propoxylated bisphenol A-terephthalate)terpoly-(propoxylated bisphenol A-dodecenyl succinate)terpoly-(propoxylated bisphenol A-fumarate) with a composition of approximately 19,400 Mw, approximately 5,000 Mn, a Tg start at approximately 60°C, a particle size of approximately 170-230 nm, and approximately 35% solids.

[0142] Crystalline polyester is a crystalline polyester resin that includes polyesters made from dodecanediic acid and 1,9-nonanediol.

[0143] Carbon black is an unoxidized, low-structure furnace black pigment.

[0144] The cyan pigment is CI Pigment Blue 15:3.

[0145] Fischer-Tropsch wax is a distilled synthetic polymethylene wax with a melting point of approximately 92°C.

[0146] EDTA is ethylenediaminetetraacetic acid.

[0147] The parent particle formation procedure for all examples is as described above. All examples were prepared using the Fuji-mill blending procedure and charge spectrograph analysis procedure described herein. The following examples use the same procedure but are distinguished by the type / amount of acid ligand and metal ion donor.

[0148] Toner formulation and blending. All toner samples were blended for 9 minutes at 9600 rpm (revolutions per minute) using a 750 ml bench blender (FujiMill) with 70-75 grams of black particles and an additive package containing fumed SiO2, colloidal SiO2, strontium titanate, cerium oxide, and wax to lubricate the photoreceptors. The blender was operated in 3-minute on, then 3-minute off (3 times) cycles to prevent the blending vessel from overheating and creating coarse particles.

[0149] Example 1 Al 3+ Dehydroacetic acid / phenylsiloxane CCA deposition particle synthesis. 80 grams of polyester particles were slurryed using 360 grams of water with the help of a small amount (approximately 20 grams) of ethanol. 0.76 grams of an acid ligand, i.e., sodium dehydroacetate, dissolved in 30 grams of water, was slowly added to the toner particle slurry while stirring. The dispersion was stirred for 1 hour, and then 0.50 grams of a metal ion, i.e., aluminum nitrate notahydrate, dissolved in 20 grams of water, was added dropwise. The pH of the resulting dispersion was adjusted to 6.5 using 0.3 M HNO3, and the mixture was stirred for 1 hour. Subsequently, 0.8 grams of phenyltriethoxysilane dissolved in 5 grams of ethanol was added to the dispersion, and the mixture was stirred for 2 hours. The resulting dispersion was then filtered, washed with 300 grams of water at pH=6.5, and freeze-dried. 3+ Dehydroacetic acid / phenylsiloxane charge control agent-deposited toner particles were obtained. The treated particles were blended using Fuji-Mill in the manner described above. The obtained toner was evaluated for peak q / d in zone A and zone J at mixing times of 5 seconds, 10 seconds, 15 seconds, and 30 seconds, and the results are provided in Tables 3 and 4.

[0150] Comparative Example 2 Comparative Example 2, which does not contain an internal charge control agent, contains the above-described parent particles having an additive package containing fumed SiO2, colloidal SiO2, strontium titanate, cerium oxide, and wax for lubricating the photoreceptors, but without the internal charge control agent. The untreated particles were blended using Fuji-Mill in the manner described above. The resulting toner was evaluated for A-zone peak q / d and J-zone peak q / d at mixing times of 5 seconds, 10 seconds, 15 seconds, and 30 seconds, and the results are provided in Tables 3 and 4. [Table 2] [Table 3] [Table 4]

[0151] Evaluation results. Each example was subjected to a mixed charge distribution using a ferrite support at a toner concentration of 5%. In this procedure, a sample developer was prepared using a toner concentration of 5 parts per hundred (pph), containing 5 parts toner per 100 parts of total developer. After acclimatization at both 80°F and 80% relative humidity (RH) and 70°F and 10% RH, the sample was mixed for 10 minutes using a Turbula mixer operating at 96 rpm. Friction was measured using a barbetta box, and a charge spectrograph (CSG) sample was prepared at this 10-minute mark. A new toner sample of 2.5 pph was added to this same developer (total TC = 7.5 pph) and mixed for 5 seconds, 10 seconds, 15 seconds, and 30 seconds using the same mixing settings. At each mixing time, a CSG sample was prepared to understand how the mixing performance was in each of the four mixing times. Next, each CSG sample is converted into a chart of particle counts plotted against q / d (charge per diameter, in units of fc / micrometer). The metrics in Tables 3 and 4 were calculated from this data to provide a measure of the developer mixing rate.

[0152] As shown in Tables 3 and 4, peak width is defined as the difference between the 98th and 2nd percentiles of the CSG, excluding tails and outliers. Low charge % is defined as the percentage of CSG greater than -0.10 fc / micrometer and represents toner particles that are expected to be difficult to develop properly. Peak q / d is the maximum value of the CSG, excluding those occurring at the tails. This metric indicates the magnitude of the triboelectric charging ability of the toner. Peak A / J is the ratio of A-zone peak q / d to J-zone peak q / d and represents the performance of the toner to charge consistently under various environmental conditions.

[0153] It is desirable to reduce the peak width at 5 seconds, increase the A / J ratio toward 1, and minimize the low charge percentage.

[0154] CSG charts for laboratory-scale particles without any CCA deposition or TiO2 additives are shown in Figures 1 and 2. Figure 1 shows the CSG for the particles of Comparative Example 2 at low humidity (J zone) of 10% RH at 21°C. Figure 2 shows the CSG for the particles of Comparative Example 2 at high humidity (A zone) of 85% RH at 28°C. The solid lines in Figures 1 and 2 represent the distribution after mixing for 10 minutes at a toner concentration of 5 pph (initial specification). The dashed lines in Figures 1 and 2 represent the mixing distribution after adding an additional 2.5 pph of fresh toner to the developer sample, measured at additional mixing times of 5, 10, 15, and 30 seconds. The mixing at a mixing time of 5 seconds in Figure 1 shows a double peak with a short peak of approximately -0.5 fC / μm (femtocoulombs per micrometer). Subsequent mixing times are more uniform, but the distribution width continues to narrow as the mixing time increases. This problem is usually solved by adding TiO2 as an external additive during blending. The peak Q / d (toner charge in fC / μm units) of the 30-second blending distribution is also an important essential parameter, especially for comparing low humidity (J zone) and high humidity (A zone). In this case, the A / J ratio is approximately 0.77 (the 30-second peak Q / d of zone A divided by the 30-second peak Q / d of zone J). Ultimately, we require that the 30-second peak is the same for all humidity conditions (A zone / J zone = 1.0), that the charge distribution width for all four blending times is the same as the initial charge distribution without any double peaks, and that all blending times have equal peak Q / d.

[0155] Figures 3 and 4 show Al deposited using the procedure of this embodiment. 3+ This is a CSG chart for Example 1, which contains a CCA molecule having ions, dehydroacetic acid, and phenyltriethoxysilane. Figure 3 shows the CSG for the particles of Example 1 at 21°C and 10% RH (low humidity zone J). Figure 4 shows the CSG for the particles of Example 1 at 28°C and 85% RH (high humidity zone A).

[0156] The data for CCA Example 1 shows a reduced peak width compared to Comparative Example 2, which does not contain CCA molecules. Furthermore, triboelectric charging was reduced without significantly increasing the low charge percentage. The reduced peak width is beneficial for zero-graphic performance, allowing for uniform development of a larger proportion of toner. In particular, reducing triboelectric charging may be beneficial in toner formulations that do not contain TiO2 as an external additive.

[0157] It will be understood that various features and functions disclosed above, or alternatives thereof, may be desirablely combined in many other different systems or applications. Furthermore, various currently unforeseen or unprecedented alternatives, modifications, variations, or improvements may subsequently be made by those skilled in the art, and these too are intended to be covered by the following "Claims." Unless specifically enumerated in the Claims, no process or component of the Claims should be implied or understood in any particular order, number, position, size, shape, angle, color, or material from this Specified or any other Claims.

Claims

1. Emulsion-aggregated toner, Toner particles containing at least one type of resin, an optional colorant, and an optional wax, A charge control agent disposed on the surface of the toner particles, A charge control agent comprising a phenyl siloxane, a metal ion donor, and a complex formed from at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof, Emulsion agglomeration toner wherein the metal ion donor of the charge control agent complex is selected from members of the group consisting of a divalent calcium ion donor, a divalent magnesium ion donor, a divalent barium ion donor, a divalent zinc ion donor, a trivalent aluminum ion donor, a trivalent iron ion donor, a tetravalent titanium ion donor, a tetravalent zirconium ion donor, and combinations thereof.

2. The toner includes a core-shell structure, The emulsion aggregated toner according to claim 1, wherein the charge control agent is disposed on the surface of the toner particle shell.

3. The emulsion agglutination toner according to claim 1, wherein the phenyl siloxane is selected from members of the group consisting of phenylsiloxane, alkylphenylsiloxane having alkyl groups with 1 to about 50 carbon atoms, diphenylsiloxane, and combinations thereof.

4. The emulsion agglutination toner according to claim 1, wherein the metal ion donor of the charge control agent complex is selected from members of the group consisting of zinc nitrate, zinc acetate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, aluminum chloride, and combinations thereof.

5. The emulsion agglutinating toner according to claim 1, wherein the ligand is selected from members of the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

6. The emulsion agglutination toner according to claim 1, wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

7. The toner is TiO 2 An emulsion agglutination toner according to claim 1, which does not contain the following.

8. It is a developer, Emulsion aggregated toner particles and toner carrier included, The emulsion aggregated toner particles comprise at least one resin, an optional colorant, an optional wax, and a charge control agent disposed on the surface of the toner particles. A charge control agent comprising a phenyl siloxane, a metal ion donor, and a complex formed from at least one ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof, A developer wherein the metal ion donor of the charge control agent complex is selected from members of the group consisting of a divalent calcium ion donor, a divalent magnesium ion donor, a divalent barium ion donor, a divalent zinc ion donor, a trivalent aluminum ion donor, a trivalent iron ion donor, a tetravalent titanium ion donor, a tetravalent zirconium ion donor, and combinations thereof.

9. The toner particles include a core-shell structure, The developer according to claim 8, wherein the charge control agent is disposed on the surface of the toner particle shell.

10. The phenyl siloxane is selected from the group consisting of phenylsiloxane, alkylphenylsiloxane having 1 to about 50 alkyl groups, diphenylsiloxane, and combinations thereof. The developer according to claim 8, wherein the ligand is selected from members of the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

11. The metal ion donor of the charge control agent complex is selected from the group consisting of zinc nitrate, zinc acetate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum chloride, and combinations thereof. The developer according to claim 8, wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

12. The toner particles are TiO 2 The developer according to claim 8, which does not contain any of the above.

13. Emulsion aggregation toner process, To obtain a latex of at least one type of resin, To selectively obtain an aqueous dispersion of a selective coloring agent, To selectively obtain an aqueous dispersion of a wax, To form a mixture of the latex of at least one type of resin, the aqueous dispersion of the optional colorant, and the aqueous dispersion of the optional wax, Heating the mixture to a first temperature, Maintaining the first temperature described above to form aggregated toner particles, Adding latex from a shell resin to form a shell on the aggregated particles, The optional addition of a chelating agent solution, Further aggregation is stopped, and the temperature is raised to a second temperature higher than the first temperature to cause the aggregated particles to fuse together. The emulsion aggregated toner particles are cooled, optionally washed, optionally dried, and recovered. Introducing a charge control agent to emulsion aggregated toner particles by adding a metal ion donor and at least one ligand selected from the group consisting of a humic acid-containing polyaromatic acid, a pyranone ligand, a furanone ligand, or a combination thereof, wherein the metal ion donor and the polyaromatic acid ligand, pyranone ligand, furanone ligand, or a combination thereof form the charge control agent, and thus form emulsion aggregated toner particles containing the charge control agent; and adding a phenyl siloxane to the emulsion aggregated toner particles. An emulsion agglomerated toner process further comprising cooling, optionally washing, and recovering the emulsion agglomerated toner particles.

14. The emulsion aggregated toner process according to claim 13, further comprising combining the emulsion aggregated toner particles containing the charge control agent and phenylsiloxane with a toner carrier to form a developer.

15. The emulsion agglomeration toner process according to claim 13, wherein the phenyl siloxane is selected from members of the group consisting of phenylsiloxane, alkylphenylsiloxane having 1 to about 50 alkyl groups, diphenylsiloxane, and combinations thereof.

16. The metal ion donor of the charge-controlling agent complex is selected from the group consisting of divalent calcium ion donors, divalent magnesium ion donors, divalent barium ion donors, divalent zinc ion donors, trivalent aluminum ion donors, trivalent iron ion donors, tetravalent titanium ion donors, tetravalent zirconium ion donors, and combinations thereof. The emulsion agglomeration toner process according to claim 13, wherein the ligand is selected from members of the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

17. The metal ion donor of the charge control agent complex is selected from the group consisting of zinc nitrate, zinc acetate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, aluminum chloride, and combinations thereof. The emulsion agglomeration toner process according to claim 13, wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

18. The toner particles are TiO 2 The emulsion agglomeration toner process according to claim 13, which does not include the following:

19. The process involves dispersing dried emulsion-aggregated toner particles in water to form a slurry of the emulsion-aggregated toner particles, The emulsion agglomeration toner process according to claim 13, further comprising: arranging the charge control agent on the surface of the dispersed emulsion agglomeration toner particles; and adding the phenylsiloxane.

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