Toner containing charge control agent

Abstract

To ensure good print 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 control agent containing a complex formed from a metal ion donor and at least one ligand selected from a group consisting of a polyaromatic acid comprising humic acid, a pyranone-based ligand, a furanone-based ligand, or a combination thereof.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] Cross - reference to Related Applications U.S. Patent Application No. 17 / 697800 (Attorney Docket No. 20210496US01 entitled "Toner Comprising Charge Control Agent"), assigned to the assignee of the present invention and filed concurrently with this specification and the entire content of which is incorporated herein by reference, describes an emulsion aggregation toner comprising toner particles containing at least one resin, an optional colorant, and 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 ligand selected from the group consisting of a polyaromatic acid containing a metal ion donor and humic acid, a pyranone - based ligand, a furanone - based ligand, or a combination thereof.

[0002] U.S. Patent Application No. 17 / 697809 ("Toner Comprising Reactive Charge Control"), filed concurrently with this specification and incorporated herein by reference as the entirety of which constitutes part of this specification, has been assigned to the assignee of this invention. Agent No. 20210498US01, titled "Agent", describes an emulsified agglomerated toner comprising toner particles comprising at least one resin, an optional colorant, and an optional wax; a reactive charge control agent disposed on the surface of the toner particles, comprising at least one positively charged compound 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, boron compounds having at least three carbon atoms, and combinations thereof; and at least one reactive anchor compound, comprising a member selected from the group consisting of amino, epoxy, carboxyl, hydroxyl, silanol, cyanide, anhydride, aldehyde, ketone, vinyl, and combinations thereof, wherein the charge control agent optionally further comprises a negatively charged compound, comprising a member selected from the group consisting of aromatic carboxylic acids, silanol, phenol, pyranone, furanone, and combinations thereof. [Background technology]

[0003] Disclosed herein is an emulsified aggregated toner comprising toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, comprising a complex formed from 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] A developer comprising emulsified aggregated toner particles and a toner carrier is further disclosed, wherein the emulsified 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, comprising a complex formed from at least one of the group consisting of a metal ion donor and polyaromatic acids including humic acid, pyranone ligands, furanone ligands, or combinations thereof, wherein the toner particles optionally further comprise a surface modifier disposed on the surface of the toner particle shell, selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

[0005] The process involves obtaining a latex of at least one type of resin, optionally obtaining an aqueous dispersion of any coloring agent, optionally obtaining an aqueous dispersion of any wax, forming a mixture of the latex of at least one type of resin, an aqueous dispersion of any coloring agent, and an aqueous dispersion of any 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 surface of 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, cooling the emulsified agglomerated toner particles, optionally washing them, optionally drying them, and recovering them, and a metal ion donor and a polyaromatic acid containing humic acid, a pyranone-based coordination Further disclosed is an emulsified toner process comprising: adding at least one ligand selected from the group consisting of a metal ion donor and a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof to emulsified agglomerated toner particles to precipitate a charge control agent on the surface of the emulsified agglomerated toner particles, wherein the polyaromatic acid containing a metal ion donor and a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof forms a charge control agent, thereby forming emulsified agglomerated toner particles containing an internal charge control agent; and optionally, arranging a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof on the surface of the toner particle shell.

[0006] The advent of chemically manufactured toner particles has enabled significant improvements in print quality and transfer efficiency over many years. However, the chemical properties involved in the formulation of these particles lead to major interactions during the manufacturing process that can compromise customer performance. In particular, the chemical properties and raw materials used in the emulsification and agglomeration (EA) process can produce particles whose environmental stability, both in terms of charging rate and average charge, can be compromised. Under low humidity conditions, typical polyester and / or styrene acrylate particles become very highly charged, requiring long kneading times with the carrier to stabilize and uniformly distribute the charge when combining new toner with old toner in the developer. In contrast, the average charge peak of these particles can be very low under high humidity conditions. This presents challenges in ensuring good print performance in all extreme environments. In the era of conventional particle processes (extrusion / grinding), internal charge control agents (CCAs) were introduced into the molten resin mixture to improve the environmental stability of the final toner. In the EA process, it has been shown to be difficult to introduce similar charge control agents into the particles without adversely impacting the particle process. The suspension polymerization method for particle formulations allows for the easy introduction of internal CCA into the particles through the use of a solvent in this process. One method to eliminate the environmental instability of EA particles is to use titanium dioxide (TiO2) as an external additive in the toner formulation. This additive tends to reduce the average charge and improve the charging rate (mix) under low humidity conditions without seriously affecting high humidity charging performance, thereby further improving environmental stability. However, since TiO2 is considered to pose a potential health risk to humans, regulations regarding TiO2 have been implemented or are expected in recent years, such as adjusting 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, there is still a need for improved toners. Furthermore, there is still a need for improved toners (emulsified aggregate toners in some embodiments) that can be prepared with reduced or no TiO2 content while providing stable charging performance in all extreme environments.

[0008] Appropriate components and processes of the aforementioned U.S. patents and patent application publications may be selected for this disclosure in several 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 Initiative]

[0009] Disclosed herein is an emulsified aggregated toner comprising toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, comprising a complex formed from 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] A developer comprising emulsified aggregated toner particles and a toner carrier is further described, wherein the emulsified 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, comprising a complex formed from at least one of members of the group consisting of a metal ion donor and polyaromatic acids including humic acid, pyranone ligands, furanone ligands, or combinations thereof, wherein the toner particles optionally further comprise a surface modifier disposed on the surface of the toner particle shell, selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

[0011] The process involves obtaining a latex of at least one type of resin, optionally obtaining an aqueous dispersion of any coloring agent, optionally obtaining an aqueous dispersion of any wax, forming a mixture of the latex of at least one type of resin, an aqueous dispersion of any coloring agent, and an aqueous dispersion of any 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 surface of 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, cooling the emulsified agglomerated toner particles, optionally washing them, optionally drying them, and recovering them, and a metal ion donor and a polyaromatic acid containing humic acid, a pyranone-based coordination Further disclosed is an emulsified toner process comprising: adding at least one ligand selected from the group consisting of a metal ion donor and a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof to emulsified agglomerated toner particles to precipitate a charge control agent on the surface of the emulsified agglomerated toner particles, wherein the polyaromatic acid containing a metal ion donor and a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof forms a charge control agent, thereby forming emulsified agglomerated toner particles containing an internal charge control agent; and optionally, arranging a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof on the surface of the toner particle shell. [Brief explanation of the drawing]

[0012] [Figure 1] This is a charge spectrograph showing data on comparative particles in the low-humidity (J zone). [Figure 2] This is a charge spectrograph showing data on comparative particles in high humidity (Zone A). [Figure 3]This is a charge spectrograph showing data for particles having a low-humidity (J zone) Zn2+ / dehydroacetic acid charge control agent according to this embodiment. [Figure 4] This is a charge spectrograph showing data for particles having a Zn2+ / dehydroacetic acid charge control agent in a high-humidity (Zone A) environment according to this embodiment. [Modes for carrying out the invention]

[0013] This document describes a method for introducing charge control agents (CCA) by precipitating CCA molecules onto the surface of toner particles in an emulsified agglutination (EA) manufacturing process. In some embodiments, the emulsified agglutination toner process includes forming a latex, agglutinating it to form agglutinated particles, bonding the agglutinated particles, cooling, optionally washing, and optionally drying to prepare emulsified agglutinated toner particles. In some embodiments of this specification, the charge control agent precipitates on the surface of the emulsified agglutinated toner particles after the cooling step. In some embodiments, the charge control agent precipitates on the surface of the emulsified agglutinated toner particles between the cooling and washing steps. In other embodiments, the charge control agent precipitates on the surface of the emulsified agglutinated toner particles after the drying step. In some embodiments, the charge control agent as used herein is an internal charge control agent. As used herein, an internal charge control agent means a charge control agent introduced during the wet process of the toner process. This is in contrast to an external additive that is added to the toner after the toner has dried.

[0014] For example, CCA ligands such as dehydroacetic acid or humic acid contain an aromatic core motif to which both a phenol substituent and a carboxylic acid substituent are attached. 3+ Ionic Zn 2+Metal ions such as ions are added to form a dehydroacetic acid complex or humic acid complex that, in some embodiments, can precipitate on the surface of toner particles after cooling but before washing and drying, or after drying. In preferred embodiments, the precipitation process is brought about by an additional redispersion process after cooling, washing, and drying. Thus, in some embodiments, the process described herein includes forming emulsified aggregated toner particles by aggregation and adhesion, cooling, washing, and drying to obtain dried emulsified aggregated toner particles, resuspending the dried emulsified aggregated toner particles, such as by resuspending them in water, to form a slurry of emulsified aggregated toner particles, and precipitating a charge control agent on the surface of the resuspended emulsified aggregated toner particles. This process makes it possible to introduce the charge control agent into the EA process, improving charge performance in the form of increasing the charging rate (mixing rate) and improving environmental stability across a wide range of humidity levels.

[0015] In some embodiments, an emulsified agglomerated toner is described, comprising toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, comprising a complex formed from a metal ion donor and a ligand selected from the group consisting of polyaromatic acids including humic acid, pyranone ligands, furanone ligands, or combinations thereof.

[0016] In a further embodiment, a developer is described comprising emulsified aggregated toner particles and a toner carrier, wherein the emulsified aggregated toner particles comprise toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, comprising a complex formed from a metal ion donor and a ligand selected from the group consisting of a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

[0017] In further embodiments, the emulsified agglomerated toner process involves obtaining a latex of at least one resin, optionally obtaining an aqueous dispersion of any coloring agent, optionally obtaining an aqueous dispersion of any wax, forming a mixture of the latex of at least one resin, the aqueous dispersion of any coloring agent, and the aqueous dispersion of any 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 surface of 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 fuse the agglomerated particles and form fused toner particles, cooling, optionally washing, optionally drying to form emulsified agglomerated toner particles, and metal The method involves adding an ion donor and at least one ligand selected from the group consisting of polyaromatic acids including humic acid, pyranone ligands, furanone ligands, or combinations thereof to emulsified aggregated toner particles to precipitate a charge control agent on the surface of the emulsified aggregated toner particles, wherein the metal ion donor and the humic acid ligand, pyranone ligand, furanone ligand, or combination thereof form a charge control agent, thereby forming emulsified aggregated toner particles containing the charge control agent; and optionally, arranging a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof on the surface of the toner particle shell.

[0018] This application provides an emulsified agglomerated toner containing a charge control agent. In some embodiments, the charge control agent is considered an internal charge control agent. The term “internal charge control agent” means that the charge control agent is introduced during the wet process of the emulsified agglomerated toner process. The internal charge control agent comprises a complex formed from an acid or an ion donor. In some embodiments, the acid and the ion donor together form a complex that, after adsorption, is precipitated onto the surface of the toner particles during the wet process of this process. In some embodiments, the process herein comprises precipitating the charge control agent molecules onto the surface of the particles in the emulsified agglomerated toner process after the drying process or between the cooling and washing processes. In preferred embodiments, the precipitation of the charge control agent is carried out after the emulsified agglomerated toner particles have been cooled, washed, and dried by an additional redispersion process.

[0019] In some embodiments, the toner particles include a core-shell structure, and the charge control agent is located on the surface of the toner particle shell.

[0020] The charge control agent comprises a complex formed from a metal ion donor and a ligand. Any suitable or desired metal ion donor can be selected. In some embodiments, the metal ion donor of the charge control agent complex is selected from members of 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. In certain embodiments, the metal ion donor of the charge control agent complex is selected from members of the group consisting of divalent zinc ion donors, trivalent aluminum ion donors, tetravalent titanium ion donors, tetravalent zirconium ion donors, and combinations thereof.

[0021] In some embodiments, 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 certain embodiments, the metal ion donor of the charge control agent complex is selected from members of the group consisting of zinc nitrate hexahydrate, aluminum nitrate nonahydrate, and combinations thereof.

[0022] In some embodiments, the charge control agent comprises a complex formed from at least one ligand selected from members of the group consisting of polyaromatic acids (in some embodiments, humic acid), metal ion donors, pyranone-based ligands, furanone-based ligands, and combinations thereof.

[0023] Any suitable or desired ligand can be selected. In some embodiments, the ligand is selected from members of the group consisting of polyaromatic acids (in some embodiments, humic acid), pyranone, furanone, and combinations thereof.

[0024] In certain embodiments, the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

[0025] In some embodiments, the ligand comprises a pyranone and / or furanone having a conjugated structure, and electrons are easily delocalized within the molecule.

[0026] Examples of pyrone include hydroxypyrone, hydroxy(thio)pyrone, maltol, tert-butyl maltol, coumaric acid, tetraacetic lactone, and keldonic acid.

[0027] Examples of furanone include 5-hydroxy-2(5H)-furanone, 5-ethyl-4-hydroxy-2-methyl-3(2H)-furanone, 2-methyl-3-furanthiol, and tetronic acid.

[0028] In a particular embodiment, the ligand is selected from the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

[0029] Any toner resin can be used when forming the toner of the present disclosure. Such a resin may then be prepared by any preferred polymerization method with any preferred monomer or two or more monomers. In some embodiments, the resin is prepared by emulsion polymerization. In some embodiments, the resin may be prepared by methods other than emulsion polymerization. In further embodiments, the resin may be prepared by condensation polymerization.

[0030] In some embodiments, the emulsified aggregated toner comprises toner particles having a core-shell structure. The core and shell of the toner particles may comprise any suitable or desired resin, including the resins described herein. In certain embodiments, 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.

[0031] The toner compositions of this disclosure, in some embodiments, include an amorphous resin. The amorphous resin may be linear or branched. In some 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, about 75°C to about 115°C in some embodiments, about 100°C to about 110°C in some embodiments, or about 104°C to about 108°C in some embodiments. When used herein, the low molecular weight amorphous polyester resin has a number-average molecular weight (Mn) of, for example, about 1,000 to about 10,000, about 2,000 to about 8,000 in some embodiments, about 3,000 to about 7,000 in some embodiments, and about 4,000 to about 6,000 in some embodiments, 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 some embodiments, about 3,000 to about 40,000 in some embodiments, about 10,000 to about 30,000 in some embodiments, and about 18,000 to about 21,000 in some 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 some 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 some embodiments, and about 10 to about 14 mg KOH / g in some embodiments.

[0032] 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 phenol 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.

[0033] In some embodiments, suitable amorphous resins include alkoxylated bisphenol A fumarate / terephthalate polyesters and copolyester resins. In some embodiments, 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.

[0034] 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.

[0035] In some 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 of various amorphous polyesters include 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 resins may also be functionalized, such as carboxylation, sulfonation, or, if particularly desired, sodium sulfonation.

[0036] 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 preferred amounts, such as about 60 to about 90% by weight of the toner or solid, and in some embodiments, about 50 to about 65% by weight.

[0037] 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.

[0038] 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 mixtures thereof. Organic diacids or diesters are selected, for example, in an amount of about 45 to about 52 mol% of the resin.

[0039] 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.

[0040] 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. Branching agents for use in forming these branched resins include, for example, 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.

[0041] The resulting unsaturated polyester is reactive (e.g., crosslinkable) in two frontmost 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 some embodiments, the unsaturated polyester resin is prepared by melt polycondensation or other polymerization processes using diacids and / or anhydrides and diols.

[0042] In some embodiments, low molecular weight amorphous polyester resins or combinations 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 resins 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.

[0043] The amount of low molecular weight amorphous polyester resin in the toner particles of the present disclosure may be present in any core, any shell, or both in an amount of 25 to about 50% by weight, in some embodiments about 30 to about 45% by weight, and in some embodiments about 35 to about 43% by weight of toner particles (i.e., toner particles excluding external additives and water).

[0044] In some 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, “semicrystalline resin” refers to a resin having a crystallinity of, for example, about 10 to about 90%, and in some embodiments, about 12 to about 70%. Furthermore, as used below, “crystalline polyester resin” and “crystalline resin” encompass both crystalline and semicrystalline resins unless otherwise specified.

[0045] In some embodiments, the crystalline polyester resin is either a saturated crystalline polyester resin or an unsaturated crystalline polyester resin.

[0046] 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 some embodiments, from about 50°C to about 90°C. Crystalline resins can have number-average molecular weights (Mn), for example, from about 1,000 to about 50,000, in some embodiments, from about 2,000 to about 25,000, in some embodiments, from about 3,000 to about 15,000, and in some embodiments, from 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 polystyrene standards, is 50,000 or less, for example, about 2,000 to about 50,000, in some embodiments about 3,000 to about 40,000, in some embodiments about 10,000 to about 30,000, and in some 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, in some 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 some embodiments about 5 to about 15 mg KOH / g, and in some embodiments about 8 to about 13 mg KOH / g.

[0047] 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)- Copoly(propylene-succinate), Copoly(5-sulfoisophthaloyl)-Copoly(butylene-succinate), Copoly(5-sulfoisophthaloyl)-Copoly(pentylene-succinate), Copoly(5-sulfoisophthaloyl)-Copoly(hexylene-succinate), Copoly(5-sulfoisophthaloyl)-Copoly(octylene-succinate), Copoly(5-sulfo-isophthaloyl)-Copoly(ethylene-sevacate), Co Poly(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)- Examples of various crystalline polyesters include copoli(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.

[0048] 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 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).

[0049] 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.

[0050] 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 an amount of about 40 to 50 mol% of the resin, for example, and alkali sulfoaliphatic diacids may be selected in an amount of about 1 to 10 mol% of the resin.

[0051] 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 as the whole content of which constitutes part of this specification. In some 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.

[0052] 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 ethylene Poly(decamethylene sebacate), poly(ethylene sverat), 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), 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.

[0053] The amount of crystalline polyester resin in the toner particles of this disclosure may be present in the core, shell, or both in an amount of 1 to about 15% by weight, in some embodiments about 5 to about 10% by weight, and in some embodiments about 6 to about 8% by weight of toner particles (i.e., toner particles excluding external additives and water).

[0054] In some embodiments, the toner of the present disclosure may also contain at least one high molecular weight branched or crosslinked amorphous polyester resin. In some embodiments, the high molecular weight resin may be, for example, a branched amorphous resin or amorphous polyester, a crosslinked amorphous resin or amorphous polyester, or a mixture thereof, or a crosslinked non-crosslinked amorphous polyester resin. 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 some embodiments, about 2% to about 50% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0055] 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 some embodiments about 2,000 to about 9,000, in some embodiments about 3,000 to about 8,000, and in some 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 some embodiments about 60,000 to about 100,000, in some embodiments about 63,000 to about 94,000, and in some 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 some embodiments, approximately 5 to approximately 10 in some embodiments, and approximately 6 to approximately 8 in some embodiments. The PD index is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). Low molecular weight amorphous polyester resins may have acid values ​​of approximately 8 to approximately 20 mg KOH / g, approximately 9 to approximately 16 mg KOH / g in some embodiments, and approximately 11 to approximately 15 mg KOH / g in some 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 some embodiments, approximately 100°C to approximately 125°C in some embodiments, and approximately 115°C to approximately 121°C in some embodiments.

[0056] High molecular weight amorphous resins, available from numerous sources, can have a variety of glass transition onset temperatures (Tg) when measured by differential scanning calorimeter (DSC), for example, about 40°C to about 80°C, in some embodiments about 50°C to about 70°C, and in some embodiments about 54°C to about 68°C. In some embodiments, linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0057] 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.

[0058] 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.

[0059] In some 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 some embodiments, 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, as well as diols such as bisphenol A ethylene oxide adduct, bisphenol A-propylene oxide adduct, and combinations thereof. In some embodiments, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0060] In some 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.

[0061] 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 some embodiments, about 22% to about 26% by weight of the reaction mixture.

[0062] 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.

[0063] 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.

[0064] 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 some embodiments, about 44% to about 60% by weight of the reaction mixture.

[0065] Examples of long-chain aliphatic carboxylic acids or aromatic monocarboxylic acids include those containing about 12 to about 26 carbon atoms, in some 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 some embodiments, about 15% to about 30% by weight of the reaction mixture.

[0066] 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.

[0067] In some 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.

[0068] In some 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 some embodiments, about 110 nanometers to about 150 nanometers.

[0069] The amount of high molecular weight amorphous polyester resin in the toner particles of this disclosure may be about 25% to about 50% by weight of the toner in any core, any shell, or both; in some embodiments, about 30% to about 45% by weight; in other embodiments, or about 40% to about 43% by weight of the toner (i.e., toner particles excluding external additives and water).

[0070] 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, in some embodiments from approximately 1:5:5 to approximately 1:9:9, and in some embodiments from approximately 1:6:6 to approximately 1:8:8.

[0071] The toners of this specification (or, in some embodiments, the core of the toners of this specification) may comprise one or a combination thereof of styrene-acrylate copolymers. In some embodiments, the resin is selected from the group consisting of styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, and combinations thereof.

[0072] Exemplary polymers that may 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(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( Examples include butyl 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.

[0073] 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 poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-butyl acrylate), 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.

[0074] In some embodiments, the resin, wax, 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, the toner particles may be formed by an emulsification flocculation method in which the resin and other components of the toner are placed in one or more surfactants to form an emulsion, causing the toner particles to agglomerate and adhere, and the charge control agent of the present invention is precipitated onto the toner surface having the charge control agent during a wet step of the process, thereby distributing the toner having the charge control agent, which is then optionally washed, dried, and recovered. Thus, in some embodiments, the toner particles of this specification include emulsified flocculated toner particles.

[0075] One, two, or more surfactants may be used. Surfactants can be selected from ionic surfactants and nonionic surfactants. Anionic surfactants and cationic surfactants are included in the term "ionic surfactants." In some 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 some embodiments, about 1% to about 3% by weight of the toner composition.

[0076] Examples of nonionic surfactants include polyvinyl alcohol, polyacrylic acid, metalose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and dialkylphenoxypoly(ethyleneoxy)ethanol, which are available from Rhone-Poulenc Inc. as IGEPAL® CA-210, IGEPAL® CA-520, IGEPAL® CA-720, IGEPAL® CO-890, IGEPAL® CO-720, IGEPAL® CO-290, IGEPAL® CA-210, ANTAROX® 890, and ANTAROX® 897. A suitable example of a nonionic surfactant is ANTAROX® 897, available from Rhone-Poulenc Inc., which mainly consists of alkylphenol ethoxylates. Other suitable examples of nonionic surfactants include block copolymers of polyethylene oxide and polypropylene oxide, including SYNPERONIC PE / F, which in some embodiments is commercially available as SYNPERONIC PE / F 108.

[0077] Suitable anionic surfactants include sulfates and sulfonates, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzenealkyl sulfates and sulfonates, such as 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. Other suitable anionic surfactants include DOWFAX® 2A1, an alkyl diphenyl disulfonate available from The Dow Chemical Company, which is used in some embodiments. Combinations of these surfactants may also be used. Combinations of these surfactants with any of the aforementioned anionic surfactants may be used in some embodiments.

[0078] Examples of cationic surfactants, typically those with a positive charge, include alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide, C12, C15, 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 some embodiments.

[0079] The latex particles produced as described above can be added to a colorant to produce toner. In some embodiments, the colorant may be in the form of a dispersion. The colorant dispersion may contain, for example, submicron colorant particles having a volume mean diameter of about 50 to about 500 nanometers, and in some embodiments, a volume mean 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. Any of the above surfactants are suitable surfactants. In some 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 some embodiments, about 1 to about 15% by weight of the colorant.

[0080] 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.

[0081] In some 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.

[0082] 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. 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, and the dye is selected in various suitable amounts, for example, about 0.5 to about 20% by weight of the toner, and in some embodiments about 5 to about 18% by weight of the toner.

[0083] In some embodiments, 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.

[0084] 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.

[0085] In certain embodiments, the colorant includes a black pigment, a cyan pigment, or a combination thereof.

[0086] 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, and in some 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, and in some embodiments, about 5 micrometers to about 8 micrometers.

[0087] 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 some embodiments, about 5% to about 20% by weight of the toner particles.

[0088] Examples of waxes that can be selected include waxes having a weight-average molecular weight of about 500 to about 20,000, and in some embodiments, about 1,000 to about 10,000. Examples of waxes that can be used include polyolefins such as polyethylene, polypropylene, and polybutene wax, which are 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 available from Sanyo Kasei KK. 550-P (trademark), low weight-average molecular weight polypropylene, 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, butyl stearate, propyl oleate, glyceride monostearate Examples include ester waxes obtained from higher fatty acids such as glyceride distearate and pentaerythritol tetrabehenate and monohydric or polyhydric lower alcohols, ester waxes obtained from higher fatty acids such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate and triglyceryl tetrastearate and polyhydric alcohol multimers, 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 some embodiments. The wax may be included, for example, as a release agent for the fuser roll.

[0089] In some embodiments, the toner composition may be prepared by an emulsification-coagulation process, such as a process comprising coagulating an emulsion containing the resin in the surfactant with a mixture of an optional wax and any other desired or required additive, and then bonding the coagulated mixture. The mixture may also be prepared by adding any wax or other material (which may optionally be in a dispersion(or more) 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 some embodiments, the pH of the mixture can be adjusted to about 2 to about 4.5. In addition, in some embodiments, the mixture may be homogenized. If the mixture is homogenized, homogenization may be achieved by mixing at about 4,000 to about 6,000 revolutions per minute. Homogenization may be achieved by any preferred means, for example, an IKA ULTRA TURRAX® T50 probe homogenizer.

[0090] 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 water-soluble metal salts including 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 some embodiments, the flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

[0091] 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 some embodiments, and about 0.5% to about 5% by weight in other embodiments. This provides a sufficient amount of the agent for flocculation.

[0092] To control particle aggregation and adhesion, in some embodiments, a flocculant may be added to the mixture by metering over time. For example, the agent may be added to the mixture by metering over a period of about 5 to about 240 minutes, and in some embodiments, over a period of 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 some embodiments, and about 100 rpm to about 500 rpm in other embodiments, and while maintaining a temperature below the glass transition temperature of the resin, which is about 30°C to about 90°C in some embodiments, and about 35°C to about 70°C in some embodiments.

[0093] 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 increasing 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, and in some embodiments, about 1 to about 5 hours, while continuing to stir and providing aggregated particles. Once the predetermined desired particle size is reached, the growth process is stopped. In some embodiments, the predetermined desired particle size is within the above toner particle size range.

[0094] The growth and molding of particles after the addition of the flocculant can be achieved under any preferred conditions. For example, growth and molding may be carried out under conditions in which aggregation occurs separately from coalescence. For other aggregation and coalescence stages, the aggregation process may be carried out under shear conditions at high temperatures, for example, about 40°C to about 90°C, which may be below the glass transition temperature of the resin, and in some embodiments about 45°C to about 80°C.

[0095] In some embodiments, the shell may be applied to the aggregated particles after aggregation but before cementation.

[0096] 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 some embodiments, an amorphous polyester of formula I can be cited as an amorphous resin that can be used to form the shell according to this disclosure.

[0097] 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 some embodiments. Examples of suitable crosslinking agents include, but are not limited to, the above-mentioned free radical or thermal reaction initiators such as organic peroxides and azo compounds, which are suitable for forming a gel within the core.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 Peroxides, 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, alkyl hydroperoxides, such as 2,5-dihydroperoxy2,5-dimethylhexane, cumene hydroperoxide, t-butyl hydroperoxide, and t-amyl hydroperoxide, and Examples include alkylperoxyketals, such as 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.Examples of 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.

[0098] The crosslinking agent and amorphous resin may be combined for a sufficient time and temperature to form a crosslinked polyester gel. In some embodiments, the crosslinking agent and amorphous resin may be heated to a temperature of about 25°C to about 99°C, in some embodiments about 30°C to about 95°C, for a period of about 1 minute to about 10 hours, in some embodiments about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell.

[0099] 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 some 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.

[0100] A single polyester resin may be used as the shell, or, as described above, in some embodiments, the first polyester resin may be combined with other resins to form the shell. Multiple resins may be used in any suitable amount. In some embodiments, the first amorphous polyester resin, for example, the low molecular weight amorphous resin of formula I described above, may be present in an amount of about 20% to about 100% by weight of the total shell resin, and in some embodiments, about 30% to about 90% by weight of the total shell resin. Accordingly, in some embodiments, the second resin, in some embodiments, 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 some embodiments, about 10% to about 70% by weight of the shell resin.

[0101] Following aggregation to a desired particle size and application of an arbitrary shell, the particles may then be cemented into a desired final shape, which is achieved, for example, by heating the mixture to a temperature of about 45°C to about 100°C, and in some 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 by reducing the stirring speed to, for example, about 100 rpm to about 400 rpm, and in some 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.

[0102] Bonding may be achieved over a period of time of approximately 0.01 to 9 hours, and in some embodiments, approximately 0.1 to 4 hours.

[0103] In some embodiments, after aggregation and / or bonding, the pH of the mixture can be lowered to about 3.5 to about 6, and in some 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 some embodiments, about 1 to about 20% by weight of the mixture.

[0104] The process described herein includes arranging the charge control agent described herein. In some embodiments, the emulsified agglomerated toner process described herein includes obtaining a latex of at least one resin, optionally obtaining an aqueous dispersion of any colorant, optionally obtaining an aqueous dispersion of any wax, forming a mixture of the latex of at least one resin, the aqueous dispersion of any colorant and the aqueous dispersion of any 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 surface of 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 fuse the agglomerated particles and form fused toner particles, cooling, optionally washing, optionally drying to form emulsified agglomerated toner particles, and a metal ion donor and fumigation The method involves adding at least one ligand selected from the group consisting of polyaromatic acids containing humic acid, pyranone ligands, furanone ligands, or combinations thereof, to emulsified aggregated toner particles to precipitate a charge control agent on the surface of the emulsified aggregated toner particles, wherein the ligand selected from the group consisting of polyaromatic acids containing humic acid, pyranone ligands, furanone ligands, or combinations thereof forms a charge control agent, thereby forming emulsified aggregated toner particles containing the charge control agent; and optionally, arranging a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof, on the surface of the toner particle shell.

[0105] The mixture may be cooled, washed, and dried. Cooling may take place at a temperature of about 20°C to about 40°C, and in some embodiments, about 22°C to about 30°C, for about 1 hour to about 8 hours, and in some embodiments, for about 1.5 hours to about 5 hours.

[0106] In some embodiments, the slurry may pass through at least one heat exchanger to rapidly cool the slurry temperature 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.

[0107] Next, the toner slurry can be washed. Washing may be carried out at a pH of about 7 to about 12, and in some 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, and in some 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.

[0108] Drying may be carried out at a temperature of approximately 35°C to approximately 75°C, and in some 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 some embodiments, below approximately 0.7% by weight.

[0109] In some embodiments, the charge control agent according to this specification precipitates on the emulsified toner particles after a cooling, washing, and drying step. In one embodiment, the charge control agent precipitates on the surface of the emulsified toner particles after cooling. In a particular embodiment, the charge control agent precipitates on the surface of the emulsified toner particles after a drying step. In a preferred embodiment, the prepared and dried emulsified toner particles, such as dispersed in water, are redispersed to form a toner slurry, and the charge control agent precipitates on the surface of the toner particles in the toner slurry. Thus, in some embodiments, the emulsified toner process according to this specification further includes dispersing dried emulsified toner particles in water to form a slurry of emulsified toner particles, and precipitating the charge control agent on the surface of the dispersed emulsified toner particles.

[0110] In some embodiments, the process further includes combining emulsified aggregated toner particles and a toner carrier to form a developer.

[0111] In some embodiments, the toner particles of this specification may include, if desired or required, any 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 some embodiments, about 1 to about 3% by weight of the toner. Examples of suitable charge control agents include, but are not limited to, 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.

[0112] In certain embodiments, the emulsified aggregated toner according to this specification further comprises a surface modifier selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof, which is placed on the surface of the toner particle shells.

[0113] Each of these external additives may be present in an amount of about 0% to about 3% by weight of the toner, and in some embodiments, about 0.25% to about 2.5% by weight of the toner, although the amount of additives may be outside these ranges. In some 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.

[0114] In certain embodiments, the toner does not contain, i.e., does not contain, external TiO2 additives.

[0115] In some embodiments, the toners of the present disclosure may be used as ultra-low melting (ULM) toners. In some embodiments, dry toner particles having a core and / or shell may have one or more of the following properties, apart from external surface modifiers.

[0116] (1) The volume-average diameter (also referred to as "volume-average particle size") is 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.

[0117] (2) Number Average Geometric Size Distribution (GSDn) and Volume Average Geometric Size Distribution (GSDv): In some embodiments, the toner particles described in (1) above may have a narrow particle size distribution with a low number ratio GSD, such as about 1.15 to about 1.38, and in other embodiments less than about 1.31. The toner particles of the Disclosure may also have a size such that the volume upper 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 be performed as follows: obtain a small amount (about 1 gram) of toner sample, filter it through a 25-micrometer sieve, and then place it in an isotonic solution to obtain a concentration of about 10%, and then measure the sample with a Beckman Coulter Multisizer 3.

[0118] (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.

[0119] The properties of toner particles can be determined by any suitable technique and apparatus, and are not limited to those described above.

[0120] The toner particles thus formed 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 some embodiments, about 2% to 15% by weight of the total weight of the developer.

[0121] 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.

[0122] The selected carrier particles may be used with or without a coating. In some embodiments, the carrier particles may comprise a core having a coating on it, 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, for example, KYNAR 301F®, and / or polymethyl methacrylate having a weight-average molecular weight of about 300,000 to about 350,000, such as available from, for example, Soken, may be used. In some 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 some embodiments, about 0.5 to about 2% by weight of the carrier.

[0123] In some 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, and in some 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.

[0124] 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.

[0125] In some embodiments, the preferred carrier may include a steel core, for example, about 25 to about 100 μm in diameter, and in some embodiments about 50 to about 75 μm in diameter, coated using the processes described in U.S. Patent Nos. 5,236,629 and 5,330,874, with a conductive polymer mixture containing, for example, methyl acrylate and carbon black, in about 0.5% to about 10% by weight, and in some embodiments about 0.7% to about 5% by weight, using a conductive polymer mixture containing, for example, methyl acrylate and carbon black.

[0126] 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.

[0127] In some embodiments, the developer herein comprises emulsified aggregated toner particles and a toner carrier, wherein the emulsified aggregated toner particles comprise toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, comprising a complex formed from a metal ion donor and ligands described herein.

[0128] Toner can be used in electrostatic or electrophotographic processes. In some embodiments, any known type of developing system can 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.

[0129] 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 some 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.

[0130] 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 some embodiments, the 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 some embodiments, the fuser member may be heated to a temperature exceeding the toner fixing temperature, for example, about 70°C to about 160°C, in some embodiments about 80°C to about 150°C, and in other embodiments about 90°C to about 140°C, after or during melting onto the image-receiving substrate.

[0131] In some embodiments where the toner resin is crosslinkable, such crosslinking can be achieved in any preferred manner. For example, the toner resin may be crosslinked to a substrate that is crosslinkable at the fixing temperature during toner fixing. Crosslinking may also be achieved by heating the fixing image to a temperature at which the toner resin is crosslinked, for example, in a post-melt operation. In some embodiments, crosslinking may be achieved at a temperature of about 160°C or less, in some embodiments at about 70°C to about 160°C, and in other embodiments at about 80°C to about 140°C. [Examples]

[0132] 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.

[0133] Polyester particle process. Emulsified aggregated toner particles were synthesized using the agglomeration / coagulation method. Core polyester latex, pigment, wax, nitric acid, and flocculant were homogenized and then agglomerated in a reaction vessel while being mixed at a temperature of approximately 46°C. A mixture of shell polyester latex and nitric acid was added to a target particle size (D50v) of approximately 5.3 micrometers, and the batch was held for a sufficient period of time until the latex was completely attached to the already existing toner aggregates. Subsequently, sodium hydroxide and ethylene diamine tetraacetic acid (EDTA) were used to stop the agglomeration reaction and raise the pH to approximately 7.8. Next, 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. Subsequently, the resulting slurry was washed and dried to obtain toner matrix particles. [Table 1]

[0134] A high MW (molecular weight) amorphous polyester was prepared from an amorphous polyester resin in an emulsion having an average molecular weight (Mw) of approximately 86,000, a number-average molecular weight (Mn) of approximately 5,600, a glass transition onset temperature (Tg onset) of approximately 56°C, a particle size of approximately 70 nm (nanometers), and approximately 35% of the solid composition tarpoly-(propoxylated bisphenol A terephthalate), tarpoly-(propoxylated bisphenol A dodecenyl succinate), and tarpoly-(propoxylated bisphenol A fumarate).

[0135] Low MW (molecular weight) amorphous polyesters were prepared from amorphous polyester resins in emulsions having approximately 35% of the solid compositions tarpoly-(propoxylated bisphenol A-terephthalate), tarpoly-(propoxylated bisphenol A-dodecenyl succinate), and tarpoly-(propoxylated bisphenol A-fumarate), with approximately 19,400 Mw, approximately 5,000 Mn, an onset Tg of approximately 60°C, a particle size of approximately 170-230 nm.

[0136] Crystalline polyester is a crystalline polyester resin that includes polyesters made from dodecanediic acid and 1,9-nonanediol.

[0137] Carbon black is an unoxidized, low-structure black pigment produced by the furnace process.

[0138] The cyan pigment is CI Pigment Blue 15:3.

[0139] Fischer-Tropsch wax is a distilled synthetic polymethylene wax with a melting point of approximately 92°C.

[0140] EDTA is ethylenediaminetetraacetic acid.

[0141] The procedure for forming the mother particles for all examples is 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.

[0142] Toner formulation and blending. Using a 750 ml bench blender (FujiMill), 70-75 g of black particles and an additive package containing fumed SiO2, colloidal SiO2, strontium titanate, cerium oxide, and wax for lubricating the photoreceptor were blended for 9 minutes at 9600 rpm (revolutions per minute). To prevent the blending container from overheating and creating coarse particles, the blender was run for 3 minutes, followed by a 3-minute stop (3 times).

[0143] Example 1 Zn 2+ Particle synthesis with precipitated dehydroacetic acid charge control agent. In a typical synthesis, 80 grams of the above polyester particles were slurryed using 360 grams of water (with a small amount of about 20 grams of ethanol added) to approximate the particles being bonded. While stirring the toner particle slurry, 0.76 grams of an acid ligand (i.e., sodium dehydroacetate) dissolved in 30 grams of water was slowly added. The dispersion was stirred for 1 hour, and 0.59 grams of a metal ion source (i.e., zinc nitrate hexahydrate) 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. The dispersion was then filtered and washed with 300 grams of pH 6.5 water, and freeze-dried to obtain Zn 2+ Toner particles were obtained by precipitating the dehydroacetic acid charge control agent. The treated particles were blended using Fuji-Mill as described above. The resulting toner was evaluated for peak q / d in zone A and zone J at mixing times of 5, 10, 15, and 30 seconds, and the results are shown in Tables 3 and 4.

[0144] Examples 2-8 Examples 2 to 8 were prepared according to the method of Example 1, except for the acid ligands, metal ion donor compounds, and their quantities, as shown in Table 2.

[0145] The examples were 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 shown in Tables 3 and 4.

[0146] Comparative Example 9 Comparative Example 9, which contains no internal charge control agents, has an additive package containing fumed SiO2, colloidal SiO2, strontium titanate, cerium oxide, and wax for lubricating the photoreceptor, but contains no internal charge control agents, and includes the mother particles described above. Untreated particles were blended using Fuji-Mill as described above. The resulting toner was evaluated for peak q / d in zone A and zone J at mixing times of 5, 10, 15, and 30 seconds, and the results are shown in Tables 3 and 4. [Table 2] [Table 3] [Table 4]

[0147] Evaluation results. Each example was subjected to a mixed charge distribution using a ferrite carrier with a toner concentration of 5%. In this procedure, a sample developer was prepared using a toner concentration of 5 parts per 100 parts (pph), containing 5 parts toner per 100 parts of developer in total. After acclimatizing to both conditions of 80°F and 80% relative humidity (RH), and 70°F and 10% RH, the sample was mixed by running a Turbula mixer at 96 rpm for 10 minutes. Friction was measured using a barbetta box, and a charge spectrograph (CSG) smear was prepared at this 10-minute sign. 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 smear was prepared to understand the mixing performance for each of the four mixing times. Next, each CSG smear was converted into a chart of particle counts plotted against q / d (charge per diameter, in units of fc / micrometer). The measurement criteria in Tables 3 and 4 were calculated from this data to measure the developer mixing rate.

[0148] 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 CSGs greater than -0.10 fc / micrometer, which represents toner particles 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 describes the magnitude of the toner's triboelectric charging ability. Peak A / J is the ratio of peak q / d in zone A to peak q / d in zone J, and represents the toner's ability to charge consistently under various environmental conditions.

[0149] It is desirable to reduce the peak width at 5 seconds, increase the A / J ratio to near 1, and minimize the low charge percentage. All examples demonstrate advantages in at least one area.

[0150] CSG charts for lab-scale particles with no CCA precipitate or no TiO2 additives are shown in Figures 1 and 2. Figure 1 shows the CSG for the particles of Comparative Example 9 at 21°C and 10% RH (low humidity zone J). Figure 2 shows the CSG for the particles of Comparative Example 9 at 28°C and 85% RH (high humidity zone A). The solid lines in Figures 1 and 2 represent the distribution after mixing for 10 minutes at a toner concentration of 5 pph (initial spectrograph). The dashed lines in Figures 1 and 2 represent the mixed distribution after adding an additional 2.5 pph of new toner to the developer sample, measured at additional mixing times of 5 seconds, 10 seconds, 15 seconds, 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. These problems are usually solved by adding TiO2 as an external additive during blending. The peak Q / d (toner charge at fC / μm) of the 30-second mixing distribution is also an important and critical parameter to look at, especially when comparing low humidity (J zone) and high humidity (A zone). In this case, the A / J ratio is approximately 0.77 (30-second peak Q / d in zone A divided by 30-second peak Q / d in zone J). Ultimately, the inventors searched for a 30-second peak that is the same width as the initial charge distribution without double peaks for all humidity conditions (A zone / J zone = 1.0) and for all four mixing times, having the same peak Q / d for all mixing times.

[0151] Figures 3 and 4 are CSG charts for Example 1, which contains Zn2+ ions and CCA molecules containing dehydroacetic acid, precipitated using the procedure of this embodiment. 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).

[0152] The CCA data for Example 1 shows that both the low charge percentage and the A / J ratio are improved compared to the control comparative example 9, which contains no CCA molecules. The A / J ratio of Example 1 is approximately 0.9, which is a significant improvement over the control comparative example 9. In both extreme environments, the amount of low charge percentage toner is minimal. The results show that Zn 2+ This study demonstrates that precipitation of CCA molecules containing ions and dehydroacetic acid has a significantly beneficial effect on the mixing rate and A / J ratio when precipitation occurs after adsorption during the emulsified aggregate particle process.

[0153] When the loading of zinc dehydroacetate (CCA) molecules is low (Example 1), both the mixing rate and A / J ratio are improved compared to the control comparative Example 9, which contains no CCA molecules (no double peaks). The peak Q / d is stable up to a mixing time of 10 seconds. The 30-second A / J ratio in Example 1 is approximately 0.9, which is a significant improvement over the control comparative Example 9. In both extreme environments, the amount of inappropriate signs and low-charge % toner is minimal. The results show that Zn 2+ This study demonstrates that the precipitation of CCA molecules containing ions and dehydroacetic acid has a significantly beneficial effect on the mixing rate and A / J ratio when precipitated after adsorption during the emulsified aggregate particle process.

[0154] As can be seen from the low relative humidity charge spectrograph data of Examples 2, 3, and 4, the peak Q / d decreases as the amount of zinc humicate CCA molecules increases. At the maximum load (Example 4), the distribution becomes unstable, with an unacceptable amount of low-charge and inappropriate toner characteristics, especially at high humidity. At low CCA molecule loads (Example 2), the mixing rate is much better than in the control comparative Example 9, which contains no CCA molecules, as the peak width decreases and the amount of low-charge % is shown to be relatively low. This is because Zn 2+ This study demonstrates that precipitation of CCA molecules containing ions and humic complexes has a beneficial effect on the charge performance (charging rate and A / J ratio) when precipitated after adsorption during the emulsification and agglomeration particle process.

[0155] 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. Another aspect of the present invention may be as follows: [1] Emulsified aggregated toner, At least one type of resin, any coloring agent, and any wax, The toner particles include a charge control agent disposed on the surface of the toner particles, An emulsifying agglutinating toner comprising a charge control agent containing a complex formed from 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. [2] The toner particles include a core-shell structure, The emulsified aggregated toner according to [1], wherein the charge control agent is disposed on the surface of the toner particle shell. [3] The emulsified agglomerated toner according to [1], 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. [4] The emulsified agglutinating toner according to [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 emulsified agglutinating toner according to [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 emulsified agglutinating toner according to [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 The emulsified aggregated toner described in [1] above, which does not contain the above. [8] The emulsified agglomerated toner according to [2], further comprising a surface modifier disposed on the surface of the toner particle shell, wherein the surface modifier is selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof. [9] A developer, It comprises emulsified aggregated toner particles and a toner carrier, The emulsified 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 comprises a complex formed from 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. A developer wherein the toner particles optionally further comprise a surface modifier disposed on the surface of the toner particle shell, the surface modifier being selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

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

[11] The metal ion donor of the charge control agent complex is selected from 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. The developer according to [9], wherein the ligand is selected from members of the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

[12] The metal ion donor of the charge control agent complex is selected from the group consisting of zinc nitrate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum sulfate, aluminum chloride and combinations thereof. The developer according to [9], wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

[13] The toner particles are TiO 2 The developer described in [9] above, which does not contain any of the above.

[14] Emulsified aggregated toner process, To obtain a latex of at least one type of resin, To obtain an aqueous dispersion of any coloring agent at will, To obtain an aqueous dispersion of any wax at will, To form a mixture of the latex of at least one of the aforementioned resins, an aqueous dispersion of the aforementioned coloring agent, and an aqueous dispersion of the aforementioned wax, Heating the mixture to a first temperature, Maintaining the temperature described above to form aggregated toner particles, Adding latex from a shell resin to form a shell on one surface of 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 coalesce. The process involves cooling the emulsified aggregated toner particles, selectively washing them, selectively drying them, and then recovering them. A charge control agent is precipitated on the surface of the emulsified agglomerated toner particles by adding at least one ligand selected from the group consisting of a metal ion donor and a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof, wherein the metal ion donor and the polyaromatic acid containing a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof form the charge control agent, and emulsified agglomerated toner particles containing the internal charge control agent are formed. An emulsified aggregated toner process comprising optionally placing a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof, on the surface of the toner particle shells.

[15] The emulsified agglomerated toner process according to

[14] , further comprising combining the emulsified agglomerated toner particles and a toner carrier to form a developer.

[16] The emulsifying aggregate toner process according to

[14] , wherein the metal ion donor of the internal 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.

[17] The emulsifying aggregate toner process according to

[14] , wherein the metal ion donor of the internal charge control agent complex is selected from members of the group consisting of zinc nitrate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum sulfate, aluminum chloride and combinations thereof.

[18] The emulsifying agglomeration toner process according to

[14] , wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid and combinations thereof.

[19] The toner particles are TiO 2 The emulsified aggregated toner process described in

[14] above, which does not include the above.

[20] Dispersing the dried emulsified aggregated toner particles in water to form a slurry of the emulsified aggregated toner particles, The emulsified agglomerated toner process according to

[14] , further comprising precipitating the charge control agent onto the surface of the dispersed emulsified agglomerated toner particles.

Claims

1. It is an emulsified aggregated toner, The toner particles comprising at least one resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles, An emulsified agglutinating toner wherein 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 containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof.

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

3. The emulsified agglomerated 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 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.

4. The emulsified agglomerated 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 emulsified 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 emulsified agglomerated 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 The emulsified aggregated toner according to claim 1, which does not contain the following.

8. The emulsified agglomerated toner according to claim 2, further comprising a surface modifier disposed on the surface of the toner particle shell, wherein the surface modifier is selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

9. It is a developer, It contains emulsified aggregated toner particles and a toner carrier, The emulsified 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 comprises a complex formed from 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. A developer wherein the toner particles optionally further comprise a surface modifier disposed on the surface of the toner particle shell, the surface modifier being selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

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

11. 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 developer according to claim 9, wherein the ligand is selected from members of the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

12. The metal ion donor of the charge control agent complex is selected from the group consisting of zinc nitrate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum sulfate, aluminum chloride, and combinations thereof. The developer according to claim 9, wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

13. The toner particles are TiO 2 A developer according to claim 9, which does not contain any of the above.

14. Emulsified and aggregated toner process, To obtain a latex of at least one type of resin, To obtain an aqueous dispersion of any coloring agent at will, To obtain an aqueous dispersion of any wax at will, To form a mixture of the latex of at least one of the aforementioned resins, an aqueous dispersion of the aforementioned coloring agent, and an aqueous dispersion of the aforementioned 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 one surface of 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 coalesce. The process involves cooling the emulsified aggregated toner particles, selectively washing them, selectively drying them, and then recovering them. The method involves adding at least one ligand selected from the group consisting of a metal ion donor and a polyaromatic acid containing humic acid, a pyranone ligand, a furanone ligand, or a combination thereof, to the emulsified agglutinated toner particles to precipitate a charge control agent on the surface of the emulsified agglutinated toner particles, wherein the metal ion donor and the polyaromatic acid containing a humic acid ligand, a pyranone ligand, a furanone ligand, or a combination thereof form the charge control agent, thereby forming emulsified agglutinated toner particles containing the internal charge control agent. An emulsified aggregated toner process comprising optionally placing a surface modifier selected from the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof on the surface of the toner particle shells.

15. The emulsified aggregated toner process according to claim 14, further comprising combining the emulsified aggregated toner particles and a toner carrier to form a developer.

16. The emulsifying aggregate toner process according to claim 14, wherein the metal ion donor of the internal 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.

17. The emulsifying aggregate toner process according to claim 14, wherein the metal ion donor of the internal charge control agent complex is selected from members of the group consisting of zinc nitrate, zinc sulfate, zinc chloride, aluminum nitrate, aluminum sulfate, aluminum chloride, and combinations thereof.

18. The emulsifying aggregated toner process according to claim 14, wherein the ligand is selected from members of the group consisting of dehydroacetic acid, humic acid, and combinations thereof.

19. The toner particles are TiO 2 The emulsified aggregated toner process according to claim 14, which does not include the following.

20. The process involves dispersing dried emulsified aggregated toner particles in water to form a slurry of the emulsified aggregated toner particles, The emulsified agglomerated toner process according to claim 14, further comprising precipitating the charge control agent onto the surface of the dispersed emulsified agglomerated toner particles.

21. Emulsified aggregated toner, The toner particles include at least one type of resin, an optional colorant, and an optional wax, and a charge control agent disposed on the surface of the toner particles. An emulsified agglutinating toner wherein the charge control agent comprises a complex formed from a metal ion donor and at least one ligand selected from the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof.

22. A developer, It contains emulsified aggregated toner particles and a toner carrier, The emulsified 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 is Metal ion donors 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, and The complex comprises at least one ligand selected from the group consisting of hydroxypyranone, thiopyranone, pyranonecarboxylic acid, hydroxyfuranone, thiofuranone, furanonecarboxylic acid, and combinations thereof, A developer wherein the toner particles optionally further comprise a surface modifier disposed on the surface of the toner particle shell, the surface modifier being selected from members of the group consisting of fumed silica, colloidal silica, polydimethylsiloxane-treated silica, strontium titanate, cerium oxide, titanium dioxide, polydimethylsiloxane-treated titanium dioxide, and combinations thereof.

23. The emulsified agglutinating toner according to claim 1, wherein the ligand is dehydroacetic acid, and 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, and combinations thereof.

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