Toner Composition and Additive

Abstract

To improve additives used in formation of EA ULM toners, and to improve sensitivity of toner compositions to environmental conditions including relative humidity.SOLUTION: A toner composition, a developer, and an additive for a toner composition are disclosed. The toner composition comprises toner particles containing at least one type of resin, an optional colorant, an optional wax, and a polymeric toner additive provided on at least portions of external surfaces of the toner particles. The polymeric toner additive comprises a polymeric resin containing a fluorinated acrylic monomer, a cross-linkable monomer containing two or more vinyl groups at 8 wt.% to 40 wt.% of the polymeric resin, and optionally a charge control agent consisting of a nitrogen-containing group at 0.1 wt.% to 1.5 wt.% of the polymeric resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure generally relates to toner compositions, and more specifically to toner compositions containing polymer additives.

Background Art

[0002] Electrophotographic printing utilizes toner particles that can be manufactured by various processes. One such process includes an emulsion aggregation (“EA”) process for forming toner particles in which a surfactant is used in the formation of a latex emulsion. For example, as an example of such a process, see U.S. Patent No. 6,120,967, the disclosure of which is incorporated herein by reference in its entirety.

[0003] A combination of an amorphous polyester and a crystalline polyester can be used in the EA process. This resin combination can provide high gloss and relatively low melting point characteristics (sometimes referred to as low melt, ultra-low melt, or ULM) that enable higher energy efficiency and faster printing. The use of additives with EA toner particles can be important for achieving optimal toner performance, particularly in the charging region.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Problems that can occur with toners include sensitivity to environmental conditions including humidity. For example, in summer, during high temperature and high humidity, users complain about the background of the image. In winter, during cold and dry conditions, users complain about bright images. Excessive background may also occur due to a decrease in the charge amount over time of the developer.

[0005] There is a continuing need to improve the additives used in the formation of EA ULM toners. There is also a need to improve the sensitivity of toner compositions to environmental conditions including relative humidity.

[0006] According to various embodiments, a toner composition is described that includes toner particles containing at least one resin, an optional colorant, an optional wax, and a polymeric toner additive on at least a portion of the outer surface of the toner particles. The polymeric toner additive includes a polymeric resin having a fluorinated acrylic monomer, 8 wt% - 40 wt% of the polymeric resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% - 1.5 wt% of the polymeric resin of a charge control agent for a nitrogen-containing group.

[0007] According to various embodiments, a developer is provided. The developer includes a toner composition and a toner carrier. The toner composition includes toner particles having at least one resin, an optional colorant, an optional wax, and a polymeric toner additive on at least a portion of the outer surface of the toner particles. The polymeric toner additive includes a polymeric resin having a fluorinated acrylic monomer, 8 wt% - 40 wt% of the polymeric resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% - 1.5 wt% of the polymeric resin of a charge control agent monomer for a nitrogen-containing group.

[0008] Disclosed herein is a toner additive that includes a polymeric resin containing a fluorinated acrylic monomer, 8 wt% - 40 wt% of the polymeric resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% - 1.5 wt% of a nitrogen-containing group of the polymeric resin.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure provides a polymeric additive for use with toner particles.

[0010] The resulting polymer may be used as an additive to a toner composition, and can enhance the sensitivity of the resulting toner to relative humidity and charge stability. The polymer additive of the present disclosure can be used at a lower density with respect to specific gravity compared to other additives, and requires far less material by weight to cover an equivalent surface area compared to inorganic additives including oxides such as titania and silica. The polymer additive of the present disclosure can also provide toner particles having a wide range of properties such as hydrophobicity and charge control depending on the monomers used to form the polymer.

[0011] In an embodiment, the toner composition includes toner particles of at least one resin. The toner composition may include an optional colorant. The toner composition may include an optional wax. The toner composition includes a polymeric toner additive on at least a portion of the outer surface of the toner particles. The polymeric toner additive includes a polymeric resin including a fluorinated acrylic monomer, 8 wt% to 40 wt% of the polymeric resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% to 1.5 wt% of the polymeric resin of a charge control agent monomer composed of a nitrogen-containing group. The polymeric toner additive has a size of 25 nanometers to about 250 nanometers. The loading amount of the polymeric toner additive is 0.1 weight percent to 5 weight percent of the toner composition.

[0012] Suitable fluorinated acrylic monomers that can be used for the formation of polymer additives include, for example, 2,4,6-trifluorophenyl acrylate, pentafluorophenyl acrylate, hexafluoro-isopropyl methacrylate, 1H,1H,3H-hexafluorobutyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (HDFDMA), 1H,1H,5H-octafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 1H,1H,2H,2H-perfluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2-[(1’,1’,1’-trifluoro-2’-(trifluoromethyl)-2’-hydroxy)propyl]-3-norbornyl methacrylate, perfluorocyclohexyl (meth)acrylate, and any combination thereof, etc.

[0013] The polymer additive also includes a crosslinkable monomer having at least two vinyl groups. Examples of monomers having at least two vinyl groups that are suitable for use in the polymer additive include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2’ - bis(4 - (acryloxy / diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 - butylene glycol dimethacrylate, 1,6 - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2’ - bis(4 - (methacryloxy / diethoxy)phenyl)propane, 2,2’ - bis(4 - (methacryloxy / polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, combinations thereof, and the like. In an embodiment, the crosslinking agent may be fluorinated. Suitable fluorinated crosslinking agents include fluorinated divinyl crosslinking agents such as 1,8 - divinylperfluoro(octane), 1,6 - divinylperfluoro(hexane), and 1,4 - divinylperfluoro(butane).

[0014] The fluorinated acrylic monomer may be present in the polymer additive in an amount of about 5 wt% to about 90 wt% of the copolymer, and in an embodiment, about 20 wt% to about 92 wt% of the polymer additive.

[0015] The crosslinkable monomer having at least two vinyl groups may be present in such a polymer additive in an amount of about 8.0 wt% to about 40 wt% of the polymer additive, in an embodiment about 10 wt% to about 25 wt% of the copolymer to the polymer additive.

[0016] In an embodiment, examples of the charge control agent monomer containing a nitrogen-containing group include, but are not limited to, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, and combinations thereof.

[0017] The charge control agent monomer containing a nitrogen-containing group in the polymer additive is 0.1 wt% to 1.5 wt%, about 0.6 wt% to 1.2 wt%, or about 0.7 wt% to about 1.1 wt% of the polymer additive.

[0018] In an embodiment, a method for forming the polymer additive includes emulsion polymerization of the monomers utilized to form the polymer additive.

[0019] In the polymerization process, the reactants may be added to a suitable reactor such as a mixing vessel. An appropriate amount of the starting materials may optionally be dissolved in a solvent, an optional initiator may be added to the solution, and contacted with at least one surfactant to form an emulsion. The copolymer may be formed in the emulsion, which is then recovered and can be used as a polymer additive for the toner composition.

[0020] When used, suitable solvents include water and / or organic solvents such as toluene, benzene, xylene, tetrahydrofuran, acetone, acetonitrile, carbon tetrachloride, chlorobenzene, cyclohexane, diethyl ether, dimethyl ether, dimethylformamide, heptane, hexane, methylene chloride, pentane, combinations thereof, etc., but are not limited thereto.

[0021] In an embodiment, the latex for forming the polymer additive may be prepared in an aqueous phase containing a surfactant or a co-surfactant, optionally under an inert gas such as nitrogen. The surfactant that may be utilized with the resin to form the latex dispersion may be an ionic or non-ionic surfactant in an amount of about 0.01 to about 15 weight percent of the solid, and in an embodiment, about 0.1 to about 10 weight percent of the solid.

[0022] Examples of anionic surfactants that may be utilized include sulfates and sulfonates, sodium dodecyl sulfate (SDS) known as sodium lauryl sulfate (SLS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, dialkylbenzene alkyl sulfates and sulfonates, acids such as abietic acid available from Aldrich, Neogen R (trademark) obtained from Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen SC (trademark), combinations thereof, and the like. Other suitable anionic surfactants include, in an embodiment, DOWFAX (trademark) 2A1, an alkyldiphenyloxide disulfonate from Dow Chemical Company, and / or Teika Power BN2060 from Teika Corporation (Japan), which are sodium branched dodecylbenzenesulfonates. Combinations of these surfactants with any of the aforementioned anionic surfactants may be utilized in an embodiment.

[0023] Examples of cationic surfactants include, but are not limited to, ammonium, such as alkylbenzyldimethylammonium chloride, dialkylbenzene alkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, C 12 ,C 15 ,C 17Examples include trimethylammonium bromide and combinations thereof. Other cationic surfactants include cetylpyridinium bromide, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, Sanizol (benzalkonium chloride) available from Kao Chemicals, and combinations thereof. In an embodiment, a suitable cationic surfactant includes SANISOL B-50 available from Kao Corp., which is mainly benzyl dimethyl alkonium chloride.

[0024] Examples of nonionic surfactants include, but are not limited to, alcohols, acids, and ethers, such as polyvinyl alcohol, polyacrylic acid, metarose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, and combinations thereof. In an embodiment, surfactants commercially available from Rhone-Poulenc, such as IGEPAL CA-210 (trademark), IGEPAL CA-520 (trademark), IGEPAL CA-720 (trademark), IGEPAL CO-890 (trademark), IGEPAL CO-720 (trademark), IGEPAL CO-290 (trademark), IGEPAL CA-210 (trademark), ANTAROX 890 (trademark), and ANTAROX 897 (trademark) can be utilized.

[0025] The selection of a particular surfactant or combinations thereof, as well as the respective usage amounts, are within the knowledge of those skilled in the art.

[0026] In an embodiment, a reaction initiator may be added for the formation of the latex used for the formation of the polymer additive. Examples of suitable reaction initiators include water-soluble reaction initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate, and organic solvent-soluble reaction initiators including organic peroxides, and azo compounds including Vazo peroxides such as VAZO 64 (trademark), 2-methyl 2-2'-azobispropionitrile, VAZO 88 (trademark), 2-2'-azobisisobutyramide anhydride, and combinations thereof. Other water-soluble initiators that can be utilized include azoamidine compounds such as 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[N-(4-hydroxyphenyl)-2-methyl-propionamidine] dihydrochloride, 2,2'-azobis[N-(4-amino-phenyl)-2-methylpropionamidine] tetrahydrochloride, 2,2'-azobis[2-methyl-N(phenylmethyl)propionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-2-propenylpropionamidine] dihydrochloride, 2,2'-azobis[N-(2-hydroxy-ethyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, and combinations thereof.

[0027] The initiator can be added in a suitable amount, for example, about 0.1 to about 8 weight percent of the monomer, and in a plurality of embodiments about 0.2 to about 5 weight percent.

[0028] When forming the emulsion, any means within the understanding of those skilled in the art can be utilized to combine the starting materials, surfactants, optional solvents, and optional initiators. In embodiments, the reaction mixture can be mixed for about 1 minute to about 72 hours, in embodiments about 4 hours to about 24 hours, while maintaining the temperature at about 10°C to about 100°C, in embodiments about 20°C to about 90°C, and in other embodiments about 45°C to about 75°C.

[0029] Those skilled in the art will understand that the reaction conditions, temperature, and initiator loading can be varied to optimize the production of polymers of various molecular weights, and that structurally related starting materials can be polymerized using equivalent techniques.

[0030] The resulting latex has the polymer additives of the present disclosure and can be applied to toner particles using any means within the purview of those skilled in the art. In embodiments, the toner particles can be immersed in or sprayed with the latex containing the polymer additive and thereby coated, and the coated particles can then be dried to leave the polymer coating thereon.

[0031] In other embodiments, once the polymer additive for the toner is formed, it can be recovered from the latex by any technique within the purview of those skilled in the art, including filtration, drying, centrifugation, spray drying, combinations thereof, and the like.

[0032] In an embodiment, once obtained, the copolymer utilized as an additive for toner can be dried into powder form by any method within the purview of those skilled in the art, including, for example, freeze-drying, optionally spray-drying in a vacuum, combinations thereof, etc. Next, the dried polymer additive of the present disclosure can be applied to toner particles using any means within the purview of those skilled in the art, including but not limited to mechanical shock and / or electrostatic attraction. An example of a mechanical mixing device is the Henschel FM high-intensity mixer from Zeppelin Systems, although other mixing devices may also be used in the embodiment.

[0033] The particles of the copolymer can have an average or median particle size (D50) of about 20 nanometers to about 250 nanometers in diameter, and in an embodiment, about 40 nanometers to about 150 nanometers in diameter. The particle size of the suspended particles in the size range of 0.0008 to 6.54 micrometers is measured using a Nanotrac 252 instrument. This instrument uses laser light scattering technology, and the Doppler-shifted light generated from each particle during motion (Brownian motion) is measured. The signals generated by these shifts are proportional to the size of the particles. The signals are mathematically converted into particle size and particle size distribution. The analysis can be performed using an external probe or by inserting the probe into a fixed sample chamber. As used herein, the term "D50" refers to the diameter (volume basis unless otherwise specified) of the particles in the sample such that 50% of the sample consists of particles having a diameter less than the diameter value. D50 can also be referred to as the "average particle size". For light scattering technology, NIST polystyrene nanosphere reference samples having diameters in the range of 15 mm to 150 mm can be used under the trademark NIST Traceable Reference Material for Nanotrac Particle Size Analyzers obtained from Microtrac.

[0034] A copolymer used as a polymer additive, in embodiments, a copolymer soluble in a solvent such as tetrahydrofuran (THF), when measured by gel permeation chromatography (GPC) using a polystyrene standard, for example, has a number average molecular weight (M n ) of about 40,000 to about 280,000 Daltons, in embodiments, about 60,000 to about 170,000 Daltons, and a weight average molecular weight (M w ) of about 200,000 to about 800,000 Daltons, in embodiments, about 400,000 to about 600,000 Daltons when measured by gel permeation chromatography. In embodiments, due to crosslinking, the solubility of the crosslinked resin is limited, and it may not be possible to measure the molecular weight by any method.

[0035] The copolymer used as a polymer additive may have a glass transition temperature (Tg) of about 85°C to about 140°C, in embodiments, about 100°C to about 130°C. In embodiments, it may not be possible to determine Tg due to crosslinking of the resin, which may make it difficult to detect Tg. In embodiments, the A-zone charge of the toner containing the polymer additive of the present disclosure may be about -15 to about -80 microcoulombs per gram, in embodiments, about -20 to about -60 microcoulombs per gram, while the J-zone charge of the toner containing the polymer additive of the present disclosure may be about -15 to about -80 microcoulombs per gram, in embodiments, about -20 to about -60 microcoulombs per gram.

[0036] The polymer additive of the present disclosure may be combined with toner particles such that the polymer additive is present in an amount of about 0.1 wt% to about 5 wt% of the toner particles, in embodiments, about 0.2 wt% to about 2 wt% of the toner particles.

[0037] Accordingly, with the polymer additive compositions and processes of the present disclosure, developers having selected high triboelectric charging characteristics and / or conductivity values can be formulated using a number of different combinations. Toner

[0038] The polymer additives thus produced may then be combined with a toner resin, optionally having a colorant, to form the toner of the present disclosure. Resin

[0039] Any toner resin can be utilized in forming the toner of the present disclosure. Such resins may then be made by any suitable polymerization method with any suitable monomer or monomers. In embodiments, the resin can be prepared by methods other than emulsion polymerization. In further embodiments, the resin can be prepared by condensation polymerization.

[0040] The toner compositions of the present disclosure include, in embodiments, an amorphous resin. The amorphous resin may be linear or branched. In embodiments, the amorphous resin may include at least one low molecular weight amorphous polyester resin. Low molecular weight amorphous polyester resins available from a number of sources may have various glass transition temperatures, for example, from about 30 °C to about 80 °C, and in embodiments from about 35 °C to about 75 °C. As used herein, low molecular weight amorphous polyester resins have, for example, a number average molecular weight (M n ) of from about 1,000 to about 10,000, and in embodiments from about 2,000 to about 8,000, and in embodiments from about 3,000 to about 7,000, and in embodiments from about 4,000 to about 6,000, as measured by, for example, gel permeation chromatography (GPC). The weight average molecular weight (M w ) of the resin is 50,000 or less, for example, in embodiments from about 2,000 to about 50,000, and in embodiments from about 3,000 to about 40,000, and in embodiments from about 10,000 to about 30,000, and in embodiments from about 18,000 to about 21,000, as determined by GPC using polystyrene standards. The molecular weight distribution (M w / Mn ) is, for example, from about 2 to about 6, and in an embodiment, from about 3 to about 4. The low molecular weight amorphous polyester resin can have an acid value of from about 8 to about 20 mg KOH / g, in an embodiment, from about 9 to about 16 mg KOH / g, and in an embodiment, from about 10 to about 14 mg KOH / g.

[0041] Examples of linear amorphous polyester resins that can be used include poly(propoxylated bisphenol A cofumarate), poly(ethoxylated bisphenol A cofumarate), poly(butyloxylated bisphenol A cofumarate), poly(copropoxylated bisphenol A coethoxylated bisphenol A cofumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol A comaleate), poly(ethoxylated bisphenol A comaleate), poly(butyloxylated bisphenol 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(butylenated bisphenol A coitaconate), poly(copropoxylated bisphenol A coethoxylated bisphenol A coitaconate), poly(1,2-propylene itaconate), and combinations thereof.

[0042] In an embodiment, suitable amorphous resins can include alkoxylated bisphenol A fumarate / terephthalate-based polyesters and copolyester resins. In an embodiment, a suitable amorphous polyester resin can be a copoly(propoxylated bisphenol A cofumarate)-copoly(propoxylated bisphenol A coterephthalate) resin having the following formula (I), [Chemical formula] In the formula, R may be a hydrogen or methyl group, m and n represent random units of the copolymer, m may be about 2 to 10, and n may be about 2 to 10. Examples of such resins and processes for their production include those disclosed in U.S. Patent No. 6,063,827, the entire disclosure of which is incorporated herein by reference.

[0043] In an embodiment, 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 the present disclosure include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypentylene terephthalate, polyhexylene terephthalate, polyheptylene terephthalate, polyoctylene terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polypentylene isophthalate, polyhexylene isophthalate, polyheptylene isophthalate, polyoctylene isophthalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polypentylene adipate, polyhexylene adipate, polyheptylene adipate, polyoctylene adipate, polyethylene glutarate, polypropylene glutarate, polybutylene glutarate, polypentylene glutarate, polyhexylene glutarate, polyheptylene glutarate, polyoctylene glutarate, polyethylene pimelate, polypropylene pimelate, polybutylene pimelate, polypentylene pimelate, polyhexylene pimelate, polyheptylene pimelate, poly(ethoxylated bisphenol A-fumarate), poly(ethoxylated bisphenol A-succinate), poly(ethoxylated bisphenol A-adipate), poly(ethoxylated bisphenol A-glutarate), 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-adipate), poly(propoxylated bisphenol A-glutarate), poly(propoxylated bisphenol A-terephthalate), poly(propoxylated bisphenol A-isophthalate),Examples of suitable polycondensation catalysts for any of the low molecular weight amorphous polyester resins include tetraalkyl titanates, dialkyl tin oxides such as dibutyl tin oxide, tetraalkyl tins such as dibutyl tin dilaurate, dialkyl tin oxide hydroxides such as butyl tin oxide hydroxide, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxide, stannous oxide, or mixtures thereof, and this catalyst can be utilized in an amount of, for example, about 0.01 mol% to about 5 mol% based on the diacid or diester which is the starting material used to produce the polyester resin.

[0044] Examples of any of the 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), CYGAL (American Cyanamide), ARMCO (Armco Composites), ARPOL (Ashland Chemical), CELANEX (Celanese Eng), RYNITE (DuPont), STYPOL (Freeman Chemical Corporation), and combinations thereof. The resin may also be functionalized, for example, by sodium sulfonation, if particularly desired, such as carboxylation, sulfonation, etc.

[0045] The low molecular weight amorphous polyester resin may be a branched resin. As used herein, the term "branched" or "branching" includes branched resins and / or cross-linked resins.

[0046] The resulting unsaturated polyester is reactive (e.g., crosslinkable) at two foremost parts, namely, (i) unsaturated sites (double bonds) along the polyester chain, and (ii) functional groups suitable for acid-base reactions such as carboxyl groups and hydroxy groups. In an embodiment, the unsaturated polyester resin is prepared by melt polycondensation or other polymerization processes using diacids and / or anhydrides and diols.

[0047] In an embodiment, a combination of low molecular weight amorphous polyester resins or low molecular weight amorphous resins may have a glass transition temperature (Tg) of, for example, about 30 °C to about 80 °C, and in an embodiment, about 35 °C to about 70 °C when measured by DSC. In a further embodiment, the combined amorphous resins have a melt viscosity of about 10 to about 1,000,000 Pa * S, and in an embodiment, about 50 to about 100,000 Pa * S at about 130 °C.

[0048] The amount of the low molecular weight amorphous polyester resin in the toner particles of the present disclosure may be present in an amount of 25 to about 50 wt%, in an embodiment, about 30 to about 45 wt%, and in an embodiment, about 35 to about 43 wt% of the toner particles (i.e., toner particles excluding external additives and water) in any core, any shell, or both.

[0049] In an embodiment, the toner composition includes at least one crystalline resin. As used herein, "crystalline" refers to a 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 an embodiment, about 12 to about 70%. Further, as used hereinafter, "crystalline polyester resin" and "crystalline resin" include both crystalline resins and semi-crystalline resins unless otherwise specified.

[0050] In an embodiment, the crystalline polyester resin is a saturated crystalline polyester resin or an unsaturated crystalline polyester resin.

[0051] Crystalline polyester resins available from many sources can have various melting points, for example, from about 30 °C to about 120 °C, and in embodiments, from about 50 °C to about 90 °C. The crystalline resin can have a number average molecular weight (M n ) of, for example, from about 1,000 to about 50,000, and in embodiments, from about 2,000 to about 25,000, and in embodiments, from about 3,000 to about 15,000, and in embodiments, from about 6,000 to about 12,000 as measured by, for example, gel permeation chromatography (GPC). w The molecular weight distribution (M n ) of the crystalline resin is, for example, from about 2 to about 6, and in embodiments, from about 3 to about 4. The crystalline polyester resin can have an acid value of from about 2 to about 20 mg KOH / g, and in embodiments, from about 5 to about 15 mg KOH / g, and in embodiments, from about 8 to about 13 mg KOH / g.

[0052] Exemplary 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 sebacate), poly(propylene sebacate), 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 dodecanedioate), poly(propylene dodecanedioate), poly(butylene dodecanedioate), poly(pentylene dodecanedioate), poly(hexylene dodecanedioate), poly(octylene dodecanedioate), poly(nonylene dodecanedioate), poly(decylene dodecanedioate), poly(undecylene dodecanedioate), poly(dodecylene dodecanedioate), poly(ethylene fumarate), poly(propylene fumarate), poly(butylene fumarate), poly(pentylene fumarate), poly(hexylene fumarate), poly(octylene fumarate), poly(nonylene fumarate), poly(decylene fumarate), copoly(5-sulfoisophthaloyl)-copoly(ethylene adipate), copoly(5-sulfoisophthaloyl)-copoly(propylene adipate), copoly(5-sulfoisophthaloyl)-copoly(butylene adipate), copoly(5-sulfoisophthaloyl)-copoly(pentylene adipate), copoly(5-sulfoisophthaloyl)-copoly(hexylene adipate), copoly(5-sulfoisophthaloyl)-copoly(octylene adipate), copoly(5-sulfoisophthaloyl)-copoly(ethylene adipate), copoly(5-sulfoisophthaloyl)-copoly(propylene adipate),Copoly(5-sulfoisophthaloyl)-copoly(butylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(pentylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(hexylene adipate), Copoly(5-sulfoisophthaloyl)-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-sulfoisophthaloyl)-copoly(ethylene sebacate), Copoly(5-sulfoisophthaloyl)-copoly(propylene sebacate), Copoly(5-sulfoisophthaloyl)-copoly(butylene(butylenes)-sebacate), Copoly(5-sulfoisophthaloyl)-copoly(pentylene sebacate), Copoly(5-sulfoisophthaloyl)-copoly(hexylene sebacate), Copoly(5-sulfoisophthaloyl)-copoly(octylene sebacate), Copoly(5-sulfoisophthaloyl)-copoly(ethylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(propylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(butylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(pentylene adipate), Copoly(5-sulfoisophthaloyl)-copoly(hexylene adipate), and any of various crystalline polyesters such as combinations thereof.

[0053] The crystalline resin can be prepared by a polycondensation process by reacting a suitable organic diol and a suitable organic diacid in the presence of a polycondensation catalyst.

[0054] Examples of organic diols selected for the preparation of the crystalline polyester resin include aliphatic diols having from about 2 to about 36 carbon atoms.

[0055] Examples of organic diacids or diesters selected for the preparation of the crystalline polyester resin 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, diesters thereof or anhydrides thereof; and alkali sulfo-organic diacids, for example, dimethyl-5-sulfo-isophthalate, dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride, 4-sulfo-phthalic acid, dimethyl-4-sulfo-phthalate, dialkyl-4-sulfo-phthalate, 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. The organic diacid is selected, for example, in an amount of about 40 to about 50 mole percent of the resin, and the alkali sulfo aliphatic diacid can be selected in an amount of about 1 to about 10 mole percent of the resin.

[0056] In an embodiment, a suitable crystalline resin may include a resin consisting of ethylene glycol or nonanediol, and a mixture of dodecanedioic acid and a fumaric acid comonomer having the following formula (II),

Chemical formula

[0057] When a semi-crystalline polyester resin is used herein, examples of the semi-crystalline resin include poly(3-methyl-1-butene), poly(hexamethylene carbonate), poly(ethylene-p-carboxyphenoxy-butyrate), 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), poly(ethylene sebacate), poly(decamethylene sebacate), poly(ethylene suberate), poly(decamethylene succinate), poly(eicosamethylene malonate), poly(ethylene-p-carboxyphenoxy-undecanoate), poly(ethylene dithioesoftalate), poly(methyl ethylene terephthalate), poly(ethylene-p-carboxyphenoxy-valerate), poly(hexamethylene-4,4'-oxydibenzoate), poly(10-hydroxycapric acid), poly(isophthalaldehyde), poly(octamethylene dodecanedioate), poly(dimethylsiloxane), poly(dipropylsiloxane), poly(tetramethylene phenylenediacetate), poly(tetramethylene trithiodiacarboxylate), poly(trimethylene dodecanedioate), poly(m-xylene), poly(p-xylylene pimelamide), and combinations thereof.

[0058] The amount of the crystalline polyester resin in the toner particles of the present disclosure may be present in an amount of 1 to about 15% by weight, in embodiments, about 5 to about 10% by weight, and in embodiments, about 6 to about 8% by weight of the toner particles (i.e., toner particles excluding external additives and water) in the core, the shell, or both.

[0059] In an embodiment, the toner of the present disclosure may also include at least one high molecular weight branched or crosslinked amorphous polyester resin. Examples of such high molecular weight resins in the embodiment include branched amorphous resins or amorphous polyesters, crosslinked amorphous resins or amorphous polyesters, or mixtures thereof, or crosslinked non-crosslinked amorphous polyester resins. According to the present disclosure, about 1 wt% to about 100 wt% of the high molecular weight amorphous polyester resin may be branched or crosslinked. In an embodiment, about 2 wt% to about 50 wt% of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0060] As used herein, a high molecular weight amorphous polyester resin may have, for example, a number average molecular weight (M n ) of about 1,000 to about 10,000 when measured by, for example, gel permeation chromatography (GPC). High molecular weight amorphous resins available from a number of sources may have various glass transition onset temperatures (Tg) of, for example, about 40°C to about 80°C, in an embodiment, about 50°C to about 70°C, and in an embodiment, about 54°C to about 68°C when measured by differential scanning calorimetry (DSC). In an embodiment, linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0061] High molecular weight amorphous polyester resins can be prepared by branching or crosslinking linear polyester resins. Branching agents such as trifunctional or polyfunctional monomers can be utilized, 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-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, combinations thereof, and the like. These branching agents can be utilized in an effective amount of about 0.1 mol% to about 20 mol% based on the diacid or diester that is the starting material used to make the resin.

[0062] In some embodiments, the crosslinked polyester resin can be made from a linear amorphous polyester resin containing unsaturated sites that can react under free radical conditions. In some embodiments, suitable unsaturated polyester-based resins can be prepared from diacids and / or anhydrides such as maleic anhydride, terephthalic acid, trimellitic acid, fumaric acid, and combinations thereof, and diols such as bisphenol A ethylene oxide adduct, bisphenol A-propylene oxide adduct, and combinations thereof. In an embodiment, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0063] In an embodiment, the crosslinked branched polyester can be utilized as a high molecular weight amorphous polyester resin. Examples of such polyesters and their synthetic methods are disclosed in U.S. Patent No. 6,592,913, the entire disclosure of which is incorporated herein by reference.

[0064] Suitable polyols contain from about 2 to about 100 carbon atoms and may have at least two or more hydroxyl groups or esters thereof. Examples of polyols may include glycerol, pentaerythritol, polyglycol, polyglycerol, etc., or mixtures thereof. The polyol may include glycerol. Suitable esters of glycerol include glycerol palmitate, glycerol sebacate, glycerol adipate, triacetin, tripropionin, etc. The polyol may be present in an amount of about 20 wt% to about 30 wt% of the reaction mixture, and in embodiments, about 22 wt% to about 26 wt% of the reaction mixture.

[0065] In embodiments, the crosslinked branched polyester of the high molecular weight amorphous polyester resin may include those resulting from the reaction of dimethyl terephthalate, 1,3 - butanediol, 1,2 - propanediol, and pentaerythritol.

[0066] In embodiments, a high molecular weight resin, such as a branched polyester, may be present on the surface of the toner particles of the present disclosure. The high molecular weight resin on the surface of the toner particles may also be inherently particulate and may be high molecular weight resin particles having a diameter of about 100 nanometers to about 300 nanometers, and in embodiments, about 110 nanometers to about 150 nanometers.

[0067] The amount of the high molecular weight amorphous polyester resin in the toner particles of the present disclosure may be about 25 wt% to about 50 wt% of the toner, in any core, any shell, or both, and in embodiments, about 30 wt% to about 45 wt%, and in other embodiments, or about 40 wt% to about 43% of the toner (i.e., toner particles excluding external additives and water).

[0068] The ratio of the crystalline resin to the low molecular weight amorphous resin to the high molecular weight amorphous polyester resin may range from about 1:1:98 to about 98:1:1 to about 1:98:1, and in embodiments, from about 1:5:5 to about 1:9:9, and in embodiments, from about 1:6:6 to about 1:8:8. Surfactant

[0069] In an embodiment, the resin, wax, and other additives used to form the toner composition may be in a dispersion containing a surfactant. Further, the toner particles may be formed by an emulsion aggregation method in which the resin and other components of the toner are placed in one or more surfactants to form an emulsion, the toner particles are aggregated, coalesced, optionally washed, dried, and recovered.

[0070] One, two, or more surfactants may be utilized. The surfactant may be selected from ionic surfactants and non-ionic surfactants. Anionic surfactants and cationic surfactants are included in the term "ionic surfactant". In an embodiment, the surfactant may be utilized to be present in an amount of about 0.01 wt% to about 5 wt% of the toner composition, for example, about 0.75 wt% to about 4 wt% of the toner composition, and in an embodiment, about 1 wt% to about 3 wt% of the toner composition.

[0071] Examples of nonionic surfactants that can be used include, for example, polyacrylic acid, metallocose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, IGEPAL CA-210 (trademark), IGEPAL CA-520 (trademark), IGEPAL CA-720 (trademark), IGEPAL CO-890 (trademark), IGEPAL CO-720 (trademark), IGEPAL CO-290 (trademark), IGEPAL CA-210 (trademark), ANTAROX 890 (trademark), and ANTAROX 897 (trademark) available from Rhone-Poulenc. Other examples of suitable nonionic surfactants include block copolymers of polyethylene oxide and polypropylene oxide, including those commercially available as Synperonic PE / F, and in some embodiments, Synperonic PE / F 108.

[0072] Examples of anionic surfactants that can be used can include those described above. Examples of cationic surfactants can include those described above. Colorant

[0073] The latex particles generated as described above can be added to a colorant to produce toner. In an embodiment, the colorant may be a dispersion. The colorant dispersion may include, for example, submicron colorant particles having a volume average diameter of about 50 to about 500 nanometers, and in an embodiment, a volume average diameter of about 100 to about 400 nanometers. The colorant particles may be suspended in an aqueous aqueous phase containing an anionic surfactant, a nonionic surfactant, or a combination thereof. Suitable surfactants include any of the above surfactants. In an embodiment, 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 an embodiment, about 1 to about 15% by weight of the colorant.

[0074] Colorants useful for forming the toner according to the present disclosure include pigments, dyes, mixtures of pigments and dyes, mixtures of pigments, mixtures of dyes, and the like. The colorant may be, for example, carbon black, cyan, yellow, magenta, red, orange, brown, green, blue, violet, or a mixture thereof.

[0075] In embodiments where the colorant is a pigment, the pigment may be, for example, carbon black, phthalocyanine, quinacridone or rhodamine B (trademark) type, red, green, orange, brown, violet, yellow, fluorescent colorant, and the like.

[0076] If desired, the resulting latex in the dispersion and the colorant dispersion are stirred and heated to a temperature of about 35°C to about 70°C, and in an embodiment, about 40°C to about 65°C, which can result in toner aggregates having a volume average diameter of about 2 micrometers to about 10 micrometers, and in an embodiment, a volume average diameter of about 5 micrometers to about 8 micrometers. Wax

[0077] Optionally, the wax may also be combined with a resin to form toner particles. When included, the wax may be present in an amount of, for example, about 1 wt% to about 25 wt% of the toner particles, and in embodiments, about 5 wt% to about 20 wt% of the toner particles.

[0078] Waxes that can be selected include, for example, waxes having a weight average molecular weight of about 500 to about 20,000, and in embodiments, about 1,000 to about 10,000. Waxes that can be used include, for example, polyolefins such as polyethylene, polypropylene, and polybutene waxes, plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, and jojoba oil, animal waxes such as beeswax, mineral waxes and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax, ester waxes obtained from higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate, ester waxes obtained from higher fatty acids and monohydric or polyhydric lower alcohols such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetrabehenate, ester waxes obtained from higher fatty acids and polyhydric alcohol multimers such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate, and triglyceryl tetrastearate, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes such as cholesteryl stearate. Preparation of Toner

[0079] Toner particles can be prepared by any method within the purview of those skilled in the art. Embodiments regarding the manufacture of toner particles are described below with respect to the emulsion aggregation process, although any suitable method for preparing toner particles, including chemical processes such as the suspension method and the encapsulation method disclosed in U.S. Patent Nos. 5,290,654 and 5,302,486, the entire disclosures of which are incorporated herein by reference in their entireties, may be used. In embodiments, the toner composition and toner particles may be prepared by an aggregation and coalescence process in which small-sized resin particles are aggregated to an appropriate toner particle size and then coalesced to achieve the final toner particle shape and morphology.

[0080] In embodiments, the toner composition can be prepared by an emulsion aggregation process, such as a process that includes aggregating a mixture of an optional wax and any other desired or necessary additives with an emulsion optionally containing the resin in the surfactant described above, and then coalescing the aggregated mixture. The mixture may be prepared by adding an optional wax or other material (which may optionally be in a dispersion (s) containing a 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, for example, with an acid such as acetic acid, nitric acid. In embodiments, the pH of the mixture can be adjusted to about 2 to about 4.5. Additionally, in embodiments, the mixture may be homogenized. When the mixture is homogenized, the homogenization may be achieved by mixing at about 1000 to about 6,000 revolutions per minute. The homogenization may be achieved by any suitable means, for example, including an IKA ULTRA TURRAX T50 probe homogenizer.

[0081] Following the preparation of the above mixture, a flocculant may be added to the mixture. Any suitable flocculant may be utilized to form the toner. Suitable flocculants include, for example, aqueous solutions of divalent or polyvalent cationic materials. Flocculants include, for example, polyaluminum halides such as polyaluminum chloride (PAC), or the corresponding bromides, fluorides, or iodides, polyaluminum silicates such as polyaluminum sulfosilicate (PASS), and water-soluble metal salts including aluminum chloride, aluminum nitrite, aluminum sulfate, calcium chloride, calcium nitrite, calcium oxyacid, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, and combinations thereof. In an embodiment, the flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

[0082] The flocculant may be added to the mixture used to form toner in an amount of about 0.1 wt% to about 8 wt% of the resin in the mixture, about 0.2% to about 5 wt% in an embodiment, and about 0.5% to about 5 wt% in other embodiments. This provides a sufficient amount of the agent for flocculation. Shell resin

[0083] In an embodiment, the shell may be applied to the aggregated particles after aggregation but before coalescence.

[0084] Resins that may be utilized to form the shell include, but are not limited to, the above amorphous resins for use in the core. Such amorphous resins may be low molecular weight resins, high molecular weight resins, or combinations thereof. In an embodiment, the amorphous polyester of Formula I above may be mentioned as an amorphous resin that may be used to form the shell according to the present disclosure.

[0085] 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, which is sometimes referred to herein as a reaction initiator in the embodiments. Examples of suitable crosslinking agents include, but are not limited to, free radical or thermal reaction initiators such as the above-mentioned organic peroxides and azo compounds that are suitable for forming a gel in the core.

[0086] The crosslinking agent and the amorphous resin may be combined at a sufficient temperature for a sufficient time to form a crosslinked polyester gel. In an embodiment, the crosslinking agent and the amorphous resin are heated to a temperature of about 25°C to about 99°C, in an embodiment about 30°C to about 95°C, for a time of about 1 minute to about 10 hours, in an embodiment about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell.

[0087] When used, the crosslinking agent may be present in an amount of about 0.001% by weight to about 5% by weight of the resin, in an embodiment about 0.01% by weight to about 1% by weight of the resin. The amount of CCA can be reduced in the presence of a crosslinking agent or reaction initiator. Consolidation

[0088] Following aggregation to the desired particle size and optional application of a shell, the particles may then be consolidated into the desired final shape, which consolidation is achieved, for example, by heating the mixture to a temperature of about 45°C to about 100°C, in an embodiment about 55°C to about 99°C (this temperature may be above the glass transition temperature of the resin used to form the toner particles), and / or reducing the agitation, for example, to about 100 rpm to about 400 rpm, in an embodiment about 200 rpm to about 300 rpm. The consolidated particles can be measured for shape factor or roundness using, for example, a SYSMEX FPIA 2100 analyzer until the desired shape is achieved.

[0089] Consolidation may be achieved over a period of about 0.01 to about 9 hours, in an embodiment about 0.1 to about 4 hours. Subsequent processing

[0090] In an embodiment, after aggregation and / or coalescence, in order to further coalesce the toner aggregates, the pH of the mixture can be lowered, for example with an acid, to about 3.5 to about 6, in an embodiment to about 3.7 to about 5.5. 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 weight percent of the mixture, in an embodiment about 1 to about 20 weight percent of the mixture.

[0091] The mixture may be cooled, washed, and dried. Cooling may be over a temperature of about 20°C to about 40°C, in an embodiment about 22°C to about 30°C, and over a time of about 1 hour to about 8 hours, in an embodiment about 1.5 hours to about 5 hours.

[0092] In an embodiment, the cooling of the coalesced toner slurry may include quenching by adding a cooling medium such as ice, dry ice, etc. and performing rapid cooling to a temperature of about 20°C to about 40°C, in an embodiment about 22°C to about 30°C. Rapid cooling may be achievable for example for small amounts of toner, such as less than about 2 liters, in an embodiment about 0.1 liter to about 1.5 liters. For example, in a larger scale process such as where the size exceeds about 10 liters, rapid cooling of the toner mixture may not be achievable or practical by either introduction of a cooling medium into the toner mixture or use of reactor cooling by a jacket.

[0093] Next, the toner slurry may be washed. The washing may be performed at a pH of about 7 to about 12, in an embodiment at a pH of about 9 to about 11. The washing may be at a temperature of about 30°C to about 70°C, in an embodiment about 40°C to about 67°C. The washing may include filtering and reslurrying a filter cake containing toner particles in deionized water. The filter cake may be washed one or more times with deionized water, or the pH of the slurry may be adjusted with an acid to a pH of about 4 and then washed with one deionized water wash followed optionally by one or more deionized water washes.

[0094] Drying may be carried out by any method within the scope of the intention of those skilled in the art. Any suitable toner particle drying method may be used, including freeze drying, spray drying, and flash airflow drying such as an Aljet dryer. Drying may continue until the moisture level of the particles falls below about 1% by weight, in an embodiment less than about 0.7% by weight, which is the set target. Additive

[0095] In embodiments, the toner particles may contain the polymer additives of the present disclosure as described above, and any other optional additives, as desired or necessary. For example, the toner may contain a positive or negative charge control agent in an amount of, for example, about 0.1 to about 10% by weight of the toner, in an embodiment about 1 to about 3% by weight of the toner. Examples of suitable charge control agents include quaternary ammonium compounds including alkylpyridinium halides, disulfates, alkylpyridinium compounds including those disclosed in U.S. Patent No. 4,298,672, which is hereby incorporated by reference in its entirety, organic sulfates and sulfonate compositions including those disclosed in U.S. Patent No. 4,338,390, which is hereby incorporated by reference in its entirety.

[0096] Also, after formation including a flow aid additive, it can be blended with external additive particles of the toner particles, and this additive may be present on the surface of the toner particles. Examples of these additives include metal oxides such as titanium oxide, silicon oxide, aluminum oxide, cerium oxide, tin oxide, mixtures thereof, colloidal silica and amorphous silica such as AEROSIL®, metal salts and fatty acid metal salts including zinc stearate, calcium stearate, or long-chain alcohols such as UNILIN 700, and mixtures thereof.

[0097] Generally, silica may be applied to the toner surface for toner flow, tribocharge enhancement, mixing control, improved development and transfer stability, and a higher toner blocking temperature. TiO2 may be applied for improved relative humidity (RH) stability, tribocharge control, and improved development and transfer stability. Zinc stearate, calcium stearate, and / or magnesium stearate may optionally be used as external additives to provide lubricating properties, developer conductivity, and tribocharge enhancement, thereby enabling a higher toner charge and charge stability by increasing the number of contacts between the toner and carrier particles. In embodiments, a commercially available zinc stearate known as Zinc Stearate L obtained from Ferro Corporation may be used. The external surface additives may be used with or without a coating.

[0098] Each of these external additives may be present in an amount of about 0 wt% to about 3 wt% of the toner, and in embodiments, about 0.25 wt% to about 2.5 wt% of the toner, although the amount of the additive can be outside of these ranges. In embodiments, the toner may include, for example, about 0 wt% to about 3 wt% titania, about 0 wt% to about 3 wt% silica, and about 0 wt% to about 3 wt% zinc stearate.

[0099] In embodiments, in addition to the polymer additives of the present disclosure, the toner particles may also have silica in an amount of about 0.1 wt% to about 5 wt% of the toner particles, and in embodiments, about 0.2 wt% to about 2 wt% of the toner particles, and titania in an amount of about 0 wt% to about 3 wt% of the toner particles, and in embodiments, about 0.1 wt% to about 1 wt% of the toner particles. Developer

[0100] The toner particles thus formed can be incorporated into a developer composition. The toner particles can be mixed with carrier particles to obtain a two-component developer composition. The toner concentration in the developer may be about 1 wt% to about 25% of the total weight of the developer, and in embodiments, about 2 wt% to about 15% of the total weight of the developer. Carrier

[0101] Examples of carrier particles that can be used for mixing with toner include particles that can triboelectrically acquire a charge of a polarity opposite to that of the toner particles. Exemplary examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrite, iron ferrite, silicon dioxide, and the like. Other carriers include those disclosed in U.S. Patent Nos. 3,847,604, 4,937,166, and 4,935,326.

[0102] In an embodiment, a suitable carrier may be coated with a conductive polymer mixture containing, for example, about 0.5 wt% to about 10 wt%, and in an embodiment, about 0.7 wt% to about 5 wt% of, for example, methyl acrylate and carbon black, using the processes described in U.S. Patent Nos. 5,236,629 and 5,330,874, and may include a steel core having a diameter of about 25 to about 100 μm, and in an embodiment, a diameter of about 50 to about 75 μm.

[0103] Carrier particles can be mixed with toner particles in various suitable combinations. The concentration can be about 1 wt% to about 20 wt% of the toner composition. However, different toner and carrier percentages can be used to obtain a developer composition having desired properties. Imaging

[0104] Toner can be used in an electrostatic copying or electrophotographic process, including those disclosed in U.S. Patent No. 4,295,990, the disclosure of which is hereby incorporated by reference in its entirety. In an embodiment, any known type of developing system can be used in a developing device, including, for example, magnetic brush development, jumping single-component development, hybrid scavengerless development (HSD), and the like. These and similar developing systems are within the scope of the skilled person's intention.

[0105] When an image is formed with toner / developer via a suitable development method such as any one of the above methods, the image can then be transferred to an image receiving medium such as paper. In an embodiment, the toner may be used for development in a developing device that utilizes a fuser roll member.

[0106] The following examples are presented to illustrate embodiments of the present disclosure. These examples are intended for illustration only and are not intended to limit the scope of the present disclosure. Also, unless otherwise specified, ratios and percentages are by weight.

Examples

[0107] Preparation of fluorinated addition latex. All of the fluorinated organic addition latexes used in this specification were prepared on a 2L bench scale. In this implementation, a number of latexes were used. All latexes were made with the same general process and formulation fill amounts except that the monomer ratio was changed. Details are shown in Table 1 below.

[0108] Comparative Example 1: Synthesis of fluorinated organic addition latex using 0% divinylbenzene (DVB).

[0109] In a 2 L Buchi reactor equipped with a P4 impeller, 6.5 g of a 30% solid Calfoam SLS (sodium lauryl sulfate) surfactant was added to 816 g of deionized water (DIW). The reactor was deoxygenated by passing a nitrogen stream through it during the reaction. The reactor was heated to 77 °C and the rpm was set to 400. Separately, in a 1 L glass container equipped with two P4 impellers, a monomer emulsion was prepared by mixing 319.5 g of trifluoroethyl methacrylate (TFEMA), 6.5 g of Calfoam SLS surfactant (30% solid), and 416 g of DIW together (at 450 rpm). 37.1 g was removed from the monomer emulsion and pumped into the 77 °C 2 L reactor. A reaction initiator solution prepared from 1.22 g of ammonium persulfate in 34.3 g of DIW was added over 20 minutes after the addition of the seed emulsion. The remaining monomer emulsion was fed to the reactor over 120 minutes. When half of the monomer emulsion was added, the rpm inside the reactor was increased to 450 rpm. At the end of the monomer feed, the latex was subjected to a 1-hour post-treatment process at 77 °C, followed by a 2-hour temperature increase to 87 °C and a 1-hour hold at 87 °C to reduce the residual monomer at the end of the emulsion polymerization process. As a result, a latex with a particle size of 99 nm and containing 20% solids was obtained.

[0110] Comparative Example 2: Synthesis of a fluorinated organic additive latex with 0% DVB. The same process and formulation as above in Comparative Example 1.

[0111] Comparative Example 3: Synthesis of a non-fluorinated organic additive latex prepared using 0.8% DMAEMA in CHMA and 25% DVB. In a 300 Gal reactor equipped with two P4-type impellers and a condenser, 0.942 kg of Calfoam SLS surfactant (30% solids) was added to 444 kg of DIW. The reactor was deoxygenated by passing a nitrogen stream through it during the reaction, and a condenser was also used. The reactor was heated to 77 °C and the rpm was set to 59. Separately, in a 100 Gal reactor equipped with one P4-type impeller, a monomer emulsion was prepared by mixing 126 kg of CHMA, 42.45 kg of DVB, 1.358 kg of DMAEMA, 5.92 kg of Calfoam SLS surfactant (30% solids), and 221.1 kg of DIW together (at 28 rpm). 0.369 kg was taken out from the monomer emulsion and pumped into the 300 Gal reactor at 77 °C. An initiator solution prepared from 0.645 kg of ammonium persulfate in 7.045 kg of DIW was added over 15 minutes after the addition of the seed emulsion. The remaining monomer emulsion was fed into the 300 Gal reactor over 120 minutes. When half of the monomer emulsion was added, the rpm in the reactor was increased to 66 rpm. At the end of the monomer supply, the condenser was turned off. The latex was subjected to a 1-hour post-treatment process at 77 °C, followed by a 2-hour temperature increase to 87 °C and a 1-hour hold at 87 °C to reduce the residual monomer at the end of the emulsion polymerization step. Also, during the post-treatment protocol, the pH of the latex was adjusted to ≧6.0 every 30 minutes using a 0.1 wt% NaOH solution. As a result, a latex with a particle size of 98 nm and containing 20% solids was obtained and filtered through a 25 micrometer filter bag. The latex was spray-dried for 3D powder coating.

[0112] Example 2: Synthesis of a fluorinated organic additive latex using DVB. It is the same as Comparative Example 1 above, except that 20% DVB and 80% TFEMA were used.

[0113] Example 3: Synthesis of fluorinated organic addition latex using DVB. It is the same as Comparative Example 1 above, except that 30% DVB and 70% TFEMA were used.

[0114] Example 4: Synthesis of fluorinated organic addition latex using CHMA and DVB. It is the same as Comparative Example 1 above, except that 30% DVB, 35% TFEMA, and 35% CHMA were used.

[0115] Since DVB has impurities, in all of the above Examples and Comparative Examples, the actual DVB content is 55% of the amount added to the resin. The following table shows the amount of DVB added to the formulation and the actual content of DVB, which is approximately 0.55x the added amount in the formulation. Most of the impurities in DVB are ethylvinylbenzene, which is also incorporated into the copolymer.

Table 1

[0116] Each additive was individually compounded at 20% SAC (surface area coverage) in a laboratory SKM Mill into the cyan eco-toner, which is the base material of the Xerox 700 Digital Color Press. Table 2 shows the weight % of the filling amount corresponding to 20% SAC.

Table 2

[0117] For each toner, 30 g of Xerox 700 Digital Color Press carrier was used with 1.50 g of the formulated toner in a 60 mL glass bottle. This resulted in a 5% toner concentration, i.e., TC. The samples were conditioned in Zone J at 21.1 °C and 10% RH and then mixed on a Turbula mixer for a total of 2 hours. Samples for SEM were taken at 15 minutes, 30 minutes, 1 hour, and 2 hours. The SEM images were examined, and if the organic polymer additive was flattened and not spherical, it was evaluated as a failure. Then, the survival time was taken as the longest time that the particles remained spherical. Thus, if the particles flattened in 2 hours, the survival time was 1 hour. As shown in Table 3, the survival time increased up to 30% DVB addition. Since the maximum time that the toner is expected to remain in the xerographic development housing is 120 minutes, the test was not continued after 120 minutes. For use as a toner additive, an approximately 20 wt% DVB added at 55% purity, or a DVB content of 11 wt%, is required to moderately toughen the fluorinated polymer additive for xerographic applications, and an approximately 30 wt% DVB added at 55% purity, or a DVB content of 16.5 wt%, may be required to obtain the highest performance.

Table 3

[0118] The toner was formulated as described above, but in this case, 100% of the SAC of each additive was used in the formulation. In this case, since the toner surface is completely covered with the additive, the performance of the toner will depend on the surface additive. In this way, a direct comparison of the relative performance of each additive was obtained. The chargeability, blocking, and cohesiveness of the toner were evaluated for each toner and are shown in Table 4.

[0119] The RX50 is an additive for typical medium-sized silica toners included herein by reference. In the J zone, the charge is a very good negative charge, but the RH sensitivity is very high. Since the ratio of the A zone is only 0.35 of the value of the J zone, the A zone retains only 35% of the charge of the J zone. Thus, silica alone provides very good low cohesive force, exhibits good fluidity, and provides a very good start of blocking, but it is an unacceptable additive.

[0120] The non-fluorinated additive of Comparative Example 3, which is CHMA / 25%DVB / 0.8%DMAEMA, is a positively charged additive. The charge is very similar in both zones and shows better RH sensitivity. Since the value is very low, the RH ratio is quite approximate. Larger-sized additives have worse fluidity than smaller-sized primary additives, so the fluid cohesive force of this additive is not good from its size. Blocking is also very good.

[0121] The TFEMA polymer organic additive is very highly negatively charged, approximately twice the charge of the J zone of silica and approximately four times the charge of the A zone of silica. Despite the very high negative charge, the RH ratio is very good, maintaining 75% of the charge from the J zone to the A zone. Furthermore, despite its large size, the fluidity is actually slightly better than that of RX50, and blocking is also considerably improved.

Table 4

[0122] The TFEMA polymer additive alone of Example 3 is clearly more negatively charged than silica and more negatively charged than those typically used in electrophotographic printers, and there are many ways to provide lower charge using this additive.

[0123] For example, fluorinated polymer additives can be utilized in smaller SACs and will result in a reduction of charge.

[0124] As described above, by using copolymers with non-fluorinated polymer additives such as TFEMA and CHMA, for example, it can be adjusted to any desired charge level between the very negative charge of TFEMA and the slightly positive charge of CHMA. This charge can also replace silica with better RH sensitivity during charging, or can directly replace the better RH sensitivity and lower charge of the silica / titania combination.

[0125] As another option to provide a charge similar to RX50 silica, a fluorinated additive with a smaller SAC can be mixed with a non-fluorinated CHMA additive with a smaller SAC, and by setting the total filling amount to 60% to about 130%, the charge between these two additives can be obtained.

[0126] Alternatively, the fluorinated polymer additive may be mixed with a positive silica such as H2050.

[0127] The fluorinated polymer additive may be mixed with an alumina additive that is very effective in reducing the charge.

[0128] In addition, in U.S. Patent No. 8,663,886, it is possible to reduce the charge by adding a positively charged monomer such as an amine to a polymer additive such as DMAEMA used with CHMA.

[0129] It will be understood that those disclosed above and other variations of features and functions, or their alternatives, may be combined in other different systems or applications. Various alternatives, modifications, variations, or improvements not currently anticipated or predicted therein may be made by those skilled in the art in the future, and these are also encompassed by the following claims. Another aspect of the present invention may be as follows. 〔1〕A toner composition comprising toner particles containing at least one resin, an optional colorant, an optional wax, and a polymer toner additive on at least a part of the outer surface of the toner particles, wherein the polymer toner additive is a polymer resin containing a fluorinated acrylic monomer, 8% to 40% by weight of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent containing a nitrogen-containing group. 〔2〕The toner composition according to 〔1〕 above, wherein the fluorinated acrylic monomer contains a fluorinated acrylate monomer or a fluorinated methacrylate monomer. 〔3〕The toner composition according to 〔1〕 above, wherein the charge control agent monomer nitrogen contains an acrylate monomer or a methacrylate monomer. 〔4〕The toner composition according to 〔1〕 above, wherein the polymer resin further contains a non-fluorinated hydrophobic monomer. 〔5〕The toner composition according to 〔1〕 above, wherein the polymer resin further contains cyclohexyl methacrylate. 〔6〕The toner composition according to 〔1〕 above, wherein the crosslinkable monomer contains divinylbenzene. 〔7〕The toner composition according to 〔1〕 above, further comprising at least one additive selected from the group consisting of silica, titania, alumina, and a crosslinked non-fluorinated organic surface additive. 〔8〕The toner composition according to 〔1〕 above, wherein the toner particles contain emulsion aggregation toner having a size of about 4 micrometers to about 10 micrometers. 〔9〕The toner composition according to 〔1〕 above, further comprising a cleaning additive selected from the group consisting of stearate, cerium oxide, and strontium titanate. 〔10〕The toner composition according to 〔1〕 above, wherein the polymer additive constitutes 0.1% to 5% by weight of the toner composition. 〔11〕The toner composition according to 〔1〕 above, wherein the polymer additive has a size of 25 nanometers to 250 nanometers. 〔12〕A developer comprising a toner composition and a toner carrier, wherein the toner composition includes toner particles containing at least one resin, an optional colorant, an optional wax, and a polymer toner additive on at least a part of the outer surface of the toner particles, and the polymer toner additive is a polymer resin containing a fluorinated acrylic monomer, 8 wt% to 40 wt% of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% to 1.5 wt% of the polymer resin of a charge control agent monomer composed of a nitrogen-containing group. 〔13〕The developer according to 〔12〕, wherein the fluorinated acrylic monomer includes a fluorinated acrylate monomer or a fluorinated methacrylate monomer. 〔14〕The developer according to 〔12〕, wherein the charge control agent monomer nitrogen includes an acrylate monomer or a methacrylate monomer. 〔15〕The developer according to 〔12〕, wherein the polymer resin further includes a non-fluorinated hydrophobic monomer. 〔16〕The developer according to 〔12〕, wherein the polymer resin further includes cyclohexyl methacrylate. 〔17〕The developer according to 〔12〕, wherein the crosslinkable monomer includes divinylbenzene. 〔18〕The developer according to 〔12〕, further including an additive selected from the group consisting of silica, titania, alumina, and a crosslinked non-fluorinated organic surface additive. 〔19〕A toner additive, comprising a polymer resin containing a fluorinated acrylic monomer, 8 wt% to 40 wt% of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and optionally 0.1 wt% to 1.5 wt% of the polymer resin of a charge control agent of a nitrogen-containing group. 〔20〕The toner additive according to 〔1〕, wherein the polymer resin includes a size of 25 nanometers to 250 nanometers.

Claims

1. An toner composition comprising emulsion agglomerated toner particles containing at least one amorphous polyester resin and one crystalline polyester resin, a surfactant, an optional colorant, an optional wax, and a polymer toner additive on at least a portion of the outer surface of the emulsion agglomerated toner particles, wherein the polymer toner additive is A polymer resin containing a fluorinated acrylic monomer, 8 wt% to 40 wt% of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and 0.1 wt% to 1.5 wt% of the polymer resin of a charge control agent monomer containing a nitrogen-containing group.

2. The toner composition according to claim 1, wherein the fluorinated acrylic monomer comprises a fluorinated acrylate monomer or a fluorinated methacrylate monomer.

3. The toner composition according to claim 1, wherein the charge control agent monomer containing a nitrogen-containing group comprises an acrylate monomer or a methacrylate monomer.

4. The toner composition according to claim 1, wherein the polymer resin further comprises a non-fluorinated hydrophobic monomer.

5. The toner composition according to claim 1, wherein the polymer resin further comprises cyclohexyl methacrylate.

6. The toner composition according to claim 1, wherein the crosslinkable monomer comprises divinylbenzene.

7. The toner composition according to claim 1, further comprising at least one additive selected from the group consisting of silica, titania, alumina, and a crosslinked non-fluorinated organic surface additive.

8. The toner composition according to claim 1, wherein the emulsion agglomerated toner particles have a size of about 4 micrometers to about 10 micrometers.

9. The toner composition according to claim 1, further comprising a cleaning additive selected from the group consisting of stearate, cerium oxide, and strontium titanate.

10. The toner composition according to claim 1, wherein the polymer additive constitutes 0.1 weight percent to 5 weight percent of the toner composition.

11. The toner composition according to claim 1, wherein the polymer additive has a size of 25 nanometers to 250 nanometers.

12. A developer comprising a toner composition, a toner carrier, the toner composition comprising emulsion agglomerated toner particles comprising at least one amorphous polyester resin and one crystalline polyester resin, a surfactant, an optional colorant, an optional wax, and a polymer toner additive on at least a portion of the outer surface of the toner particles, the polymer toner additive being A developer comprising a polymer resin containing a fluorinated acrylic monomer, 8% to 40% by weight of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and 0.1% to 1.5% by weight of the polymer resin of a charge control agent monomer containing a nitrogen-containing group.

13. The developer according to claim 12, wherein the fluorinated acrylic monomer comprises a fluorinated acrylate monomer or a fluorinated methacrylate monomer.

14. The developer according to claim 12, wherein the charge control agent monomer containing a nitrogen-containing group comprises an acrylate monomer or a methacrylate monomer.

15. The developer according to claim 12, wherein the polymer resin further comprises a non-fluorinated hydrophobic monomer.

16. The developer according to claim 12, wherein the polymer resin further comprises cyclohexyl methacrylate.

17. The developer according to claim 12, wherein the crosslinkable monomer comprises divinylbenzene.

18. The developer according to claim 12, further comprising an additive selected from the group consisting of silica, titania, alumina, and a crosslinked non-fluorinated organic surface additive.

19. A toner composition comprising emulsion agglomerated toner particles comprising at least one amorphous polyester resin and one crystalline polyester resin, a surfactant, A polymer resin containing a fluorinated acrylic monomer, the polymer resin comprising 8% to 40% by weight of the polymer resin of a crosslinkable monomer containing two or more vinyl groups, and 0.1% to 1.5% by weight of the polymer resin of a charge control agent monomer of a nitrogen-containing group.

20. The toner composition according to claim 19, wherein the polymer resin has a size of 25 nanometers to 250 nanometers.

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