Toner Compositions and Additives

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, developer, and additive for a toner composition are disclosed. The toner composition comprises toner particles containing a 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 includes a polymeric resin containing a fluorinated monomer, where the polymeric resin is less than 10 wt.% crosslinked, and optionally a charge control agent containing a nitrogen-containing group at 0.1 wt.% to 1.5 wt.% of the polymeric resin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates generally to toner compositions, and more specifically to toner compositions that include polymeric additives. [Background technology]

[0002] Electrophotographic printing utilizes toner particles that can be produced by a variety of processes. One such process includes an emulsion aggregation ("EA") process in which surfactants are used to form a latex emulsion to form toner particles. See, for example, U.S. Pat. No. 6,120,967, the disclosure of which is incorporated herein by reference in its entirety, for an example of such a process.

[0003] A combination of amorphous and crystalline polyesters can be used in the EA process. This resin combination can provide high gloss and relatively low melting point properties (sometimes called low melt, ultra-low melt, or ULM), which allows for more energy efficiency and faster printing. The use of additives with EA toner particles can be important to achieve optimal toner performance, especially in the charging area. Summary of the Invention [Problem to be solved by the invention]

[0004] Potential problems with toners include sensitivity to environmental conditions, including humidity. For example, in the summer, users complain about background in images when it is hot and humid. In the winter, users complain about bright images when it is cold and dry. Excessive background can also occur due to a loss of charge as the developer ages.

[0005] There is a continuing need to improve the additives used in forming 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, there is provided a toner composition comprising at least one resin toner particle, an optional colorant, an optional wax, and a polymeric toner additive on at least a portion of the outer surface of the toner particle, the polymeric toner additive comprising a polymer resin comprising a fluorinated monomer, the polymer resin being less than 10% by weight crosslinked, and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group.

[0007] According to various embodiments, a developer is provided that includes a toner composition and a toner carrier. The toner composition includes toner particles that include 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 that includes a fluorinated monomer, where the polymeric resin is less than 10% by weight crosslinked, and optionally 0.1% to 1.5% by weight of the polymeric resin of a charge control agent that includes a nitrogen-containing group.

[0008] Disclosed herein is a toner additive comprising a polymer resin, the polymer resin being less than 10% by weight crosslinked and comprising a fluorinated monomer, and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group. [Brief explanation of the drawings]

[0009] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the present teachings and, together with the description, serve to explain the principles of the present teachings.

[0010] [Figure 1] FIG. 1 shows the charge of a single additive formulated at 17% SAC (surface area coverage) on the surface of a toner according to various embodiments disclosed herein.

[0011] [Figure 2]FIG. 2 shows the DVB0% TFEMA latex on cyan parent toner after 15 minutes of developer aging according to various embodiments disclosed herein.

[0012] [Figure 3] FIG. 3 shows Comparative Example 3 with DVB 30% crosslinked TFEMA latex on cyan parent toner after 120 minutes of developer aging.

[0013] It should be noted that some details of these figures have been simplified and strict structural accuracy, detail, and scale are not maintained, but rather are drawn to facilitate understanding of the embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present disclosure provides polymeric additives for use with toner particles.

[0015] The resulting polymers may be used as additives with toner compositions to enhance the sensitivity to relative humidity and charge stability of the resulting toner. The polymer additives herein can be used at lower densities compared to other additives, and require much less material by weight to cover an equivalent surface area compared to inorganic additives, including oxides such as titania and silica. The polymer additives of the present disclosure can also provide toner particles with a wide range of properties, such as hydrophobicity and charge control, depending on the monomers used to form the polymer.

[0016] In an embodiment, the toner additive is a non-crosslinked emulsion-polymerized organic polymer latex containing a fluorinated monomer. This non-crosslinked polymer additive can be added to other toner surface additives and blended onto the toner surface, where the additive is leveled and embedded in the toner surface. The resulting toner can provide better blocking than one that does not contain the non-crosslinked fluorinated polymer. One embodiment is poly(trifluoroethyl methacrylate) polymer.

[0017] Suitable fluorinated monomers that may be utilized in forming the polymer additive include, for example, 2,4,6-fluorophenyl acrylate, pentafluorophenyl acrylate, hexafluoro-iso-propyl 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-heneicosafluorododecyl 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 1H,1H,2H,2H-Perfluorodecyl 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-Tetrafluorodecyl Examples of suitable crosslinkers include fluoropropyl 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. In embodiments, the crosslinker may be fluorinated.Suitable fluorinated crosslinkers include fluorinated divinyl crosslinkers such as 1,8-divinylperfluoro(octane), 1,6-divinylperfluoro(hexane), and 1,4-divinylperfluoro(butane) and perfluorocyclohexyl(meth)acrylate.

[0018] The polymer additive is not crosslinked.

[0019] The fluorinated acrylic monomer may be present in the polymeric additive in an amount from about 5% by weight of the polymeric additive to about 90% by weight of the polymeric additive, in embodiments from about 20% by weight of the polymeric additive to about 92% by weight of the polymeric additive.

[0020] In embodiments, charge control agent monomers include nitrogen-containing groups, including, but not limited to, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, and combinations thereof.

[0021] The charge control agent monomer comprises from 0.1% to 1.5%, from about 0.6% to 1.2%, or from about 0.7% to about 1.1% by weight of nitrogen-containing groups in the polymer additive.

[0022] Methods for forming the polymeric additive, in embodiments, include emulsion polymerization of the monomers utilized to form the polymeric additive.

[0023] In the polymerization process, reactants may be added to a suitable reactor, such as a mixing vessel. Appropriate amounts of starting materials may be dissolved in an optional solvent, and an optional initiator may be added to the solution and contacted with at least one surfactant to form an emulsion. A polymer additive may be formed in the emulsion, which may then be recovered and used as a polymer additive for a toner composition.

[0024] If used, suitable solvents include, but are not limited to, 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, and the like.

[0025] In embodiments, a latex for forming the polymeric additive may be prepared in an aqueous phase containing a surfactant or co-surfactant, optionally under an inert gas such as nitrogen. The surfactant may be utilized with the resin to form the latex dispersion and may be an ionic or non-ionic surfactant in an amount of from about 0.01 to about 15 percent by weight of solids, in embodiments from about 0.1 to about 10 percent by weight of solids.

[0026] Anionic surfactants that can be utilized include sulfates and sulfonates, sodium dodecyl sulfate (SDS), also known as sodium lauryl sulfate (SLS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzene alkyl sulfates and sulfonates, acids such as abietic acid available from Aldrich, NEOGEN R™ and NEOGEN SC™ from Dai-ichi Kogyo Seiyaku Co., Ltd., combinations thereof, and the like. Other suitable anionic surfactants, in embodiments, include DOWFAX™ 2A1, an alkyldiphenyloxide disulfonate from Dow Chemical Company, and / or Teika Power BN2060 from Teika Corporation (Japan), which are branched sodium dodecylbenzenesulfonates. Combinations of these surfactants with any of the aforementioned anionic surfactants may also be utilized in embodiments.

[0027] Examples of cationic surfactants include, but are not limited to, ammonium, such as alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, C 12 ,C 15 ,C 17 trimethylammonium bromide, combinations thereof, and the like. Other cationic surfactants include cetylpyridinium bromide, halide salts of quaternized polyoxyethyl alkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, Sanizol (benzalkonium chloride) available from Kao Chemicals, combinations thereof, and the like. In embodiments, suitable cationic surfactants include SANISOL B-50 available from Kao Corp., which is primarily benzyldimethylalkonium chloride.

[0028] Examples of nonionic surfactants include, but are not limited to, alcohols, acids and ethers, such as polyvinyl alcohol, polyacrylic acid, metallose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, combinations thereof, and the like. In embodiments, surfactants commercially available from Rhone-Poulenc may be utilized, such 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™.

[0029] The selection of a particular surfactant or combination thereof, as well as the amount of each to use, is within the knowledge of one skilled in the art.

[0030] In embodiments, an initiator may be added to form the latex utilized in forming the polymer additive. Examples of suitable initiators include water-soluble initiators, such as ammonium persulfate, sodium persulfate, and potassium persulfate, and organic solvent-soluble initiators, including organic peroxides, and azo compounds, including Vazo peroxides, such as VAZO 64™, 2-methyl-2-2′-azobispropanenitrile, VAZO 88™, 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] amidine] 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.

[0031] The initiator may be added in a suitable amount, for example, from about 0.1 to about 8 weight percent, and in embodiments from about 0.2 to about 5 weight percent of the monomers.

[0032] In forming the emulsion, the starting materials, surfactant, optional solvent, and optional initiator can be combined using any means within the purview of one of ordinary skill in the art. In embodiments, the reaction mixture may be mixed for about 1 minute to about 72 hours, and in certain embodiments, for about 4 hours to about 24 hours, while maintaining a temperature of about 10° C. to about 100° C., in certain embodiments, about 20° C. to about 90° C., and in other certain embodiments, about 45° C. to about 75° C.

[0033] Those skilled in the art will understand that optimization of reaction conditions, temperatures, and initiator loadings can be varied to produce polymers of various molecular weights, and that equivalent techniques can be used to polymerize structurally related starting materials.

[0034] The average particle size of the polymer nanoparticles was measured by dynamic light scattering using a Nanotrac252 instrument (Microtrac, Inc.).

[0035] As used herein, the term "average particle size" refers to the diameter value where 50% of the particles in a sample (by volume unless otherwise specified) have a diameter less than that value. The average particle size may also be referred to as "D50."

[0036] The particle size of latex particles ranging in size from 0.0008 to 6.54 micrometers is measured using a Nanotrac 252 instrument. This instrument uses laser light scattering technology to measure the Doppler shift of light generated by each particle in motion (Brownian motion). These shifts generate a signal proportional to the particle size. The signal is mathematically converted to particle size and size distribution. Analysis can be performed using an external probe or by inserting the probe into a fixed sample chamber.

[0037] For light scattering techniques, NIST polystyrene nanosphere control samples with diameters in the range of 15 nm to 150 nm, available from Microtrac under the trade name NIST Traceable Reference Material for Nanotrac Particle Size Analyzers, can be used.

[0038] The resulting latex, having the polymer additive of the present disclosure, may be applied to the toner particles utilizing any means within the purview of those skilled in the art. In embodiments, the toner particles may be dipped into or sprayed with the latex containing the polymer additive, thus coating the particles, and the coated particles may then be dried, leaving the polymer coating thereon.

[0039] In other embodiments, once the polymer additive for the toner is formed, it may 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.

[0040] In embodiments, once obtained, the polymer additive utilized as a toner additive may be dried to a powder form by any method within the purview of those skilled in the art, including, for example, freeze drying, spray drying, optionally in a vacuum, combinations thereof, etc. The dried polymer additive of the present disclosure may then be applied to toner particles using any means within the purview of those skilled in the art, including, but not limited to, mechanical impact and / or electrostatic attraction. An example of a mechanical mixing device is a Henschel FM high-intensity mixer from Zeppelin Systems, although other mixing devices may also be used in embodiments.

[0041] The particles of the polymeric additive may have an average or medium particle size (D50) of from about 20 nanometers to about 250 nanometers in diameter, in embodiments from about 40 nanometers to about 150 nanometers in diameter.

[0042] In embodiments, polymeric additives utilized as polymeric additives soluble in solvents such as tetrahydrofuran (THF) have a number average molecular weight (M) of, for example, about 40,000 to about 280,000 daltons, in embodiments, about 60,000 to about 170,000 daltons, as measured by gel permeation chromatography (GPC) using polystyrene standards. n ), and a weight average molecular weight (M), as measured by gel permeation chromatography, of, for example, about 200,000 to about 800,000 daltons, in embodiments, about 400,000 to about 600,000 daltons. w In embodiments, the crosslinking may limit the solubility of the crosslinked resin, making it impossible to measure the molecular weight by any method.

[0043] The polymer or polymer additives utilized as the polymer additive may have a glass transition temperature (Tg) of from about 85°C to about 140°C, in embodiments from about 100°C to about 130°C. In embodiments, it may be impossible to determine the Tg due to crosslinking of the resin, which may make detection of the Tg difficult. In embodiments, the A-zone charge of toners including polymer additives of the present disclosure may be from about -15 to about -80 microcoulombs per gram, in embodiments from about -20 to about -60 microcoulombs per gram, while the C-zone charge of toners including polymer additives of the present disclosure may be from about -15 to about -80 microcoulombs per gram, in embodiments from about -20 to about -60 microcoulombs per gram.

[0044] The polymer additives of the present disclosure may be combined with the toner particles such that the polymer additive is present in an amount of from about 0.1% by weight of the toner particles to about 5% by weight of the toner particles, in embodiments from about 0.2% by weight of the toner particles to about 2% by weight of the toner particles.

[0045] Thus, the polymeric additive compositions and processes of the present disclosure allow a number of different combinations to be utilized to formulate developers with selected high triboelectric charging properties and / or conductivity values. toner

[0046] The polymeric additive thus produced may then be combined with a toner resin, optionally with a colorant, to form a toner of the present disclosure. resin

[0047] Any toner resin can be utilized in forming the toner of the present disclosure. Such resins may then be made with any suitable monomer or monomers by any suitable polymerization method. In embodiments, the resins may be prepared by methods other than emulsion polymerization. In further embodiments, the resins may be prepared by condensation polymerization.

[0048] The toner composition of the present disclosure, in embodiments, comprises an amorphous resin. The amorphous resin may be linear or branched. In embodiments, the amorphous resin may comprise at least one low molecular weight amorphous polyester resin. Low molecular weight amorphous polyester resins, available from a number of sources, may have a variety of glass transition temperatures, for example, from about 30°C to about 80°C, in embodiments from about 35°C to about 75°C. As used herein, a low molecular weight amorphous polyester resin refers to a resin having a number average molecular weight (M), for example, as measured by gel permeation chromatography (GPC), of from about 1,000 to about 10,000, in embodiments from about 2,000 to about 8,000, in embodiments from about 3,000 to about 7,000, and in embodiments from about 4,000 to about 6,000. n The weight average molecular weight (M w ) is 50,000 or less, for example, in embodiments, from about 2,000 to about 50,000, in embodiments, from about 3,000 to about 40,000, 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. w / Mn ) is, for example, from about 2 to about 6, and in embodiments, from about 3 to about 4. The low molecular weight amorphous polyester resin may have an acid number of from about 8 to about 20 mg KOH / g, and in embodiments, from about 9 to about 16 mg KOH / g, and in embodiments, from about 10 to about 14 mg KOH / g.

[0049] Examples of linear amorphous polyester resins that can be utilized include poly(propoxylated bisphenol A co-fumarate), poly(ethoxylated bisphenol A co-fumarate), poly(butyloxylated bisphenol A co-fumarate), poly(co-propoxylated bisphenol A co-ethoxylated bisphenol A co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol A co-maleate), poly(ethoxylated bisphenol A co-maleate), poly(butyl ... Poly(1,2-propylene itaconate), poly(butylenated bisphenol A coitaconate), poly(copropoxylated bisphenol A coethoxylated bisphenol A co-maleate), poly(1,2-propylene itaconate), 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.

[0050] In embodiments, suitable amorphous resins may include alkoxylated bisphenol A fumarate / terephthalate-based polyester and copolyester resins. In embodiments, suitable amorphous polyester resins may be copoly(propoxylated bisphenol A co-fumarate)-copoly(propoxylated bisphenol A co-terephthalate) resins having the following formula (I): [ka] wherein R may be hydrogen or a methyl group, m and n represent random units of the polymer additive, where 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. Pat. No. 6,063,827, the disclosure of which is incorporated herein by reference in its entirety.

[0051] In embodiments, the low molecular weight amorphous polyester resin may be a saturated or unsaturated amorphous polyester resin. Illustrative 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, polyheptadene terephthalate, polyoctalene terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polypentylene isophthalate, and polyhexylene isophthalate. , Polyheptadene-isophthalate, Polyoctalene-isophthalate, Polyethylene-sebacate, Polypropylene-sebacate, Polybutylene-sebacate, Polyethylene-adipate, Polypropylene-adipate, Polybutylene-adipate, Polypentylene-adipate, Polyhexylene-adipate, Polyheptadene-adipate, Polyoctalene-adipate, Polyethylene-glutarate, Polypropylene-glutarate, Polybutylene-glutarate, Polypentylene-glutarate, Polyhexylene- Glutarate, polyheptadene-glutarate, polyoctalene-glutarate, polyethylene-pimelate, polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate, polyhexylene-pimelate, polyheptadene-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) 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 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. Resins may also be functionalized, such as by carboxylation, sulfonation, or sodium sulfonation, if desired.

[0052] Examples of suitable polycondensation catalysts for any of the low molecular weight amorphous polyester resins include tetraalkyl titanates, dialkyl tin oxides such as dibutyltin oxide, tetraalkyl tins such as dibutyltin dilaurate, dialkyl tin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxide, stannous oxide, or mixtures thereof, which may be utilized in amounts of, for example, from about 0.01 mol % to about 5 mol % based on the starting diacid or diester used to produce the polyester resin.

[0053] The low molecular weight amorphous polyester resin may be a branched resin. As used herein, the terms "branched" or "branched" include branched and / or crosslinked resins.

[0054] The resulting unsaturated polyester is reactive (e.g., crosslinkable) at two fronts: (i) the sites of unsaturation (double bonds) along the polyester chain, and (ii) functional groups suitable for acid-base reactions, such as carboxyl groups, hydroxyl groups, etc. In embodiments, the unsaturated polyester resin is prepared by melt polycondensation or other polymerization processes using diacids and / or anhydrides and diols.

[0055] In embodiments, the low molecular weight amorphous polyester resin or combination of low molecular weight amorphous resins may have a glass transition temperature of from about 30° C. to about 80° C., in embodiments from about 35° C. to about 70° C. In further embodiments, the combined amorphous resins may have a glass transition temperature of from about 10 to about 1,000,000 Pa at about 130° C. * S, in embodiments, about 50 to about 100,000 Pa * It may have a melt viscosity of S.

[0056] 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 from 25 to about 50% by weight, in embodiments from about 30 to about 45% by weight, and in embodiments from about 35 to about 43% by weight of the toner particles (i.e., toner particles excluding external additives and water).

[0057] In embodiments, the toner composition includes at least one crystalline resin. As used herein, "crystalline" refers to a polyester having three-dimensional order. As used herein, "semi-crystalline resin" refers to a resin having a crystallinity of, for example, about 10 to about 90%, and in embodiments, about 12 to about 70%. Furthermore, as used hereinafter, "crystalline polyester resin" and "crystalline resin" encompass both crystalline resins and semi-crystalline resins unless otherwise specified.

[0058] In embodiments, the crystalline polyester resin is a saturated crystalline polyester resin or an unsaturated crystalline polyester resin.

[0059] Crystalline polyester resins available from many sources may have a variety of melting points, for example, from about 30° C. to about 120° C., in embodiments, from about 50° C. to about 90° C. The crystalline resins may have a number average molecular weight (M), for example, as measured by gel permeation chromatography (GPC), of from about 1,000 to about 50,000, in embodiments, from about 2,000 to about 25,000, in embodiments, from about 3,000 to about 15,000, and in embodiments, from about 6,000 to about 12,000. n The molecular weight distribution (M w / M n ) is, for example, from about 2 to about 6, and in embodiments, from about 3 to about 4. The crystalline polyester resin may 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.

[0060] Illustrative 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(ethylene sebacate), poly(propylene sebacate), poly(ethylene succinate), 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(ethylene sebacate), poly(ethylene succinate ... 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) t), 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(ethylene sebacate), copoly(5-sulfoisophthaloyl)-copoly(ethylene succinate ... copoly(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)

[0033] Examples of the crystalline polyester include any of a variety of crystalline polyesters, such as 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 combinations thereof.

[0061] The crystalline resins can be prepared by a polycondensation process by reacting a suitable organic diol with a suitable organic diacid in the presence of a polycondensation catalyst.

[0062] Examples of organic diols selected for preparing the crystalline polyester resin include aliphatic diols having from about 2 to about 36 carbon atoms.

[0063] Examples of organic diacids or diesters selected for preparing 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, their diesters, or anhydrides thereof; and alkali sulfo-organic diacids, such as dimethyl-5-sulfo-isophthalate, dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic acid, and the like. Examples of suitable diacids include sodium, lithium, or potassium salts of sulfophthalic acid, 4-sulfophthalic acid, dimethyl-4-sulfophthalate, dialkyl-4-sulfophthalates, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfoterephthalic acid, dimethyl-sulfoterephthalate, 5-sulfoisophthalic acid, dialkyl-sulfoterephthalates, sulfo-p-hydroxybenzoic acid, 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 sulfoaliphatic diacid can be selected in an amount of about 1 to about 10 mole percent of the resin.

[0064] In embodiments, suitable crystalline resins may include resins comprised of ethylene glycol or nonanediol, and a mixture of dodecanedioic acid and fumaric acid comonomers having the following formula (II): [ka] In the formula, b is about 5 to about 2,000, and d is about 5 to about 2,000.

[0065] As used herein, semi-crystalline polyester resins 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 sebacatenol), poly(ethylene olefin copolymer ... ate), poly(decamethylene sebacate), poly(ethylene suberate), poly(decamethylene succinate, poly(eicosamethylene malonate), poly(ethylene-p-carboxyphenoxy-undecanoate), poly(ethylene dithionesophthalate), poly(methylethylene terephthalate), poly(ethylene-p-carboxyphenoxy-valerate), poly(hexamethylene-4,4'-oxydibenzoate), poly Poly(10-hydroxycapric acid), poly(isophthalaldehyde), poly(octamethylene dodecanedioate), poly(dimethylsiloxane), poly(dipropylsiloxane), poly(tetramethylene phenylene diacetate), poly(tetramethylene trithiodicarboxylate), poly(trimethylene dodecanedioate), poly(m-xylylene), poly(p-xylylene pimelamide), and combinations thereof.

[0066] The amount of crystalline polyester resin in the toner particles of the present disclosure may be present in the core, shell, or both, in an amount of from 1 to about 15% by weight, in embodiments from about 5 to about 10% by weight, and in embodiments from about 6 to about 8% by weight of the toner particles (i.e., toner particles excluding external additives and water).

[0067] In embodiments, toners of the present disclosure may also include at least one high molecular weight branched or crosslinked amorphous polyester resin. The high molecular weight resin may, in embodiments, include, for example, a branched amorphous resin or amorphous polyester, a crosslinked amorphous resin or amorphous polyester, or a mixture thereof, or a crosslinked, non-crosslinked amorphous polyester resin. According to the present disclosure, from about 1% to about 100% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked, and in embodiments, from about 2% to about 50% by weight of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0068] As used herein, a high molecular weight amorphous polyester resin is a polyester having, for example, a number average molecular weight (M) of about 1,000 to about 10,000 as measured by, for example, gel permeation chromatography (GPC). n High molecular weight amorphous resins available from a number of sources may have a variety of glass transition onset temperatures (Tg), as measured by differential scanning calorimetry (DSC), for example, from about 40° C. to about 80° C., in embodiments from about 50° C. to about 70° C., and in embodiments from about 54° C. to about 68° C. In embodiments, the linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0069] 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-naphthalenetricarboxylic 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 starting diacid or diester used to make the resin.

[0070] In some embodiments, crosslinked polyester resins can be made from linear amorphous polyester resins containing unsaturated sites that can react under free radical conditions. In some embodiments, suitable unsaturated polyester resins can be prepared from diacids and / or anhydrides, such as, for example, maleic anhydride, terephthalic acid, trimellitic acid, fumaric acid, and the like, and combinations thereof, and diols, such as, for example, bisphenol A ethylene oxide adducts, bisphenol A-propylene oxide adducts, and the like, and combinations thereof. In embodiments, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0071] In embodiments, crosslinked branched polyesters may be utilized as high molecular weight amorphous polyester resins. Examples of such polyesters and their synthesis methods include those disclosed in U.S. Patent No. 6,592,913, the disclosure of which is incorporated herein by reference in its entirety.

[0072] Suitable polyols may contain from about 2 to about 100 carbon atoms and have at least two or more hydroxyl groups, or esters thereof. Polyols may include glycerol, pentaerythritol, polyglycols, polyglycerols, and the like, or mixtures thereof. The polyol may include glycerol. Suitable esters of glycerol include glycerol palmitate, glycerol sebacate, glycerol adipate, triacetin tripropionin, and the like. The polyol may be present in an amount of from about 20% to about 30% by weight of the reaction mixture, in embodiments from about 22% to about 26% by weight of the reaction mixture.

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

[0074] In embodiments, a high molecular weight resin, such as a branched polyester, may be present on the surface of the toner particles of the present disclosure. The high molecular weight resin on the surface of the toner particles may also be particulate in nature, and may be high molecular weight resin particles having diameters of from about 100 nanometers to about 300 nanometers, in embodiments from about 110 nanometers to about 150 nanometers.

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

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

[0077] In embodiments, the resins, waxes, and other additives used to form the toner composition may be in a dispersion with a surfactant. Additionally, the toner particles may be formed by emulsion aggregation techniques in which the resin and other components of the toner are placed in one or more surfactants to form an emulsion, and the toner particles are aggregated, coalesced, and optionally washed, dried, and recovered.

[0078] One, two, or more surfactants may be utilized. The surfactants may be selected from ionic surfactants and nonionic surfactants. Anionic surfactants and cationic surfactants are encompassed by the term "ionic surfactant." In embodiments, the surfactant may be utilized in an amount of from about 0.01% to about 5% by weight of the toner composition, such as from about 0.75% to about 4% by weight of the toner composition, in embodiments from about 1% to about 3% by weight of the toner composition.

[0079] Examples of nonionic surfactants that can be utilized include, for example, polyacrylic acid, metallose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, 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™ 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, in some embodiments, Synperonic PE / F 108.

[0080] Anionic surfactants that can be utilized include those previously described. Examples of cationic surfactants include those mentioned above. coloring agent

[0081] The latex particles produced as described above can be added to a colorant to produce a toner. In embodiments, the colorant may be in a dispersion. The colorant dispersion may include submicron colorant particles having a volume average diameter of, for example, about 50 to about 500 nanometers, and in embodiments, about 100 to about 400 nanometers. The colorant particles may be suspended in an aqueous phase containing an anionic surfactant, a nonionic surfactant, or a combination thereof. Suitable surfactants include any of the surfactants described above. In embodiments, the surfactant may be ionic and may be present in the dispersion in an amount of about 0.1 to about 25% by weight of the colorant, and in embodiments, about 1 to about 15% by weight of the colorant.

[0082] Colorants useful in forming toners according to the present disclosure include pigments, dyes, mixtures of pigments and dyes, mixtures of pigments, mixtures of dyes, etc. The colorant may be, for example, carbon black, cyan, yellow, magenta, red, orange, brown, green, blue, violet, or mixtures thereof.

[0083] In embodiments where the colorant is a pigment, the pigment may be, for example, carbon black, phthalocyanine, quinacridone or Rhodamine B™ type, red, green, orange, brown, violet, yellow, fluorescent colorants, and the like.

[0084] The resulting latex in the dispersion, and the colorant dispersion, may be optionally stirred and heated to a temperature of from about 35°C to about 70°C, in embodiments from about 40°C to about 65°C, which may result in toner aggregates having a volume average diameter of from about 2 micrometers to about 10 micrometers, in embodiments from about 5 micrometers to about 8 micrometers. wax

[0085] Optionally, a wax may also be combined with the resin to form the toner particles. If included, the wax may be present in an amount of, for example, from about 1% to about 25% by weight of the toner particles, in embodiments from about 5% to about 20% by weight of the toner particles.

[0086] Examples of waxes that can be selected include waxes having a weight-average molecular weight of about 500 to about 20,000, and in embodiments, about 1,000 to about 10,000. Examples of waxes that can be used include polyolefins such as polyethylene, polypropylene, and polybutene wax; vegetable waxes such as carnauba wax, rice wax, candelilla wax, Japan 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; butyl stearate; propyl oleate; Examples of such waxes include ester waxes obtained from higher fatty acids and monohydric or polyhydric lower alcohols, such as 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. Toner Preparation

[0087] Toner particles may be prepared by any method within the purview of those skilled in the art. Although embodiments relating to the manufacture of toner particles are described below with respect to emulsion aggregation processes, any suitable method for preparing toner particles may be used, including chemical processes such as suspension and encapsulation methods disclosed in U.S. Pat. Nos. 5,290,654 and 5,302,486, the disclosures of each of which are incorporated herein by reference in their entireties. In embodiments, toner compositions and toner particles may be prepared by an aggregation and coalescence process, in which small resin particles are aggregated to the appropriate toner particle size and then coalesced to achieve the final toner particle shape and morphology.

[0088] In embodiments, the toner composition may be prepared by an emulsion aggregation process, such as a process comprising aggregating an emulsion containing the resin described above, optionally in a surfactant, with a mixture of optional wax and any other desired or required additives, and then coalescing the aggregate mixture. The mixture may be prepared by adding optional wax or other materials (which may be in dispersion(s) optionally containing surfactant) to the emulsion (which may be a mixture of two or more emulsions containing the resin). The pH of the resulting mixture may be adjusted with an acid, such as, for example, acetic acid or nitric acid. In embodiments, the pH of the mixture may be adjusted to about 2 to about 4.5. Additionally, in embodiments, the mixture may be homogenized. If the mixture is homogenized, homogenization may be achieved by mixing at about 600 to about 6,000 revolutions per minute. Homogenization may be achieved by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer.

[0089] Following preparation of the mixture, a coagulant may be added to the mixture. Any suitable coagulant may be utilized to form the toner. Suitable coagulants include, for example, aqueous solutions of divalent or polyvalent cation materials. Examples of suitable coagulants include 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 oxyacids, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, and combinations thereof. In embodiments, the coagulant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

[0090] The aggregating agent may be added to the mixture utilized to form the toner in an amount of from about 0.1% to about 8% by weight, in embodiments from about 0.2% to about 5% by weight, and in other embodiments from about 0.5% to about 5% by weight of the resin in the mixture, which provides a sufficient amount of agent for aggregation. Shell Resin

[0091] In embodiments, a shell may be applied to the aggregated particles after aggregation but before coalescence.

[0092] Resins that can be used to form the shell include, but are not limited to, the amorphous resins described above for use in the core. Such amorphous resins can be low molecular weight resins, high molecular weight resins, or combinations thereof. In embodiments, amorphous resins that can be used to form the shell according to the present disclosure can include amorphous polyesters of Formula I described above.

[0093] In some embodiments, the amorphous resin used to form the shell may be crosslinked. For example, crosslinking may be achieved by combining the amorphous resin with a crosslinking agent, sometimes referred to herein in embodiments as an initiator. Examples of suitable crosslinking agents include, but are not limited to, free radical or thermal initiators, such as the organic peroxides and azo compounds described above, suitable for forming a gel within the core.

[0094] The crosslinker and amorphous resin may be combined for a time and at a temperature sufficient to form a crosslinked polyester gel. In embodiments, the crosslinker and amorphous resin may be heated to a temperature of from about 25° C. to about 99° C., in embodiments from about 30° C. to about 95° C., for a time of from about 1 minute to about 10 hours, in embodiments from about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell.

[0095] If used, the crosslinker may be present in an amount of from about 0.001% to about 5% by weight of the resin, in embodiments from about 0.01% to about 1% by weight of the resin. The amount of CCA can be reduced in the presence of a crosslinker or initiator. Combine

[0096] Following aggregation to the desired particle size and optional application of a shell, the particles may then be coalesced into the desired final shape, which coalescence may be achieved by heating the mixture, for example, to a temperature of from about 45° C. to about 100° C., in embodiments from about 55° C. to about 99° C. (which may be at or above the glass transition temperature of the resin utilized to form the toner particles), and / or reducing the agitation, for example, to from about 100 rpm to about 400 rpm, in embodiments from about 200 rpm to about 300 rpm. The fused particles may be measured for shape factor or circularity, such as with a SYSMEX FPIA 2100 analyzer, until the desired shape is achieved.

[0097] Coalescence may be achieved over a period of from about 0.01 to about 9 hours, in embodiments from about 0.1 to about 4 hours. Subsequent processing

[0098] In embodiments, after aggregation and / or coalescence, the pH of the mixture may be lowered to about 3.5 to about 6, in embodiments from about 3.7 to about 5.5, for example, with an acid, to further coalesce 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 from about 0.1 to about 30 weight percent of the mixture, in embodiments from about 1 to about 20 weight percent of the mixture.

[0099] The mixture may be cooled, washed, and dried. Cooling may be at a temperature of about 20°C to about 40°C, in embodiments about 22°C to about 30°C, for about 1 hour to about 8 hours, in embodiments about 1.5 hours to about 5 hours.

[0100] In embodiments, cooling the coalesced toner slurry may include quenching, for example, by adding a cooling medium such as ice or dry ice, and effecting rapid cooling to a temperature of from about 20° C. to about 40° C., in embodiments from about 22° C. to about 30° C. Rapid cooling may be feasible for small quantities of toner, for example, less than about 2 liters, in embodiments from about 0.1 liters to about 1.5 liters. In larger scale processes, for example, greater than about 10 liters in size, rapid cooling of the toner mixture may not be feasible or practical, either by introducing a cooling medium into the toner mixture or by using jacketed reactor cooling.

[0101] The toner slurry may then be washed. Washing may be carried out at a pH of from about 7 to about 12, in embodiments from about 9 to about 11. Washing may be at a temperature of from about 30° C. to about 70° C., in embodiments from about 40° C. to about 67° C. Washing may include filtering and reslurrying the filter cake containing the 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 washed with one deionized water wash, optionally followed by one or more deionized water washes.

[0102] Drying may be carried out by any method within the purview of those skilled in the art. Any suitable method for drying the toner particles may be used, including freeze drying, spray drying, and flash air drying, such as an Aljet dryer. Drying may be continued until the moisture level of the particles falls below a set target of about 1% by weight, in embodiments less than about 0.7% by weight. additives

[0103] In embodiments, the toner particles may contain the polymer additives of the present disclosure, as well as other optional additives, as desired or required. For example, the toner may contain a positive or negative charge control agent in an amount of, for example, from about 0.1 to about 10% by weight of the toner, in embodiments from 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. Pat. No. 4,298,672, which is incorporated herein by reference in its entirety; and organic sulfate and sulfonate compositions, including those disclosed in U.S. Pat. No. 4,338,390, which is incorporated herein by reference in its entirety.

[0104] The toner particles may also be blended with external additive particles after formation, including flow aid additives, which 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 and amorphous silicas such as AEROSIL®, metal salts including zinc stearate, calcium stearate, and fatty acid metal salts, or long chain alcohols such as UNILIN 700, and mixtures thereof.

[0105] In general, silica may be applied to the toner surface for toner flow, triboelectric charge enhancement, admix control, improved development and transfer stability, and higher toner blocking temperature. TiO2 may be applied for improved relative humidity (RH) stability, triboelectric charge control, and improved development and transfer stability. Zinc stearate, calcium stearate, and / or magnesium stearate may optionally be used as an external additive to provide lubrication properties, developer conductivity, triboelectric charge enhancement, thereby enabling higher toner charge and charge stability by increasing the number of contacts between the toner and carrier particles. In embodiments, commercially available zinc stearate known as Zinc Stearate L, available from Ferro Corporation, may be used. External surface additives may be used with or without a coating.

[0106] Each of these external additives may be present in an amount of from about 0% to about 3% by weight of the toner, in embodiments from about 0.25% to about 2.5% by weight of the toner, although the additive amounts can be outside these ranges. In embodiments, the toner may include, for example, from about 0% to about 3% by weight of titania, from about 0% to about 3% by weight of silica, and from about 0% to about 3% by weight of zinc stearate.

[0107] In embodiments, in addition to the polymer additive of the present disclosure, the toner particles may also comprise silica in an amount of from about 0.1% to about 5% by weight of the toner particles, in embodiments from about 0.2% to about 2% by weight of the toner particles, and titania in an amount of from about 0% to about 3% by weight of the toner particles, in embodiments from about 0.1% to about 1% by weight of the toner particles. Developer

[0108] The toner particles thus formed may be formulated into a developer composition. The toner particles may be mixed with carrier particles to form a two-component developer composition. The toner concentration in the developer may be from about 1% to about 25% by weight of the total weight of the developer, and in embodiments, from about 2% to about 15% by weight of the total weight of the developer. Career

[0109] Examples of carrier particles that can be used to mix with the toner include particles that can triboelectrically obtain a charge of opposite polarity to that of the toner particles. Illustrative examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrite, iron ferrite, silicon dioxide, etc. Other carriers include those disclosed in U.S. Patent Nos. 3,847,604, 4,937,166, and 4,935,326.

[0110] In embodiments, a suitable carrier may comprise, for example, a steel core having a diameter of from about 25 to about 100 μm, in embodiments from about 50 to about 75 μm, coated with from about 0.5% to about 10% by weight, in embodiments from about 0.7% to about 5% by weight, of a conductive polymer blend including, for example, methyl acrylate and carbon black, using the processes described in U.S. Pat. Nos. 5,236,629 and 5,330,874.

[0111] The carrier particles can be mixed with the toner particles in various suitable combinations. The concentration can be from about 1% to about 20% by weight of the toner composition. However, different toner and carrier percentages can be used to obtain a developer composition with desired properties. Imaging

[0112] The toners may be utilized in electrostatographic or electrophotographic processes, such as those disclosed in U.S. Pat. No. 4,295,990, the disclosure of which is incorporated herein by reference in its entirety. In embodiments, any known type of development system may be used in the development device, including, for example, magnetic brush development, jumping single component development, hybrid scavengeless development (HSD), etc. These and similarly developed systems are within the purview of those skilled in the art.

[0113] Once the image has been formed with toner / developer via a suitable development method, such as any one of those described above, the image may then be transferred to an image receiving medium, such as paper. In embodiments, the toner may be used for development in a development device that utilizes a fuser roll member.

[0114] 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 stated, parts and percentages are by weight. [Example]

[0115] Preparation of fluorinated additive latex.

[0116] All fluorinated organic additive latexes used herein were prepared on a 2 L bench scale. Multiple latexes were used. All latexes were made using the same general process and formulation loadings, except for varying monomer ratios. Details are shown in Table 1 below.

[0117] Example 1: Synthesis of fluorinated organic loaded latex with 0% DVB.

[0118] In a 2-L Buch reactor equipped with a P4 impeller, 6.5 g of Calfoam SLS surfactant (30% solids) was added to 816 g of deionized water (DIW). The reactor was deoxygenated by passing a stream of nitrogen 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 vessel equipped with two P4 impellers, a monomer emulsion was prepared by mixing together (at 450 rpm) 319.5 g of trifluoroethyl methacrylate (TFEMA), 6.5 g of Calfoam SLS surfactant (30% solids), and 416 g of DIW. 37.1 g of seeds were removed from the monomer emulsion and pumped into the 2-L reactor at 77°C. An initiator solution, prepared from 1.22 g of ammonium persulfate in 34.3 g of DIW, was added over 20 minutes after the seed emulsion was added. The remaining monomer emulsion was fed into the reactor over 120 minutes. At half the monomer emulsion addition, the rpm in the reactor was increased to 450 rpm. At the end of the monomer feed, the latex was subjected to a post-treatment protocol of 1 hour at 77°C, followed by a 2 hour temperature ramp to 87°C and a 1 hour hold at 87°C to reduce residual monomer at the end of the emulsion polymerization process. The resulting latex contained 20% solids with an average particle size of 99 nm.

[0119] Example 2: Synthesis of fluorinated organic additive latex with 0% DVB. Same process and formulation as above.

[0120] Comparative Example 1: Synthesis of fluorinated organic loaded latex with DVB. Same as Example 2 except 10% DVB and 90% TFEMA were used.

[0121] Comparative Example 2: Synthesis of fluorinated organic-added latex with DVB. Same as Example 2, except 20% DVB and 80% TFEMA were used.

[0122] Comparative Example 3: Synthesis of fluorinated organic-added latex with DVB. Same as Example 2, except 30% DVB and 70% TFEMA were used.

[0123] Comparative Example 4: Synthesis of fluorinated organic additive latex using CHMA and DVB. This was the same as Example 2, except that 30% DVB, 35% TFEMA, and 35% CHMA were used. Because DVB has impurities, the actual DVB content in all of the above examples and comparative examples is 55% of the amount added to the resin. The table below shows the amount of DVB added to the formulation, as well as the actual DVB content, which is approximately 0.55 x the amount added in the formulation. The majority of the impurities in DVB are ethylvinylbenzene, which is also incorporated into polymer additives.

[0124] Comparative Example 5: Synthesis of a non-fluorinated organic additive latex prepared with CHMA and 25% DVB with 0.8% DMAEMA. 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 stream of nitrogen through it during the reaction, and a condenser was used. The reactor was heated to 77°C and the rpm was set at 59. Separately, in a 100-gal reactor equipped with one P4-type impeller, a monomer emulsion was prepared by mixing together (at 28 rpm) 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. 0.369 kg of seeds were removed from the monomer emulsion and pumped into a 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 seed emulsion was added. The remaining monomer emulsion was fed into the 300-gal reactor over 120 minutes. Once half of the monomer emulsion had been added, the rpm in the reactor was increased to 66 rpm. At the end of the monomer feed, the condenser was turned off. The latex underwent a 1-hour post-treatment protocol at 77°C, followed by a 2-hour temperature increase to 87°C and a 1-hour hold at 87°C to reduce residual monomer at the end of the emulsion polymerization process. During the post-treatment protocol, the pH of the latex was adjusted to ≥6.0 every 30 minutes using 0.1 wt% NaOH solution. The resulting latex had an average particle size of 98 nm and contained 20% solids, and was filtered through a 25-micrometer filter bag. The latex was spray dried to form the final dry powder.

[0125] In all examples and comparative examples, the DVB contains impurities, so the actual DVB content in all of the above examples and comparative examples is 55% of the amount added to the resin. The table below shows the amount of DVB added to the formulation, as well as the actual DVB content, which is approximately 0.55 x the amount added in the formulation. The majority of the impurity in DVB is ethylvinylbenzene, which is also incorporated into polymer additives. [Table 1] ND = Not Detected Flattening test of toner additives over time

[0126] Each additive was blended singly into a Xerox 700 Digital Color Press parent cyan eco-toner at 18% SAC (surface area coverage) in a laboratory SKM Mill. The general ideal equation for the surface area coverage (%) of spherical organic surface additives on the toner particle surface is given by (100% w D P) / (0.363 d p), where D is the D50 average size in micrometers and P is grams / cm for the toner. 3 and for organic emulsion polymerization latex, d is the D50 average size in nanometers and p is the particle size in grams / cm 3 where w is the true density of the mixture in pph and w is the weight added to the mixture. The weight percent loading corresponding to an 18% SAC is shown in Table 2. [Table 2]

[0127] For each toner, 30 g of Xerox 700 Digital Color Press carrier was used with 1.50 g of formulated toner in a 60 mL glass bottle. This resulted in a 5% toner concentration, or TC. Samples were conditioned in the J-zone and then mixed on a Turbula mixer for a total of 2 hours, with SEM samples taken at 15 minutes, 30 minutes, 1 hour, and 2 hours. SEM images were inspected, and failure was assessed if the organic polymer additive had flattened and lost its spherical shape. The survival time was then determined as the maximum time the particles remained spherical. Thus, if the particles flattened at 2 hours, the survival time was 1 hour. As shown in Figure 1, increasing the DVB to 30 wt% increased the survival time. The toner with the non-crosslinked TFEMA polymer additive was already flattened on the toner surface before the developer aging test, i.e., it was flattened during the toner formulation process. [Table 3] Single additive charging test at 17% SAC single additive

[0128] J-zone charging was evaluated for each of the toners in Table 2 formulated with 18% SAC. Samples were taken at 15 and 120 minutes in the aging test described above. The results are shown in Table 3 and Figure 1. The decrease in charge with increasing crosslinking is very clear from the data. For the unplaned or unaffected crosslinked additives, the additive has very little surface coverage, so it is theorized that the charge is mostly coming from the uncovered parent surface, and the additive has only a minor effect on charge. Because the uncrosslinked additives are completely planarized, it was expected that even at time zero in this aging test, these additives would be fully embedded in the toner and therefore provide even less charge benefit. However, these examples without crosslinking charge much more negatively. During planarization, the uncrosslinked TFEMA particles cover more of the toner surface, increasing the cross-sectional area covered on the surface.

[0129] Figure 2 shows Example 2, a non-crosslinked TFEMA latex with 0% DVB on a cyan parent toner after 15 minutes of developer aging (first aging point). Most of the additive has flattened onto the toner surface and is visible as flakes of flat and merged particles, except in protected areas in the deep toner crevices. Thus, the additive does not remain spherical at the 15-minute first aging point, with a survival time of 0 minutes.

[0130] Figure 3 shows Comparative Example 3 with 30% DVB crosslinked TFEMA latex on a cyan parent toner after 120 minutes of developer aging (the last aging point tested). Although some of the additive is embedded in the toner surface, the additive particles remain spherical at 120 minutes. Thus, the additive lifetime is at least 120 minutes. [Table 4]

[0131] Because the non-crosslinked additive is thus leveled, resulting in a higher surface coverage of this additive than the crosslinked version, the non-crosslinked additive was added to the Pinot surface additive design shown in Table 4 to evaluate the effect on charge, flow, and blocking. Both toners had the same additive package shown in Table 4, except that one toner had 1.3 wt% non-crosslinked TFEMA latex added at 16% SAC. Surprisingly, as shown in Table 5, there was no effect on charge, flow cohesion increased somewhat, but blocking was significantly improved. [Table 5] [Table 6] The uncrosslinked TFEMA polymer had a measured Tg of 67°C. The low Tg allows the additive to level off very easily. Also, because the Tg is not much higher than the resin, any effect on melting will be less than that of silica and titania at the same loading, and less than the effect of using, for example, CHMA or PMMA polymers, both of which have Tg > 100°C. On the other hand, fluorination causes the polymer to have a lower surface energy, which aids in blocking.

[0132] TFEMA non-crosslinked latex can be used in additive formulations to improve blocking without affecting charge and with little effect on flow cohesion.

[0133] The polymer resins disclosed herein do not contain significant amounts of crosslinking and comprise a fluorinated monomer and, optionally, a charge control agent comprising a nitrogen-containing group, at 0.1% to 1.5% by weight of the polymer resin. In embodiments, the crosslinking of the polymer resin is less than 10% by weight of the polymer resin. In embodiments, the crosslinking is less than about 5% by weight of the polymer resin. In embodiments, the crosslinking is less than about 2% by weight of the polymer resin. In embodiments, the crosslinking is less than about 1% by weight of the polymer resin. This low amount of crosslinking does not interfere with the planarization of the polymer additive.

[0134] It will be understood that variations of the above-disclosed and other features and functions, or alternatives thereof, may be combined into other different systems or applications. Various alternatives, modifications, variations, or improvements therein, presently not anticipated or foreseen, may be made by those skilled in the art, which are also encompassed by the following claims. Another aspect of the present invention may be as follows. [1] A toner composition comprising toner particles comprising at least one resin, an optional colorant, an optional wax, and a polymeric toner additive on at least a portion of an outer surface of said toner particles, said polymeric toner additive comprising: 1. A toner composition comprising: a polymer resin comprising a fluorinated monomer, wherein the polymer resin is less than 10% by weight crosslinked; and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group. [2] The toner composition according to [1], wherein the fluorinated monomer includes a fluorinated acrylate monomer or a fluorinated methacrylate monomer. [3] The toner composition according to [1], wherein the charge control agent monomer nitrogen includes an acrylate monomer or a methacrylate monomer. [4] The toner composition according to [1], wherein the polymer resin further comprises a non-fluorinated hydrophobic monomer. [5] The toner composition according to [1], wherein the polymer resin further contains cyclohexyl methacrylate. [6] The toner composition according to [1], wherein the polymer resin is flattened on the surface of the toner particles. [7] The toner composition according to [1], further comprising at least one additive selected from the group consisting of silica, titania, alumina, and crosslinked non-fluorinated organic surface additives. [8] The toner composition according to [1], wherein the toner particles comprise emulsion aggregation toner having a size of about 4 micrometers to about 10 micrometers. [9] The toner composition according to [1], further comprising a cleaning additive selected from the group consisting of stearates, cerium oxide, and strontium titanate.

[10] The toner composition according to [1], wherein the polymer additive comprises 0.1 weight percent to 5 weight percent of the toner composition.

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

[12] A developer comprising a toner composition and a toner carrier, the toner composition comprising toner particles comprising at least one resin, an optional colorant, an optional wax, and a polymeric toner additive on at least a portion of an outer surface of the toner particles, the polymeric toner additive being 1. A developer comprising: a polymer resin comprising a fluorinated monomer, wherein the polymer resin is less than 10% by weight crosslinked; and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group.

[13] The developer according to

[12] , wherein the non-crosslinked fluorinated 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 contains a non-fluorinated hydrophobic monomer.

[16] The developer according to

[12] , wherein the polymer resin further contains cyclohexyl methacrylate.

[17] The developer according to

[12] , wherein the polymer resin is flattened on the surface of the toner particles.

[18] The developer according to

[12] , further comprising an additive selected from the group consisting of silica, titania, alumina, and bridged non-fluorinated organic surface additives.

[19] A toner additive, 1. A toner additive comprising: a polymer resin comprising a fluorinated monomer, wherein the polymer resin is less than 10% by weight crosslinked; and optionally 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group.

[20] The toner additive according to

[19] , wherein the polymer resin has a size ranging from 25 nanometers to 250 nanometers.

Claims

1. 1. A toner composition comprising: emulsion aggregation toner particles comprising at least one amorphous polyester resin and one crystalline polyester resin; A surfactant, an optional colorant; and an optional wax; a polymeric toner additive on at least a portion of the outer surface of said emulsion aggregation toner particles; The polymer toner additive is a polymer resin comprising a fluorinated monomer consisting of trifluoromethacrylate, said polymer resin being less than 10% by weight crosslinked; and optionally 0.1% to 1.5% by weight of said polymer resin of a charge control agent comprising a nitrogen-containing group monomer; Toner composition.

2. The toner composition of claim 1 , wherein the charge control agent monomer comprises an acrylate monomer or a methacrylate monomer.

3. The toner composition of claim 1 , wherein the polymer resin further comprises a non-fluorinated hydrophobic monomer.

4. 10. The toner composition of claim 1, wherein the polymer resin further comprises cyclohexyl methacrylate.

5. The toner composition of claim 1 , wherein the polymer resin is leveled on the surface of the toner particles.

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

7. 10. The toner composition of claim 1, wherein said emulsion aggregation toner particles have a size of from about 4 micrometers to about 10 micrometers.

8. 10. The toner composition of claim 1, further comprising a cleaning additive selected from the group consisting of stearates, cerium oxide, and strontium titanate.

9. 10. The toner composition of claim 1, wherein said polymer additive comprises from 0.1 weight percent to 5 weight percent of said toner composition.

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

11. a developer comprising a toner composition and a toner carrier; The toner composition comprises emulsion aggregation toner particles comprising at least one amorphous polyester resin and one crystalline polyester resin; A surfactant, an optional colorant; and an optional wax; a polymeric toner additive on at least a portion of the outer surface of said emulsion aggregation toner particles; The polymer toner additive is a polymer resin comprising a fluorinated monomer consisting of trifluoromethacrylate, the polymer resin being less than 10% by weight crosslinked; and 0.1% to 1.5% by weight of the polymer resin of a charge control agent comprising a nitrogen-containing group. Developer.

12. The developer of claim 11 , wherein the charge control agent monomer comprises an acrylate monomer or a methacrylate monomer.

13. The developer of claim 11 , wherein the polymer resin further comprises a non-fluorinated hydrophobic monomer.

14. The developer of claim 11 , wherein the polymer resin further comprises cyclohexyl methacrylate.

15. The developer of claim 11 , wherein the polymer resin is planarized on the surface of the toner particles.

16. 12. The developer of claim 11, further comprising an additive selected from the group of silica, titania, alumina, and bridged non-fluorinated organic surface additives.

17. 1. A toner additive composition comprising: emulsion aggregation toner particles comprising at least one amorphous polyester resin and one crystalline polyester resin; A surfactant, a polymer resin comprising a fluorinated monomer consisting of trifluoromethacrylate, the polymer resin being less than 10% by weight crosslinked; and 0.1% to 1.5% by weight of the polymer resin of a charge control agent monomer comprising a nitrogen-containing group; Toner additive composition.

18. 18. The toner composition of claim 17, wherein the polymer resin comprising fluorinated monomers consisting of trifluoromethacrylate comprises a size of 25 nanometers to 250 nanometers.

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