Source: https://patents.google.com/patent/US8178274
Timestamp: 2018-02-20 10:07:07
Document Index: 618245702

Matched Legal Cases: ['Application No. 2006', 'Application No. 2005', 'Application No. 2003', 'Application No. 2006', 'Application No. 2007', 'Application No. 2007', 'Application No. 2006']

US8178274B2 - Toner process - Google Patents
US8178274B2
US8178274B2 US12176558 US17655808A US8178274B2 US 8178274 B2 US8178274 B2 US 8178274B2 US 12176558 US12176558 US 12176558 US 17655808 A US17655808 A US 17655808A US 8178274 B2 US8178274 B2 US 8178274B2
US12176558
US20100015544A1 (en )
The present disclosure provides toners and processes for preparing toner particles possessing excellent charging characteristics. The process includes forming a dispersion including at least one organic and/or organometallic charge control agent, and then combining that dispersion with an emulsion suitable for use in forming toner particles.
The present disclosure relates to toners suitable for electrophotographic apparatuses and processes for making such toners.
The present disclosure provides processes for preparing toners, as well as toners prepared by such processes. In embodiments, processes of the present disclosure may include contacting at least one amorphous resin with at least one crystalline resin in an emulsion to form small particles, wherein the emulsion includes an optional colorant, an optional surfactant, and an optional wax, aggregating the small particles to form a plurality of larger aggregates, passing at least one charge control agent in a dispersion through a high energy disperser at a pressure of from about 3,000 pounds per square inch to about 30,000 pounds per square inch to form a charge control dispersion, contacting the larger aggregates with the charge control dispersion to form a resin coating thereon, coalescing the larger aggregates to form toner particles, and recovering the toner particles.
In embodiments of the present disclosure, toner particles may be prepared utilizing chemical processes which involve the aggregation and fusion of a latex resin with a charge control agent, an optional colorant, an optional wax and other optional additives.
In embodiments, the toners herein may be low melt or ultra low melt toners. A low melt or ultra low melt toner may have a glass transition temperature of, for example, from about 45° C. to about 85° C., in embodiments from about 50° C. to about 65° C., or in embodiments about 55° C. to about 60° C. Such toners may also exhibit a desirably low fixing or fusing temperature, for example a minimum fusing temperature of from about 75° C. to about 150° C., in embodiments from about 80° C. to about 145° C., or in embodiments from about 90° C. to about 130° C. Such low melt characteristics are desirable in enabling the toner to be fixed or fused onto an image receiving substrate such as paper at a lower temperature, which can result in energy savings as well as increased device speed.
Examples of crystalline resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, mixtures thereof, and the like. Specific crystalline resins may be polyester based, such as poly(ethylene-adipate), poly(propylene-adipate), poly(butylene-adipate), poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate), poly(ethylene-succinate), poly(propylene-succinate), poly(butylene-succinate), poly(pentylene-succinate), poly(hexylene-succinate), poly(octylene-succinate), poly(ethylene-sebacate), poly(propylene-sebacate), poly(butylene-sebacate), poly(pentylene-sebacate), poly(hexylene-sebacate), poly(octylene-sebacate), alkali copoly(5-sulfoisophthaloyl)-copoly(ethylene-adipate), poly(decylene-sebacate), poly(decylene-decanoate), poly-(ethylene-decanoate), poly-(ethylene-dodecanoate), poly(nonylene-sebacate), poly(nonylene-decanoate), copoly(ethylene-fumarate)-copoly(ethylene-sebacate), copoly(ethylene-fumarate)-copoly(ethylene-decanoate), and copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate). Examples of polyamides include poly(ethylene-adipamide), poly(propylene-adipamide), poly(butylenes-adipamide), poly(pentylene-adipamide), poly(hexylene-adipamide), poly(octylene-adipamide), poly(ethylene-succinamide), and poly(propylene-sebecamide). Examples of polyimides include poly(ethylene-adipimide), poly(propylene-adipimide), poly(butylene-adipimide), poly(pentylene-adipimide), poly(hexylene-adipimide), poly(octylene-adipimide), poly(ethylene-succinimide), poly(propylene-succinimide), and poly(butylene-succinimide). The crystalline resin may be present, for example, in an amount of from about 5 to about 50 percent by weight of the toner components, in embodiments from about 10 to about 35 percent by weight of the toner components. The crystalline resin can possess various melting points of, for example, from about 30° C. to about 120° C., in embodiments from about 50° C. to about 90° C. as measured, for example, by Differential Scanning Calorimetry (DSC). The crystalline resin may have a number average molecular weight (Mn), of, for example, from about 1,000 to about 50,000, in embodiments from about 2,000 to about 25,000, and a weight average molecular weight (Mw) of, for example, from about 2,000 to about 100,000, in embodiments from about 3,000 to about 80,000, as determined by Gel Permeation Chromatography (GPC) using polystyrene standards. The molecular weight distribution (Mw/Mn) of the crystalline resin may be, for example, from about 2 to about 6, in embodiments from about 3 to about 4.
Examples of nonionic surfactants that can be utilized include, for example, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl 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, dialkylphenoxy poly(ethyleneoxy) ethanol, available from Rhone-Poulenc Industries SA as IGEPAL CA-210™, IGEPAL CA-520™, IGEPAL CA-720™, IGEPAL CO-890™, IGEPAL CO-720™, IGEPAL CO-290™, IGEPAL CA-210™, ANTAROX 890™ and ANTAROX 897™. Other examples of suitable nonionic surfactants include a block copolymer of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC PE/F, in embodiments SYNPERONIC PE/F 108.
Anionic surfactants which may be utilized include sulfates and sulfonates, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecyinaphthalene sulfate, dialkyl benzenealkyl sulfates and sulfonates, acids such as abitic acid available from Aldrich, NEOGEN R™, NEOGEN SC™ obtained from Daiichi Kogyo Seiyaku Co. Ltd., combinations thereof, and the like. Other suitable anionic surfactants include, in embodiments, DOWFAX™ 2A1, an alkyldiphenyloxide disulfonate from The Dow Chemical Company, and/or TAYCAPOWER BN2060 from Tayca Corporation, which are branched sodium dodecyl benzene sulfonates. Combinations of these surfactants and any of the foregoing anionic surfactants may be utilized in embodiments.
Examples of the cationic surfactants, which are usually positively charged, include, for example, alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C12, C15, C17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL™ and ALKAQUAT™, available from Alkaril Chemical Company, SANIZOL™ (benzalkonium chloride), available from Kao Corporation, and the like, and mixtures thereof.
Thus, in embodiments, it may be desirable to incorporate a charge control agent (CCA) into the toner formulation. Suitable negative or positive charge CCAs may include, in embodiments, organic and/or organometallic complexes. For example, negative CCAs may include azo-metal complexes, for instance, VALIFAST® BLACK 3804, BONTRON® S-31, BONTRON® S-32, BONTRON® S-34, BONTRON® S-36, (commercially available from Orient Chemical Industries, Ltd.), T-77, AIZEN SPILON BLACK TRH (commercially available from Hodogaya Chemical Co., Ltd.); amorphous metal complex salt compounds with monoazo compounds as ligands, including amorphous iron complex salts having a monoazo compound as a ligand (see, for example, U.S. Pat. No. 6,197,467, the disclosure of which is hereby incorporated by reference in its entirety); azo-type metal complex salts including azo-type iron complexes (see, for example, U.S. Patent Application No. 2006/0257776, the disclosure of which is hereby incorporated by reference in its entirety); monoazo metal compounds (see, for example, U.S. Patent Application No. 2005/0208409, the disclosure of which is hereby incorporated by reference in its entirety); copper phthalocyanine complexes; carboxylic acids, substituted carboxylic acids and metal complexes of said acids; salicylic acid, substituted salicylic acid, and metal complexes of said acids, including 3,5-di-tert-butylsalicylic acid; metal complexes of alkyl derivatives of salicylic acid, for instance, BONTRON® E-81, BONTRON® E-82, BONTRON® E-84, BONTRON® E-85, BONTRON® E-88 (commercially available from Orient Chemical Industries, Ltd.); metal complexes of alkyl-aromatic carboxylic acids, including zirconium complexes of alkyl-aromatic carboxylic acids, such as 3,5-di-t-butylsalicylic acid (see, for example, U.S. Pat. No. 7,371,495, the disclosure of which is hereby incorporated by reference in its entirety); zinc compounds of alkylsalicylic acid derivatives including zinc compounds of 3,5-di-tert-butylsalicylic acid (see, for example, U.S. Patent Application No. 2003/0180642, the disclosure of which is hereby incorporated by reference in its entirety); salicylic acid compounds including metals or boron complexes including zinc dialkyl salicylic acid or boro bis(1,1-diphenyl-1-oxo-acetyl potassium salt) (see, for example, U.S. Patent Application No. 2006/0251977, the disclosure of which is hereby incorporated by reference in its entirety); naphthoic acids, substituted naphthoic acids and metal complexes of said acids including zirconium complexes of 2-hydroxy-3-naphthoic acid (see, for example, U.S. Pat. No. 7,371,495, the disclosure of which is hereby incorporated by reference in its entirety); hydroxycarboxylic acids, substituted hydroxycarboxylic acids and metal complexes of said acids including metal compounds having aromatic hydroxycarboxylic acids as ligands (see, for example, U.S. Pat. No. 6,326,113, the disclosure of which is hereby incorporated by reference in its entirety); dicarboxylic acids, substituted dicarboxylic acids and metal complexes of said acids including metal compounds having aromatic dicarboxylic acids as ligands (see, for example, U.S. Pat. No. 6,326,113, the disclosure of which is hereby incorporated by reference in its entirety); nitroimidazole derivatives; boron complexes of benzilic acid including potassium borobisbenzylate, for instance LR-147 (commercially available from Japan Carlit Co., Ltd.); calixarene compounds, for instance BONTRON® E-89 and BONTRON® F-21 (commercially available from Orient Chemical Industries, Ltd.); metal compounds obtainable by reacting one or two or more molecules of a compound having a phenolic hydroxy group, including calixresorcinarenes or derivatives thereof and one or two or more molecules of a metal alkoxide (see, for example, U.S. Pat. No. 6,762,004, the disclosure of which is hereby incorporated by reference in its entirety); metal carboxylates and sulfonates (see, for example, U.S. Pat. No. 6,207,335, the disclosure of which is hereby incorporated by reference in its entirety); organic and/or organometallic compounds containing sulfonates including copolymers selected from styrene-acrylate-based copolymers and styrene-methacrylate-based copolymers with sulfonate groups (see, for example, U.S. Patent Application No. 2007/0269730, the disclosure of which is hereby incorporated by reference in its entirety); sulfone complexes comprising alkyl and/or aromatic groups (see, for example, U.S. Patent Application No. 2007/0099103, the disclosure of which is hereby incorporated by reference in its entirety); organometallic complexes of dimethyl sulfoxide with metal salts (see, for example, U.S. Patent Application No. 2006/0188801, the disclosure of which is hereby incorporated by reference in its entirety); calcium salts of organic acid compounds having one or more acid groups including carboxyl groups, sulfonic groups and/or hydroxyl groups (see, for example, U.S. Pat. No. 6,977,129, the disclosure of which is hereby incorporated by reference in its entirety); barium salts of sulfoisophthalic acid compounds (see, for example, U.S. Pat. No. 6,830,859, the disclosure of which is hereby incorporated by reference in its entirety); polyhydroxyalkanoates comprising substituted phenyl units (see, for example, U.S. Pat. No. 6,908,720, the disclosure of which is hereby incorporated by reference in its entirety); acetamides including N-substituted 2-(1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)acetamide (see, for example, U.S. Pat. No. 6,184,387, the disclosure of which is hereby incorporated by reference in its entirety); benzenesulfonamides including N-(2-(1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)-2-cyanoacetyl)benzenesulfonamide (see, for example, U.S. Pat. No. 6,165,668, the disclosure of which is hereby incorporated by reference in its entirety); combinations thereof, and the like.
Positive CCAs which may be utilized include Nigrosine compounds, for instance, NIGROSINE BASE EX, OIL BLACK BS, OIL BLACK SO, BONTRON® N-01, BONTRON® N-04, BONTRON® N-07, BONTRON® N-09, BONTRON® N-11, BONTRON® N-21 (commercially available from Orient Chemical Industries, Ltd.); triphenylmethane-based compounds containing a tertiary amine as a side chain; quaternary ammonium salt compounds, for instance, BONTRON® P-51, BONTRON® P-52 (commercially available from Orient Chemical Industries, Ltd.), TP415, TP-302, TP-4040 (commercially available from Hodogaya Chemical Co., Ltd.), COPY CHARGE PSY (commercially available from Clariant Ltd.); cetyltrimethylammonium bromide, COPY CHARGE PX VP435 (commercially available from Clariant Ltd.); alkyl pyridinium halides including cetyl pyridinium tetrafluoroborates; alkyl pyridinium compounds (see, for example, U.S. Pat. No. 4,298,672, the disclosure of which is hereby incorporated by reference in its entirety); organic sulfate and sulfonate compositions, for instance distearyl dimethyl ammonium methyl sulfate (DDAMS) (see, for example, U.S. Pat. No. 4,560,635, the disclosure of which is hereby incorporated by reference in its entirety); bisulfates including distearyl dimethyl ammonium bisulfate (DDABS) (see, for example, U.S. Pat. No. 5,114,821, the disclosure of which is hereby incorporated by reference in its entirety); quaternary ammonium nitrobenzene sulfonates; polyamine resins, for instance, AFP-B (commercially available from Orient Chemical Industries, Ltd.); guanidine derivatives; imidazole derivatives, for instance, PLZ-2001, PLZ-8001 (commercially available from Shikoku Kasei K.K.); combinations thereof, and the like.
In embodiments, a CCA may be in an emulsion or dispersion including water and/or any surfactant described above. The CCA dispersion, in turn, may be combined with an emulsion or dispersion possessing at least one resin. In embodiments, a CCA dispersion may be formed using a high energy disperser, including high pressure homogenizers commercially available from APV Homogeniser Group and/or Niro Soavi North America, LLC, an ULTIMAIZER™ high shear disperser available from Sugino Machine Ltd., a MICROFLUIDIZER® high shear processor available from Microfluidics, a division of MFIC Corporation, a CAVITRON™ high energy stator/rotor mixer available from Arde-Barinco Inc., combinations thereof, and the like. Still other dispersion technologies may be utilized in accordance with the present disclosure, such as impeller mills including agitators and blenders, ball mills including pebble mills and attritors, small-media mills including sand mills, vibratory mills, multiple roll mills, ultrasonic dispersers, combinations thereof, and the like.
Due to the high energy input during homogenization, it may be desirable to cool the product between homogenization passes. For example, for water, the heat generated during homogenization may result in a temperature rise per pass of about 17° C. for each 10,000 pounds per square inch (70 megapascals) of homogenization pressure. Thus, in embodiments it may be desirable to cool the materials between passes to a temperature of from about 5° C. to about 50° C., in embodiments from about 10° C. to about 40° C.
Waxes that may be selected include waxes having, for example, a weight average molecular weight of from about 500 to about 20,000, in embodiments from about 1,000 to about 10,000. Waxes that may be used include, for example, polyolefins such as polyethylene, polypropylene, and polybutene waxes such as commercially available from Allied Chemical Corporation and Baker Petrolite Polymers Division, Baker Hughes Inc., for example POLYWAX™ polyethylene waxes from Baker Petrolite, wax emulsions available from Michaelman, Inc. and the Daniels Products Company, EPOLENE N-15™ commercially available from Eastman Chemical Products, Inc., and VISCOL 550-P™, a low weight average molecular weight polypropylene available from Sanyo Kasei K. K.; plant-based waxes, such as carnauba wax, rice wax, candelilla wax, sumacs wax, and jojoba oil; animal-based waxes, such as beeswax; mineral-based waxes and petroleum-based waxes, such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; ester waxes obtained from higher fatty acid and higher alcohol, such as stearyl stearate and behenyl behenate; ester waxes obtained from higher fatty acid and monovalent or multivalent lower alcohol, such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetra behenate; ester waxes obtained from higher fatty acid and multivalent alcohol multimers, such as diethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryl distearate, and triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes, such as cholesteryl stearate. Examples of functionalized waxes that may be used include, for example, amines, amides, for example AQUA SUPERSLIP 6550™, SUPERSLIP 6530™ available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™, POLYSILK 14™ available from Micro Powder Inc., mixed fluorinated, amide waxes, for example MICROSPERSION 19™ also available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example JONCRYL 74™, 89™, 130™, 537™, and 538™, all available from S.C. Johnson & Son, Inc., and chlorinated polypropylenes and polyethylenes available from Allied Chemical Corporation, Baker Petrolite and S.C. Johnson & Son, Inc. Mixtures and combinations of the foregoing waxes may also be used in embodiments. Waxes may be included as, for example, fuser roll release agents.
In order to control aggregation and coalescence of the particles, in embodiments the aggregating agent may be metered into the mixture over time. For example, the agent may be metered into the mixture over a period of from about 5 to about 240 minutes, in embodiments from about 30 to about 200 minutes, although more or less time may be used as desired or required. The addition of the agent may also be done while the mixture is maintained under stirred conditions, in embodiments from about 50 revolutions per minute (rpm) to about 1,000 revolutions per minute, in other embodiments from about 100 revolutions per minute to about 500 revolutions per minute, and at a temperature that is below the glass transition temperature of the resin as discussed above, in embodiments from about 30° C. to about 90° C., in embodiments from about 35° C. to about 70° C.
In embodiments, the toner particles may also contain other optional additives, as desired or required. For example, there can be blended with the toner particles external additive particles including flow aid additives, which additives may be present on the surface of the toner particles. Examples of these additives include metal oxides such as titanium oxide, silicon oxide, tin oxide, mixtures thereof, and the like; colloidal and amorphous silicas, such as AEROSIL®, metal salts and metal salts of fatty acids inclusive of zinc stearate, aluminum oxides, cerium oxides, and mixtures thereof. Each of these external additives may be present in an amount of from about 0.1 percent by weight to about 5 percent by weight of the toner, in embodiments of from about 0.25 percent by weight to about 3 percent by weight of the toner. Suitable additives include those disclosed in U.S. Pat. Nos. 3,590,000, 3,800,588, and 6,214,507, the disclosures of each of which are hereby incorporated by reference in their entirety. Again, these additives may be applied simultaneously with the shell resin described above or after application of the shell resin.
(1) Volume average diameter (also referred to as “volume average particle diameter”) of from about 3 to about 20 micrometers, in embodiments from about 4 to about 15 micrometers, in other embodiments from about 5 to about 9 micrometers as measured, for example, with a Coulter counter.
(4) Glass transition temperature of from about 40° C. to about 65° C., in embodiments from about 55° C. to about 62° C. as measured by, for example, differential scanning calorimetry (DSC).
In further embodiments, the toner may have a relative humidity sensitivity of, for example, from about 0.5 to about 10, in embodiments from about 0.5 to about 5. Relative humidity (RH) sensitivity is a ratio of the charging of the toner at high humidity conditions to charging at low humidity conditions. That is, the RH sensitivity is defined as the ratio of toner charge at 15 percent relative humidity and a temperature of about 12° C. (denoted herein as C-zone) to toner charge at 85 percent relative humidity and a temperature of about 28° C. (denoted herein as A-zone); thus, RH sensitivity is determined as (C-zone charge)/(A-zone charge). Ideally, the RH sensitivity of a toner is as close to 1 as possible, indicating that the toner charging performance is the same in low and high humidity conditions, that is, that the toner charging performance is unaffected by the relative humidity.
Toners prepared in accordance with the present disclosure also possess excellent heat cohesion/blocking performance and improved charging performance, with Q/m (Toner charge per mass ratio) in A- and C-zone of from about 10 microcoulombs per gram to about 50 microcoulombs per gram, in embodiments from about 20 microcoulombs per gram to about 40 microcoulombs per gram, and an onset of heat cohesion (HC) greater than about 50° C., and in embodiments greater than about 52° C.
The selected carrier particles can be used with or without a coating. In embodiments, the carrier particles may include a core with a coating thereover which may be formed from a mixture of polymers that are not in close proximity thereto in the triboelectric series. The coating may include fluoropolymers, such as polyvinylidene fluoride resins, terpolymers of styrene, methyl methacrylate, and/or silanes, such as triethoxy silane, tetrafluoroethylenes, other known coatings and the like. For example, coatings containing polyvinylidenefluoride, available, for example, as KYNAR 301F™, and/or polymethylmethacrylate, for example having a weight average molecular weight of about 300,000 to about 350,000, such as commercially available from Soken, may be used. In embodiments, polyvinylidenefluoride and polymethylmethacrylate (PMMA) may be mixed in proportions of from about 30 to about 70 percent by weight to about 70 to about 30 percent by weight, in embodiments from about 40 to about 60 percent by weight to about 60 to about 40 percent by weight. The coating may have a coating weight of, for example, from about 0.1 to about 5 percent by weight of the carrier, in embodiments from about 0.5 to about 2 percent by weight of the carrier.
EXAMPLES Example 1 CCA Dispersion
About 720 grams of deionized water, about 200 grams of BONTRON® E-84 CCA, which is a zinc complex of 3,5-di-tert-butylsalicylic acid in powder form obtained from Orient Chemical Industries, Ltd., and about 95.6 grams of a surfactant solution containing about 16 grams of TAYCAPOWER BN 2060 anionic surfactant, which is a branched sodium dodecylbenzene sulfonate commercially available from Tayca Corporation, and about 79.6 grams deionized water, were dispensed into a 4 liter glass beaker and stirred at a speed of about 200 revolutions per minute with the aid of a mechanical stirrer to mix the dry CCA powder, anionic surfactant solution and water. The resultant CCA mixture was predispersed for about 5 minutes using an IKA ULTRA TURRAX® T50 probe homogenizer operating at a speed starting at about 3,000 revolutions per minute and ending at about 7,000 revolutions per minute. The resulting predispersed CCA mixture was then further stirred at a speed of about 200 revolutions per minute overnight to deair the mixture and then poured into the feed hopper of a RANNIE LAB 2000 high pressure homogenizer. The homogenizer was turned on to pump the CCA mixture through the homogenizer at a rate of about 11 liters per hour. The product was collected in a product container wherein the container was cooled to room temperature by means of an ice bath. In the initial pass through the homogenizer, the primary and secondary valves of the homogenizer were kept substantially open, so the resulting homogenization pressure was less than 1,000 pounds per square inch (7 megapascals).
The material thus obtained was a stable CCA dispersion including about 17.86 percent by weight of BONTRON® E-84 CCA and about 1.43 percent by weight of TAYCAPOWER BN 2060 anionic surfactant as measured gravimetrically utilizing a hot plate. The CCA particles of the dispersion had a volume median diameter of about 291 nanometers as determined by a Microtrac UPA150 particle size analyzer.
Comparative Example 1 Toner with Wax, without CCA
This Comparative Example synthesized a polyester emulsion aggregation toner and a wax, but not including the CCA dispersion from Example 1. The following components were added to a 4 liter glass beaker: about 1,132 grams of deionized water; about 6.65 grams of DOWFAX™ 2A1 anionic surfactant, which is an alkyldiphenyloxide disulfonate commercially available from The Dow Chemical Company; about 230 grams of an amorphous polyester resin emulsion (Amorphous Resin Emulsion A) containing about 29.9 percent by weight of a linear amorphous polyester resin derived from terephthalic acid, dodecenylsuccinic acid, trimellitic acid, ethoxylated bisphenol A and propoxylated bisphenol A; about 237 grams of another amorphous polyester resin emulsion (Amorphous Resin Emulsion B) containing about 31.85 percent by weight of a linear amorphous polyester resin derived from terephthalic acid, fumaric acid, dodecenylsuccinic acid, ethoxylated bisphenol A and propoxylated bisphenol A; about 123 grams of a crystalline polyester resin emulsion containing about 17.8 percent by weight crystalline polyester resin derived from 1,12-dodecanedioic acid and 1,9-nonanediol; about 97 grams of a wax emulsion containing about 30.6 percent by weight FNP92 polymethylene wax available from Nippon Seiro Co., Ltd.; and about 111 grams of a cyan pigment dispersion containing about 17.2 percent by weight Pigment Blue 15:3 pigment. The pH of the mixture was adjusted to about 4.2 using a 0.3 M solution of HNO3. The mixture was stirred using an IKA ULTRA TURRAX® T50 probe homogenizer operating at about a speed of from about 3,500 to about 4,000 revolutions per minute. During homogenization, about 64 grams of a flocculent mixture containing about 1 percent by weight solution of Al2(SO4)3 was added dropwise. The mixture was subsequently transferred to a 3 liter glass kettle, and heated to about 40° C. for aggregation while mixing continued at about 450 revolutions per minute. The particle size was monitored with a Coulter Counter until the core particles reached a volume average particle size of about 5 micrometers and a volume average geometric standard deviation (GSDv) of about 1.23.
About 3.24 grams of DOWFAX™ 2A1 anionic surfactant, about 127 grams of Amorphous Resin Emulsion A adjusted to a pH of about 3.2, and about 131 grams of Amorphous Resin Emulsion B adjusted to a pH of about 3.2, were added to the reactor mixture to further aggregate until the particles reached a volume average particle size of about 5.7 micrometers and a GSDv of about 1.21.
Thereafter, the pH of the toner slurry was increased to about 7.5 using about 1 M NaOH followed by the addition of about 4.9 grams of a chelating solution containing about 39 percent by weight EDTA to freeze the toner growth. After freezing, the reactor mixture was heated to about 80° C. to enable the toner particles to coalesce and spherodize. The reactor heater was then turned off and the reactor mixture was rapidly cooled to room temperature with the addition of ice, and then filtered through a 25 micrometer sieve, washed and dried.
The final toner had a volume average particle size diameter of about 5.7 micrometers and a GSDv of about 1.21 as measured by a Coulter Counter, and a circularity of about 0.968 as measured with a SYSMEX® FPIA-2100 flow-type histogram analyzer.
Example 2 Toner with Wax and CCA
This Example synthesized a polyester emulsion aggregation toner including a wax and the CCA dispersion from Example 1. The following components were added to a 2 liter glass beaker: about 464.1 grams of deionized water; about 3.6 grams of DOWFAX™ 2A1 anionic surfactant; about 124.4 grams of an amorphous polyester resin emulsion (Amorphous Resin Emulsion A) containing about 29.9 percent by weight of a linear amorphous polyester resin derived from terephthalic acid, dodecenylsuccinic acid, trimellitic acid, ethoxylated bisphenol A and propoxylated bisphenol A; about 116.8 grams of amorphous polyester resin emulsion (Amorphous Resin Emulsion B) containing about 31.85 percent by weight of a linear amorphous polyester resin derived from terephthalic acid, fumaric acid, dodecenylsuccinic acid, ethoxylated bisphenol A and propoxylated bisphenol A; about 57.6 grams of a crystalline polyester resin emulsion containing about 17.8 percent by weight crystalline polyester resin derived from 1,12-dodecanedioic acid and 1,9-nonanediol; about 45.25 grams of wax emulsion containing about 30.6 percent by weight FNP92 polymethylene wax; and about 52.3 grams of a cyan pigment dispersion containing about 17.2 percent by weight Pigment Blue 15:3 pigment. The pH of the mixture was adjusted to about 4.2 using a 0.3 M solution of HNO3. The mixture was stirred using an IKA ULTRA TURRAX® T50 probe homogenizer operating at about a speed of from about 3,500 to about 4,000 revolutions per minute. During homogenization, about 75 grams of a flocculent mixture containing about 1 percent by weight solution of Al2(SO4)3 was added dropwise. The mixture was subsequently transferred to a 2 liter glass kettle, and heated to about 40° C. for aggregation while mixing continued at about 450 revolutions per minute. The particle size was monitored with a Coulter Counter until the core particles reached a volume average particle size of about 5 micrometers and a volume average geometric standard deviation (GSDv) of about 1.23.
About 1.79 grams of DOWFAX™ 2A1 anionic surfactant, about 70.2 grams of Amorphous Resin Emulsion A adjusted to a pH of about 3.2, about 65.9 grams of Amorphous Resin Emulsion B adjusted to a pH of about 3.2, and about 8.75 grams of the CCA dispersion produced in Example 1 above, were added to the reactor mixture to further aggregate until the particles reached a volume average particle size of about 5.7 micrometers and a GSDv of about 1.21.
Thereafter, the pH of the toner slurry was increased to about 7.5 using about 1 M NaOH followed by the addition of about 5.77 grams of a chelating solution containing about 39 percent by weight EDTA to freeze the toner growth. After freezing, the reactor mixture was heated to about 85° C. to enable the toner particles to coalesce and spherodize. The reactor heater was then turned off and the reactor mixture was rapidly cooled to room temperature with the addition of ice, and then filtered through a 25 micrometer sieve, washed and dried.
The final toner had a volume average particle size diameter of about 5.7 micrometers and a GSDv of about 1.22 as measured by a Coulter Counter, and a circularity of about 0.97 as measured with a SYSMEX® FPIA-2100 flow-type histogram analyzer.
This Comparative Example synthesized a polyester emulsion aggregation toner not including wax, and not including the CCA dispersion from Example 1. The following components were added to a 2 liter glass beaker: about 281.8 grams of deionized water; about 1.83 grams of DOWFAX™ 2A1 anionic surfactant; about 398 grams of an amorphous polyester resin emulsion (Amorphous Resin Emulsion C) containing about 17 percent by weight of a linear amorphous propoxylated bisphenol A fumarate polyester resin, about 74.3 grams of a crystalline polyester resin emulsion containing about 20 percent by weight unsaturated crystalline polyester resin derived from of ethylene glycol, dodecanedioic acid and fumaric acid co-monomers with the following formula:
wherein b is from 5 to 2000 and d is from 5 to 2000 in an emulsion (about 19.3 weight % resin), synthesized following the procedures described in U.S. Patent Application Publication No. 2006/0222991, the disclosure of which is hereby incorporated by reference in its entirety; and about 29.2 grams of cyan pigment dispersion containing about 17 percent by weight of Pigment Blue 15:3 pigment. The pH of the mixture was adjusted to about 3.2 using a 0.3 M solution of HNO3. The mixture was stirred using an IKA ULTRA TURRAX® T50 homogenizer operating at a speed of from about 3,500 to about 4,000 revolutions per minute. About 36 grams of a flocculent mixture containing 1 percent by weight solution of Al2(SO4)3 was added dropwise to the mixture. The mixture was subsequently transferred to a 2 liter stainless steel Buchi reactor, and heated to about 40 to 46° C. for aggregation at about 750 revolutions per minute. The particle size was monitored with a Coulter Counter until the core particles reach a volume average particle size of about 6.83 micrometers and a GSDv of about 1.21.
Subsequently, about 1.43 grams of DOWFAX™ 2A1 anionic surfactant and about 198.3 grams of Amorphous Resin Emulsion C adjusted to a pH of about 3.2 were added to the reactor mixture to further aggregate until the particles reached a volume average particle size of about 8.33 micrometers and a GSDv of about 1.21. Thereafter, the pH of the toner slurry was increased to about 6.7 using 1.0 M NaOH followed by the addition of about 1.39 grams of a chelating solution containing about 39 percent by weight EDTA to freeze the toner growth. After freezing, the reactor mixture was heated to about 69° C. to enable the toner particles to coalesce and spherodize. The reactor heater was then turned off and the reactor mixture was cooled to room temperature over a period of about 90 minutes, and then filtered through a 25 micrometer sieve, washed and dried.
The final toner had a volume average particle size diameter of about 8.07 micrometers, a GSDv of about 1.22 as measured by a Coulter Counter, and a circularity of about 0.976 as measured with a SYSMEX® FPIA-2100 flow-type histogram analyzer.
Example 3 Toner without Wax and with CCA
This Example synthesized a polyester emulsion aggregation toner not including a wax, but including the CCA dispersion from Example 1. The following components were added to a 2 liter glass beaker: about 271.2 grams of deionized water; about 1.83 grams of DOWFAX™ 2A1 anionic surfactant; about 398.2 grams of an amorphous polyester resin emulsion (Amorphous Resin Emulsion C) containing about 17.0 percent by weight of a linear amorphous propoxylated bisphenol A fumarate polyester resin, about 84.65 grams of a crystalline polyester resin emulsion containing about 19.3 percent by weight unsaturated crystalline polyester resin derived from of ethylene glycol, dodecanedioic acid and fumaric acid herein; and about 29.2 grams of cyan pigment dispersion containing about 17 percent by weight of Pigment Blue 15:3 pigment. The pH of the mixture was adjusted to about 3.2 using a 0.3 M solution of HNO3. The mixture was stirred using an IKA ULTRA TURRAX® T50 homogenizer operating at a speed of from about 3,500 to about 4,000 revolutions per minute. About 36 grams of a flocculent mixture containing 1 percent by weight solution of Al2(SO4)3 was added dropwise to the mixture. The mixture was subsequently transferred to a 2 liter stainless steel Buchi reactor, and heated to about 40° C. for aggregation at about 750 revolutions per minute. The particle size was monitored with a Coulter Counter until the core particles reach a volume average particle size of about 7.19 micrometers and a GSDv of about 1.25.
Subsequently, about 1.43 grams of DOWFAX™ 2A1 anionic surfactant, about 189.7 grams of Amorphous Resin Emulsion C adjusted to a pH of about 3.2, and about 6.7 grams of the CCA dispersion from Example 1 were added to the reactor mixture to further aggregate until the particles reached a volume average particle size of about 8.33 micrometers and a GSDv of about 1.21. Thereafter, the pH of the toner slurry was increased to about 6.2 using about 1 M NaOH followed by the addition of about 1.39 grams of a chelating solution containing about 39 percent by weight EDTA to freeze the toner growth. After freezing, the reactor mixture was heated to about 69° C. to enable the toner particles to coalesce and spherodize. The reactor heater was then turned off and the reactor mixture was cooled to room temperature over a period of about 90 minutes, and then filtered through a 25 micrometer sieve, washed and dried.
The final toner had a volume average particle size diameter of about 7.99 micrometers, a GSDv of about 1.22 as measured by a Coulter Counter, and a circularity of about 0.966 as measured with a SYSMEX® FPIA-2100 flow-type histogram analyzer.
Zn concentration Zn weight in
concentration in wash filtrate Zn weight wash filtrate
in toner (ppm) (ppm) in toner (g) (g)
Toner of 21 >74 0.003 >0.072
Toner of 363 78 0.044 0.077
Charging data for the toners of Comparative Examples 1 and 2, and Examples 2 and 3, are provided in Tables 2 and 3 below. Developers for bench charging evaluations were prepared by using 100 grams of 65 micrometer PMMA coated iron carrier and 4.5 grams of toner. The developer toner concentration is 4.5 parts per hundred. Two developers were prepared and conditioned in two chambers with different zone conditions, the A-zone chamber with a temperature and RH settings of 28° C. and 85 percent RH and the C-zone chamber with a temperature and RH settings of 12° C. and 15 percent RH. Developer charging was done in two steps, a short 5 minutes and a long 60 minutes paint shaking time. Desirably, a stable charge is attained in a short time and maintained at this level with minimal change with increasing charging time.
A-zone C-zone Onset
60′ 60′ 2′ 60′ 60′ Temp
Sample ID Q/d Q/m Q/m Q/d Q/m (° C.)
EA toner without 8.8 30.8 36.1 14.3 48.7 50.8
EA toner with 8.5 37.2 42.6 14.7 53.5 52.0
Q/m Q/m Q/m Q/m
Sample ID (5 min) (60 min) (5 min) (60 min)
EA toner 3.7 3.6 16.7 13.8
EA toner with 6.2 4.1 28.3 33.7
For fusing, there was insufficient toner from Example 2 to carry out a fusing evaluation. Therefore, only fusing results for the toners of Comparative Example 2 and Example 3 are presented in Table 4 below. The fusing data was generated by the following method. Unfused test images were made using a Xerox Corporation DC12 color copier/printer. Images were removed from the printer/copier before the document passed through the fuser. These unfused test samples were then fused using a Xerox Corporation iGen3® fuser. Test samples were directed through the fuser at 100 prints per minute. Fuser roll temperature was varied during the experiments so that gloss and crease area could be determined as a function of the fuser roll temperature. Print gloss was measured using a BYK Gardner 75 degree gloss meter. Gloss 40 Temperature is the temperature at which the gloss equals 40 gloss units. Toner adhesion to the paper was determined by its crease fix Minimum Fusing Temperature (MFT). The fused image was folded and an 860 gram weight of toner was rolled across the fold after which the page was unfolded and wiped to remove the fractured toner from the sheet. This sheet was then scanned using an Epson flatbed scanner and the area of toner which had been removed from the paper was determined by image analysis software such as the National Instruments IMAQ.
Sample ID MFT (° C.) TG40 (° C.)
EA toner 136 139
EA toner with 148 151
As can be seen from Table 4 above, the addition of CCA to the EA toner formulation had only a moderate effect on fusing performance; wherein the MFT increased only by about 12° C. which is still within acceptable limits. Likewise, a moderate increase in Gloss 40 Temperature was noted.
13. A process according to claim 12, wherein the optional colorant comprises dyes, pigments, combinations of dyes, combinations of pigments, and combinations of dyes and pigments in an amount of from about 0.1 to about 35 percent by weight of the toner, and the wax is selected from the group consisting of polyolefins, carnauba wax, rice wax, candelilla wax, sumacs wax, jojoba oil, beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, stearyl stearate, behenyl behenate, butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, pentaerythritol tetra behenate, diethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryl distearate, triglyceryl tetrastearate, sorbitan monostearate.
US12176558 2008-07-21 2008-07-21 Toner process Active 2030-11-29 US8178274B2 (en)
US12176558 US8178274B2 (en) 2008-07-21 2008-07-21 Toner process
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US20100015544A1 true US20100015544A1 (en) 2010-01-21
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US12176558 Active 2030-11-29 US8178274B2 (en) 2008-07-21 2008-07-21 Toner process
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