Patent Description:
<CIT> relates to a toner designed for a clear UV red fluorescence toner having a high lanthanide complex pigment loading, including methods of making the fluorescence toner using a saccharide or sugar acid to avoid complexation of lanthanide ions from the pigment, with lower aggregation and coalescence temperatures in the preparation of toner particles, wherein the particles exhibit a narrow size distribution and good xerographic performance.

<CIT> relates to a toner comprising a binder resin and a colorant, wherein the colorants specifically includes solvent red <NUM>, and the toner has an acid value of <NUM> mgKOH/g or greater but <NUM> mgKOH/g or less.

<CIT> relates to a toner composition that includes at least one low molecular weight amorphous polyester resin, at least one high molecular weight amorphous polyester resin, at least one crystalline polyester resin, at least one wax, at least one biocide and at least one colorant, wherein the toner composition has a minimum fusing temperature of from about <NUM> to about <NUM>.

The present disclosure provides fluorescent pink toners, methods of making the toners, and methods of using the toners.

In one aspect, methods of making fluorescent pink toners are provided. In embodiments, such a method comprises forming one or more fluorescent latexes which comprise a red fluorescent agent, a yellow fluorescent agent, a first type of amorphous resin, and a second type of amorphous resin, wherein the first and second types of amorphous resins are present at a ratio in a range of from <NUM>:<NUM> to <NUM>:<NUM>, wherein the yellow fluorescent agent is not pigment yellow <NUM>; forming a mixture comprising the one or more fluorescent latexes; one or more emulsions which comprise a crystalline resin, the first type of amorphous resin, the second type of amorphous resin; and optionally, a wax dispersion; aggregating the mixture to form particles of a predetermined size; forming a shell over the particles of the predetermined size to form core-shell particles; and coalescing the core-shell particles to form a fluorescent pink toner. Fluorescent pink toners made using such methods are also provided.

In another aspect, fluorescent pink toners are provided. In embodiments, such a fluorescent pink toner comprises a core comprising a red fluorescent agent-incorporated first type of amorphous polyester resin; a yellow fluorescent agent-incorporated first type of amorphous polyester resin; a red fluorescent agent-incorporated second type of amorphous polyester; a yellow fluorescent agent-incorporated second type of amorphous polyester; a crystalline polyester resin; an additional amount of the first type of amorphous polyester resin; an additional amount of the second type of the amorphous polyester resin; and optionally, a wax; and a shell over the core, the shell comprising the first type of amorphous polyester resin and the second type of the amorphous polyester resin; wherein the yellow fluorescent agent is not pigment yellow <NUM>. Methods of using the fluorescent pink toners are also provided.

The fluorescent pink toners comprise a core comprising a red fluorescent agent and a yellow fluorescent agent dispersed within one or more polymeric resins, and a shell over the core, the shell also comprising one or more polymeric resins which may or may not be the same as the resin(s) within the core. Although some fluorescent toners have been developed, it is particularly challenging to incorporate fluorescent agents into a toner without negatively affecting the optical properties of the fluorescent agents. For example, the fluorescence of the fluorescent agents is easily quenched within the toner, resulting in the toner have little to no fluorescence. The present disclosure is based, at least in part, on the development of an improved toner preparation process that prevents such quenching and results in fluorescent pink toners having certain optical properties, including high lightness L* values, color channel a* values, and color channel b* values for the toner.

The present toners comprise both a red fluorescent agent and a yellow fluorescent agent within the core of the toner. In embodiments, the red/yellow fluorescent agent is an ultraviolet (UV) fluorescent agent that absorbs light having a wavelength in the UV portion of the electromagnetic spectrum (from <NUM> to <NUM>). This includes red/yellow fluorescent agents having a maximum (peak) absorption in the UV portion of the electromagnetic spectrum. The red fluorescent agent generally emits (upon illumination with UV light) fluorescence having a wavelength in a range of from <NUM> to <NUM>. This wavelength range may refer to the location of the peak in the fluorescence emission. The yellow fluorescent agent generally emits (upon illumination with UV light) fluorescence having a wavelength in a range of from <NUM> to <NUM>. This wavelength range may refer to the location of the peak in the fluorescence emission.

Illustrative red fluorescent agents include Solvent Red <NUM>, Solvent Red <NUM>, Solvent Red <NUM>, Solvent Red <NUM>, and Solvent Red <NUM>. Generally, the red fluorescent agent is not a water-soluble red dye, e.g., basic red <NUM>: <NUM> or basic red <NUM>. Illustrative yellow fluorescent agents include Solvent Yellow <NUM>:<NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, Solvent Yellow <NUM>, and the like. Generally, the yellow fluorescent agent is not a water-soluble yellow dye, e.g., basic yellow <NUM>. The yellow fluorescent agent is not pigment yellow <NUM> and the toner is free of pigment yellow <NUM>. Combinations of different types of red fluorescent agents and combinations of different types of yellow fluorescent agents may be used.

Generally, no other fluorescent agents are included in the toners, i.e., in embodiments, the red and yellow fluorescent agents (selected from those listed above) are the only fluorescent agents included in the toners. Generally, no pigments are included in the toners, i.e., in embodiments, the toners are free from any pigments.

Both the red and yellow fluorescent agents are generally encapsulated within the particles of the toner (i.e., the core-shell particles) such that no red/yellow fluorescent agent is present at or on the surface of the particles. In embodiments, no red/yellow fluorescent agent is present within or on the shell of the toner. Similarly, the red and yellow fluorescent agents are generally homogenously distributed throughout the resin matrix of the core of the particles of the toner. As noted above and further described below, it is challenging to prevent fluorescence quenching when fluorescent agents are combined with other components such as in toner particles, or when the toner particles are highly saturated with fluorescent agents. However, the present disclosure is based, at least in part, upon the development of a toner preparation process that achieves a homogeneous distribution of fluorescent agents and encapsulation as well as addresses the problem of quenching. As further described below, the process involves the use of a separate latex(es) comprising the red/yellow fluorescent agents and two amorphous resins (each a different type of amorphous resin) in forming the core of the toner particles.

The red and yellow fluorescent agents are present in the toner in a certain weight ratio. The specific weight ratio depends upon the particular red fluorescent agent and the particular yellow fluorescent agent. However, in embodiments, the weight ratio of red:yellow is in a range of from <NUM>:<NUM> to <NUM>:<NUM>, including <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, <NUM>:<NUM> to <NUM>:<NUM>, and <NUM>:<NUM> to <NUM>:<NUM>.

The red fluorescent agent may be present in the toner in an amount of from <NUM> weight% to <NUM> weight% by weight of the toner. This includes an amount of from <NUM> weight% to <NUM> weight%, <NUM> weight% to <NUM> weight%, and from <NUM> weight% to <NUM> weight%. Outside these ranges, fluorescence quenching is problematic. If more than one type of red fluorescent agent is used, these amounts refer to the total amount of red fluorescent agent in the toner. The amount of red fluorescent agent used and the selected weight ratio determines the amount of the yellow fluorescent agent in the toner.

The present toners may comprise a variety of resins, which provides a polymeric matrix to contain the red and yellow fluorescent agents described above. The present toners may comprise more than one different type of resin. The resin may be an amorphous resin, a crystalline resin, or a mixture of crystalline and amorphous resins. The resin may be a polyester resin, including an amorphous polyester resin, a crystalline polyester resin, or a mixture of crystalline polyester and amorphous polyester resins.

The resin may be a crystalline polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst. For forming a crystalline polyester, suitable organic diols include aliphatic diols with from about <NUM> to about <NUM> carbon atoms, such as <NUM>,<NUM>-ethanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-dimethylpropane-<NUM>,<NUM>-diol, <NUM>,<NUM>-hexanediol, <NUM>,<NUM>-heptanediol, <NUM>,<NUM>-octanediol, <NUM>,<NUM>-nonanediol, <NUM>,<NUM>-decanediol, <NUM>,<NUM>-dodecanediol, combinations thereof, and the like including their structural isomers. The aliphatic diol may be, for example, selected in an amount of from about <NUM> to about <NUM> mole percent of the resin, from about <NUM> to about <NUM> mole percent of the resin, or from about <NUM> to about <NUM> mole percent of the resin, and a second diol may be selected in an amount of from about <NUM> to about <NUM> mole percent of the resin or from about <NUM> to about <NUM> mole percent of the resin.

Examples of organic diacids or diesters including vinyl diacids or vinyl diesters selected for the preparation of crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethyl itaconate, cis, <NUM>,<NUM>-diacetoxy-<NUM>-butene, diethyl fumarate, diethyl maleate, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-<NUM>,<NUM>-dicarboxylic acid, naphthalene-<NUM>,<NUM>-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, a diester or anhydride thereof. The organic diacid may be selected in an amount of, for example, from about <NUM> to about <NUM> mole percent of the resin, from about <NUM> to about <NUM> mole percent of the resin, or from about <NUM> to about <NUM> mole percent of the resin, and a second diacid can be selected in an amount of from about <NUM> to about <NUM> mole percent of the resin.

Polycondensation catalysts which may be utilized in forming crystalline (as well as amorphous) polyesters include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, and dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or combinations thereof. Such catalysts may be utilized in amounts of, for example, from about <NUM> mole percent to about <NUM> mole percent based on the starting diacid or diester used to generate the polyester resin.

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), 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), copoly(ethylene-fumarate)-copoly(ethylene-dodecanoate), copoly(<NUM>,<NUM>-dimethylpropane-<NUM>,<NUM>-diol-decanoate)-copoly(nonylene-decanoate), poly(octylene-adipate), and mixtures thereof. Examples of polyamides include poly(ethylene-adipamide), poly(propylene-adipamide), poly(butylenes-adipamide), poly(pentylene-adipamide), poly(hexylene-adipamide), poly(octylene-adipamide), poly(ethylene-succinimide), poly(propylene-sebecamide), and mixtures thereof. 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), poly(butylene-succinimide), and mixtures thereof.

In embodiments, the crystalline polyester resin has the following formula (I)
<CHM>
wherein each of a and b may range from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM> and further wherein p may range from <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. In embodiments, the crystalline polyester resin is poly(<NUM>,<NUM>-hexylene-<NUM>,<NUM>-dodecanoate), which may be generated by the reaction of dodecanedioc acid and <NUM>,<NUM>-hexanediol.

As noted above, the disclosed crystalline polyester resins may be prepared by a polycondensation process by reacting suitable organic diols and suitable organic diacids in the presence of polycondensation catalysts. A stoichiometric equimolar ratio of organic diol and organic diacid may be utilized, however, in some instances where the boiling point of the organic diol is from about <NUM> to about <NUM>, an excess amount of diol, such as ethylene glycol or propylene glycol, of from about <NUM> to <NUM> mole equivalent, can be utilized and removed during the polycondensation process by distillation. The amount of catalyst utilized may vary, and can be selected in amounts, such as for example, from about <NUM> to about <NUM> or from about <NUM> to about <NUM> mole percent of the crystalline polyester resin.

The crystalline resin may be present, for example, in an amount of from about <NUM> weight% to about <NUM> weight% by weight of the toner, from about <NUM> weight% to about <NUM> weight% by weight of the toner, or from about <NUM> weight% to about <NUM> weight% by weight of the toner.

The crystalline resin can possess various melting points of, for example, from about <NUM>° C. to about <NUM>° C. , from about <NUM>° C. to about <NUM>° C, or from about <NUM>° C. to about <NUM>° C. The crystalline resin may have a number average molecular weight (Mn), as measured by gel permeation chromatography (GPC) of, for example, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, or from about <NUM>,<NUM> to about <NUM>,<NUM>, and a weight average molecular weight (Mw) of, for example, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, or from about <NUM>,<NUM> to about <NUM>,<NUM>, as determined by GPC. The molecular weight distribution (Mw/Mn) of the crystalline resin may be, for example, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

The resin may be an amorphous polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst. Examples of diacids or diesters including vinyl diacids or vinyl diesters utilized for the preparation of amorphous polyesters include dicarboxylic acids or diesters such as terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, dimethyl fumarate, dimethyl itaconate, cis, <NUM>,<NUM>-diacetoxy-<NUM>-butene, diethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, and combinations thereof. The organic diacids or diesters may be present, for example, in an amount from about <NUM> to about <NUM> mole percent of the resin, from about <NUM> to about <NUM> mole percent of the resin, or from about <NUM> to about <NUM> mole percent of the resin.

Examples of diols which may be utilized in generating an amorphous polyester include <NUM>,<NUM>-propanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-butanediol, pentanediol, hexanediol, <NUM>,<NUM>-dimethylpropanediol, <NUM>,<NUM>,<NUM>-trimethylhexanediol, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(<NUM>-hydroxypropyl)-bisphenol A, <NUM>,<NUM>-cyclohexanedimethanol, <NUM>,<NUM>-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(<NUM>-hydroxyethyl) oxide, dipropylene glycol, dibutylene, and combinations thereof. The amount of organic diols selected may vary, for example, the organic diols may be present in an amount from about <NUM> to about <NUM> mole percent of the resin, from about <NUM> to about <NUM> mole percent of the resin, or from about <NUM> to about <NUM> mole percent of the resin.

Examples of suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, and the like, and mixtures thereof.

An unsaturated amorphous polyester resin may be utilized as a resin. Examples of such resins include those disclosed in <CIT>. Exemplary unsaturated amorphous polyester resins include, but are not limited to, poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-fumarate), poly(<NUM>,<NUM>-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyloxylated bisphenol co-maleate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate), poly(<NUM>,<NUM>-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-itaconate), poly(<NUM>,<NUM>-propylene itaconate), and combinations thereof.

A suitable polyester resin may be an amorphous polyester such as a poly(propoxylated bisphenol A co-fumarate) resin. Examples of such resins and processes for their production include those disclosed in <CIT>.

Suitable polyester resins include amorphous acidic polyester resins. An amorphous acid polyester resin may be based on any combination of propoxylated bisphenol A, ethoxylated bisphenol A, terephthalic acid, fumaric acid, and dodecenyl succinic anhydride, such as poly(propoxylated bisphenol-co-terephthlate-fumarate-dodecenylsuccinate). Another amorphous acid polyester resin which may be used is poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenylsuccinate-trimellitic anhydride).

An example of a linear propoxylated bisphenol A fumarate resin which may be utilized as a resin is available under the trade name SPAMII from Resana S/A Industrias Quimicas, Sao Paulo Brazil. Other propoxylated bisphenol A fumarate resins that may be utilized and are commercially available include GTUF and FPESL-<NUM> from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, N. , and the like.

An amorphous resin or combination of amorphous resins may be present, for example, in an amount of from about <NUM> weight% to about <NUM> weight% by weight of the toner, from about <NUM> weight% to about <NUM> weight% by weight of the toner, or from about <NUM> weight% to about <NUM> weight% by weight of the toner.

The amorphous resin or combination of amorphous resins may have a glass transition temperature of from about <NUM>° C. to about <NUM>° C. , from about <NUM>° C. to about <NUM>° C, or from about <NUM>° C. to about <NUM>° C. The glass transition temperature may be measured using differential scanning calorimetry (DSC). The amorphous resin may have a Mn, as measured by GPC of, for example, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, or from about <NUM>,<NUM> to about <NUM>,<NUM>, and a Mw of, for example, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, from about <NUM>,<NUM> to about <NUM>,<NUM>, or from about <NUM>,<NUM> to about <NUM>,<NUM>, as determined by GPC.

One, two, or more resins may be used in the present toners. Where two or more resins are used, the resins may be in any suitable ratio (e.g., weight ratio) such as for instance of from about <NUM>% (first resin)/<NUM>% (second resin) to about <NUM>% (first resin)/<NUM>% (second resin), from about <NUM>% (first resin)/<NUM>% (second resin) to about <NUM>% (first resin)/<NUM>% (second resin). Where the resins include a combination of amorphous and crystalline resins, the resins may be in a weight ratio of, for example, from about <NUM>% (crystalline resin)/<NUM>% (amorphous resin) to about <NUM>% (crystalline resin)/<NUM>% (amorphous resin), or from about <NUM>% (crystalline resin)/<NUM>% (amorphous resin) to about <NUM>% (crystalline resin)/<NUM>% (amorphous resin). In some embodiments, the weight ratio of the resins is from about <NUM> weight% to about <NUM> weight% of the amorphous resin and from about <NUM> weight% to about <NUM> weight% of the crystalline resin. In such embodiments, the amorphous resin may be a combination of amorphous resins, e.g., a combination of two amorphous resins.

The resin(s) in the present toners may possess acid groups which may be present at the terminal of the resin. Acid groups which may be present include carboxylic acid groups, and the like. The number of carboxylic acid groups may be controlled by adjusting the materials utilized to form the resin and reaction conditions. In embodiments, the resin is a polyester resin having an acid value from about <NUM> KOH/g of resin to about <NUM> KOH/g of resin, from about <NUM> KOH/g of resin to about <NUM> KOH/g of resin, or from about <NUM> KOH/g of resin to about <NUM> KOH/g of resin. The acid containing resin may be dissolved in tetrahydrofuran solution. The acid number may be detected by titration with KOH/methanol solution containing phenolphthalein as the indicator. The acid number may then be calculated based on the equivalent amount of KOH/methanol required to neutralize all the acid groups on the resin identified as the end point of the titration.

Optionally, a wax may be included in the present toners. A single type of wax or a mixture of two or more different waxes may be used. A single wax may be added, for example, to improve particular toner properties, such as toner particle shape, presence and amount of wax on the toner particle surface, charging and/or fusing characteristics, gloss, stripping, offset properties, and the like. Alternatively, a combination of waxes can be added to provide multiple properties to the toner composition.

When included, the wax may be present in an amount of, for example, from about <NUM> weight% to about <NUM> weight% by weight of the toner or from about <NUM> weight% to about <NUM> weight% by weight of the toner particles.

When a wax is used, the wax may include any of the various waxes conventionally used in emulsion aggregation toners. Waxes that may be selected include waxes having, for example, an average molecular weight of from about <NUM> to about <NUM>,<NUM> or from about <NUM>,<NUM> to about <NUM>,<NUM>. Waxes that may be used include, for example, polyolefins such as polyethylene including linear polyethylene waxes and branched polyethylene waxes, polypropylene including linear polypropylene waxes and branched polypropylene waxes, polymethylene waxes, polyethylene/amide, polyethylenetetrafluoroethylene, polyethylenetetrafluoroethylene/amide, and polybutene waxes such as commercially available from Allied Chemical and Petrolite Corporation, for example POLYWAX™ polyethylene waxes such as commercially available from Baker Petrolite, wax emulsions available from Michaelman, Inc. and the Daniels Products Company, EPOLENE N-<NUM>™ commercially available from Eastman Chemical Products, Inc. , and VISCOL <NUM>-P™, a low weight average molecular weight polypropylene available from Sanyo Kasei 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 such as waxes derived from distillation of crude oil, silicone waxes, mercapto waxes, polyester waxes, urethane waxes; modified polyolefin waxes (such as a carboxylic acid-terminated polyethylene wax or a carboxylic acid-terminated polypropylene wax); 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 diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate, and triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes, such as cholesteryl stearate. Examples of functionalized waxes that may be used include, for example, amines, amides, for example AQUA SUPERSLIP <NUM>™, SUPERSLIP <NUM>™ available from Micro Powder Inc. , fluorinated waxes, for example POLYFLUO <NUM>™, POLYFLUO <NUM>™, POLYSILK <NUM>™, POLYSILK <NUM>™ available from Micro Powder Inc. , mixed fluorinated, amide waxes, such as aliphatic polar amide functionalized waxes; aliphatic waxes consisting of esters of hydroxylated unsaturated fatty acids, for example MICROSPERSION <NUM>™ also available from Micro Powder Inc. , imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example JONCRYL <NUM>™, <NUM>™, <NUM>™, <NUM>™, and <NUM>™, all available from SC Johnson Wax, and chlorinated polypropylenes and polyethylenes available from Allied Chemical and Petrolite Corporation and SC Johnson wax. 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 embodiments, the waxes may be crystalline or non-crystalline.

In order to form the present toners, any of the resins described above may provided as an emulsion(s), e.g., by using a solvent-based phase inversion emulsification process. The emulsions may then be utilized as the raw materials to form the toners, e.g., by using an emulsion aggregation and coalescence (EA) process. However, the toners may be prepared using other processes.

As noted above, in order to achieve similar encapsulation and homogeneous distribution of the red/yellow fluorescent agent as well as to prevent fluorescence quenching, a separate latex (a fluorescent latex) comprising the red and yellow fluorescent agents is generally used in the preparation process. One separate latex comprising the desired fluorescent agents and the desired amorphous resins may be used or multiple separate latexes may be used (e.g., one separate latex comprising a red fluorescent agent and the two types of amorphous resins and another separate latex comprising a yellow fluorescent agent and the two types of amorphous resins, etc.). Either way, the latex(es) being used to form the toner provide the fluorescent agents and two amorphous resins (each a different type of amorphous resin), wherein these latex(es) provide the two amorphous resins in a weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>. This includes a weight ratio of <NUM>:<NUM>. That is, if more than one latex is used, together, the latex(es) provide the two amorphous resins within this range of weight ratios. It has been found that these ranges are important for obtaining encapsulation and a homogeneous distribution of the fluorescent agents in the toner particles as well as to prevent fluorescence quenching. Outside these ranges the fluorescent properties of the toner deteriorate, due at least in part, to quenching of the fluorescence. In embodiments, the amorphous resins are amorphous polyester resins. In embodiments, one of the amorphous resins has an Mn or Mw that is greater than the other.

In addition, to prevent fluorescence quenching, it is useful to use an amount of the fluorescent agents (i.e., combined amount of both the red and the yellow fluorescent agents) in the fluorescent latex in a range of from <NUM> weight% to <NUM> weight% by weight as compared to the total weight of the fluorescent latex. Outside this range, the fluorescent properties of the toner deteriorate, due at least in part, to quenching of the fluorescence. If the fluorescent latex includes more than one type of red fluorescent agent, more than one type of yellow fluorescent agent, or if more than one fluorescent latex is used, these amounts refer to the total amount of fluorescent agents in the toner.

The fluorescent agents/amorphous resins, once incorporated into the toner particles using the process and fluorescent agent amounts immediately described above, may be referred to as "fluorescent agent-incorporated amorphous resins". The fluorescence and optical properties of the resulting toner may be confirmed using an in-line spectrophotometer (ILS), e.g., an X-Rite ILS, to measure lightness L*, color channel a*, color channel b*, and reflectance as described in the Example, below.

If a resin is incorporated into the toner particles using an emulsion free of a fluorescent agent, that resin may be referred to as a resin not incorporated with the fluorescent agent, or simply as the "resin," i.e., not modified with the phrase "fluorescent agent-incorporated.

If a wax is used, it may be incorporated into the toner as a separate dispersion of the wax in water.

In embodiments, the present toners are prepared by EA processes, such as by a process that includes aggregating a mixture of an emulsion comprising resin; the red fluorescent agent; the yellow fluorescent agent; and optionally, a wax; and then coalescing the mixture. As described above, the red/yellow fluorescent agents are generally provided to the mixture as one or more separate fluorescent latexes as described above. The emulsion comprising the resin may comprise one or more resins or different resins may be provided as different emulsions. The emulsion(s) comprising the resin generally do not comprise and thus, are free of the fluorescent agents.

Next, the mixture may be homogenized which may be accomplished by mixing at about <NUM> to about <NUM>,<NUM> revolutions per minute. Homogenization may be accomplished by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer. An aggregating agent may be added to the mixture after its pH is adjusted to below <NUM>. Any suitable aggregating agent may be utilized. Suitable aggregating agents include, for example, aqueous solutions of a divalent cation or a multivalent cation material. The aggregating agent may be, for example, an inorganic cationic aggregating agent such as a polyaluminum halide such as polyaluminum chloride (PAC), or the corresponding bromide, fluoride, or iodide; a polyaluminum silicate such as polyaluminum sulfosilicate (PASS); or a water soluble metal salt including aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, and copper sulfate; or combinations thereof. The aggregating agent may be added to the mixture at a temperature that is below the glass transition temperature (Tg) of the resin (s). The aggregating agent may be added to the mixture under homogenization.

The aggregating agent may be added to the mixture in an amount of, for example, from about <NUM> weight% to about <NUM> weight% by weight of the total amount of resin, from about <NUM> weight% to about <NUM> weight% by weight of the total amount of resin, or from about <NUM> weight% to about <NUM> weight% by weight of the total amount of resin.

The particles of the mixture may be permitted to aggregate until a predetermined desired particle size is obtained. A predetermined desired size refers to the desired particle size to be obtained as determined prior to formation, and the particle size being monitored during the growth process until such particle size is reached. Samples may be taken during the growth process and analyzed, for example with a Coulter Counter, for volume average particle size. The aggregation thus may proceed by maintaining an elevated temperature, or slowly raising the temperature to, for example, in embodiments, from about <NUM>° C. to about <NUM>° C. , in embodiments from about <NUM>° C to about <NUM>° C, or in embodiments from about <NUM>° C to about <NUM>° C. The temperature may be held for a period time of from about <NUM> hours to about <NUM> hours, or in embodiments from about hour <NUM> to about <NUM> hours, while stirring, to provide the aggregated particles. Once the predetermined desired particle size is reached, a shell may be added. The volume average particle size of the particles prior to application of a shell may be, for example, from about <NUM> to about <NUM>, in embodiments, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

After aggregation, but prior to coalescence, a resin coating may be applied to the aggregated particles to form a shell thereover. Any of the resins described above may be utilized in the shell. In embodiments, an amorphous polyester resin is utilized in the shell. In embodiments, two amorphous polyester resins are utilized in the shell. In embodiments, a crystalline polyester resin and two different types of amorphous polyester resins are utilized in the core and the same two types of amorphous polyester resins are utilized in the shell. The shell resins generally do not comprise, and thus, are free of, fluorescent agent.

The shell may be applied to the aggregated particles by using the shell resins in the form of emulsion(s) as described above. Such emulsions may be combined with the aggregated particles under conditions sufficient to form a coating over the aggregated particles. For example, the formation of the shell over the aggregated particles may occur while heating to a temperature of from about <NUM>° C to about <NUM>° C or from about <NUM>° C to about <NUM>° C. The formation of the shell may take place for a period of time from about <NUM> minutes to about <NUM> hours or from about <NUM> minutes to about <NUM> hours.

Once the desired size of the toner particles is achieved, the pH of the mixture may be adjusted with a pH control agent, e.g., a base, to a value of from about <NUM> to about <NUM>, or in embodiments from about <NUM> to about <NUM>. The adjustment of the pH may be utilized to freeze, that is to stop, toner growth. The base utilized to stop toner growth may include any suitable base such as, for example, alkali metal hydroxides such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, and the like. In embodiments, a chelating agent such as ethylene diamine tetraacetic acid (EDTA) may be added to help adjust the pH to the desired values noted above. Other chelating agents may be used.

In embodiments, the size of the core-shell toner particles (prior to coalescence) may be from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

Following aggregation to the desired particle size and application of the shell, the particles may then be coalesced to the desired final shape, the coalescence being achieved by, for example, heating the mixture to a temperature of from about <NUM>° C to about <NUM>° C, from about <NUM>° C to about <NUM>° C, or about <NUM>° C to about <NUM>° C, which may be at or above the glass transition temperature of the resins utilized to form the toner particles. Heating may continue or the pH of the mixture may be adjusted (e.g., reduced) over a period of time to reach the desired circularity. The period of time may be from about <NUM> hours to about <NUM> hours or from about <NUM> hours to about <NUM> hours. Various buffers may be used during coalescence. The total time period for coalescence may be from about <NUM> to about <NUM> hours, from about <NUM> to about <NUM> hours, or from about <NUM> to about <NUM> hours. Stirring may be utilized during coalescence, for example, from about <NUM> rpm to about <NUM> rpm or from about <NUM> rpm to about <NUM> rpm.

After aggregation and/or coalescence, the mixture may be cooled to room temperature. The cooling may be rapid or slow, as desired. A suitable cooling process may include introducing cold water to a jacket around the reactor. After cooling, the toner particles may be screened with a sieve of a desired size, filtered, washed with water, and then dried. Drying may be accomplished by any suitable process for drying including, for example, freeze-drying.

In embodiments, the present toners may also contain other optional additives. For example, the toners may include positive or negative charge control agents. Surface additives may also be used. Examples of surface additives include metal oxides such as titanium oxide, silicon oxide, aluminum oxides, cerium oxides, tin oxide, mixtures thereof, and the like; colloidal and amorphous silicas, such as AEROSIL®, metal salts and metal salts of fatty acids such as zinc stearate, calcium stearate, and magnesium stearate, mixtures thereof and the like; long chain alcohols such as UNILIN <NUM>; and mixtures thereof. Each of these surface additives may be present in an amount of from about <NUM> weight% to about <NUM> weight% by weight of the toner or from about <NUM> weight% by weight to about <NUM> weight% by weight of the toner.

In embodiments, the dry toner particles, exclusive of external surface additives, exhibit one or more of the following characteristics:.

These characteristics may be measured according to the techniques described in the Example, below.

Regarding lightness L*, the CIELAB color space (also known as CIE L*a*b* or sometimes abbreviated as simply "Lab" color space) is a color space defined by the International Commission on Illumination (CIE). It expresses color as three values: L* for the lightness from black (<NUM>) to white (<NUM>), a* from green (-) to red (+), and b* from blue (-) to yellow (+).

Because three parameters are measured, the space itself is a three-dimensional real number space, which allows for infinitely many possible colors. In practice, the space is usually mapped onto a three-dimensional integer space for digital representation, and thus the L*, a*, and b* values are usually absolute, with a pre-defined range. The lightness value, L*, represents the darkest black at L* = <NUM>, and the brightest white at L* = <NUM>. The color channels, a* and b*, represent true neutral gray values at a* = <NUM> and b* = <NUM>. The a* axis represents the green-red component, with green in the negative direction and red in the positive direction. The b* axis represents the blue-yellow component, with blue in the negative direction and yellow in the positive direction. The scaling and limits of the a* and b* axes will depend on the specific implementation, but they often run in the range of ±<NUM> or -<NUM> to +<NUM> (signed <NUM>-bit integer).

Both lightness L* color channel a* and b* and reflectance may be measured using an ILS such as an X-Rite ILS, operated in accordance with the manufacturer's instructions. Two settings that are typically used with the X-Rite ILS to measure Lab values are M0 (white light and undefined UV) and M1 (white light and defined UV). M0 is most commonly used for assessing base color. M1 is most commonly used for assessing a measure of fluorescence. The M1 setting is used to obtain the L* and reflectance values for the present toners described above.

The present toners may be formulated into a developer composition. Developer compositions can be prepared by mixing the toners of the present disclosure with known carrier particles, including coated carriers, such as steel, ferrites, and the like. Such carriers include those disclosed in <CIT> and <CIT>. The toners may be present in the carrier in amounts of from about <NUM> weight% to about <NUM> weight% by weight, from about <NUM> weight% to about <NUM> weight% by weight, or from about <NUM> weight% to about <NUM> weight% by weight. The carrier particles can also include a core with a polymer coating thereover, such as polymethylmethacrylate (PMMA), having dispersed therein a conductive component like conductive carbon black. Carrier coatings include silicone resins such as methyl silsesquioxanes, fluoropolymers such as polyvinylidiene fluoride, mixtures of resins not in close proximity in the triboelectric series such as polyvinylidiene fluoride and acrylics, thermosetting resins such as acrylics, mixtures thereof and other known components.

The present toners may be used in a variety of xerographic processes and with a variety of xerographic printers. A xerographic imaging process includes, for example, preparing an image with a xerographic printer comprising a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fusing component. In embodiments, the development component may include a developer prepared by mixing a carrier with any of the toners described herein. The xerographic printer may be a high-speed printer, a black and white high-speed printer, a color printer, and the like. Once the image is formed with the toners/developers, the image may then be transferred to an image receiving medium such as paper and the like. Fuser roll members may be used to fuse the toner to the image-receiving medium by using heat and pressure.

The following Example is being submitted to illustrate various embodiments of the present disclosure. The Example is intended to be illustrative only and is not intended to limit the scope of the present disclosure. Also, parts and percentages are by weight unless otherwise indicated. As used throughout this patent specification, "room temperature" refers to a temperature of from <NUM> to <NUM>° C.

Toner Preparation. First, fluorescent latexes were prepared as follows. A red fluorescent latex was prepared from a mixture of <NUM> of a first type of an amorphous polyester resin, <NUM> of a second type of an amorphous polyester resin, and <NUM> of a red fluorescent agent dissolved in a mixture of ethyl acetate, isopropyl-alcohol and aqueous ammonia solution with a ratio of (<NUM>/<NUM>/<NUM>) in a <NUM> reactor at <NUM>. To this mixture was added <NUM> deionized water containing a surfactant (Calfax DB-<NUM> from Pilot Chemical Company) to form an emulsion. The reactor was charged a distillation column and the organic solvent was distilled off. Finally, the resulting emulsion was filtered through a <NUM> sieve. The emulsion had an average particle size of about <NUM>, and the solids content was about <NUM>-<NUM> weight%. The red fluorescent agent content in the emulsion was about <NUM> weight%. A yellow fluorescent latex was similarly prepared, but using about <NUM> weight% of a yellow fluorescent agent. The resulting emulsion had an average particle size of about <NUM>, and the solids content was about <NUM>-<NUM> weight%.

Next, fluorescent pink toners were prepared as follows. A mixture was formed by combining the following: the red fluorescent latex; the yellow fluorescent latex; a first emulsion comprising a crystalline polyester resin; a second emulsion comprising the first type of amorphous polyester resin; and the third emulsion comprising the second type of amorphous polyester resin. Various amounts of the red and yellow fluorescent latexes were added in order to achieve mixtures (and final toners) having different ratios of (red fluorescent agent):(yellow fluorescent agent). Next, the mixture was acidified. Next, aluminum sulfate (ALS) solution was added slowly while homogenizing the mixture after its pH was adjusted to below <NUM>. The highly viscous mixture was transferred to a <NUM> reactor and aggregation initiated by increasing the temperature to about <NUM>. When the particle size (D50v) reached about <NUM>, an emulsion containing the two amorphous polyester resins was added to the mixture to form a shell over the particles and the particles were allowed to continue grow. The particles were frozen by adding a chelating agent (EDTA) and a base (NaOH). The reactor temperature was increased to about <NUM> for coalescence. The heating was stopped when the particles reached the desired circularity. The particle slurry was quenched, the particles were then sieved, and filtered under vacuum. The filtered particles were washed with deionized water and freeze-dried.

The fluorescent pink toner particles had a total of about <NUM> to <NUM> weight% of the combined red and yellow fluorescent agents and various ratios of (red fluorescent agent):(yellow fluorescent agent) including <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, and <NUM>:<NUM>.

Toner Characterization. Toner particle size was analyzed from dry toner particles, exclusive of external surface additives, using a Beckman Coulter Multisizer <NUM> operated in accordance with the manufacturer's instructions. Representative sampling occurred as follows: a small amount of toner sample, about <NUM> gram, was obtained and filtered through a <NUM> screen, then put in isotonic solution to obtain a concentration of about <NUM>%, with the sample then run in the multisizer. The D50v sizes for fluorescent pink toners having ratios of (red fluorescent agent):(yellow fluorescent agent) of about <NUM>:<NUM> were about <NUM>.

Circularity was analyzed from dry toner particles, exclusive of external surface additives, using a Sysmex <NUM> operated in accordance with the manufacturer's instructions. The circularities for fluorescent pink toners having ratios of (red fluorescent agent):(yellow fluorescent agent) of about <NUM>:<NUM> were about <NUM>.

The optical properties of the fluorescent pink toners were analyzed using an X-Rite ILS, operated in accordance with the manufacturer's instructions. The results showed that fluorescent pink toners having ratios of (red fluorescent agent):(yellow fluorescent agent) of about <NUM>:<NUM> (e.g., <NUM>:<NUM> and <NUM>:<NUM>) achieved a* of about <NUM>, b* of about -<NUM> and L* of about <NUM> at a TMA of <NUM>/cm<NUM>. In addition, the lightness L* was in the range of from <NUM><NUM> over a TMA range of from <NUM>/cm<NUM> to <NUM>/cm<NUM>. At the same time, a reflectance of <NUM> to <NUM> between wavelengths of <NUM> to <NUM> was obtained (the TMA was <NUM>/cm<NUM>) and a reflectance of above <NUM> between wavelengths of <NUM> to <NUM> was obtained over a TMA range of <NUM>/cm<NUM> to <NUM>/cm<NUM>.

Claim 1:
A method of making a fluorescent pink toner, the method comprising:
forming one or more fluorescent latexes which comprise a red fluorescent agent, a yellow fluorescent agent, a first type of amorphous resin, and a second type of amorphous resin, wherein the first and second types of amorphous resins are present at a weight ratio in a range of from <NUM>:<NUM> to <NUM>:<NUM>; wherein the yellow fluorescent agent is not pigment yellow <NUM>;
forming a mixture comprising the one or more fluorescent latexes; one or more emulsions which comprise a crystalline resin, the first type of amorphous resin, the second type of amorphous resin; and optionally, a wax dispersion;
aggregating the mixture to form particles of a predetermined size;
forming a shell over the particles of the predetermined size to form core-shell particles; and
coalescing the core-shell particles to form a fluorescent pink toner, wherein the toner is free of pigment yellow <NUM>.