Titania-free toner additive formulation having a crosslinked organic polymer additive

Abstract

To provide a toner including a parent toner particle and a surface additive formulation.SOLUTION: A surface additive formulation comprises at least one medium silica surface additive, at least one large cross-linked organic polymeric additive, at least one positive charging surface additive. The at least one positive charging surface additive is (a) a titanium dioxide surface additive, wherein the parent toner particles further contain a small silica, or (b) a non-titanium dioxide positive charging metal oxide surface additive, wherein the parent toner particles further optionally contain a small silica. A total surface area coverage of all of the surface additives combined is 100 to 140 percent of the parent toner particle surface area.SELECTED DRAWING: None

Description

Technical Field

[0001] (Cross - reference to related applications) U.S. Patent Application No. 16 / 822, filed simultaneously with this specification and assigned to the assignee of the present invention, which is hereby incorporated by reference in its entirety,No. 438 (Title of Invention: "Toner Including Toner Additive Formulation", Attorney Docket No. 20190268US01) describes a toner comprising toner parent particles including at least one resin in combination with an optional colorant and an optional wax, and a surface additive formulation comprising at least one medium-sized silica surface additive having a volume average primary particle size of 30 to 50 nanometers, wherein the at least one medium-sized silica is provided at a surface area coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized silica surface additive having a volume average primary particle size of 80 to 120 nanometers, wherein the at least one large-sized silica is provided at a surface area coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively chargeable surface additive, wherein the at least one positively chargeable surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein the titanium dioxide is present in an amount of 1 part or less per 100 parts of the toner parent particles, and the toner parent particles further contain small-sized silica having a volume average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having a volume average primary particle size of 8 to 30 nanometers, wherein the non-titanium dioxide positively chargeable metal oxide surface additive is present at a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized silica having a volume average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area, and the total surface area coverage rate of all of the combined surface additives is 100 to 140 percent of the toner parent particle surface area.,

Background Art

[0002] Disclosed herein is a toner comprising toner parent particles containing at least one resin in combination with an optional colorant and an optional wax, and a surface additive formulation comprising at least one medium-sized silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein the at least one medium-sized silica is provided at a surface area coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein the at least one large-sized crosslinked organic polymer additive is provided at a surface area coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively chargeable surface additive, wherein the at least one positively chargeable surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein the titanium dioxide is present in an amount of 1 part or less per 100 parts of the toner parent particles, and the toner parent particles further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, wherein the non-titanium dioxide positively chargeable metal oxide surface additive is present at a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area, and a surface additive formulation comprising all of the combined surface additives having a total surface area coverage rate of 100 to 140 percent of the toner parent particle surface area.

[0003] Further disclosed is a toner process comprising contacting at least one resin, optional wax, optional colorant, and optional aggregating agent; heating to form aggregated toner particles; optionally adding a shell resin to the aggregated toner particles and heating to a higher temperature to coalesce the particles; and adding a surface additive, wherein the surface additive comprises at least one medium-sized silica surface additive having an average primary particle size of 30 to 50 nanometers, the at least one medium-sized silica being provided at a surface area coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, the at least one large-sized crosslinked organic polymer additive being provided at a surface area coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively chargeable surface additive, wherein the at least one positively chargeable surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, the titanium dioxide being present in an amount of 1 part or less per 100 based on 100 parts of the toner parent particles, the toner parent particles further containing small-sized silica having an average primary particle size of 8 to 16 nanometers, the small-sized silica being present at a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, the non-titanium dioxide positively chargeable metal oxide surface additive being present at a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, the toner parent particles optionally further containing small-sized silica having an average primary particle size of 8 to 16 nanometers, the small-sized silica being present at a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area; and the total surface area coverage rate of all of the combined surface additives is 100 to 140 percent of the toner parent particle surface area, and adding the surface additive; and optionally recovering the toner particles.It is a toner process.

[0004] Electrophotographic printing utilizes toner particles that can be manufactured by various processes. One such process includes an emulsion aggregation (“EA”) process for forming toner particles in which surfactants are used in the formation of a latex emulsion. For example, as an example of such a process, see U.S. Patent No. 6,120,967, the disclosure of which is incorporated herein by reference in its entirety.

[0005] A combination of an amorphous polyester and a crystalline polyester can be used in the EA process. This resin combination can result in high gloss and relatively low melting point characteristics (sometimes referred to as low melt, ultra-low melt, or ULM) that enable higher energy efficiency and faster printing. Other toner resins such as styrene or styrene acrylate copolymers can also be selected for the toner. Such resins may include one or more resins selected from the group consisting of styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, copolymers thereof, and combinations thereof. The toner may also be a hybrid toner in which a combination of a polyester resin and another resin such as styrene is used for the toner particles.

[0006] Using additives with EA toner particles can be important for achieving optimal toner performance, for example, providing improved charge characteristics, improved flow characteristics, etc. Insufficient fixing causes problems with paper adhesion and printing performance. Aggregation of insufficient toner flow affects toner distribution and causes problems in gravity feed cartridges, which can result in disappearance on the paper. In addition, using additives with EA toner particles may reduce contamination of the bias charge roller (BCR).

[0007] U.S. Patent No. 8,663,886, which is hereby incorporated by reference in its entirety, describes in summary a polymer additive for use with toner particles. The polymer additive includes a copolymer having at least one monomer having a high carbon to oxygen ratio, a monomer having two or more vinyl groups, and at least one amine-functionalized monomer.

[0008] U.S. Patent Application No. 15 / 914,411, entitled "Toner Compositions And Surface Polymer Additives", which is hereby incorporated by reference in its entirety, describes in summary a polymer composition for use with toner particles. The polymer composition includes a silicone-polyether copolymer and a polymer additive, the silicone-polyether copolymer includes polysiloxane units and polyether units, and the polymer additive includes a copolymer having at least one monomer having a high carbon to oxygen ratio, a monomer having two or more vinyl groups, and at least one amine-functional monomer.

[0009] There is a continuing need to improve additives used in toners, including improving toner flow, poor toner flow or toner blocking that causes toner fixing at high temperatures, improving toner charging, and forming EA toners, particularly low melt EA toners, that reduce BCR contamination. The need to develop low-cost EA toners also continues to exist.

[0010] Due to certain regulatory requirements, compositions such as toners having 1% or more titania are expected to eventually require special labeling. Further, having titania in a toner formulation is expected to be an issue for Blue Angel certification. In addition, silica and titania additives add a significant cost to the toner formulation. Therefore, it is desirable to reduce or remove titania from the toner formulation.

[0011] Currently available toners and toner processes are suitable for their intended purposes. However, improved toners and toner processes are needed. Further, improved emulsion aggregation toners and toner processes are needed. Further, there is a need for a toner composition having performance characteristics equal to or better than those of conventional compositions while meeting the desire for a reduced amount of titania. Further, there is a need for a toner composition that can function as desired without the need for a titania additive.

[0012] Appropriate components and process aspects of each of the above U.S. patents and published patent applications can be selected for the present disclosure in its embodiments. Further, throughout this application, various publications, patents, and published patent applications are referenced by specific citation. The disclosures of the publications, patents, and published patent applications referenced in this application are incorporated by reference into this disclosure to more fully describe the state of the art relevant to the present invention. SUMMARY OF THE INVENTION

[0013] Described is a toner, which in combination with an optional colorant and an optional wax, comprises toner parent particles containing at least one resin, and a surface additive formulation, which comprises at least one medium-sized silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein this at least one medium-sized silica is provided with a surface coverage rate of 40 to 100 percent of the toner parent particle surface area, at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein this at least one large-sized crosslinked organic polymer additive is provided with a surface coverage rate of 5 to 29 percent of the toner parent particle surface area, at least one positively chargeable surface additive, which is either (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein titanium dioxide is present in an amount of 1 part or less per 100 parts of the toner parent particles, the toner parent particles further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present with a surface coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, wherein the non-titanium dioxide positively chargeable metal oxide surface additive is present with a surface coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present with a surface coverage rate of 0 to 75 percent of the toner parent particle surface area, and a surface additive formulation, wherein the total surface coverage rate of all of the combined surface additives is 100 to 140 percent of the toner parent particle surface area.

[0014] Also described is a toner process comprising contacting at least one resin, optional wax, optional colorant, and optional aggregating agent, heating to form aggregated toner particles, optionally adding a shell resin to the aggregated toner particles and heating to a higher temperature to coalesce the particles, and adding surface additives, wherein the surface additives include at least one medium-sized silica surface additive having an average primary particle size of 30 to 50 nanometers, and this at least one medium-sized silica is provided with a surface area coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, and this at least one large-sized crosslinked organic polymer additive is provided with a surface area coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively charged surface additive, wherein this at least one positively charged surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, and the titanium dioxide is present in an amount of 1 part or less per 100 based on 100 parts of the toner parent particles, and the toner parent particles further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present with a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively charged metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, and the non-titanium dioxide positively charged metal oxide surface additive is present with a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present with a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area, and the total surface area coverage rate of all the combined surface additives is 100 to 140 percent of the toner parent particle surface area, and adding the surface additives, and optionally recovering the toner particles.It is a toner process.,

Mode for Carrying Out the Invention

[0015] The present disclosure provides a toner that provides desired performance characteristics including one or a combination of more of sufficient, acceptable, or excellent flow, charge, charge distribution, photoreceptor cleanability, colorant flow characteristics, and storage performance after processing under high humidity conditions. A toner composition having a toner surface additive formulation is provided to reduce or replace the titania surface additive.

[0016] In an embodiment, a toner includes toner parent particles including at least one resin in combination with an optional colorant and an optional wax, and a surface additive formulation including at least one medium-sized silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein the at least one medium-sized silica is provided at a surface coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein the at least one large-sized crosslinked organic polymer additive is provided at a surface coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively chargeable surface additive, wherein the at least one positively chargeable surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein the titanium dioxide is present in an amount of 1 part or less per 100 parts of the toner parent particles, the toner parent particles further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, wherein the non-titanium dioxide positively chargeable metal oxide surface additive is present at a surface coverage rate of 5 to 15 percent of the toner parent particle surface area, the toner parent particles optionally further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface coverage rate of 0 to 75 percent of the toner parent particle surface area, and a surface additive formulation including the total surface coverage rate of all of the combined surface additives being 100 to 140 percent of the toner parent particle surface area is provided.

[0017] The toner surface additive formulation may be combined with a toner resin optionally having a colorant to form the toner of the present disclosure.

[0018] When forming the toner of the present disclosure, any toner resin can be utilized. Such a resin may then be made from any suitable monomer or monomers by any suitable polymerization method. In embodiments, the resin can be prepared by a method other than emulsion polymerization. In further embodiments, the resin can be prepared by condensation polymerization.

[0019] The toner may include one or more polyester resins. In embodiments, the polyester resin may be amorphous, crystalline, or a combination of amorphous polyester and crystalline polyester. In other embodiments, the toner includes a styrene or styrene acrylate resin. In other embodiments, the toner may include a hybrid toner containing two or more toner resins such as polyester and styrene-acrylate.

[0020] Amorphous resin.

[0021] In embodiments, the toner composition includes at least one amorphous polyester. In embodiments, the toner composition includes at least one amorphous polyester and at least one crystalline polyester. In certain embodiments, at least one polyester includes a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester. In further embodiments, at least one polyester in the toner includes a first amorphous polyester, a second amorphous polyester different from the first amorphous polyester, and a crystalline polyester.

[0022] It may also be an amorphous polyester resin formed by reacting an amorphous resin with a diol and a dibasic acid in the presence of an optional catalyst. Examples of the diacid or diester containing a vinyl diacid or vinyl diester used for the preparation of the amorphous polyester include terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, dimethyl fumarate, dimethyl itaconate, cis-1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl phthalate, phthalic anhydride, diethyl phthalate, dimethyl succinate, dimethyl fumarate, dimethyl maleate, dimethyl glutarate, dimethyl adipate, dimethyl dodecyl succinate, and combinations thereof, such as dicarboxylic acids or diesters. The organic dibasic acid or diester may be present, for example, in an amount of about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, or about 45 to about 50 mole percent of the resin.

[0023] Examples of diols that can be used in the production of amorphous polyesters include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(2-hydroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl)oxide, dipropylene glycol, dibutylene, and combinations thereof. The amount of the organic diol selected may vary and the organic diol may be present, for example, in an amount of about 40 to about 60 mole percent of the resin, about 42 to about 55 mole percent of the resin, or about 45 to about 53 mole percent of the resin.

[0024] Examples of suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, etc., and mixtures thereof.

[0025] An unsaturated amorphous polyester resin may be used as the resin. Examples of such resins include those disclosed in U.S. Patent No. 6,063,827, the entire disclosure of which is incorporated herein by reference. Exemplary unsaturated non-crystalline polyester resins include, but are not limited to, poly(propoxylated bisphenol cofumarate), poly(ethoxylated bisphenol cofumarate), poly(butyloxylated bisphenol cofumarate), poly(copropoxylated bisphenol coethoxylated bisphenol cofumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol comaleate), poly(ethoxylated bisphenol comaleate), poly(butyloxylated bisphenol comaleate), poly(copropoxylated bisphenol coethoxylated bisphenol comaleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol coitaconate), poly(ethoxylated bisphenol coitaconate), poly(butyloxylated bisphenol coitaconate), poly(copropoxylated bisphenol coethoxylated bisphenol coitaconate), poly(1,2-propylene itaconate), and combinations thereof.

[0026] A suitable polyester resin may be an amorphous polyester such as poly(propoxylated bisphenol A cofumarate) resin. Examples of such resins and their manufacturing processes include those disclosed in U.S. Patent No. 6,063,827, the entire disclosure of which is incorporated herein by reference.

[0027] Suitable polyester resins include amorphous acidic polyester resins. The amorphous acid polyester resin may be any combination of propoxylated bisphenol A, ethoxylated bisphenol A, terephthalic acid, fumaric acid, and dodecenyl succinic anhydride, for example, a polymer of (propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate). Another amorphous acid polyester resin that can be used is poly(propoxylate-ethoxylated bisphenol-co-terephthalate-dodecenyl succinic-trimellitic anhydride).

[0028] An example of a linear propoxylated bisphenol A fumarate resin that can be used as a resin is available under the trade name SPARII from Resana S / A Industrias Quimicas (Sao Paulo, Brazil). Other commercially available propoxylated bisphenol A fumarate resins that can be used include GTUF and FPESL-2 from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, N.C., etc.

[0029] The crystalline resin or combination of crystalline resins may be present, for example, in an amount of about 5 to about 95 wt%, about 30 to about 90 wt%, or about 35 to about 85 wt% of the toner.

[0030] In an embodiment, the toner composition contains crystalline polyester in an amount of about 73 to about 78 wt% based on the total weight of the toner composition. In a particular embodiment, the toner composition contains a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester, and the total amount of the amorphous polyester containing both the first and second amorphous polyesters is about 73 to about 78 wt% based on the total weight of the toner composition.

[0031] An amorphous resin or a combination of amorphous resins may have a glass transition temperature of about 30°C to about 80°C, about 35°C to about 70°C, or about 40°C to about 65°C. The glass transition temperature can be measured using differential scanning calorimetry (DSC). The amorphous resin may have an Mn of, for example, about 1,000 to about 50,000, about 2,000 to about 25,000, or about 1,000 to about 10,000 when measured by GPC, and may have an Mw of, for example, about 2,000 to about 100,000, about 5,000 to about 90,000, about 10,000 to about 90,000, about 10,000 to about 30,000, or about 70,000 to about 100,000 when determined by GPC.

[0032] In embodiments, one, two, or more resins may be used. When two or more resins are used, the resins may be in any suitable ratio (e.g., weight ratio), such as about 1% (first resin) / 99% (second resin) to about 99% (first resin) / 1% (second resin), about 10% (first resin) / 90% (second resin) to about 90% (first resin) / 10% (second resin), etc. When the resin includes a combination of an amorphous resin and a crystalline resin, the resin may be, for example, in a weight ratio of about 1% (crystalline resin) / 99% (amorphous resin) to about 99% (crystalline resin) / 1% (amorphous resin), or about 10% (crystalline resin) / 90% (amorphous resin) to about 90% (crystalline resin) / 10% (amorphous resin). In some embodiments, the weight ratio of the resin is about 80% to about 60% amorphous resin and about 20% to about 40% crystalline resin. In such embodiments, the amorphous resin may be a combination of amorphous resins, for example, two amorphous resins.

[0033] Crystalline resin.

[0034] In an embodiment, the toner of this specification contains a crystalline polyester resin. The crystalline resin in this specification may be a polyester resin formed by reacting a diol and a diacid in the presence of an optional catalyst. Suitable organic diols for forming the crystalline polyester include aliphatic diols having about 2 to about 36 carbon atoms, including their structural isomers, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and combinations thereof. The aliphatic diol can be selected, for example, in an amount of about 40 to about 60 mole percent of the resin, about 42 to about 55 mole percent of the resin, or about 45 to about 53 mole percent of the resin, and the second diol can be selected in an amount of about 0 to about 10 mole percent of the resin, or about 1 to 4 mole percent of the resin.

[0035] Examples of organic diacids or diesters containing vinyl diacids or vinyl diesters selected for the preparation of the crystalline resin include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethyl itaconate, cis-1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, and mesaconic acid, and their diesters or anhydrides. The organic diacid can be selected, for example, in an amount of about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, or about 45 to about 50 mole percent of the resin, and the second diacid can be selected in an amount of about 0 to about 10 mole percent of the resin.

[0036] As polycondensation catalysts that can be used to form crystalline (as well as amorphous) polyesters, there can be mentioned tetraalkyl titanates, dialkyl tin oxides such as dibutyl tin oxide, tetraalkyl tins such as dibutyl tin dilaurate, and dialkyl tin oxide hydroxides such as butyl tin oxide hydroxide, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxide, stannous oxide, or combinations thereof. Such catalysts may be used, for example, in an amount of about 0.01 mole percent to about 5 mole percent based on the starting diacid or diester used to produce the polyester resin.

[0037] 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(2,2-dimethylpropane-1,3-diol decanoate)-copoly(nonylene decanoate), poly(octylene adipate), and mixtures thereof. Examples of polyamides include poly(ethylene adipamide), poly(propylene adipamide), poly(butylene adipamide), poly(pentylene adipamide), poly(hexylene adipamide), poly(octylene adipamide), poly(ethylene succinimide), poly(propylene sebacamide), 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.

[0038] In an embodiment, the crystalline polyester is of the following formula:

Chemical formula

[0039] Each of a and b may be in the range of 1 to 12, 2 to 12, or 4 to 12. Further, p may be in the range of 10 to 100, 20 to 80, or 30 to 60. In an embodiment, the crystalline polyester is poly(1,6-hexylene-1,12-dodecanoate) and can be produced by the reaction of dodecanedioic acid and 1,6-hexanediol.

[0040] The notations, "CX:CY", "CX:Y", "X:Y", and their forms, when used herein, denote a crystalline resin, where C is carbon, X is a positive non-zero integer specifying the number of methylene groups of the acid / ester monomer used to produce the crystalline polyester (CPE), and Y is a positive non-zero integer specifying the number of methylene groups of the alcohol monomer used to produce the CPE. Thus, for example, C10 can represent dodecanedioic acid, and C6 can represent hexanediol. Each of X and Y is 10 or less. In an embodiment, the sum of X and Y is 16 or less. In a particular embodiment, the sum and X and Y are 14 or less.

[0041] In an embodiment, the crystalline polyester is a C10:9 resin containing a polyester made from dodecanedioic acid (C10) and 1,9-nonanediol (C9).

[0042] As described above, the crystalline polyester can be prepared by a polycondensation process in which a suitable organic diol and a suitable organic diacid are reacted in the presence of a polycondensation catalyst. A stoichiometric equimolar ratio of the organic diol and the organic diacid can be utilized, but when the boiling point of the organic diol is from about 180°C to about 230°C, an excess amount of diol such as about 0.2 to 1 molar equivalent of ethylene glycol or propylene glycol can be utilized and removed during the polycondensation process by distillation. The amount of catalyst utilized may vary and can be selected, for example, in an amount such as about 0.01 to about 1 or about 0.1 to about 0.75 mole percent of the crystalline polyester resin.

[0043] The crystalline resin can be present in the toner in any suitable or desired amount. In embodiments, the crystalline resin may be present, for example, in an amount of about 1 to about 85 weight percent of the toner, about 5 to about 50 weight percent of the toner, or about 10 to about 35 weight percent of the toner. In certain embodiments, the crystalline polyester is present in an amount of about 6 to about 7 weight percent based on the total weight of the toner composition. In certain embodiments, the crystalline polyester is the C10:9 resin present in the toner and is in an amount of about 6 to about 7 weight percent based on the total weight of the toner composition.

[0044] The crystalline resin may have various melting points, for example, about 30°C to about 120°C, about 50°C to about 90°C, or about 60°C to about 80°C. When measured by gel permeation chromatography (GPC), the crystalline resin may have, for example, a number average molecular weight (Mn) of about 1,000 to about 50,000, about 2,000 to about 25,000, or about 5,000 to about 20,000, and when determined by GPC, a weight average molecular weight (Mw) of about 2,000 to about 100,000, about 3,000 to about 80,000, or about 10,000 to about 30,000. The molecular weight distribution (Mw / Mn) of the crystalline resin may be, for example, about 2 to about 6, about 3 to about 5, or about 2 to about 4.

[0045] In an embodiment, the toner includes a core-shell structure, the core includes at least one amorphous polyester and at least one crystalline polyester, and the shell includes at least one amorphous polyester.

[0046] In another embodiment, the toner includes a core-shell structure, the core includes at least one amorphous polyester and at least one crystalline polyester, and the shell includes a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester.

[0047] In another embodiment, the toner includes a core-shell structure, and the core includes a first amorphous polyester containing poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) and a second amorphous polyester containing poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0048] In an embodiment, the toner core further includes a third amorphous polyester resin and a fourth amorphous polyester resin. In an embodiment, the third and fourth amorphous polyester resins are different. In an embodiment, the third amorphous polyester resin is present in an amount of about 1 to about 20, or about 3 to about 18, or about 5 to about 15 weight percent, based on the total weight of the toner. In an embodiment, the fourth amorphous polyester resin is present in an amount of about 1 to about 20, or about 3 to about 18, or about 5 to about 15 weight percent, based on the total weight of the toner. In a particular embodiment, the third amorphous polyester is poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate), and the fourth amorphous polyester is poly(propoxylated-ethoxylated bisphenol-co-terephthalate-dodecenyl succinate-trimellitic anhydride).

[0049] In an embodiment, the third amorphous polyester resin and the fourth amorphous polyester resin are present in equal amounts in the toner core.

[0050] In a particular embodiment, the toner includes a core-shell configuration, the shell includes a resin, and the shell resin occupies about 28 weight percent of the toner composition, based on the total weight of the toner composition including the core and the shell. The shell resin(s) that occupy 28 percent of the toner can be selected from any of the resins described herein. In an embodiment where the shell resin occupies about 28 percent of the toner particle mass and the shell resin includes two different amorphous polyesters, in an embodiment where the shell includes a combination of a low molecular weight amorphous polyester and a high molecular weight amorphous polyester.

[0051] In an embodiment, the amorphous resin may include at least one low molecular weight amorphous polyester resin. Low molecular weight amorphous polyester resins available from a number of sources may have various melting points, for example, from about 30 °C to about 120 °C, in an embodiment from about 75 °C to about 115 °C, in an embodiment from about 100 °C to about 110 °C, or in an embodiment from about 104 °C to about 108 °C. As used herein, the low molecular weight amorphous polyester resin has, for example, a number average molecular weight (Mn) of from about 1,000 to about 10,000, in an embodiment from about 2,000 to about 8,000, in an embodiment from about 3,000 to about 7,000, and in an embodiment from about 4,000 to about 6,000, as measured by, for example, gel permeation chromatography (GPC). The weight average molecular weight (Mw) of the resin is 50,000 or less when determined by GPC using polystyrene standards, for example, in an embodiment from about 2,000 to about 50,000, in an embodiment from about 3,000 to about 40,000, in an embodiment from about 10,000 to about 30,000, and in an embodiment from about 18,000 to about 21,000. The molecular weight distribution (Mw / Mn) of the low molecular weight amorphous resin is, for example, from about 2 to about 6, in an embodiment from about 3 to about 4. The low molecular weight amorphous polyester resin may have an acid value of from about 8 to about 20 mg KOH / g, in an embodiment from about 9 to about 16 mg KOH / g, and in an embodiment from about 10 to about 14 mg KOH / g.

[0052] In an embodiment, the toner of the present disclosure may also include at least one high molecular weight branched or crosslinked amorphous polyester resin. Examples of such high molecular weight resins include, in an embodiment, branched amorphous resins or amorphous polyesters, crosslinked amorphous resins or amorphous polyesters, or mixtures thereof, or crosslinked non-crosslinked amorphous polyester resins. According to the present disclosure, from about 1 wt% to about 100 wt% of the high molecular weight amorphous polyester resin may be branched or crosslinked, and in an embodiment, from about 2 wt% to about 50 wt% of the high molecular weight amorphous polyester resin may be branched or crosslinked.

[0053] As used herein, a high molecular weight amorphous polyester resin may have a number average molecular weight (Mn) of, for example, about 1,000 to about 10,000, in embodiments about 2,000 to about 9,000, in embodiments about 3,000 to about 8,000, and in embodiments about 6,000 to about 7,000 when measured by, for example, gel permeation chromatography (GPC). The weight average molecular weight (Mw) of the resin is greater than 55,000, for example, about 55,000 to about 150,000, in embodiments about 60,000 to about 100,000, in embodiments about 63,000 to about 94,000, and in embodiments about 68,000 to about 85,000 when determined by GPC using polystyrene standards. The polydispersity index (PD) is greater than about 4, for example, greater than about 4, in embodiments about 4 to about 20, in embodiments about 5 to about 10, and in embodiments about 6 to about 8 when measured by GPC relative to a standard polystyrene resin. The PD index is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The low molecular weight amorphous polyester resin may have an acid value of about 8 to about 20 mg KOH / g, in embodiments about 9 to about 16 mg KOH / g, and in embodiments about 11 to about 15 mg KOH / g. High molecular weight amorphous polyester resins available from a number of sources may have various melting points, for example, about 30°C to about 140°C, in embodiments about 75°C to about 130°C, in embodiments about 100°C to about 125°C, and in embodiments about 115°C to about 121°C.

[0054] High molecular weight amorphous resins available from a number of sources may have various glass transition onset temperatures (Tg) of, for example, about 40°C to about 80°C, in embodiments about 50°C to about 70°C, and in embodiments about 54°C to about 68°C when measured by differential scanning calorimetry (DSC). In embodiments, linear and branched amorphous polyester resins may be saturated or unsaturated resins.

[0055] High molecular weight amorphous polyester resins can be prepared by branching or crosslinking linear polyester resins. Branching agents such as trifunctional or polyfunctional monomers can be utilized, and these agents usually increase the molecular weight and polydispersity of the polyester. Suitable branching agents include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, diglycerol, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, combinations thereof, and the like. These branching agents can be utilized in an effective amount of about 0.1 mol% to about 20 mol% based on the diacid or diester that is the starting material used to make the resin.

[0056] Compositions containing modified polyester resins having polybasic carboxylic acids that can be utilized in forming high molecular weight polyester resins include those disclosed in U.S. Patent No. 3,681,106, and branched or crosslinked polyesters derived from polybasic acids or alcohols exemplified in U.S. Patent Nos. 4,863,825, 4,863,824, 4,845,006, 5,143,809, 5,057,596, 4,988,794, 4,981,939, 4,980,448, 4,933,252, 4,931,370, 4,917,983, and 4,973,539, the disclosures of each of which are incorporated herein by reference in their entirety.

[0057] In some embodiments, the crosslinked polyester resin can be made from a linear amorphous polyester resin containing unsaturated sites that can react under free radical conditions. Examples of such resins include those disclosed in U.S. Patent Nos. 5,227,460, 5,376,494, 5,480,756, 5,500,324, 5,601,960, 5,629,121, 5,650,484, 5,750,909, 6,326,119, 6,358,657, 6,359,105, and 6,593,053, each disclosure of which is incorporated herein by reference in its entirety. In an embodiment, a suitable unsaturated polyester resin can be prepared from diacids and / or anhydrides such as maleic anhydride, terephthalic acid, trimellitic acid, fumaric acid, etc., and combinations thereof, and diols such as bisphenol A ethylene oxide adduct, bisphenol A-propylene oxide adduct, etc., and combinations thereof. In an embodiment, a suitable polyester is poly(propoxylated bisphenol A co-fumaric acid).

[0058] In an embodiment, the crosslinked branched polyester can be utilized as a high molecular weight amorphous polyester resin. Such a polyester resin may be formed from at least two prepolymer compositions comprising at least one polyol having two or more hydroxyl groups or esters thereof, at least one aliphatic or aromatic polyfunctional acid or an ester thereof, or a mixture of these having at least three functional groups, and optionally, at least one long-chain aliphatic carboxylic acid or an ester thereof, or an aromatic monocarboxylic acid or an ester thereof, or a mixture of these. The two components may be reacted and substantially completed in separate containers to produce a first composition containing a prepolymer having a carboxyl end group in a first reactor and a second composition containing a prepolymer having a hydroxyl end group in a second reactor. Then, the two compositions may be mixed to produce a crosslinked branched polyester high molecular weight resin. Examples of such polyesters and their synthetic methods are disclosed in U.S. Patent No. 6,592,913, the entire disclosure of which is incorporated herein by reference.

[0059] Suitable polyols may contain from about 2 to about 100 carbon atoms and may have at least two or more hydroxyl groups, or esters thereof. The polyols may include glycerol, pentaerythritol, polyglycol, polyglycerol, etc., or a mixture of these. The polyol may include glycerol. Suitable esters of glycerol include glycerol palmitate, glycerol sebacate, glycerol adipate, triacetin, tripropionin, etc. The polyol may be present in an amount of about 20 wt% to about 30 wt% of the reaction mixture, and in an embodiment, about 22 wt% to about 26 wt% of the reaction mixture.

[0060] Examples of aliphatic polyfunctional acids having at least two functional groups include saturated and unsaturated acids containing from about 2 to about 100 carbon atoms, and in some embodiments from about 4 to about 20 carbon atoms, or esters thereof. Other aliphatic polyfunctional acids include malonic acid, succinic acid, tartaric acid, malic acid, citric acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, sebacic acid, etc., or mixtures thereof. Other aliphatic polyfunctional acids that can be used include dicarboxylic acids containing a C3-C6 cyclic structure and its positional isomers, such as cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, or cyclopropanedicarboxylic acid.

[0061] Examples of aromatic polyfunctional acids having at least two functional groups that can be used include terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and naphthalene 1,4-, 2,3-, and 2,6-dicarboxylic acids.

[0062] The aliphatic polyfunctional acid or aromatic polyfunctional acid may be present in an amount of about 40% to about 65% by weight of the reaction mixture, and in embodiments, about 44% to about 60% by weight of the reaction mixture.

[0063] Examples of the long-chain aliphatic carboxylic acid or aromatic monocarboxylic acid include those containing about 12 to about 26 carbon atoms, in embodiments, those containing about 14 to about 18 carbon atoms, or esters thereof. The long-chain aliphatic carboxylic acid may be saturated or unsaturated. Suitable saturated long-chain aliphatic carboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, cerotic acid, etc., or combinations thereof. Suitable unsaturated long-chain aliphatic carboxylic acids include dodecenoic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, etc., or combinations thereof. Examples of the aromatic monocarboxylic acid include benzoic acid, naphthoic acid, and substituted naphthoic acid. Suitable substituted naphthoic acids include naphthoic acids substituted with a linear or branched alkyl group containing about 1 to about 6 carbon atoms, such as 1-methyl-2-naphthoic acid and / or 2-isopropyl-1-naphthoic acid. The long-chain aliphatic carboxylic acid or aromatic monocarboxylic acid may be present in an amount of about 0 wt% to about 70 wt% of the reaction mixture, and in embodiments, about 15 wt% to about 30 wt% of the reaction mixture.

[0064] If desired, additional polyols, ionic species, oligomers, or derivatives thereof may be used. These additional glycols or polyols may be present in an amount of about 0 wt% to about 50 wt% of the reaction mixture. Examples of the additional polyol or its derivative include propylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, triacetin, trimethylolpropane, pentaerythritol, cellulose ether, cellulose acetate, cellulose esters such as sucrose acetate isobutyl, etc.

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

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

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

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

[0069] The resin(s) in this toner may have acid groups that can be present at the ends of the resin. Examples of the acid groups that can be present include carboxylic acid groups. The number of carboxylic acid groups may be controlled by adjusting the materials and reaction conditions used to form the resin. In an embodiment, the resin is a polyester resin having an acid value of about 2 mg KOH / resin g to about 25 mg KOH / resin g, about 5 mg KOH / resin g to about 20 mg KOH / resin g, or about 5 mg KOH / resin g to about 15 mg KOH / resin g. The acid-containing resin may be dissolved in a tetrahydrofuran solution. The acid value may be detected by titrating with a KOH / methanol solution containing phenolphthalein as an indicator. The acid value 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.

[0070] Additional exemplary polymers that can be used in toner resins include styrene acrylate, styrene butadiene, styrene methacrylate, and more specifically, poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), and combinations thereof. The polymer may be a block, random, or alternating copolymer.,

[0071] In an embodiment, the resin is selected from the group consisting of styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, and combinations thereof.

[0072] In a specific embodiment, the resin is selected from the group consisting of poly(styrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methyl styrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-butyl acrylate), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butadiene-acrylic acid), poly(styrene-isoprene-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), and combinations thereof.

[0073] Coagulant.

[0074] The toner in this specification may also contain coagulants such as monovalent metal coagulants, divalent metal coagulants, polyion coagulants, etc. Various coagulants are known in the art. As used herein, "polyion coagulant" refers to a coagulant that is a salt or oxide such as a metal salt or metal oxide formed from metal species having at least 3, desirably at least 4 or 5 valences. Thus, suitable coagulants include, for example, aluminum-based coagulants such as polyhalogenated aluminum such as aluminum fluoride and polyaluminum chloride (PAC), polyaluminum sulfosilicate (PASS), polyaluminum hydroxide, and polyaluminum silicate such as polyaluminum phosphate. Other suitable coagulants include, but are not limited to, tetraalkyl titanates, dialkyl tin oxides, tetraalkyl tin oxide hydroxides, dialkyl tin oxide hydroxides, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxide, tin oxide, dibutyl tin oxide, dibutyl tin oxide hydroxide, tetraalkyl tin, combinations thereof, etc. When the coagulant is a polyion coagulant, the coagulant can have any desired number of polyion atoms present. For example, in an embodiment, a suitable polyaluminum compound can have about 2 to about 13, or about 3 to about 8 aluminum ions present in the compound.

[0075] Such coagulants can be incorporated into the toner particles during particle aggregation. Thus, the coagulant can be present in the toner particles on a dry weight basis, excluding external additives, in an amount of about 0 to about 5 weight percent, or about 0 weight percent to about 3 weight percent of the toner particles.

[0076] Surfactant.

[0077] When preparing toner by an emulsion aggregation procedure, one or more surfactants may be used in the process. Suitable surfactants include anionic, cationic, and nonionic surfactants. In embodiments, the use of anionic and nonionic surfactants is preferred to promote the stabilization of the aggregation process in the presence of a coagulant that may otherwise cause aggregation instability.

[0078] Examples of anionic surfactants include sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, dialkylbenzene alkyl sulfates and sulfonates, abietic acid, and anionic surfactants of the NEOGEN® brand. Examples of suitable anionic surfactants are NEOGEN® RK available from Daiichi Kogyo Seiyaku co., Ltd., or TAYCA POWER BN2060 from Tayca Corporation (Japan), which consists mainly of sodium branched dodecylbenzenesulfonate.

[0079] Examples of cationic surfactants include dialkylbenzene alkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, ethylpyridinium bromide, trimethylammonium bromide C12, C15, C17, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride. MIRAPOL® and ALKAQUAT® available from Alkaril Chemical Company, SANISOL® (benzalkonium chloride) available from Kao Chemicals, etc. An example of a suitable cationic surfactant is SANISOL® B-50 available from Kao Corp., which consists mainly of benzyl dimethyl alkonium chloride.

[0080] Examples of nonionic surfactants include polyvinyl alcohol, polyacrylic acid, metallocose, methylcellulose, ethylcellulose, propylcellulose, hydroxylethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, available from Rhone-Poulenc Inc. as IGEPAL® CA-210, IGEPAL® CA-520, IGEPAL® CA-720, IGEPAL® CO-890, IGEPAL® CO-720, IGEPAL® CO-290, IGEPAL® CA-210, ANTAROX® 890 and ANTAROX® 897. An example of a preferred nonionic surfactant is ANTAROX® 897 available from Rhone-Poulenc Inc., which consists mainly of alkylphenol ethoxylate.

[0081] Examples of bases used to raise the pH, and thus ionize the aggregated particles, provide stability and thereby prevent the growth of the size of the aggregates, can be selected, inter alia, from sodium hydroxide, potassium hydroxide, ammonium hydroxide, cesium hydroxide, etc.

[0082] Acids that can be used include, for example, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, trifluoroacetic acid, succinic acid, salicylic acid, etc., and these acids are used in diluted form, in embodiments, in water in the range of about 0.5 to about 10 weight percent, or in water in the range of about 0.7 to about 5 weight percent.

[0083] In embodiments, a naphthalenesulfonic acid polymer surfactant is selected.

[0084] Optional additives.

[0085] Optionally, the toner particles can contain other optional additives. For example, the toner can contain a positive or negative charge control agent in any desired or effective amount, in one embodiment at least about 0.1 weight percent of the toner, in another embodiment at least about 1 weight percent of the toner, in one embodiment about 10 weight percent or less of the toner, and in another embodiment about 3 weight percent or less of the toner. Examples of suitable charge control agents include, but are not limited to, quaternary ammonium compounds such as alkylpyridinium halides, bisulfates, alkylpyridinium compounds, etc. disclosed in U.S. Patent No. 4,298,672, which is hereby incorporated by reference in its entirety; organic sulfates and sulfonate compositions, including those disclosed in U.S. Patent No. 4,338,390, which is hereby incorporated by reference in its entirety; cetylpyridinium tetrafluoroborate; distearyldimethylammonium methyl sulfate; aluminum salts such as BONTRON E84 (trademark) or E88 (trademark) (Hodogaya Chemical); and mixtures thereof. Such charge control agents can be applied simultaneously with the shell resin or after application of the shell resin.

[0086] Alternatively, it can also be blended with toner particle external additive particles containing a flow aid additive, which can be present on the surface of the toner particles. Examples of these additives include, but are not limited to, metal oxides such as titanium oxide, silicon oxide, tin oxide, and mixtures thereof, colloidal and amorphous silica such as AEROSIL® (registered trademark), metal salts, and metal salts of fatty acids including zinc stearate, aluminum oxide, cerium oxide, and mixtures thereof. Each of these external additives can be present in any desired or effective amount, in embodiments, at least about 0.1 weight percent of the toner, or at least about 0.25 weight percent of the toner, or about 5 weight percent or less of the toner, or about 3 weight percent or less of the toner. Suitable additives include, but are not limited to, those disclosed in U.S. Patent Nos. 3,590,000 and 6,214,507, each of which is incorporated herein by reference. Such additives may be applied simultaneously with the shell resin or after the application of the shell resin.

[0087] The emulsion agglomerated polyester toner generally uses sodium dodecylbenzenesulfonate as a dispersant for the NIPex® (registered trademark) carbon black dispersion in the toner at about 7.2 parts per 100 parts (pph) of the TaycaPower B2060 surfactant.

[0088] In embodiments, the amount of the TaycaPower surfactant can be reduced to as little as 2 pph in the pigment dispersion while adding 3.2 pph of DEMOL SN-B (Kao Corporation), a polymeric surfactant of butylnaphthalenesulfonic acid / 2-naphthalenesulfonic acid / sodium formaldehyde sulfoxylate. Then, the dispersion can be used to make the toner.

[0089] To reduce dielectric loss, similar products can be used. For example, sodium arylsulfonate formaldehyde condensate powder DEMOL M, sodium arylsulfonate formaldehyde condensate DEMOL SS-L, sodium naphthalenesulfonate formaldehyde condensate powder DEMOL N, DEMOL RN, DEMOL T and DEMOL T-45, sodium naphthalenesulfonate formaldehyde condensate liquid DEMOL NL. Other manufacturers provide similar sulfonate formaldehyde condensates such as 1-naphthalenesulfonic acid, formaldehyde polymer, sodium salt CAS NO. 32844-36-3 available from Anyang Double Circle Auxiliary Co., LTD (China), and sodium naphthalenesulfonate formaldehyde CAS NO. 9084-06-4 available from Chemtrade International (China).

[0090] Colorant.

[0091] The toner may optionally contain a colorant. Any suitable or desired surfactant can be selected. In embodiments, the colorant can be a pigment, a dye, a mixture of a pigment and a dye, a mixture of pigments, a mixture of dyes, etc. For the sake of brevity, as used herein, the term "colorant" is meant to include such colorants, dyes, pigments, and mixtures thereof unless specified as a particular pigment or other colorant component. In embodiments, the colorant includes pigments, dyes, mixtures thereof, in embodiments, carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, mixtures thereof, in an amount of about 1 weight percent to about 25 weight percent based on the total weight of the toner composition. In embodiments, the colorant is selected from cyan, magenta, yellow, black, or combinations thereof. In certain embodiments, the colorant includes a combination of carbon black and cyan. It should be understood that other useful colorants will be readily apparent based on the present disclosure.

[0092] In certain embodiments, the colorant comprises a pigment present in an amount of about 5 to about 8 weight percent, based on the total weight of the toner composition.

[0093] Useful colorants include Paliogen® Violet 5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Uhlrich), Permanent Violet VT2645 (Paul Uhlrich), Heliogen® Green L8730 (BASF), Argyle Green XP-111-S (Paul Uhlrich), Brilliant Green Toner GR0991 (Paul Uhlrich), Lithol® Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD Red (Aldrich), Lithol® Rubine Toner (Paul Uhlrich), Lithol® Scarlet 4440, NBD 3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Uhlrich), Oracet® Pink RF (Ciba Geigy), Paliogen® Red 3340 and 3871K (BASF), Lithol® Fast Scarlet L4300 (BASF), Heliogen® Blue D6840, D7080, K7090, K6910, and L7020 (BASF), Sudan Blue OS (BASF), Neopen® Blue FF4012 (BASF), PV Fast Blue B2G01 (American Hoechst), Irgalite® Blue BCA (Ciba Geigy), Paliogen® Blue6470 (BASF), Sudan II, III, and IV (Matheson, Coleman, Bell), Sudan Orange (Aldrich), Sudan Orane 220 (BASF), Paliogen® Orange 3040 (BASF), Ortho Orange OR2673 (Paul Uhlrich), Paliogen® Yellow 152 and 1560 (BASF), Lithol® Fast YellowExamples include 0991K (BASF), Paliotol® Yellow 1840 (BASF), Novaperm® Yellow FGL (Hoechst), Permanent Yellow YE 0305 (Paul Uhlrich), Lumogen® Yellow 00790 (BASF), Suco-Gelb 1250 (BASF), Suco-Yellow D1355 (BASF), Suco Fast Yellow D1165, D1355, and D1351 (BASF), Hostaperm® Pink E (Hoechst), Fanal® Pink D4830 (BASF), Cinquasia® Magenta (DuPont), Paliogen® BlackL9984 (BASF), Pigment Black K801 (BASF), and in particular, carbon blacks such as REGAL® 330 (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals), or mixtures thereof.

[0094] Additional useful colorants include pigments in aqueous dispersions such as those commercially available from Sun Chemical, for example, SUNSPERSE® BHD 6011X (Blue 15 Typ), SUNSPERSE® BHD9312X (Pigment Blue 15 74160), SUNSPERSE® BHD6000X (Pigment Blue 15:3 74160), SUNSPERSE® GHD9600X and GHD6004X (Pigment Green7 74260), SUNSPERSE® QHD6040X (Pigment Red122 73915), SUNSPERSE® RHD 9668X (Pigment Red185 12516), SUNSPERSE® RHD9365X and 9504X (Pigment Red57 15850:1), SUNSPERSE® YHD6005X (Pigment Yellow83 21108), FLEXIVERSE® YFD 4249 (Pigment Yellow17 21105), SUNSPERSE® YHD 6020X and 6045X (Pigment Yellow74 11741), SUNSPERSE® YHD600X and 9604X (Pigment Yellow14 21095), FLEXIVERSE® LFD4343 and LFD9736 (Pigment Black7 77226), etc., or mixtures thereof. Other useful water-based colorant dispersions include those commercially available from Clariant, for example, HOSTAFINE® Yellow GR, HOSTAFINE® Black T and Black TS, HOSTAFINE® Blue B2G, HOSTAFINE® Rubine F6B, and magenta dry pigments such as Toner Magenta6BVP2213 and Toner Magenta EO2 that can be dispersed in water and / or surfactant before use.

[0095] Other useful colorants include Mobay magnetite M08029, M98960, Columbian magnetite MAPICO® BLACKS and surface-treated magnetite, Pfizer magnetite CB4799, CB5300, CB5600, MXC6369, Bayer magnetite BAYFERROX® 8600, 8610, Northern Pigments magnetite NP-604, NP-608, Magnox magnetite TMB-100 or TMB-104, etc., or mixtures thereof. Additional examples of pigments include phthalocyanine HELIOGEN® BLUE L6900, D6840, D7080, D7020, PYLAM® OIL BLUE, PYLAM® OIL YELLOW, PIGMENT BLUE 1 available from Paul Uhlrich & Company, Inc., PIGMENT VIOLET 1, PIGMENT RED 48, LEMON CHROME YELLOW DCC 1026, ED.TOLUIDINE RED, and BON RED C available from Dominion Color Corporation, Ltd. (Toronto, Ontario), NOVAPERM® YELLOW FGL, HOSTAPERM® PINK E, and CINQUASIA® MAGENTA (DuPont) from Hoechst, etc. Examples of magenta include 2,9-dimethyl-substituted quinacridone and anthraquinone dyes identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dyes identified in the Color Index as CI 26050, CI Solvent Red 19, etc., and mixtures thereof. Examples of cyan include copper tetra(octadecylsulfonamide) phthalocyanine, x-copper phthalocyanine pigments listed in the Color Index as CI 74160, DI 69810, Cl Pigment Blue, Anthrathrene Blue, etc. identified in the Color Index as Special Blue X-2137, or mixtures thereof.Examples of yellow that can be selected include diarylide yellow 3,3-dichlorobenzidine acetoacetanilide, a monoazo pigment specified as CI 12700 in the Color Index, CI Solvent Yellow 16, a nitrophenylamine sulfonamide specified as Foron Yellow SE / GLN in the Color Index, CI Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,4-dimethoxyacetoacetanilide, and Permanent Yellow FGL. Colored magnetite such as a mixture of MAPICO® BLACK and a cyan component can also be selected as a pigment.

[0096] Colorants such as carbon black, cyan, magenta, and / or yellow coloring are incorporated in an amount sufficient to impart the desired color to the toner. Generally, the pigment or dye is used in an amount of about 1 weight percent to about 35 weight percent, or about 5 weight percent to about 25 weight percent, or about 5 weight percent to about 15 weight percent of the toner particles on a solids basis. However, in embodiments, amounts outside of these ranges can also be used.

[0097] In an embodiment, the toner contains a carbon black colorant. As a specific emulsion agglomerated toner, non-oxidized low-structure furnace black NIPex® 35 can be mentioned. On the other hand, for other emulsion agglomerated toners, Regal® 330 is used. In order to enable as low dielectric loss as possible, low-conductive carbon black such as NIPex® 35 is selected. Since carbon black is a semiconductor, it is desirable to maintain the carbon black as pure as possible. Heteroatoms such as oxygen and sulfur dope the carbon black semiconductor and increase the conductivity. NIPex® 35 has a very high carbon content of more than 99.5% on the surface and a very low At% of O and S of less than 0.5% in total when measured by XPS. The carbon black is very pure and has almost no strong dopant oxygen and sulfur on the surface, so the conductivity is very low. This results in a lower dielectric loss than that of low-purity carbon black such as Regal® 330 having more than 1% oxygen and sulfur. The difference in purity is most dramatically shown by carbon, and the oxygen ratio of the carbon black is 499:1 for NIPex® 35, while it is 139:1 for Regal® 330.

[0098] In an embodiment, the colorant includes a combination of carbon black and cyan, and in the embodiment, it is cyan PB15:3.

[0099] In an embodiment, the toner contains 5 to 8% by weight of a pigment. In a specific embodiment, the toner is 5 to 8% by weight of a pigment, wherein the pigment is a combination of carbon black and cyan, 5 to 8% by weight of a pigment, 73 to 78% by weight of an amorphous polyester, wherein the amorphous polyester contains a first amorphous polyester and a second amorphous polyester different from the first amorphous polyester, 73 to 78% by weight of an amorphous polyester, and in an embodiment where the crystalline polyester is a C10:C9 crystalline polyester, 6 to 7% by weight of a crystalline polyester, where the weight percentages are based on the total weight of the toner composition. In an embodiment, the toner contains a cyan pigment present in an amount of about 1% by weight and a carbon black pigment present in an amount of about 6.9% by weight based on the total weight of the toner composition.

[0100] In other embodiments, the toner contains a colorant including a combination of two or more of cyan, in an embodiment cyan PB15:3, magenta, in an embodiment one or both of magenta PR269 and magenta RE05, yellow, in an embodiment yellow PY74, and carbon black. In other embodiments, the toner contains 5 to 8% of a pigment including a combination of two or more of cyan, in an embodiment cyan PB15:3, magenta, in an embodiment one or both of magenta PR269 and magenta RE05, yellow, in an embodiment yellow PY74, and carbon black.

[0101] Wax.

[0102] Optionally, the wax may also form toner particles in combination with a resin. When included, the wax may be present in an amount of, for example, about 1% to about 25% by weight of the toner particles, and in an embodiment, about 5% to about 20% by weight of the toner particles.

[0103] Waxes that can be selected include, for example, waxes having a weight average molecular weight of about 500 to about 20,000, and in embodiments about 1,000 to about 10,000. Waxes that can be used include, for example, polyolefins such as polyethylene, polypropylene, and polybutene waxes as commercially available from Allied Chemical and Petrolite Corporation, such as POLYWAX (trademark) polyethylene wax manufactured by BAKER Petrolite, wax emulsions available from Michaelman, Inc. and Daniels Products Company, EPOLENE N-15 (trademark) commercially available from Eastman Chemical Products, Inc., and VISCOL 550-P (trademark) available from Sanyo Kasei K.K., plant-based waxes such as low weight average molecular weight polypropylene, carnauba wax, rice wax, candelilla wax, urushi wax, and jojoba oil, animal-based waxes such as beeswax, mineral waxes and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax, ester waxes obtained from higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate, ester waxes obtained from higher fatty acids and monovalent or polyvalent lower alcohols such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetrabehenate, ester waxes obtained from higher fatty acids and polyhydric alcohol multimers such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate, and triglyceryl tetrastearate, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes such as cholesteryl stearate.Examples of functionalized waxes that can be used include, for example, amines, amides, such as AQUA SUPERSLIP 6550(trademark), SUPERSLIP 6530(trademark) available from Micro Powder Inc., fluorinated waxes, such as POLYFLUO 190(trademark), POLYFLUO 200(trademark), POLYSILK 19(trademark), POLYSILK 14(trademark) available from Micro Powder Inc., mixed fluorinated amide waxes (e.g., MICROSPERSION 19(trademark) available from Micro Powder Inc.), imides, esters, quaternary amines, carboxylic acids, or acrylic polymer emulsions (e.g., JONCRYL 74(trademark), 89(trademark), 130(trademark), 537(trademark), and 538(trademark) 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 aforementioned waxes may also be used in embodiments. The wax may be included, for example, as a fuser roll release agent.

[0104] In certain embodiments, the toner herein may be a dual wax toner as described in U.S. Patent Application No. 16 / 800,176 (Attorney Docket No. 20190262US01), which is incorporated herein by reference in its entirety. In an embodiment, the toner composition includes a first wax, a second wax different from the first wax, the first wax includes a paraffin wax, the second wax includes a polymethylene wax, at least one polyester, and an optional colorant.

[0105] Surface additive formulation.

[0106] In an embodiment, the toner herein includes toner parent particles containing at least one resin in combination with an optional colorant and an optional wax. The resin, colorant, and wax can be selected from those described herein. In an embodiment, the toner includes a surface additive formulation provided on the toner parent particles, and this surface additive formulation is At least one medium-sized particle silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein this at least one medium-sized particle silica is provided at a surface coverage rate of 40 to 100 percent of the toner parent particle surface area, at least one medium-sized particle silica surface additive and at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein this at least one large-sized crosslinked organic polymer additive is provided at a surface coverage rate of 5 to 29 percent of the toner parent particle surface area, at least one large-sized crosslinked organic polymer additive, and at least one positive charge surface additive, wherein this at least one positive charge surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein titanium dioxide is present in an amount of 1 part or less per 100 based on 100 parts of the toner parent particles, and the toner parent particles further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface coverage rate of 5 to 75 percent of the toner parent particle surface area, a titanium dioxide surface additive, or (b) a non-titanium dioxide positive charge metal oxide surface additive, wherein this non-titanium dioxide positive charge metal oxide surface additive has an average primary particle size of 8 to 30 nanometers, and the non-titanium dioxide positive charge metal oxide surface additive is present at a surface coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized silica having an average primary particle size of 8 to 16 nanometers, and the small-sized silica is present at a surface coverage rate of 0 to 75 percent of the toner parent particle surface area, a non-titanium dioxide positive charge metal oxide surface additive, at least one positive charge surface additive, and the total surface coverage rate of all the combined surface additives is 100 to 140% of the toner parent particle surface area, a surface additive formulation. In an embodiment, (b) the titanium dioxide positive charge metal oxide surface additive has a volume average primary particle size of 8 to 30 nanometers, or 8 to 25 nanometers, or 8 to 21 nanometers. The average primary particle size is the volume-based D50 diameter measured by the additive manufacturer or vendor. The method for measuring the particle size is SEM (scanning electron microscopy) or TEM (transmission electron microscopy).In some cases, indirect methods such as the dynamic light scattering method (DLS) can be used. Examples of suitable DLS devices include Nanotrac Wave and Nanotrac Wave II.

[0107] In an embodiment, the surface area coverage (SAC) of the additive with respect to the toner parent particles is SAC = 100●(w●D●P) / (0.363●d●p)

[0108] and can be calculated as, where for the toner parent particles, D is the D50 volume average diameter in microns, P is the true bulk density in g / cm 3 units, for the toner surface additive, d is the D50 volume average particle diameter in nanometers, p is the true bulk density in g / cm 3 units, and w is the weight of the toner surface additive added to the mixture in percentage units based on the toner parent particles.

[0109] As used herein, medium particle size silica means silica having an average volume primary particle diameter of 30 to 50 nanometers.

[0110] In an embodiment, the medium particle size silica has a hydrophobic treatment on its surface. In an embodiment, the hydrophobic treatment includes polydimethylsiloxane (HMDS). In an embodiment, the hydrophobic treatment includes an alkylsilane such as hexamethyldisilazane (HMDS). The medium particle size silica can be medium particle size treated silica such as Wacker HDK® HO5TD (40 nm, PDMS), HDK® HO5TM (40 nm, HMDS), HDK® HO5TX (40 nm, HMDS / PDMS), Evonik NY50 (30 nm, PDMS), NAX50 (30 nm, HMDS), RY50 (40 nm, PDMS), and RX50 (40 nm, HMDS).

[0111] When the toner parent particles have 100 percent total surface area, the medium particle size silica is provided in an embodiment with a surface area coverage of 40 to 100 percent of the toner parent particle surface area.

[0112] In certain embodiments, at least one medium-sized silica comprises two or more medium-sized silicas, and the two or more medium-sized silicas comprise surface-treated medium-sized silicas selected from the group consisting of alkylsilane-treated silica, polydimethylsiloxane-treated silica, and combinations thereof.

[0113] In certain embodiments, at least one medium-sized silica comprises a first medium-sized silica that is alkylsilane-treated silica and a second medium-sized silica that is polydimethylsiloxane-treated silica.

[0114] The surface additive formulation comprises at least one large-sized crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, and the at least one large-sized crosslinked organic polymer additive is provided at a surface coverage of 5 to 29 percent of the toner parent particle surface area.

[0115] As used herein, a large-sized crosslinked organic polymer additive means a crosslinked organic polymer additive having a volume average primary particle size of 75 to 120 nanometers, or 80 to 120 nanometers.

[0116] When the toner parent particles have a total surface area of 100 percent, the large-sized crosslinked organic polymer additive is provided, in embodiments, at a surface coverage of 5 to 29 percent, or 5 to 15 percent, of the toner parent particle surface area.

[0117] In an embodiment, the large particle size crosslinked organic polymer additive is a highly crosslinked polymer additive. In an embodiment, the large particle size crosslinked organic polymer additive is a copolymer comprising a first monomer having a high carbon to oxygen ratio of about 3 to about 8 and a second monomer containing two or more vinyl groups, wherein the second monomer is present in the copolymer in an amount greater than about 8 wt% to about 60 wt% based on the weight of the copolymer. In an embodiment, the copolymer further comprises a third monomer containing an amine, and this third monomer is present in an amount of about 0.5 wt% to about 5 wt% based on the weight of the copolymer.

[0118] The large particle size crosslinked organic polymer additive, also referred to herein as a polymer toner additive, or a copolymer, or a copolymer toner additive, is in an embodiment a latex formed using emulsion polymerization. The latex comprises at least one monomer having a high carbon to oxygen (C / O) ratio combined with a monomer having two or more vinyl groups and combined with a monomer containing an amine functional group. The aqueous latex is then dried and can be used in place of, or in combination with, other toner additives. The use of the high C / O ratio monomer provides good relative humidity (RH) stability, and the use of the amine functional monomer provides desirable charge control properties to the resulting toner composition. The use of a monomer having two or more vinyl groups, sometimes referred to herein in embodiments as a crosslinking monomer or a crosslinking vinyl monomer, provides crosslinking characteristics to the polymer, thereby providing the mechanical robustness required for developer containment. For further details, see U.S. Patent Application No. 16 / 369,013, which is incorporated herein by reference in its entirety. For further details, also see U.S. Patent Application No. 16 / 369,126, which is incorporated herein by reference in its entirety.

[0119] As used herein, a polymer or copolymer is defined by the monomers from which the polymer is made. Thus, for example, in a polymer made using an acrylate monomer as a monomer reagent, although the acrylate moiety itself no longer exists for the polymerization reaction, when used herein, the polymer is said to contain the acrylate monomer. Thus, the organic polymer additives made by the processes disclosed herein can be prepared, for example, by the polymerization of monomers including cyclohexyl methacrylate, divinylbenzene, and dimethylaminoethyl methacrylate. The resulting organic polymer additive can be said to contain cyclohexyl methacrylate when the monomer was used to make the organic polymer additive, and can be said to consist of or contain divinylbenzene when divinylbenzene is the monomer reagent of the polymer, and so on. Thus, herein, a polymer is defined based on one or more of the constituent monomer reagents that provide a means for naming the organic polymer additives herein.

[0120] As described above, the polymer additive may be a latex. In an embodiment, the latex copolymer utilized as a polymer surface additive may include a first monomer such as acrylate or methacrylate having a high C / O ratio. The C / O ratio of such a monomer may be about 3 to about 8, in an embodiment about 4 to about 7, or about 5 to about 6. In an embodiment, the monomer having a high C / O ratio may be an aliphatic cycloacrylate. Suitable aliphatic cycloacrylates that can be utilized for the formation of the polymer additive include, for example, cyclohexyl methacrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, isobornyl acrylate, benzyl methacrylate, phenyl methacrylate, combinations thereof, and the like.

[0121] A first monomer having a high carbon-to-oxygen ratio, in embodiments cycloacrylate, may be present in the copolymer utilized as a polymer additive in any suitable or desired amount. In embodiments, cycloacrylate may be present in the copolymer in an amount of about 40 wt% to about 99.4 wt% of the copolymer, or about 50 wt% to about 95 wt% of the copolymer, or about 60 wt% to about 95 wt% of the copolymer. In embodiments, the first monomer is present in the copolymer in an amount of about 40 wt% to about 90 wt% based on the weight of the copolymer, or about 45 wt% to about 90 wt% based on the weight of the copolymer.

[0122] The copolymer toner additive also includes a second monomer, the second monomer includes a crosslinking monomer, and in embodiments, the second monomer includes a crosslinking monomer having a vinyl group, and in certain embodiments, two or more vinyl groups.

[0123] Examples of monomers having a vinyl group suitable for use as the crosslinking vinyl-containing monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy / diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 - butylene glycol dimethacrylate, 1,6 - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy / diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy / polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, combinations thereof, and the like. In certain embodiments, the crosslinking monomer is divinylbenzene.

[0124] The copolymer toner additive herein includes a second monomer that results in a copolymer toner additive that is a highly crosslinked copolymer. In embodiments, the second monomer containing two or more vinyl groups is present in the copolymer in an amount of greater than about 8 wt% to about 60 wt% based on the weight of the copolymer, or greater than about 10 wt% to about 60 wt% based on the weight of the copolymer, or greater than about 20 wt% to about 60 wt% based on the weight of the copolymer, or greater than about 30 wt% to about 60 wt% based on the weight of the copolymer. In certain embodiments, the second monomer is present in the copolymer in an amount of greater than about 40 wt% to about 60 wt%, or greater than about 45 wt% to about 60 wt% based on the weight of the copolymer.

[0125] The copolymers of the present specification optionally further include a third monomer containing an amine functional group. Monomers having an amine functional group can be derived from acrylates, methacrylates, combinations thereof, etc. In embodiments, suitable amine-functional monomers include dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, combinations thereof, and the like.

[0126] In embodiments, the copolymers of the present specification do not contain a third monomer. In other embodiments, the copolymers of the present specification contain a third monomer containing an amine-functional monomer. The amine-functional monomer, when present, may be present in the copolymer in an amount of about 0.1 wt% to about 40 wt% of the copolymer, or about 0.5 wt% to about 5 wt% of the copolymer, or about 0.5 wt% to about 1.5 wt% of the copolymer.

[0127] In embodiments, the copolymer additive includes cyclohexyl methacrylate as a hydrophobic monomer and divinylbenzene as a crosslinkable monomer. In certain embodiments, the copolymer additive includes cyclohexyl methacrylate as a hydrophobic monomer, divinylbenzene as a crosslinkable monomer, and dimethylaminoethyl methacrylate as a nitrogen-containing monomer.

[0128] Methods for forming the copolymer toner surface additive are within the purview of those skilled in the art and, in embodiments, include emulsion polymerization of the monomers utilized to form the polymer additive.

[0129] In the polymerization process, the reactants may be added to a suitable reactor such as a mixing vessel. An appropriate amount of starting materials may optionally be dissolved in a solvent, an optional initiator may be added to the solution, and it may be contacted with at least one surfactant to form an emulsion. The copolymer may be formed in the emulsion (latex), which is then recovered and can be used as a polymer additive for the toner composition.

[0130] When used, suitable solvents include water and / or organic solvents such as toluene, benzene, xylene, tetrahydrofuran, acetone, acetonitrile, carbon tetrachloride, chlorobenzene, cyclohexane, diethyl ether, dimethyl ether, dimethylformamide, heptane, hexane, methylene chloride, pentane, combinations thereof, and the like, but are not limited thereto.

[0131] In an embodiment, the latex for forming the polymer additive may be prepared in an aqueous phase containing a surfactant or co-surfactant, optionally under an inert gas such as nitrogen. The surfactant that may be utilized with the resin to form the latex dispersion may be an ionic or non-ionic surfactant in an amount of about 0.01 to about 15 weight percent of the solid, and in an embodiment, about 0.1 to about 10 weight percent of the solid.

[0132] Examples of anionic surfactants that can be used include sulfates and sulfonates, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, dialkylbenzene alkyl sulfates and sulfonates, acids such as abietic acid available from Aldrich, Neogen R (trademark), Neogen SC (trademark) obtained from Dai-ichi Kogyo Seiyaku Co., Ltd., combinations thereof, and the like. Other suitable anionic surfactants include, in embodiments, DOWFAX (trademark) 2A1, an alkyldiphenyloxide disulfonate from Dow Chemical Company, and / or Teika Power BN2060 from Teika Corporation (Japan), which are sodium branched dodecylbenzenesulfonates. Combinations of these surfactants with any of the aforementioned anionic surfactants may be utilized in embodiments.

[0133] Examples of cationic surfactants include, but are not limited to, ammonium, such as alkylbenzyldimethylammonium chloride, dialkylbenzene alkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, C12, C15, C17 trimethylammonium bromide, combinations thereof, and the like. Other cationic surfactants include cetylpyridinium bromide, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL (registered trademark) and ALKAQUAT (registered trademark) available from Alkaril Chemical Company, SANISOL (benzalkonium chloride) available from Kao Chemicals, combinations thereof, and the like. In embodiments, suitable cationic surfactants include SANISOL B-50 available from Kao Corp., which is mainly benzyl dimethyl alkonium chloride.

[0134] Examples of non-ionic surfactants include, but are not limited to, alcohols, acids, and ethers, such as polyvinyl alcohol, polyacrylic acid, metallocose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, combinations thereof, and the like. In embodiments, surfactants commercially available from Rhone-Poulenc, such as IGEPAL CA-210 (trademark), IGEPAL CA-520 (trademark), IGEPAL CA-720 (trademark), IGEPAL CO-890 (trademark), IGEPAL CO-720 (trademark), IGEPAL CO-290 (trademark), IGEPAL CA-210 (trademark), ANTAROX 890 (trademark), and ANTAROX 897 (trademark) can be utilized.

[0135] The selection of a particular surfactant or combination thereof, as well as the respective amounts used, are within the knowledge of those skilled in the art.

[0136] In an embodiment, a reaction initiator may be added for the formation of the latex used for the formation of the polymer additive. Examples of suitable reaction initiators include water-soluble reaction initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate, and organic solvent-soluble reaction initiators containing organic peroxides, and azo compounds containing Vazo peroxides such as VAZO 64 (trademark), 2-methyl-2,2'-azobispropionitrile, VAZO 88 (trademark), 2,2'-azobisisobutyramide anhydride, and combinations thereof. Other water-soluble initiators that can be utilized include azoamidine compounds such as 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[N-(4-hydroxyphenyl)-2-methyl-propionamidine] dihydrochloride, 2,2'-azobis[N-(4-amino-phenyl)-2-methylpropionamidine] tetrahydrochloride, 2,2'-azobis[2-methyl-N(phenylmethyl)propionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-2-propenylpropionamidine dihydrochloride, 2,2'-azobis[N-(2-hydroxy-ethyl)2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, and combinations thereof, etc.

[0137] The initiator can be added in a suitable amount, for example, from about 0.1 to about 8 weight percent, or from about 0.2 to about 5 weight percent of the monomer.

[0138] When forming the emulsion, any means within the understanding of those skilled in the art can be utilized to combine the starting materials, surfactants, optional solvents, and optional initiators. In embodiments, the reaction mixture can be mixed for about 1 minute to about 72 hours, in embodiments about 4 hours to about 24 hours, while maintaining the temperature at about 10°C to about 100°C, or about 20°C to about 90°C, or about 45°C to about 75°C.

[0139] Those skilled in the art will understand that the optimization of reaction conditions, temperature, and initiator loading can be varied to produce polymers of various molecular weights, and that structurally related starting materials can be polymerized using equivalent techniques.

[0140] The resulting latex having the polymer additive of the present disclosure can have a C / O ratio of about 3 to about 8, in embodiments about 4 to about 7.

[0141] The resulting latex has the polymer additive of the present disclosure and can be applied to toner particles using any means within the contemplation of those skilled in the art. In embodiments, the toner particles may be immersed in or sprayed with the latex containing the polymer additive and thus coated therewith, and the coated particles can then be dried to leave the polymer coating thereon.

[0142] In other embodiments, when the copolymer utilized as an additive for toner is formed, it can be recovered from the latex by any technique within the contemplation of those skilled in the art, including filtration, drying, centrifugation, spray drying, combinations thereof, and the like.

[0143] In an embodiment, once obtained, the copolymer utilized as an additive for toner can be dried into a powder form by any method within the purview of one skilled in the art, including, for example, freeze drying, optionally spray drying in a vacuum, combinations thereof, and the like. Next, the dried polymer additive of the present disclosure can be applied to toner particles using any means within the purview of one skilled in the art, including, without limitation, mechanical shock and / or electrostatic attraction.

[0144] The particles of the copolymer can have an average or median particle size (d50) of from about 70 nanometers to about 250 nanometers in diameter, or from about 80 nanometers to about 200 nanometers in diameter, or from about 80 to about 120 nanometers, or from about 80 to about 115 nanometers. Advantageously, the teachings of the present disclosure facilitate reaching the desired particle size, the size of the copolymer described herein in the embodiment.

[0145] In an embodiment, the copolymer used as a polymer additive is not soluble in solvents such as tetrahydrofuran (THF) due to its highly cross-linked nature. Thus, the number average molecular weight (Mn) or weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) cannot be measured.

[0146] The copolymer utilized as a polymer additive can have a glass transition temperature (Tg) of from about 85°C to about 140°C, or in an embodiment, from about 100°C to about 130°C. In an embodiment, the A-zone charge of the toner containing the polymer additive of the present disclosure can be from about -15 to about -80 microcoulombs per gram, or in an embodiment, from about -20 to about -60 microcoulombs per gram, while the J-zone charge of the toner containing the polymer additive of the present disclosure can be from about -15 to about -80 microcoulombs per gram, or in an embodiment, from about -20 to about -60 microcoulombs per gram.

[0147] The polymer composition of the present disclosure may be combined with toner particles such that the polymer composition is present in any suitable or desired amount, in embodiments, in an amount of about 0.1 wt% to about 5 wt%, or about 0.2 wt% to about 4 wt%, or about 0.5 wt% to about 1.5 wt% based on the weight of the toner particles. In embodiments, the polymer composition is provided to coat about 5 to about 29 percent, or about 5 to about 15 percent of the surface area of the toner particles. In embodiments, the polymer composition is provided to coat about 10 to about 30 percent of the surface area of the toner particles.

[0148] The polymer additive thus produced may optionally be combined with a toner resin with a colorant to form the toner of the present disclosure.

[0149] The surface additive formulation includes at least one positively chargeable surface additive.

[0150] In an embodiment, the surface additive formulation is at least one positively charged surface additive, and this at least one positively charged surface additive is (a) a titanium dioxide surface additive having a volume average primary particle size of 15 to 40 nanometers, where the titanium dioxide is present in an amount of 1 part or less per 100 based on 100 parts of toner parent particles, the toner parent particles further contain small particle size silica having a volume average primary particle size of 8 to 16 nanometers, and the small particle size silica is present with a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positively charged metal oxide surface additive, where this non-titanium dioxide positively charged metal oxide surface additive has a volume average primary particle size of 8 to 30 nanometers, the non-titanium dioxide positively charged metal oxide surface additive is present with a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, the toner parent particles optionally further contain small particle size silica having a volume average primary particle size of 8 to 16 nanometers, and the small particle size silica is present with a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area, and includes at least one positively charged surface additive which is a non-titanium dioxide positively charged metal oxide surface additive. In an embodiment, the non-titanium dioxide positively charged metal oxide surface additive is a metal oxide containing at least one member of the group consisting of Bronsted bases, Lewis bases, and amphoteric compounds.

[0151] In an embodiment, the toner surface additive formulation does not contain titanium dioxide, that is, it does not contain titanium dioxide or contains a reduced amount of titanium dioxide compared to a conventionally known toner additive formulation. In an embodiment, the toner additive formulation includes a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, where the titanium dioxide is present in an amount of 1 part or less per 100 based on 100 parts of toner parent particles. In this embodiment, the toner additive formulation may further include small particle size silica having an average primary particle size of 8 to 16 nanometers, where this small particle size silica is present with a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area.

[0152] Titanium dioxide can be selected from any suitable or desired titanium dioxide having a desired particle size, such as JMT-150IB manufactured by Tayca Corp. having a volume average particle size of 15 nanometers, JMT2000 manufactured by Tayca Corp. having a particle size of 15×15×40 nanometers, T805 manufactured by Evonik having a volume average particle size of about 21 nanometers, SMT5103 manufactured by Tayca Corporation having a particle size of about 40 nanometers, and STT-100H manufactured by Inabata America Corporation having an average particle size of about 40 nanometers. See U.S. Patent Nos. 8,163,450, 8,916,317, 8,507,166, and 7,300,734, each of which is incorporated herein by reference in its entirety.

[0153] As used herein, small particle size silica means silica having an average volume primary particle size of 8 to 16 nanometers.

[0154] When the toner parent particles have 100 percent total surface area, the small particle size silica is provided, in embodiments, with a surface area coverage of 0 to 75 percent of the toner parent particle surface area, or, in embodiments, 5 to 75 percent of the toner parent particle surface area, or 30 to 75 percent of the toner parent particle surface area.

[0155] The small particle size silica can be selected from any suitable or desired silica having a desired particle size, such as RY200L available from Evonik Industries. In embodiments, the small particle size silica is selected from the group consisting of alkylsilane-treated silica, polydimethylsiloxane-treated silica, and combinations thereof. In embodiments, examples of the small particle size silica include treated silica Wacker HDK® H13TD (16 nm, PDMS), HDK® H13TM (16 nm, HMDS), HDK® H13TX (16 nm, HMDS / PDMS), HDK® H20TD (12 nm, PDMS), HDK® H20TM (12 nm, HMDS), HDK® H20TX (12 nm, HMDS / PDMS), HDK® H30TD (8 nm, PDMS), HDK® H30TM (8 nm, HMDS), HDK® H30TX (8 nm, HMDS / PDMS), HDK® H3004 (12 nm, HMDS), Evonik R972 (16 nm, DDS), RY200S (16 nm, PDMS), R202 (16 nm, PDMS), R974 (12 nm, DDS), RY200 (12 nm, PDMS), RX200 (12 nm, HMDS), R8200 (12 nm, HMDS), R805 (12 nm, alkylsilane), R104 (12 nm, alkylsilane), RX300 (8 nm, HMDS), R812 (8 nm, HMDS), R812S (8 nm, HMDS), and R106 (8 nm, alkylsilane), and Cabot TS530 (8 nm, HMDS).

[0156] In an embodiment, the toner surface additive formulation contains a non-titanium dioxide positively chargeable metal oxide surface additive. The non-titanium dioxide positively chargeable metal oxide surface additive can be any suitable metal oxide additive that provides positive chargeability. The positively chargeable metal oxide additive can be so identified by an additive manufacturer or additive vendor. In an embodiment, an additive that is either a Bronsted base or a Lewis base is a suitable positively chargeable metal oxide additive. Suitable positively chargeable metal oxide additives also include amphoteric compounds. Amphoteric means that the material has both acidic and basic groups such that the compound acts as either a Bronsted acid and Bronsted base, or a Lewis acid and Lewis base. In an embodiment, the positively chargeable metal oxide surface additive includes at least one member of the group consisting of Bronsted bases, Lewis bases, and amphoteric compounds. Purely acidic compounds such as silica are not suitable for positive chargeability. In some embodiments, silica can be treated with a basic or amphoteric surface treatment to be suitable as a positively chargeable metal oxide additive. Examples of such basic treatments include, for example, NR2 / NR3 +Bases include, where R is, in embodiments, an alkyl group such as the alkyl group of Wacker positively charged silica. One such known positively charged treatment suitable for silica having a basic functional group is aminopropyltriethoxysilane. Metal oxides that are either basic or amphoteric include metal oxides having an oxidation state of 3 for amphoteric oxides or 2 for basic oxides. Note that some metal oxides having 2 can be considered amphoteric. Thus, both TiO2 and ZnO2 are basic oxides, but they still have some amphoteric characteristics. Other examples of basic metal oxides having an oxidation state of 2 include CaO, MgO, FeO, CrO, and MnO. Examples of amphoteric inorganic materials suitable as positive additives are BeO, Al2O3, GA2O3, In2O3, Tl2O3, GeO2, SnO, SnO2, PbO, PBO2, AS2O3, Sb2O3, Bi2O3, and Fe2O3. Titanates are oxides composed of two different metals, titanium in the +2 or +4 oxidation state and another metal in the +2 oxidation state. Ti in the +4 oxidation state is acidic, while the metal in the +2 oxidation state is basic. Thus, titanates based on Ti+4 are amphoteric and, in embodiments, are suitable as positively charged metal oxide additives. Examples of suitable titanates include CaTiO3, BaTiO3, MgTiO3, MnTiO3, and SrTiO3. Aluminum titanate Al2TiO5 having Al in the +3 oxidation state and Ti in the +2 oxidation state is amphoteric and is similarly suitable as a positively charged metal oxide additive. In embodiments, the non-titanium dioxide positively charged surface additive is selected from the group consisting of aluminum oxide, strontium titanate, and combinations thereof. In embodiments, the non-titanium dioxide positively charged surface additive is aluminum oxide. In embodiments, the non-titanium dioxide positively charged metal oxide additive is an additive containing a nitrogen-containing molecular structure.

[0157] The non-titanium dioxide positively charged metal oxide surface additive can be surface-treated. In an embodiment, the non-titanium dioxide positively charged metal oxide surface additive is selected from the group consisting of alkylsilane-treated aluminum oxide, polydimethylsiloxane-treated aluminum oxide, and combinations thereof. In a particular embodiment, the alkylsilane treatment of the non-titanium dioxide positively charged metal oxide surface additive may contain amino groups such as, for example, amines, imides, or amides. In an embodiment, as a specific positively charged surface additive, there are Wacker-treated silica HDK® H13TA (16 nm, PDMS-NR2 / NR3 + )、HDK® H30TA (8 nm, PDMS-NR2 / NR3 + )、HDK® H2015EP (12 nm, PDMS-NR2 / NR3 + )、HDK® H2050EP (10 nm, PDMS-NR2 / NR3 + )、HDK® H2150VP (10 nm, PDMS-NR2 / NR3 + )、HDK® H3050VP (8 nm, PDMS-NR2 / NR3 + ), Cabot TG-820 F (8 nm), Evonik C805 (13 nm, octylsilane), Aluminum Oxide C (13 nm, untreated), Aeroxide Alu C 100 (10 nm, untreated), Aeroxide Alu C 130 (13 nm, untreated), Cabot SpectrAL 81 (21 nm, untreated), and Cabot SpectrAl 100 (18 nm, untreated), and the like.

[0158] In an embodiment, the total surface area coverage rate of all of the combined surface additives is 100 to 140 percent of the toner parent particle surface area. The toner parent particles are toner particles that do not contain external additives.

[0159] Preparation of toner.

[0160] Toner particles can be prepared by any method within the purview of those skilled in the art. Embodiments regarding the manufacture of toner particles are described below with respect to the emulsion aggregation process, although each disclosure incorporates by reference in its entirety U.S. Patent Nos. 5,290,654 and 5,302,486, and any suitable method for preparing toner particles, including chemical processes such as the suspension method and the encapsulation method disclosed therein, may be used. In embodiments, the toner composition and toner particles may be prepared by an aggregation and coalescence process, in which small resin particles are aggregated to an appropriate toner particle size and then coalesced to achieve the final toner particle shape and morphology.

[0161] In embodiments, the toner composition can be prepared by an emulsion aggregation process, such as a process that includes aggregating a mixture of an optional wax and any other desired or necessary additives with an emulsion optionally containing the resin in the surfactant described above, and then coalescing the aggregated mixture. The mixture may be prepared by adding an optional wax or other material (which may optionally be in a dispersion (s) containing a surfactant) to an emulsion (which may be a mixture of two or more emulsions containing the resin). The pH of the resulting mixture can be adjusted, for example, with an acid such as acetic acid or nitric acid. In embodiments, the pH of the mixture can be adjusted to about 2 to about 4.5. Additionally, in embodiments, the mixture may be homogenized. When the mixture is homogenized, the homogenization may be achieved by mixing at about 600 to about 4,000 revolutions per minute. The homogenization may be achieved by any suitable means, including, for example, an IKA ULTRA TURRAX® T50 probe homogenizer.

[0162] Following the preparation of the above mixture, a flocculant may be added to the mixture. Any suitable flocculant may be utilized to form toner. Suitable flocculants include, for example, aqueous solutions of divalent or polyvalent cationic materials. Flocculants include, for example, polyaluminum halides such as polyaluminum chloride (PAC), or corresponding bromides, fluorides, or iodides, polyaluminum silicates such as polyaluminum sulfosilicate (PASS), and water-soluble metal salts including aluminum chloride, aluminum nitrite, aluminum sulfate, calcium chloride, calcium nitrite, calcium oxyacid, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, and combinations thereof. In an embodiment, the flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

[0163] The flocculant may be added to the mixture in an amount to form toner in the mixture in an amount of about 0.1 wt% to about 8 wt% of the resin in the mixture, in an embodiment about 0.2% to about 5 wt%, and in other embodiments about 0.5% to about 5 wt%. This provides a sufficient amount of the agent for flocculation.

[0164] To control the flocculation and coalescence of the particles, in an embodiment, the flocculant may be metered into the mixture over time. For example, the agent may be metered into the mixture over about 5 to about 240 minutes, in an embodiment about 30 to about 200 minutes. The addition of the agent may be carried out while maintaining the mixture under stirring conditions of about 50 rpm to about 1,000 rpm, in an embodiment about 100 rpm to about 500 rpm, and at a temperature below the glass transition temperature of the resin of about 30°C to about 90°C, in an embodiment about 35°C to about 70°C.

[0165] The particles may be aggregated until a predetermined desired particle size is obtained. The predetermined desired size refers to the desired particle size obtained when determined before formation, and the particle size is monitored during the growth process until such a particle size is reached. Samples may be taken during the growth process and analyzed for average particle size, for example, with a Coulter Counter. Thus, aggregation may proceed by maintaining a high temperature, or by slowly raising the temperature, for example, from about 40°C to about 100°C, and holding the mixture at this temperature for about 0.5 hour to about 6 hours, in embodiments about 1 to about 5 hours, while continuing stirring, to provide aggregated particles. When the predetermined desired particle size is reached, the growth process is stopped. In embodiments, the predetermined desired particle size is within the toner particle size range described above.

[0166] Growth and shaping of the particles after addition of the aggregating agent can be achieved under any suitable conditions. For example, growth and shaping may be performed under conditions where aggregation occurs separately from coalescence. For another aggregation stage and coalescence stage, the aggregation process may be carried out under shear conditions at a high temperature, for example, from about 40°C to about 90°C, which may be below the glass transition temperature of the resin, in some embodiments from about 45°C to about 80°C.

[0167] In embodiments, a shell may be applied to the aggregated particles after aggregation but before coalescence.

[0168] Resins that can be utilized to form the shell include, but are not limited to, the amorphous resins described above for use in the core. Such amorphous resins may be low molecular weight resins, high molecular weight resins, or combinations thereof. In embodiments, the amorphous polyester of formula I above can be cited as an amorphous resin that can be used to form the shell according to the present disclosure.

[0169] In some embodiments, the amorphous resin used to form the shell may be crosslinked. For example, crosslinking can be achieved by combining the amorphous resin with a crosslinking agent, which is sometimes referred to herein as a reaction initiator in embodiments. Examples of suitable crosslinking agents include, but are not limited to, free radical or thermal reaction initiators such as the above-mentioned organic peroxides and azo compounds that are suitable for forming a gel within the core.Examples of suitable organic peroxides include diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, and benzoyl peroxide; ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; alkyl peroxy esters such as t-butyl peroxy neodecanoate, 2,5-dimethyl 2,5-di(2-ethylhexanoylperoxy)hexane, t-amyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxyacetate, t-amyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, co-t-butyl o-isopropyl monoperoxycarbonate, 2,5-dimethyl 2,5-di(benzoylperoxy)hexane, co-t-butyl o-(2-ethylhexyl) monoperoxycarbonate, and co-t-amyl o-(2-ethylhexyl) monoperoxycarbonate; alkyl peroxides such as dicumyl peroxide, 2,5-dimethyl 2,5-di(t-butylperoxy)hexane, t-butyl cumyl peroxide, α-α-bis(t-butylperoxy)diisopropylbenzene, di-t-butyl peroxide, and 2,5-dimethyl 2,5-di(t-butylperoxy)hexyne-3; alkyl hydroperoxides such as 2,5-dihydroperoxy 2,5-dimethylhexane, cumene hydroperoxide, t-butyl hydroperoxide, and t-amyl hydroperoxide; and alkyl peroxyketals such as n-butyl 4,4-di(t-butylperoxy)valerate, 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, ethyl 3,3-di(t-butylperoxy)butyrate, and ethyl 3,3-di(t-amylperoxy)butyrate, and combinations thereof.Examples of suitable azo compounds include 2,2'-azobis(2,4-dimethylpentanenitrile), azobisisobutyronitrile, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'-azobis(cyanocyclohexane), other similar known compounds, and combinations thereof.

[0170] The crosslinking agent and the amorphous resin may be combined at a sufficient temperature for a sufficient time to form a crosslinked polyester gel. In an embodiment, the crosslinking agent and the amorphous resin are heated to a temperature of about 25°C to about 99°C, in an embodiment about 30°C to about 95°C, for a time of about 1 minute to about 10 hours, in an embodiment about 5 minutes to about 5 hours, to form a crosslinked polyester resin or polyester gel suitable for use as a shell.

[0171] When used, the crosslinking agent may be present in an amount of about 0.001% by weight to about 5% by weight of the resin, in an embodiment about 0.01% by weight to about 1% by weight of the resin. The amount of CCA can be reduced in the presence of a crosslinking agent or a reaction initiator.

[0172] A single polyester resin may be utilized as the shell, or as described above, in an embodiment, a first polyester resin may be combined with other resins to form the shell. The plurality of resins may be utilized in any suitable amount. In an embodiment, the first amorphous polyester resin, such as the low molecular weight amorphous resin of Formula I above, may be present in an amount of about 20% to about 100% by weight of the total shell resin, in an embodiment about 30% to about 90% by weight of the total shell resin. Thus, in an embodiment, the second resin, in an embodiment the high molecular weight amorphous resin, may be present in the shell resin in an amount of about 0% to about 80% by weight of the shell resin, in an embodiment about 10% to about 70% by weight of the shell resin.

[0173] Following aggregation to the desired particle size and optional application of a shell, the particles may then be conformed to the desired final shape, which may be achieved, for example, by heating the mixture to a temperature of from about 45°C to about 100°C, in embodiments from about 55°C to about 99°C (this temperature may be above the glass transition temperature of the resin utilized to form the toner particles), and / or reducing the agitation, for example, to from about 100 rpm to about 400 rpm, in embodiments from about 200 rpm to about 300 rpm. The fused particles may be measured for shape factor or circularity using, for example, a SYSMEX FPIA 2100 analyzer until the desired shape is achieved.

[0174] Conformation may be achieved over a time of from about 0.01 to about 9 hours, in embodiments from about 0.1 to about 4 hours.

[0175] In embodiments, after aggregation and / or conformation, the pH of the mixture may be lowered, for example with an acid, to from about 3.5 to about 6, in embodiments from about 3.7 to about 5.5, to further conform the toner aggregates. Suitable acids include, for example, nitric acid, sulfuric acid, hydrochloric acid, citric acid, and / or acetic acid. The amount of acid added may be from about 0.1 to about 30 weight percent of the mixture, in embodiments from about 1 to about 20 weight percent of the mixture.

[0176] The mixture may be cooled, washed, and dried. Cooling may be over a temperature of from about 20°C to about 40°C, in embodiments from about 22°C to about 30°C, and over a time of from about 1 hour to about 8 hours, in embodiments from about 1.5 hours to about 5 hours.

[0177] In an embodiment, the cooling of the combined toner slurry may include rapid cooling by, for example, adding a cooling medium such as ice or dry ice and performing rapid cooling to a temperature of about 20°C to about 40°C, and in an embodiment, about 22°C to about 30°C. The rapid cooling may be achievable for a small amount of toner, for example, less than about 2 liters, and in an embodiment, about 0.1 liter to about 1.5 liters. For example, in a larger scale process such as where the size exceeds about 10 liters, rapid cooling of the toner mixture may not be achievable or practical by either introducing a cooling medium into the toner mixture or using jacket cooling of the reactor.

[0178] Next, the toner slurry can be washed. The washing may be performed at a pH of about 7 to about 12, and in an embodiment, about 9 to about 11. The washing may be at a temperature of about 30°C to about 70°C, and in an embodiment, about 40°C to about 67°C. The washing may include filtering and reslurrying a filter cake containing toner particles in deionized water. The filter cake may be washed one or more times with deionized water, or the pH of the slurry may be adjusted with an acid to a pH of about 4 followed by one deionized water wash and optionally one or more additional deionized water washes.

[0179] Drying may be performed at a temperature of about 35°C to about 75°C, and in an embodiment, about 45°C to about 60°C. The drying may continue until the moisture level of the particles is below the set target of about 1 wt%, and in an embodiment, less than about 0.7 wt%.

[0180] The surface additive formulations described herein can be blended with the toner particles after formation. The surface additive formulations can be applied to the toner particles using any means within the scope of those skilled in the art, including but not limited to mechanical impaction and / or electrostatic attraction.

[0181] In an embodiment, the toner process of this specification includes contacting at least one resin, an optional wax, an optional colorant, and an optional aggregating agent, heating to form aggregated toner particles, optionally adding a shell resin to the aggregated toner particles and heating to a higher temperature to fuse the particles together, and adding a surface additive, where the surface additive is at least one medium-sized particle silica surface additive having an average primary particle size of 30 to 50 nanometers, and this at least one medium-sized particle silica is provided with a surface area coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large-sized particle crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, and this at least one large-sized particle crosslinked organic polymer additive is provided with a surface area coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positive chargeable surface additive, where this at least one positive chargeable surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, where titanium dioxide is present in an amount of 1 part or less per 100 based on 100 parts of the toner parent particles, and the toner parent particles further contain small-sized particle silica having an average primary particle size of 8 to 16 nanometers, and the small-sized particle silica is present with a surface area coverage rate of 5 to 75 percent of the toner parent particle surface area, or (b) a non-titanium dioxide positive chargeable metal oxide surface additive, where this non-titanium dioxide positive chargeable metal oxide surface additive has an average primary particle size of 8 to 30 nanometers, and the non-titanium dioxide positive chargeable metal oxide surface additive is present with a surface area coverage rate of 5 to 15 percent of the toner parent particle surface area, and the toner parent particles optionally further contain small-sized particle silica having an average primary particle size of 8 to 16 nanometers, and the small-sized particle silica is present with a surface area coverage rate of 0 to 75 percent of the toner parent particle surface area; including and adding a surface additive where the total surface area coverage rate of all the combined surface additives is 100 to 140 percent of the toner parent particle surface area, and optionally recovering the toner particles.It is a toner process.

[0182] In an embodiment, the toner of the present disclosure may be utilized as an ultra-low melt (ULM) toner. In an embodiment, the dry toner particles having a core and / or a shell may have one or more of the following characteristics, excluding external surface additives.

[0183] (1) The volume average diameter (also referred to as "volume average particle size") is about 3 to about 25 micrometers (μm), in an embodiment about 4 to about 15 μm, and in other embodiments about 5 to about 12 μm.

[0184] (2) Number Average Geometric Size Distribution (GSDn) and Volume Average Geometric Size Distribution (GSDv): In an embodiment, the toner particles described in (1) above may have a narrow particle size distribution with a low number ratio GSD, such as about 1.15 to about 1.38, and in other embodiments less than about 1.31. The toner particles of the present disclosure may also have a size such that the upper GSD by volume ranges from about 1.20 to about 3.20, and in other embodiments from about 1.26 to about 3.11. The volume average particle size D50V, GSDv, and GSDn can be measured by a measuring instrument such as a Beckman Coulter Multisizer 3 operated according to the manufacturer's instructions. Representative sampling may be performed as follows: Obtain a small amount (about 1 gram) of toner sample, filter it through a 25 micrometer sieve, then place it in an isotonic solution to obtain a concentration of about 10%, and then measure the sample with a Beckman Coulter Multisizer 3.

[0185] (3) Shape factor SFl of about 105 to about 170, in an embodiment about 110 to about 160 *a. Using a scanning electron microscope (SEM), shape factor analysis of toner can be performed by SEM and image analysis (IA). The average particle shape is quantified by using the following shape factor (SFl * a) as defined by the formula.

[0186] SFl * a = 1007πd 2 / (4A)

[0187] where A is the area of the particle and d is its major axis. Perfectly circular or spherical particles have a shape factor of exactly 100. The shape factor SFl * a increases as the shape becomes more irregular or elongates into a shape with a higher surface area.

[0188] (4) Circularity of about 0.92 to about 0.99, or about 0.94 to about 0.975 in other embodiments. The instrument used to measure the circularity of the particles may be the FPIA - 2100 manufactured by SYSMEX, in accordance with the manufacturer's instructions.

[0189] The characteristics of the toner particles can be determined by any suitable technique and apparatus and are not limited to the above - mentioned instruments and techniques.

[0190] The toner particles thus formed can be incorporated into a developer composition. The toner particles can be mixed with carrier particles to obtain a two - component developer composition. The toner concentration in the developer can be about 1 wt% to about 25 wt% of the total weight of the developer, or in an embodiment, about 2 wt% to about 15 wt% of the total weight of the developer.

[0191] Examples of carrier particles that can be used for mixing with toner include particles that can triboelectrically acquire a charge of the opposite polarity to that of the toner particles. Exemplary examples of suitable carrier particles include granular zircon, granular silicon, glass, steel, nickel, ferrite, iron ferrite, silicon dioxide, and the like. Other carriers include those disclosed in U.S. Patent Nos. 3,847,604, 4,937,166, and 4,935,326.

[0192] The carrier particles selected may be used with or without a coating. In an embodiment, the carrier particles may include a core having a coating thereon, and this core may be formed from a mixture of polymers that are not in close proximity in the triboelectric system. The coating may include fluoropolymers, such as polyvinylidene fluoride-based resins, terpolymers of styrene, methyl methacrylate, and / or silanes, such as triethoxysilane, tetrafluoroethylene, and other known coatings. For example, a coating containing polyvinylidene fluoride available, for example, as KYNAR 301F (trademark) and / or polymethyl methacrylate having a weight average molecular weight of about 300,000 to about 350,000 as available, for example, from Soken may be used. In an embodiment, polyvinylidene fluoride and polymethyl methacrylate (PMMA) may be mixed in a ratio of about 30 to about 70 wt% to about 70 to about 30 wt%, and in an embodiment, about 40 to about 60 wt% to about 60 to about 40 wt%. The coating may have a coating weight of, for example, about 0.1 to about 5 wt% of the carrier, and in an embodiment, about 0.5 to about 2 wt% of the carrier.

[0193] In an embodiment, PMMA may optionally be copolymerized with any desired comonomer, provided that the resulting copolymer retains a suitable particle size. Suitable comonomers include monoalkyl or dialkyl amines, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, or t-butylaminoethyl methacrylate. The carrier particles can be prepared by mixing the polymer and the carrier core in an amount of about 0.05 to about 10 wt%, in an embodiment about 0.01 to about 3 wt%, based on the weight of the coated carrier particles, until they adhere to the carrier core by mechanical impact and / or electrostatic attraction.

[0194] The polymer can be applied to the surface of the carrier core particles using various effective and suitable means, such as cascade roll mixing, tumbling, milling, vibration, electrostatic powder cloud spraying, fluidized bed, electrostatic disk treatment, electrostatic curtain, combinations thereof, etc. The mixture of the carrier core particles and the polymer can then be heated to allow the polymer to melt and fuse to the carrier core particles. The coated carrier particles can then be cooled and subsequently classified to the desired particle size.

[0195] In an embodiment, a suitable carrier may be a steel core having a diameter of about 25 to about 100 μm, in an embodiment about 50 to about 75 μm, coated with a conductive polymer mixture containing, for example, about 0.5 wt% to about 10 wt%, in an embodiment about 0.7 wt% to about 5 wt%, of, for example, methyl acrylate and carbon black, using the processes described in U.S. Patent Nos. 5,236,629 and 5,330,874.

[0196] The carrier particles can be mixed with the toner particles in various suitable combinations. The concentration can be about 1 wt% to about 20 wt% of the toner composition. However, different toner and carrier percentages can be used to obtain a developer composition having the desired properties.

[0197] The toner can be used in an electrophotographic or electronic photographic process. In embodiments, any known type of developing system can be used in a developing device, including, for example, magnetic brush development, jumping single component development, hybrid scavengeless development (HSD), and the like. These and similar development systems are within the purview of those skilled in the art.

[0198] The imaging process includes preparing an image with an electrophotographic device, which includes, for example, a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fixing component. In embodiments, the developing component may include a developer prepared by mixing a carrier with the toner composition described herein. The electrophotographic device may include a high-speed printer, a black-and-white high-speed printer, a color printer, and the like.

[0199] When an image is formed with toner / developer via a suitable developing method such as any one of the methods described above, the image can then be transferred to an image receiving medium such as paper. In embodiments, the toner may be used for development in a developing device that utilizes a fuser roll member. The fuser roll member is a contact fusing device within the purview of those skilled in the art and can use heat and pressure from the roll to fuse the toner to the image receiving medium. In embodiments, the fuser member may be heated to a temperature above the fixing temperature of the toner, for example, about 70°C to about 160°C, in embodiments, about 80°C to about 150°C, and in other embodiments, about 90°C to about 140°C, during or after melting onto the image receiving substrate.

[0200] In embodiments where the toner resin is crosslinkable, such crosslinking can be achieved by any suitable method. For example, the toner resin may be crosslinked to a substrate on which the toner resin is crosslinkable at the fixing temperature during fixing of the toner. Crosslinking can also be achieved by heating the molten image, for example, in a post-melting operation, to a temperature at which the toner resin is crosslinked. In embodiments, crosslinking can be achieved at a temperature of about 160 °C or less, in embodiments, about 70 °C to about 160 °C, and in other embodiments, about 80 °C to about 140 °C.

Examples

[0201] The following examples are presented to further define various types of the present disclosure. These examples are intended for illustration only and are not intended to limit the scope of the present disclosure. Also, unless otherwise specified, ratios and percentages are by weight.

[0202] Crosslinked organic polymer surface additive.

[0203] A crosslinked organic polymer additive latex was prepared on a 300 - gallon scale. The latex was prepared via emulsion polymerization using a monomer mixture containing 74.2 wt% cyclohexyl methacrylate (CHMA), 25 wt% divinylbenzene (DVB), and 0.8 wt% dimethylaminoethyl methacrylate (DMAEMA). To prepare the latex, an aqueous phase of 433.5 kg of distilled water and 0.96 kg of sodium lauryl sulfate was added to a 300 - gallon reactor. An emulsified monomer was separately prepared using 221 kg of distilled water, 5.91 kg of sodium lauryl sulfate, 126.5 kg of cyclohexyl methacrylate, 42.5 kg of divinylbenzene, and 1.36 g of dimethylaminoethyl methacrylate (DMAEMA). 5 wt% (19.8 kg) of the emulsified monomer was added to the aqueous phase in the 300 - gallon reactor and allowed to act as a seed for polymerization. Then, the 300 - gallon reactor was heated to a polymerization temperature of 77 °C. Separately, an initiator solution of 0.645 kg of ammonium persulfate was prepared with 18.2 kg of distilled water. Then, the reactor solution was added to the reactor. After the initiator addition was complete, the remainder of the emulsified monomer was added over 2 hours. After the addition of the emulsified monomer was complete, the latex was heated according to the following protocol: 1 hour at 77 °C, heated to 87 °C over 2 hours, and 2 hours at 87 °C. During heating, a 0.4% NaOH solution was added as needed to maintain a pH of about 5 - 6. Then, the latex was cooled to room temperature. The final latex was 95 nanometers (nm) in size. The latex was spray - dried under drying conditions using a dual - liquid nozzle DL41 spray dryer manufactured by Yamato Scientific Co., with an atomization pressure of 4 kgf / cm 2 , a sample feed rate setting of 3, a temperature of 140 °C, and an aspirator flow rate of 4 m 3 / min. The dried crosslinked organic polymer additive is represented as COPA in the examples.

[0204] Measurement protocol.

[0205] As described in Table 1, 50 grams of toner and toner surface additives were added to an SKM blender and then blended at approximately 12,500 rpm for approximately 30 seconds to perform the toner additive blend for all toners. Black Xerox® 700 Digital Color Press emulsion aggregation parent toner was used for these blends.

[0206] The toner charging of all toners blended with the surface additive package was performed according to the following procedure. 5 pph of toner (1.5 grams) was added into 30 grams of Xerox® 700 carrier in a 60 mL glass bottle. Samples were conditioned for 3 days in a low humidity zone (Zone J) at 21.1 °C and 10% relative humidity and in another sample in a high humidity zone (Zone A) at approximately 28 °C / 85% relative humidity. The developer was charged for 60 minutes using a Turbula mixer.

[0207] The charge of all toners was measured as the charge-to-mass ratio (Q / M) by the total blow-off charging method of measuring the charge of the Faraday cage containing the developer after removing the toner by blow-off in an air stream. The total charge collected in the cage was divided by the mass of the toner removed by blow-off by weighing the cage before and after blow-off to obtain the Q / M ratio. The charge of the toner was also measured in the form of the charge-to-diameter ratio Q / D. Q / D was measured using a charge spectrogram with an electric field of 100 V / cm and visually measured as the midpoint of the toner charging distribution. The charge was reported as the millimeter value of the displacement from the zero line (mm displacement can be converted to femtocoulomb / micron (fC / μm) by multiplying by 0.092).

[0208] Measurement of toner blocking.

[0209] For toners blended with a surface additive, the blocking of all toners was determined by measuring the toner cohesive force at a high temperature above room temperature. The measurement of toner blocking was completed as follows. Toner blended with 2 grams of the additive was weighed into an open dish and conditioned in an environmental chamber at a specific high temperature and 50% relative humidity. After 17 hours, the samples were taken out and allowed to equilibrate under ambient conditions for about 30 minutes. Each re-equilibrated sample was measured by sieving through two pre-weighed mesh sieves stacked as follows: 1000 μm on top and 106 μm on the bottom. The sieves were vibrated using a Hosokawa flow tester at an amplitude of about 1 mm for about 90 seconds. After vibration was completed, the sieves were re-weighed, and toner blocking was calculated as a percentage of the starting weight from the total amount of toner remaining on both sieves. Thus, for a 2-gram toner sample, when A is the weight of the toner remaining on the top 1000-μm sieve and B is the weight of the toner remaining on the bottom 106-μm sieve, the toner blocking rate is calculated as blocking % = 50(A + B).

[0210] Measurement of toner flow cohesion.

[0211] For all toners, 2 grams of blended toner under laboratory ambient conditions was placed on the top screen within a stack of three pre-weighed mesh sieves, which were stacked in a Hosokawa flow tester as follows: 53 μm on the top, 45 μm in the middle, and 38 μm on the bottom. Vibration with an amplitude of 1 mm was applied to the stack for 90 seconds. The flow cohesion % is calculated as % cohesion = (50 × A + 30 × B + 10 × C).

[0212] Table 1 shows the surface additive compositions, and Table 2 shows the measured values of charging, blocking, and fluid agglomeration for all examples and comparative examples. The SAC (surface area coverage ratio) of each additive in the table, as well as the total SAC of all additives except for the optional additives added to BCR and photoreceptor cleaning, 0.18% zinc stearate, and 0.2% strontium titanate, are calculated. Since these cleaning additives can be varied independently for cleaning without significantly affecting the charge, blocking, and flow properties, they can be ignored in the discussion of the following examples.

[0213] All of the additive packages in Table 1 preferably have less than 1% titanium dioxide. All packages have either a first medium particle size silica and a second medium particle size silica, or a large particle size silica or an organic polymer additive. Comparative Example 1 has titania, medium particle size silica, and large particle size silica, but no small particle size silica, resulting in a high additive filling weight percentage of 5.8 wt%. Since the cost of the additive is based on weight, this additive package is expensive. Also, the large particle size silica is the most expensive additive. However, for good blocking and aging performance in a printer, it is desirable to keep the SAC relatively high, ideally at least 100%. Therefore, it is difficult to reduce the cost of the additive while maintaining the required SAC.

[0214] Comparative Example 2 adds small particle size silica to the design of Comparative Example 1, but reduces the medium particle size silica and increases the titanium dioxide. These changes maintain a similar SAC as desired for good aging performance, but reduce the total weight percentage of the additives, thereby improving the cost. The developer performance shown in the table is the same as that of Comparative Example 1.

[0215] Example 1 with titania is the same additive formulation as Comparative Example 2, except that the large-particle-size silica is replaced by an organic polymer additive. The results are the same SAC as in Comparative Example 2. Since the overall total additive loading is lower than that of Comparative Example 2, this example has a lower-cost additive formulation. Also, since the organic polymer additive is less expensive in weight percent than the large-particle-size silica, the cost of this additive formulation is further reduced. The developer performance of this additive formulation is the same as in the comparative examples, with a slightly lower blocking temperature of about 1 °C, improved RH sensitivity of the charge, and a desirable higher A-zone / J-zone charge ratio.

[0216] Example 2 replaces all of the titania with aluminum oxide C805 as a positively charged metal oxide additive and replaces the large-particle-size silica with a crosslinked organic polymer additive. This toner does not have small-particle-size silica. To increase the SAC, the medium-particle-size silica content is increased, and as a result, the final total SAC is higher than in the other examples. Such a higher SAC may have some benefit for stabilizing the aging performance in a printer. Due to this higher SAC, the total weight percent of the additive without optional additives is higher than in the other examples. Compared to Comparative Example 1, the higher SAC would tend to make this additive package more expensive, but this is offset by the lower cost of the organic polymer additive relative to the very expensive large-particle-size silica. This design has the same performance as the comparative examples, with the advantages of a slightly better blocking of 1 °C, the best RH sensitivity, and no titanium dioxide at all.

[0217] Example 3 has the same additive formulation as Example 1, except that the titania is replaced with the positively charged aluminum oxide additive C805. The additive loading in weight % is lower than that of Comparative Example 2 and lower than that of Example 1, but has a similar SAC. Also, Example 3 uses a less expensive organic polymer additive to replace the large particle size silica of the comparative examples. Thus, Example 3 is the least expensive additive formulation while maintaining the desirable high SAC. The performance is very similar to the comparative examples, except that the blocking is slightly worse.

[0218] Comparative Example 4 has the same additive formulation as Example 3, except that large particle size silica is used instead of the organic polymer additive. To maintain the same SAC, more large particle size silica is used, resulting in a higher additive loading than Example 3. Also, since large particle size silica is the most expensive additive and is more expensive than the organic polymer additive, Comparative Example 4 is more expensive than Example 3. The performance is similar to the other comparative examples, except that the blocking is worse. The blocking is the same as in Example 3.

Table 1

Table 2

[0219] It will be understood that various of the features and functions disclosed above, as well as alternatives thereof, may be combined in other different systems or applications. Also, various presently unforeseen or unprecedented alternatives, modifications, variations, or improvements may be made by those skilled in the art, and these are also intended to be encompassed by the following "claims". Unless specifically recited in the claims, the steps or components of the claims should not be implied or construed from this specification or any other claims with respect to a particular order, number, position, size, shape, angle, color, or material.

Claims

Claim 1 A toner comprising: toner parent particles including at least one resin in combination with an optional colorant and an optional wax; a surface additive formulation comprising: at least one medium particle size silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein the at least one medium particle size silica is provided at a surface coverage rate of 40 to 100 percent of the toner parent particle surface area; at least one large particle size crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein the at least one large particle size crosslinked organic polymer additive is provided at a surface coverage rate of 5 to 29 percent of the toner parent particle surface area; at least one positively chargeable surface additive, wherein the at least one positively chargeable surface additive is: either (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein the titanium dioxide is present in an amount of 0.3 parts or less per 100 parts of the toner parent particles, the toner parent particles further contain small particle size silica having an average primary particle size of 8 to 16 nanometers, and the small particle size silica is present at a surface coverage rate of 5 to 75 percent of the toner parent particle surface area; or (b) a non-titanium dioxide positively chargeable metal oxide surface additive having an average primary particle size of 8 to 30 nanometers, wherein the non-titanium dioxide positively chargeable metal oxide surface additive is present at a surface coverage rate of 5 to 15 percent of the toner parent particle surface area, the toner parent particles optionally further contain small particle size silica having an average primary particle size of 8 to 16 nanometers, the small particle size silica is present at a surface coverage rate of 0 to 75 percent of the toner parent particle surface area, and the non-titanium dioxide positively chargeable metal oxide surface additive is selected from the group consisting of aluminum oxide, strontium titanate, alkylsilane-treated aluminum oxide, polydimethylsiloxane-treated aluminum oxide, and combinations thereof, the at least one positively chargeable surface additive. A toner comprising a surface additive blend in which the total surface area coverage rate of all of the combined surface additives is 100 to 140% of the toner parent particle surface area.

2. The toner according to claim 1, wherein the at least one medium particle size silica includes two or more medium particle size silicas, and the two or more medium particle size silicas include surface-treated medium particle size silicas selected from the group consisting of alkylsilane-treated silica, polydimethylsiloxane-treated silica, and combinations thereof.

3. The toner according to claim 1, wherein the at least one medium particle size silica includes a first medium particle size silica that is alkylsilane-treated silica and a second medium particle size silica that is polydimethylsiloxane-treated silica.

4. The at least one large particle size crosslinked organic polymer additive is a copolymer, a first monomer having a high carbon to oxygen ratio of 3 to 8, a second monomer containing two or more vinyl groups, the second monomer being present in the copolymer in an amount of more than 8% by weight to 60% by weight based on the weight of the copolymer, and optionally a third monomer containing an amine, the third monomer being present in an amount of 0.5% by weight to 5% by weight based on the weight of the copolymer, the toner according to claim 1, which is a copolymer containing the third monomer.

5. The first monomer of the copolymer includes aliphatic cycloacrylates selected from the group consisting of cyclohexyl methacrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, and combinations thereof. The second monomer of the copolymer includes a member of the group consisting of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy / diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 - butylene glycol dimethacrylate, 1,6 - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy / diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy / polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and combinations thereof. The toner according to claim 4, wherein the third monomer includes a member of the group consisting of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, and combinations thereof.

6. The toner according to claim 1, wherein the non - titanium dioxide positive - chargeable metal oxide surface additive is selected from the group consisting of metal oxides including at least one member of the group consisting of Bronsted bases, Lewis bases, and amphoteric compounds.

7. The toner according to claim 1, wherein the non - titanium dioxide positive - chargeable metal oxide surface additive is silica treated with a basic or amphoteric surface treatment.

8. The toner according to claim 1, wherein the small - particle - size silica is present and is selected from the group consisting of alkylsilane - treated silica, polydimethylsiloxane - treated silica, and combinations thereof.

9. The toner according to claim 1, wherein the small particle size silica is present at a surface area coverage rate of 30 to 75 percent of the surface area of the toner parent particles.

10. The toner according to claim 1, wherein the at least one resin of the toner parent particles includes at least one amorphous polyester and at least one crystalline polyester.

11. The toner according to claim 1, wherein the at least one resin of the toner parent particles includes a first amorphous polyester, a second amorphous polyester different from the first amorphous polyester, and a crystalline polyester.

12. The toner according to claim 1, wherein the at least one resin of the toner parent particles is selected from the group consisting of styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, copolymers thereof, and combinations thereof.

13. The toner includes a core-shell structure, the core includes at least one amorphous polyester and at least one crystalline polyester, the shell includes at least one amorphous polyester, the toner according to claim 1.

14. The toner according to claim 1, wherein the colorant is selected from cyan, magenta, yellow, black, or combinations thereof.

15. A toner process, contacting at least one resin, an optional wax, an optional colorant, and an optional aggregating agent; heating to form aggregated toner particles; optionally adding a shell resin to the aggregated toner particles and heating at a higher temperature to coalesce the particles; adding a surface additive, wherein the surface additive is at least one medium particle size silica surface additive having an average primary particle size of 30 to 50 nanometers, wherein the at least one medium particle size silica is provided at a surface area coverage rate of 40 to 100 percent of the surface area of the toner parent particles; at least one large particle size crosslinked organic polymer additive having an average primary particle size of 75 to 120 nanometers, wherein the at least one large particle size crosslinked organic polymer additive is provided at a surface area coverage rate of 5 to 29 percent of the surface area of the toner parent particles. At least one positively charged surface additive, wherein the at least one positively charged surface additive is (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, wherein the titanium dioxide is present in an amount of 0.3 parts or less per 100 based on 100 parts of the toner parent particles, and the toner parent particles further contain small particle size silica having an average primary particle size of 8 to 16 nanometers, and the small particle size silica is present at a surface coverage rate of 5 to 75 percent of the surface area of the toner parent particles, or (b) a non-titanium dioxide positively charged metal oxide surface additive, wherein the non-titanium dioxide positively charged metal oxide surface additive has an average primary particle size of 8 to 30 nanometers, and the non-titanium dioxide positively charged metal oxide surface additive is present at a surface coverage rate of 5 to 15 percent of the surface area of the toner parent particles, and the toner parent particles optionally further contain small particle size silica having an average primary particle size of 8 to 16 nanometers, and the small particle size silica is present at a surface coverage rate of 0 to 75 percent of the surface area of the toner parent particles, and the non-titanium dioxide positively charged metal oxide surface additive is selected from the group consisting of aluminum oxide, strontium titanate, alkylsilane-treated aluminum oxide, polydimethylsiloxane-treated aluminum oxide, and combinations thereof, at least one positively charged surface additive, and and the total surface coverage rate of all of the combined surface additives is 100 to 140 percent of the surface area of the toner parent particles, adding a surface additive, and optionally, recovering the toner particles, a toner process.

16. The toner process according to claim 15, wherein the at least one medium particle size silica includes two or more medium particle size silicas, and the two or more medium particle size silicas include surface-treated medium particle size silicas selected from the group consisting of alkylsilane-treated silica, polydimethylsiloxane-treated silica, and combinations thereof.

17. The at least one large particle size crosslinked organic polymer additive is a copolymer, and a first monomer having a high carbon to oxygen ratio of 3 to 8, A second monomer containing two or more vinyl groups, wherein the second monomer is present in the copolymer in an amount of more than 8% by weight to 60% by weight based on the weight of the copolymer, a second monomer, Optionally, a third monomer containing an amine, wherein the third monomer is present in an amount of 0.5% by weight to 5% by weight based on the weight of the copolymer, a third monomer, a toner process according to claim 15, which is a copolymer comprising

18. The first monomer of the copolymer contains an aliphatic cycloacrylate selected from the group consisting of cyclohexyl methacrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, and combinations thereof, The second monomer of the copolymer includes a member of the group consisting of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy / diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 - butylene glycol dimethacrylate, 1,6 - hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy / diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy / polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and combinations thereof. The toner process according to claim 17, wherein the third monomer includes a member of the group consisting of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, dibutylaminoethyl methacrylate, and combinations thereof.

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