toner

Abstract

To provide toners exhibiting reduced VOC emission while maintaining excellent printing performance.SOLUTION: Toners are provided which may comprise toner particles, a colorant, and optionally a wax, where the toner particles comprise a resin comprising a polymerization product of reactants comprising a dioxane / dioxolane monomer and a vinyl co-monomer, where the dioxane / dioxolane monomer is an ester of (meth)acrylic acid with an alcohol comprising a dioxane moiety, an ester of (meth)acrylic acid with an alcohol comprising a dioxolane moiety, or both.SELECTED DRAWING: None

Description

[Background technology]

[0001] Many styrene-acrylate resins have been developed and used to provide a variety of toners, generally via emulsion aggregation processes, encompassing a wide range of desirable properties. However, emissions of volatile organic compounds (VOCs) can be a problem in multifunction printers under certain conditions, such as when using such toners in enclosed spaces with limited air circulation or when running at high print speeds for extended periods of time. To address this issue, residual monomer levels have been kept low, processes for making resins and toners have been improved, and carbon filters have been added to printers. Summary of the Invention

[0002] The present disclosure provides latexes comprising resin particles polymerized from dioxane / dioxolane monomers. The latexes can be used to form a variety of compositions, including toners and paints, which are also encompassed by the present disclosure. At least embodiments of the dioxane / dioxolane-based resin particles provide toners that exhibit reduced VOC emissions while maintaining excellent print performance.

[0003] In one aspect, a toner is provided that includes toner particles, a colorant, and optionally a wax, wherein the toner particles include a resin that includes the polymerization product of a reactant that includes a dioxane / dioxolane monomer and a vinyl comonomer, and the dioxane / dioxolane monomer is an ester of (meth)acrylic acid with an alcohol that includes a dioxane moiety, an ester of (meth)acrylic acid with an alcohol that includes a dioxolane moiety, or both.

[0004] Other principal features and advantages of the present disclosure will become apparent to those skilled in the art upon review of the following detailed description and the appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0005] latex

[0006] In one aspect, a latex is provided. Such a latex contains resin particles synthesized from various monomers to form the polymeric material from which the resin particles are composed. At least one type of monomer is used that is an ester of (meth)acrylic acid with an alcohol containing a dioxane moiety or an alcohol containing a dioxolane moiety. (The use of "(meth)," as in, for example, (meth)acrylic acid, refers to both acrylic acid and methacrylic acid.) In the present disclosure, this type of monomer may be referred to as a "dioxane / dioxolane monomer." The term dioxane / dioxolane monomer encompasses both a monomer that is an ester of (meth)acrylic acid with an alcohol containing a dioxane moiety, a monomer that is an ester of (meth)acrylic acid with an alcohol containing a dioxolane moiety, and such monomers. The dioxane moiety may be a 1,3-dioxane moiety, and the dioxolane moiety may be a 1,3-dioxolane moiety. The alcohol containing a dioxane / dioxolane moiety may be an acetal of a triol, a ketal of a triol, or a carbonate of a triol. Exemplary triols include glycerol and trimethylolpropane. Triols can be unsubstituted or substituted. "Substituted" means that one or more bonds to carbon(s) or hydrogen(s) are replaced with bonds to non-hydrogen and non-carbon atoms. Dioxane / dioxolane monomers can have formula I (dioxane) or II (dioxolane) as shown below, where R is selected from hydrogen and methyl, R' is selected from hydrogen and ethyl, and Z is selected from hydrogen, carbonyl, alkyl, aryl, and alkoxy oxygen. Either or both types of monomers can be used in the resin particles. [ka]

[0007] Carbonyl group refers to a C=O group, i.e., Z is O covalently attached to a carbon via a double bond, thereby forming a carbonyl group between the two oxygens of a 5- or 6-membered ring.

[0008] Alkyl groups can be straight-chained or branched. Alkyl groups can have 1 to 20 carbons. This includes groups having 1 to 18 carbons and groups having 1 to 10 carbons, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbons. Alkyl groups can be substituted or unsubstituted. Aryl groups can be monocyclic, having one aromatic ring, such as benzene, or polycyclic, having one or more fused rings. Aryl groups can be unsubstituted or substituted as described above for alkyl groups, but substituted aryl groups also include aryl groups in which a bond to a hydrogen(s) is replaced by a bond to an unsubstituted or substituted alkyl group as described above. An alkoxy group refers to an -O-alkyl group.

[0009] Exemplary dioxane / dioxolane monomers include glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate, and isopropylidene glycerol (meth)acrylate. A single type or a combination of different types of dioxane / dioxolane monomers can be used. However, in embodiments, the dioxane / dioxolane monomer is glycerol formal (meth)acrylate. In this disclosure, the name "glycerol formal (meth)acrylate" (and the names of the other dioxane / dioxolane monomers described in this paragraph) refers to either the dioxane isomer, the dioxolane isomer, or both. That is, all possibilities are encompassed by the name.

[0010] At least one vinyl comonomer is also used to form the resin particles. Exemplary vinyl comonomers include styrene, acrylate, methacrylate, butadiene, and isoprene. Exemplary vinyl comonomers also include acidic and basic monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternary ammonium halides of dialkyl or trialkyl acrylamide or methacrylamide, vinylpyridine, vinylpyrrolidone, and vinyl-N-methylpyridinium chloride. Exemplary vinyl comonomers also include those containing carboxylic acid groups, such as acrylic acid, methacrylic acid, itaconic acid, beta-carboxyethyl acrylate (β-CEA), 2-carboxyethyl methacrylate, maleic acid, and cinnamic acid. A single type or a combination of different types of vinyl comonomers can be used. In embodiments, at least two vinyl comonomers are used, including styrene and an alkyl (meth)acrylate (e.g., methyl (meth)acrylate, ethyl (meth)acrylate), butyl (meth)acrylate), or a combination thereof. Accordingly, the alkyl group of the alkyl (meth)acrylate can have 1 or more carbons, 2 or more carbons, 4 or more carbons, or 1 to 6 carbons. In embodiments, at least three vinyl comonomers are used, including styrene, an alkyl (meth)acrylate, and a vinyl comonomer comprising a carboxylic acid group. In embodiments, the alkyl (meth)acrylate is n-butyl acrylate. In embodiments, the third vinyl comonomer is β-CEA.

[0011] A crosslinking agent can be used to form the resin particles. Exemplary crosslinking agents include decanediol diacrylate (ADOD), trimethylolpropane, pentaerythritol, trimellitic acid, pyromellitic acid, and combinations thereof. The crosslinking agent can also be referred to as a branching agent.

[0012] A chain transfer agent can be used to form the resin particles. The chain transfer agent can be a mercaptan or a thiol. Suitable chain transfer agents include n-dodecylmercaptan (NDM), n-dodecanethiol (DDT), tert-dodecylmercaptan, 1-butanethiol, 2-butanethiol, octanethiol, and combinations thereof. Halocarbons such as carbon tetrabromide, carbon tetrachloride, and combinations thereof can be used as chain transfer agents.

[0013] In embodiments, certain monomers may be excluded when forming the resin particles. The excluded monomers may include one or more of the following: vinyl-imidazolium monomers, urethane (meth)acrylate monomers, and silyl ester monomers such as (meth)acrylic acid triisoproylsilyl ester.

[0014] In forming a latex containing resin particles, various combinations of the above-mentioned monomers can be used in a monomer emulsion that includes a solvent, an initiator (which can be included in the monomer emulsion as described herein or added separately in a separate step(s) during the polymerization process), and optionally one or more of a crosslinker, a chain transfer agent, and a surfactant. Water is commonly used as the solvent, but water-soluble or water-miscible organic solvents (e.g., ethanol) can also be included.

[0015] The types of monomers used in the monomer emulsion and their relative amounts can be selected to tailor the properties of the resin particles. g This includes adjusting the relative amounts of dioxane / dioxolane monomer and vinyl comonomer (including two or three such vinyl comonomers) to achieve a value. Similarly, the presence, type, and amount of crosslinker and chain transfer agent can also be selected to adjust the properties of the resin particles.

[0016] Dioxane / dioxolane monomers may be used in the monomer emulsion in amounts ranging from, for example, 1% to 50%, 5% to 40%, and 5% to 30% by weight, where weight % is the total weight of dioxane / dioxolane monomers divided by the total weight of monomers, crosslinker (if present), and chain transfer agent (if present) in the monomer emulsion. * (The weight percentages refer to 100.) The vinyl comonomer may be used in the monomer emulsion in an amount ranging from 50 to 98 weight percent, 60 to 90 weight percent, and 65 to 85 weight percent, for example, where weight percent is the total weight of the vinyl comonomer / total weight of the monomer, crosslinker (if present), and chain transfer agent (if present) in the monomer emulsion. * (Referring to 100.) In embodiments where multiple types of vinyl comonomers are used, e.g., two or three, the first vinyl comonomer (e.g., styrene) may constitute, e.g., 40% to 95% by weight of the total vinyl comonomer weight, the second vinyl comonomer (e.g., alkyl (meth)acrylate) may constitute, e.g., at least 15%, at least 30%, or 5% to 60% by weight of the total vinyl comonomer weight, and the third vinyl comonomer (e.g., β-CEA) may constitute, e.g., up to 10% by weight of the total vinyl comonomer weight. Other ranges include, e.g., 50% to 80% and 50% to 70% by weight for the first vinyl comonomer, 10% to 50% and 10% to 30% by weight for the second vinyl comonomer, and 0.1% to 8% and 0.1% to 5% by weight for the third vinyl comonomer. In embodiments, with respect to alkyl (meth)acrylates as possible vinyl comonomers, they are present in an amount of at least 15% by weight of the total weight of the monomers, crosslinker (if present), and chain transfer agent (if present) in the monomer emulsion, including at least 20% by weight and at least 25% by weight.

[0017] If used, the crosslinking agent may be present in the monomer emulsion in an amount of, for example, up to 20% by weight, 0.01% to 20% by weight, 0.1% to 5% by weight, where weight % is the total weight of crosslinking agent / total weight of monomers, crosslinking agent, and chain transfer agent (if present) in the monomer emulsion. * (referring to 100).

[0018] When used, the chain transfer agent may be present in the monomer emulsion in an amount of, for example, up to 10% by weight, 0.05% to 10% by weight, 0.25% to 5% by weight, where weight % is (total weight of chain transfer agent) / (total weight of monomer, crosslinker (if present), and chain transfer agent in the monomer emulsion). * (referring to 100).

[0019] The initiator initiates the polymerization reaction between the various monomers in the monomer emulsion. Examples of suitable initiators include water-soluble initiators such as ammonium persulfate (APS), sodium persulfate, and potassium persulfate. Other water-soluble initiators that can be used include azoamidine compounds such as 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[N-(4-hydroxyphenyl)-2-methyl-propionamidine] dihydrochloride, 2,2'-azobis[N-(4-amino-phenyl)-2-methylpropionamidine] tetrahydrochloride, 2,2'-azobis[2-methyl-N(phenylmethyl)propionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-2-propenylpropionamidine] dihydrochloride, 2,2'-azobis[N-(2-hydroxy-ethyl)-2-methylpropionamidine] amidine] dihydrochloride, 2,2'-azobis[2(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-( Examples of initiators include 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. Redox initiators can be used. As noted above, the initiator can be added separately at a separate step or steps in the polymerization process. The initiator can be added as an initiator solution containing the initiator and a solvent, such as water. The amount of initiator used can range from 0.1% to 5% by weight, for example. (Wt % is the total weight of initiator divided by the total weight of monomers in the monomer emulsion.)* 100).

[0020] The surfactant used in the monomer emulsion can be selected from anionic surfactants, cationic surfactants, nonionic surfactants, and combinations thereof. The amount can be, for example, up to 5% by weight, from 0.01% to 5% by weight (wherein weight % is the total weight of surfactants divided by the total weight of monomers in the monomer emulsion). * (Reference is made to 100.) Examples of anionic surfactants include sulfates and sulfonates, disulfonates, such as sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate, and sodium dodecylnaphthalene sulfate; dialkylbenzene alkyl sulfates; acids, such as palmitic acid, and NEOGEN or NEOGEN SC, available from Daiichi Kogyo Seiyaku. Other suitable anionic surfactants include DOWFAX™ 2A1, an alkyldiphenyloxide disulfonate, available from The Dow Chemical Company, and TAYCA POWER BN2060, a branched sodium dodecylbenzenesulfonate, available from Tayca Corporation (Japan).

[0021] Examples of cationic surfactants include alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide, trimethylammonium bromide, halogen salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL® and ALKAQUAT® available from Alkaril Chemical Company, SANISOL® (benzalkonium chloride) available from Kao Chemicals, and the like.

[0022] Examples of nonionic surfactants include polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy)ethanol, etc. Commercially available surfactants from Rhone-Poulenc, such as IGEPAL CA-210™, IGEPAL CA520™, IGEPAL CA-720™, IGEPAL CO-890™, ANTAROX 890™, IGEPAL CO-720™, IGEPAL CO-290™, IGEPAL CA-210™, and ANTAROX 897™, may be selected. Other examples of suitable nonionic surfactants include block copolymers of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC® PR / F and SYNPERONIC® PR / F 108.

[0023] Latex containing resin particles can be prepared using seed emulsion polymerization. Such techniques can involve preparing a surfactant solution in a suitable reactor. In a separate vessel, a monomer emulsion can be prepared having any of the compositions described above, including, for example, dioxane / dioxolane monomer, two or three vinyl comonomers, a chain transfer agent, and a surfactant. An aliquot of the monomer emulsion (e.g., 0.5% to 10% of the total amount of monomer emulsion) can be added to the surfactant solution in the reactor. To enable seed particle formation, an initiator solution can be added to the reactor. An additional amount of monomer emulsion (e.g., the remaining amount) can be fed to the reactor to grow the seeds to the desired size. The reaction conditions used during the steps, such as mixing, heating, etc., are selected to promote polymerization and provide resin particles with the desired properties. Exemplary reaction conditions are described in the examples below. Reaction conditions described in U.S. Patent Nos. 6,841,329 and 7,413,842 can also be used, each of which is incorporated herein by reference in its entirety.

[0024] The seeded emulsion polymerization technique described above provides a latex comprising resin particles dispersed in a solvent. The latex can be used to form any of the toners described herein. However, further processing steps can be used, for example, to recover the resin particles from the solvent. These processing steps can include, for example, filtration, drying, centrifugation, spray drying, freeze drying, etc.

[0025] Resin particles formed by the seeded emulsion polymerization technique described above can be characterized by their composition. As noted above, the polymeric material of the resin particles is the result of a polymerization reaction between various combinations of monomers to form a polymerization product. For clarity, the composition of the polymeric material / resin particles can be identified by reference to the monomers being polymerized and recognizing that the chemical form of these monomers generally changes as a result of the polymerization reaction. The polymerization product, and therefore the resin particles, can include other components present in the emulsion described above. For example, an initiator (or a portion thereof, e.g., a sulfate group) can be incorporated into the beginning and end of the polymer chain. Similarly, crosslinkers, if used, are generally incorporated into the polymer chain. Surfactants, if used, can become entangled with the polymer chain and be embedded within the resin particles due to, for example, strong non-covalent or adsorption forces.

[0026] In embodiments, the resin particles comprise (or consist of) the polymerization product of reactants including a dioxane / dioxolane monomer, a vinyl comonomer, an initiator, and optionally a crosslinker. Any of the dioxane / dioxolane monomers, vinyl comonomers, crosslinkers, and initiators described herein can be used. In embodiments, the resin particles comprise (or consist of) the polymerization product of reactants including a dioxane / dioxolane monomer, two different vinyl comonomers, an initiator, and optionally a crosslinker. In embodiments, the resin particles comprise (or consist of) the polymerization product of reactants including a dioxane / dioxolane monomer, three different vinyl comonomers, an initiator, and optionally a crosslinker. In each of these embodiments, the monomers, crosslinkers, and initiators can be present in the resin particles in the amounts described above. (Experiments have shown that monomer conversion is greater than 99.9%). For example, the amount of dioxane / dioxolane monomer in the resin particles can range from 1% to 50% by weight. As stated above, this weight percent is calculated as follows: (total weight of dioxane / dioxolane monomer) / (total weight of monomer, crosslinker (if present), and chain transfer agent (if present) in the resin particles). * It points to 100.

[0027] In any of the embodiments referenced in the above paragraphs, one or more of the following variations can be used: Glycerol formal methacrylate can be used as the dioxane / dioxolane monomer; Styrene, alkyl (meth)acrylate (e.g., n-butyl acrylate), vinyl comonomers containing carboxylic acid groups (e.g., β-CEA), and combinations thereof can be used as vinyl comonomers; Decanediol diacrylate can be used as the crosslinker.

[0028] Using a specific exemplary composition, the composition of the resin particles may also be identified as poly[(styrene)-ran-(n-butyl acrylate)-ran-(glycerol formal (meth)acrylate)-ran-(β-CEA)], including crosslinked versions thereof. In this description, different chemical moieties resulting from the polymerization reaction are identified by reference to the corresponding monomer within the parentheses, with "ran" referring to the random incorporation of different monomers into the copolymer. Use of this description encompasses the presence of an initiator (or portion thereof) at the start of each copolymer chain and crosslinking via a crosslinker (if present).

[0029] In embodiments in which certain monomers are excluded from forming the resin particles, it follows that such monomers are not involved in the polymerization reaction to form the polymer matrix of the resin particles. Thus, in these embodiments, the composition of the resin particles may be described as being free of (i.e., not including) one or more of vinyl-imidazolium monomers, urethane (meth)acrylate monomers, and silyl ester monomers, such as (meth)acrylic acid triisopropylsilyl ester.

[0030] In embodiments, the latex may be described as being free of (i.e., containing) no resins / polymers other than those provided by the resin of the resin particles of the present invention themselves, including the absence of polyurethanes, polyurethane (meth)acrylates, poly(meth)acrylates (other than the resin particles themselves), polyesters, silyl ester copolymers, silyl (meth)acrylate polymers, or combinations thereof.

[0031] The latex itself is generally not curable because the resin / polymer that makes up the resin particles has already been polymerized, and therefore it is free of (i.e., does not contain) initiator. This does not preclude the presence of small amounts of unreacted or reacted initiator that may be incorporated into the polymer chain. Similarly, the latex may be described as free of (i.e., does not contain) monomer.

[0032] In embodiments, the latex may also be described as being free of (i.e., not including) fungicides / biocides such as medetomidine.

[0033] The water content of the latex can be at least 50% by weight, including at least 60% by weight and at least 70% by weight, where these weight percentages refer to the weight of water compared to the total weight of the latex.

[0034] The resin particles may be characterized by their size. The size of the particles is determined by the D 50 The particle size may be reported as the diameter at which 50% of the sample (by volume) is made up of particles with a diameter less than that diameter value. In embodiments, the resin particles have a D in the range of 100 nm to 400 nm. 50 The particle size includes, for example, the ranges of 100 nm to 300 nm and 200 nm to 350 nm. 50 The particle size may refer to a value measured at a pH range of 2 to 3. 50Particle size can be measured using a Nanotrac 252 instrument. This instrument uses laser light scattering technology to measure the Doppler shift of light generated by each particle in motion (Brownian motion). These shifts generate a signal proportional to the particle's size. The signal is mathematically converted to particle size and size distribution. Analysis can be performed using an external probe or by inserting a probe into a fixed sample chamber. The light scattering technique can be calibrated using NIST polystyrene nanosphere reference samples with diameters ranging from 15 mm to 300 mm, available from Microtrac under the trade name NIST Traceable Reference Material for Nanotrac Particle Size Analyzers.

[0035] The resin particles are heated to their onset glass transition temperature (T g ) T g The value can be measured as described in the Examples below. g is in the range of 40°C to 90°C, which includes the ranges of 45°C to 85°C and 50°C to 75°C.

[0036] The polymeric material (resin) of the resin particles has a weight average molecular weight (M) measured as described in the Examples below. w ) and its number average molecular weight (M n ) M w M can be in the range of 25,000 daltons to 75,000 daltons, including, for example, 30,000 daltons to 70,000 daltons and 40,000 daltons to 60,000 daltons. n can be in the range of 10,000 daltons to 30,000 daltons, including, for example, 15,000 daltons to 25,000 daltons and 20,000 daltons to 30,000 daltons.

[0037] toner

[0038] Any of the above-described latexes can be utilized to form a toner containing toner particles. The composition of the toner particles depends on the composition of the resin particles of the latex(s) used. However, the toner may contain other components such as waxes, colorants, and other additives. In preparing the toner, such waxes, colorants, and other additives can be utilized in a dispersion containing any of the above-described solvents and surfactants.

[0039] wax

[0040] Waxes can be combined with the above-described latexes in forming the toner particles. A single type or a combination of different types of waxes can be used. The waxes can be present in various suitable amounts, such as from about 3% to about 20% by weight of the toner particles in total, including from about 4% to about 20% by weight of the toner particles and from about 5% to about 15% by weight of the toner particles.

[0041] Exemplary waxes include alkylene waxes (e.g., alkylene waxes having 1 to 25 carbon atoms), polyethylene waxes, polypropylene waxes, paraffin waxes, and Fischer-Tropsch waxes (e.g., FNP-0092® available from Nippon Seiro, which contains a Fischer-Tropsch wax containing 42 carbon atoms). Commercially available polypropylenes and polyethylenes from Alliged Chemical and Petrolite Corporation can be used. Wax emulsions available from Michaelman Inc. and Daniels Products Company can be used. Epolene N-15® available from Eastman Chemical Products, Inc.; Viscol 550-P®, a low weight average molecular weight polypropylene available from Sanyo Kasei KK; and similar waxes can be used. Commercially available polyethylenes are believed to have molecular weights of about 1,000 to about 5,000, and commercially available polypropylenes are believed to have molecular weights of about 4,000 to about 10,000.Examples of functionalized waxes that can be used include, for example, amines, amides, such as Aqua Superslip 6550™, Superslip 6530™ available from Micro Powder Inc., fluorinated waxes such as Polyfluo 190™, Polyfluo 200™, Polyfluo 523XF™, Aqua Polyfluo 411™, Aqua Polysilk 19™, Polysilk 14™ available from Micro Powder Inc., mixed fluorinated amide waxes such as Microspersion 19™ also available from Micro Powder Inc., imide, ester, quaternary amine, carboxylic acid or acrylic polymer emulsions such as Joncryl 74™, 89™, 130™, 537™ and 538™, all available from SC Johnson Wax, and Allied Chemical and Petrolite Corporation and SC Johnson. Waxes available from Polyvinyl Chloride, Inc. include chlorinated polypropylene as well as polyethylene available from Polyvinyl Chloride, Inc. A single type or a combination of different types of wax can be used.

[0042] coloring agent

[0043] A colorant can be combined with the latex described above when forming toner particles. A single type or a combination of different types of colorants can be used. Colorants include, for example, pigments, dyes, and mixtures thereof, such as mixtures of dyes, pigments, and mixtures of dyes and pigments. The colorant can be added in an amount sufficient to impart the desired color, hue, and shade. The colorant can be present in a total amount of from about 1% to about 25% by weight of the toner particles, including, for example, from about 1% to about 20% by weight of the toner particles or from about 2% to about 15% by weight of the toner particles.

[0044] Carbon black, available in the form of furnace black, thermal black, etc., is a suitable colorant. Carbon black may be used with one or more other colorants, such as a cyan colorant, to produce a desired hue.

[0045] Examples of cyan pigments include copper tetra(octadecylsulfonamido)phthalocyanine, a copper phthalocyanine colorant identified in the Color Index as CI 74160, HELIOGEN BLUE L6900™, D6840™, D7080™, D7020™, PYLAM OIL BLUE™, PYLAM OIL YELLOW™, and PIGMENT BLUE™ available from Paul Uhlich & Co., Inc., CI Pigment Blue (PB), PB15:3, PB15:4, Anthrazine Blue X-2137 identified as CI 69810, mixtures thereof, and the like.

[0046] Examples of magenta pigments include the disazo dye identified as CI 26050, 2,9-dimethyl-substituted quinacridone, CI 60710, anthraquinone dye identified as CI Dispersed Red 15, CINQUASIA MAGENTA™ available from EI DuPont de Nemours & Co., CI Solvent Red 19, Pigment Red (PR) 122, PR 269, PR 185, mixtures thereof, and the like.

[0047] Examples of yellow colorants include diaryl ylide yellow, 3,3-dichlorobenzidene acetoacetanilide, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, nitrophenylamine sulfonamide identified in the Color Index as Foron Yellow SE / GLN, LEMON CHROME YELLOW DCC 1026™ CI from sanofi, NOVAPERM YELLOW FGL™, Paliogen Yellow 152, 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (sanofi), Permanent Yellow YE 0305 (Paul Uhlich), Pigment Yellow 74, and Lumogen Yellow. D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), SUCD-Yellow D1355 (BASF), Permanent Yellow FGL, Disperse Yellow, 3,2,5-dimethoxy-4-sulfonanilidephenylazo-4'-chloro-2,5-dimethoxyacetanilide, and mixtures thereof.

[0048] Other colorants that may be used include the following: Paliogen Violet 5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Ulrich), Permanent Violet VT2645 (Paul Ulrich), Heliogen Green L8730 (BASF), Argyle Green XP-111-S (Paul Ulrich), Brilliant Green Toner GR 0991 (Paul Ulrich), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD Red (Aldrich), Lithol Rubine Toner (Paul Ulrich), Lithol Scarlet 4440, NBD 3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Ulrich), 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 Paliogen Yellow 152 and 1560 (BASF), Lithol Fast Yellow 0991K (BASF), Paliotol Yellow 1840 (BASF), Novaperm YellowFGL (Hoechst), Permanerit Yellow YE 0305 (Paul Ulrich), Lumogen Yellow D0790 (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 Black L9984 9 (BASF), Pigment Black K801 (BASF) and, in particular, carbon blacks such as REGAL® 330 (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals).

[0049] Additional useful colorants include pigments in aqueous dispersions, such as those commercially available from Sun Chemical, e.g., SUNSPERSE BHD 6011 (Blue 15 Type), SUNSPERSE BHD 9312 (Pigment Blue 15), SUNSPERSE BHD 6000 (Pigment Blue 15:3 74160), SUNSPERSE GHD 9600 and GHD 6004 (Pigment Green 7 74260), SUNSPERSE QHD 6040 (Pigment Red 122), SUNSPERSE RHD 9668 (Pigment Red 185), SUNSPERSE RHD 9365 and 9504 (Pigment Red 57), SUNSPERSE YHD 6005 (Pigment Yellow 83), FLEXIVERSE YFD 4249 (Pigment Yellow 17), SUNSPERSE YHD 6020 and 6045 (Pigment Yellow 74), SUNSPERSE YHD 600 and 9604 (Pigment Yellow 14), FLEXIVERSE LFD 4343 and LFD 9736 (Pigment Black 7). Other useful water-based colorant dispersions include those commercially available from Clariant, such as HOSTAFINE Yellow GR, HOSTAFINE Black T and Black TS, HOSTAFINE Blue B2G, HOSTAFINE Rubine F6B, and magenta dry pigments such as Toner Magenta 6BVP2213 and Toner Magenta EO2, which can be dispersed in water and / or a surfactant before use.

[0050] Other useful colorants include magnetites such as, for example, Mobay magnetite MO8029, MO8960; Columbian magnetite, MAPICO BLACKS and surface-treated magnetite; Pfizer magnetite CB4799, CB5300, CB5600, MCX6369; Bayer magnetite, BAYFERROX 8600, 8610; Northern Pigments magnetite NP-604, NP-608, Magnox magnetite TMB-100 or TMB-104.

[0051] Toner Preparation

[0052] Various techniques can be used to form toner particles for the toner, including emulsion aggregation (EA) processes. In embodiments, the EA process involves aggregating a mixture containing a latex, a colorant, and optionally a wax, and then combining the aggregated mixture. Any of the latices described above can be used, including a single type of latex or a combination of different types of latices, each containing a different type of resin particle. The colorant and wax can be utilized as an aqueous dispersion, as described above. The mixture can be homogenized during the EA process, which can be accomplished by mixing at about 600 to about 6,000 revolutions per minute.

[0053] Flocculation can be achieved by adding any suitable flocculating agent (coagulant) to the mixture. The flocculating agent can be, for example, a polyaluminum halide, such as polyaluminum chloride (PAC), or the corresponding bromide, fluoride, or iodide; a polyaluminum silicate, such as polyaluminum sulfosilicate (PASS); or an inorganic cationic coagulant, such as aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxynitride, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, or a mixture thereof. The flocculating agent acts to dissolve the T of the resin particles of the latex. g The aggregating agent may be added to the mixture at a temperature below 100°C. The aggregating agent may be added to the mixture in any suitable amount, for example, in the range of 0.05% to 5% by weight of the toner particles. The aggregating agent may be added in a solution of nitric acid or a similar acid. To control particle aggregation, the aggregating agent may be metered into the mixture over time, for example, over a period of about 5 minutes to about 240 minutes. The addition of the aggregating agent may be accomplished with continuous homogenization. After addition, the mixture may be further homogenized.

[0054] The particles may be aggregated until a predetermined desired particle size is obtained. The predetermined desired size refers to the desired particle size to be obtained as determined prior to formation, and the particle size may be monitored during the growth process. Samples may be taken during the growth process and D 50 The D of the particles can be analyzed, for example, with a Nanotrac™ 252. The aggregation can be carried out by maintaining the mixture at an elevated temperature, or by slowly increasing the temperature, for example, from about 40°C to about 100°C, and holding the mixture at this temperature for a period of time, for example, from about 0.5 hours to about 10 hours, while maintaining stirring or homogenization, to provide aggregated particles. Once a predetermined desired particle size is reached, the growth process is stopped. The D of the particles can be analyzed by a Nanotrac™ 252 ... 50The particle size can be, for example, about 3 μm to about 10 μm, about 3 μm to about 8 μm, or about 3 μm to about 6 μm.

[0055] Shell Resin

[0056] In embodiments, after aggregation but before coalescence, a resin coating may be applied to the aggregated particles (cores) to form a shell thereon. The shell may be applied by using any of the latices described above. The shell latex may be different from the core latex, but this is not required. The resin particles of the shell latex and the resin particles of the core latex may have, for example, different onset glass transition temperatures T g Value, different M w / M n They may differ from one another by having a molecular weight, being crosslinked or non-crosslinked, and combinations thereof.

[0057] Once the desired final size of the toner particles is achieved, the pH of the mixture can be adjusted with a pH control agent, for example, to a value of about 3 to about 10. Suitable pH control agents include various bases, including alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, and combinations thereof. A chelating agent (sequestering agent) can also be added. Various suitable chelating agents are available, such as ethylenediaminetetraacetic acid (EDTA), salts of EDTA, tartaric acid, gluconol, hydroxyl-2,2'iminodisuccinic acid (HIDS), dicarboxylmethyl glutamic acid (GLDA), methyl glycidyl diacetic acid (MGDA), hydroxydiethyliminodiacetic acid (HDI), and the like. Acid, HIDA), sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate, humic acid, fulvic acid; alkali metal salts of EDTA, gluconic acid, oxalic acid, polyacrylates, sugar acrylates, citric acid, polyaspartic acid, diethylenetriamine, pentaacetate, 3-hydroxy-4-pyridinone, dopamine, eucalyptus, iminodisuccinic acid, ethylenediamine disuccinate, polysaccharides, sodium ethylenedinitrilotetraacetate, thiamine pyrophosphate, farnesyl pyrophosphate, 2-aminoethyl pyrophosphate, hydroxylethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, mixtures thereof, and the like can be used. Various suitable amounts of the chelating agent can be used, for example, from about 0.1% to about 1% by weight of the toner particles, from about 0.2% to about 0.7% by weight of the toner particles, or from about 0.3% to about 0.5% by weight of the toner particles.

[0058] Combine

[0059] Following aggregation and application of a shell (if desired), the particles are coalesced into the desired final shape, which may be achieved, for example, by the addition of a Teflon® or Teflon® to the resin(s) utilized to form the toner particles. g This is achieved by heating the mixture to a temperature of about 80°C to about 110°C, which may be at or above that temperature. The specific temperature selection depends on the resin used. The mixture may be stirred, for example, at about 100 rpm to about 1,000 rpm. Coalescence may be carried out for a period of time, for example, from about 1 minute to about 10 hours. The particles may be coalesced until the desired roundness is achieved. During coalescence, the pH may be adjusted to a value of, for example, about 3 to about 10, using a pH control agent, including various acids such as nitric acid.

[0060] After coalescence, the mixture may be cooled to room temperature, such as from about 20°C to about 25°C. Cooling may be rapid or slow, as desired. During cooling, a pH control agent may be used to adjust the pH, for example, to a value of from about 3 to about 10. After cooling, the toner particles may optionally be washed with water and then dried. Drying may be accomplished by any suitable method, including, for example, freeze-drying.

[0061] Toner particles containing a single type of resin or multiple types of resins are included. Toner particles containing multiple types of resins may contain various relative amounts of the different types of resins. In embodiments, two different types of resins are used, with the first resin being present in an amount of, for example, 25% to 99% by weight of the toner particle and the second resin being present in an amount of, for example, up to 35% by weight of the toner particle. This includes the first resin being present in amounts of 30% to 80% and 40% to 70% by weight, and the second resin being present in amounts of 10% to 50% and 15% to 40% by weight. In embodiments, the first resin forms the core of the toner particle, while the second resin forms the shell of the toner particle.

[0062] The toner particles may contain various total amounts of resin, for example, from about 60% to about 95% by weight of the toner particles, from about 65% to about 90% by weight of the toner particles, or from 75% to about 85% by weight of the toner particles.

[0063] The composition of the toner particles depends on the resin(s) used and therefore follows that described above for the various resin particles.

[0064] Variations of the above exemplary toner preparation processes may be applied, including those described in U.S. Pat. Nos. 6,841,329 and 7,413,842, each of which is incorporated herein by reference in its entirety.

[0065] additives

[0066] The toner can further contain various additives to enhance the properties of the toner. The toner can include, for example, a charge additive in an amount of about 0.1% to about 10% by weight of the toner. Suitable charge additives include alkylpyridinium halides, bisulfates, charge control additives described in U.S. Patent Nos. 3,944,493, 4,007,293, 4,079,014, 4,394,430, and 4,560,635 (each of which is incorporated herein by reference in its entirety), negative charge enhancing additives such as aluminum complexes, any other charge additives, mixtures thereof, and the like.

[0067] The toner may contain surface additives. Surface additives that may be added to the toner particles after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silica, metal oxides, strontium titanate, and mixtures thereof, each of which may be present in an amount of from about 0.1% to about 10% by weight of the toner. Examples of such additives include those disclosed in U.S. Pat. Nos. 3,590,000, 3,720,617, 3,655,374, and 3,983,045, the disclosures of each of which are incorporated herein by reference in their entirety. Other additives include zinc stearate and AEROSIL R972®, available from Degussa. The coated silicas of U.S. Pat. Nos. 6,190,815 and 6,004,714, the disclosures of each of which are incorporated herein by reference in their entirety, may also be selected, for example, in amounts of from about 0.05% to about 5% by weight of the toner; these additives may be added during the aggregation process or blended into the formed toner particles.

[0068] In this disclosure, the phrases "toner" and "toner composition" refer to those compositions configured for use in an electrophotographic printer to form images therewith. Thus, in addition to the resin, colorant, organic additives present, and optionally waxes and others, the toner may include any other ingredients generally used in such compositions to form an object using the desired electrophotographic printer.

[0069] The toner of the present invention may be described as being free of (i.e., free of) any resin other than that provided by the resin of the resin particles of the present invention. This includes the absence of polyurethane, poly(meth)acrylate (other than the resin particles themselves), polyester, or a combination thereof. A single type of resin may be used. Similarly, the toner composition itself is generally not curable, and therefore is free of (i.e., free of) initiator. This does not exclude the presence of small amounts of unused or used initiator from the resin particles that may be incorporated into the polymer chains of the resin particles. Note that any other exclusions referenced above regarding resin particles and latex may apply to embodiments of the toner composition.

[0070] Toner characteristics

[0071] In embodiments, the dry toner particles, excluding external surface additives, have the following properties:

[0072] (1) Volume average particle size D of 2 μm to 20 μm, 5 μm to 15 μm, or 5 μm to 10 μm 50 .

[0073] (2) A number average geometric size distribution (GSDn) and / or a volume average geometric size distribution (GSDv) of 1.05 to 1.35, 1.15 to 1.30, or about 1.20 to 1.15.

[0074] (3) Circularity of 0.92 to 0.99, 0.94 to 0.97, or 0.95 to 0.96 (e.g., as measured by a Sysmex 3000).

[0075] (4) Onset glass transition temperature (T) of 48°C to 85°C, 50°C to 90°C, or 52°C to 85°C g ) (e.g., as measured by differential scanning calorimetry).

[0076] Volume average particle size D50 With respect to GSD, GSDv and GSDn, these properties may be measured using a measuring instrument such as a Nanotrac™ 252 operated according to the manufacturer's instructions.

[0077] Both the latex and toner of the present invention can be characterized by their volatile organic content (VOC). In embodiments, the VOC content is less than 500 ppm as measured by a gas chromatography system equipped with a flame ionization detector. This includes less than 250 ppm, less than 100 ppm, less than 50 ppm, and 1 ppm to 50 ppm. The measurement includes the amount of residual monomer and potential by-products of polymerization, as well as impurities derived from the starting monomer.

[0078] The toners of the present invention may be characterized by their residual aluminum and sodium levels, as measured using Inductively Coupled Plasma (ICP) as described in the Examples below. The aluminum levels may be less than 300 ppm, less than 275 ppm, or less than 250 ppm. The sodium levels may be less than 250 ppm, less than 225 ppm, or less than 200 ppm.

[0079] Developer and carrier

[0080] The toner may be formulated into a developer composition. The developer composition can be prepared by mixing the toner with known carrier particles, including coated carriers such as steel, ferrite, and the like. Such carriers include those disclosed in U.S. Pat. Nos. 4,937,166 and 4,935,326, the entire disclosures of each of which are incorporated herein by reference. The carrier may be present in an amount of from about 2% to about 8% by weight of the toner. The carrier particles may also include a core having a polymer coating, such as polymethylmethacrylate (PMMA), within which a conductive component, such as conductive carbon black, is dispersed. Carrier coatings include silicone resins such as methylsilsesquioxane, fluoropolymers such as polyvinylidene fluoride, mixtures of resins not adjacent in the triboelectric series, such as polyvinylidene fluoride and acrylic, thermosetting resins such as acrylic, combinations thereof, and other known components.

[0081] Toner can be incorporated into a number of devices, ranging from enclosures or containers, such as flexible containers like vials, bottles, bags, or packages, to devices that perform functions beyond storage. Toner can also be incorporated into dedicated devices, for example, for delivery of the same for purposes such as forming an image. Accordingly, specialized toner delivery devices are available; see, for example, U.S. Pat. No. 7,822,370. Such devices include cartridges, tanks, reservoirs, and the like, and may be replaceable, disposable, or reusable. Such devices may include storage portions; dispensing or delivery portions, etc.; along with various ports or openings that allow for the addition and removal of toner from the device; optional portions for monitoring the amount of toner within the device; and formed or molded portions to allow the device to rest and seat, for example, within an imaging device. The toner of interest can be included in devices dedicated to its delivery, for example, to recharge or replenish toner within imaging device components, such as cartridges, where the imaging device components require replaceable or reusable toner (see, for example, U.S. Pat. No. 7,817,944).

[0082] Imaging

[0083] The toners can be used in electrophotographic processes, including those disclosed in U.S. Pat. No. 4,295,990, the disclosure of which is incorporated herein by reference in its entirety. In embodiments, any known type of development system can be used in the image development device, including, for example, magnetic brush development, jumping single-component development, two-component development, hybrid scavengeless development (HSD), etc. These and similar development systems are within the purview of those skilled in the art.

[0084] The imaging process includes, for example, preparing an image with an electrophotographic device including a charging component, an imaging component, a photoconductive component, a development component, a transfer component, and a fusing component. In embodiments, the development component may include a developer prepared by mixing a carrier with a toner composition described herein. The electrophotographic device may include a high-speed printer, a high-speed black and white printer, a color printer, etc.

[0085] Once the image has been formed with the toner / developer via a suitable development method, such as any one of the methods described above, the image may then be transferred to an image receiving medium, such as paper. In embodiments, the toner may be used for development in a development device utilizing a fuser roll member. A fuser roll member is a contact fusing device within the contemplation of those skilled in the art that can fuse the toner to the image receiving medium using heat and pressure from a roll. In embodiments, the fuser member may be heated to a temperature above the fixing temperature of the toner, for example, from about 70° C. to about 160° C., after or during fusing onto the image receiving substrate.

[0086] The use of the latex / resin particles of the present invention is not limited to providing toner. By way of example, a latex can be used to provide a latex paint. In addition to water and any of the disclosed resin particles, latex paints generally include a colorant. Any of the disclosed colorants can be used. Often, a surfactant, such as any of the surfactants disclosed herein, is also included. Other additives that may be included include fillers, such as inorganic particles (e.g., silica), dispersants, defoamers, wetting agents, viscosity-adjusting additives, waxes, coalescents, and the like. These additives can be present in any amount to achieve the desired properties for the latex paint. Any of the exclusions noted above regarding latex and toner may also apply to latex paint embodiments. [Example]

[0087] The following examples are presented to further define the various classes of the present disclosure. These examples are intended for illustrative purposes only and are not intended to limit the scope of the present disclosure. Also, unless otherwise indicated, parts and percentages are by weight. As used herein, "room temperature" refers to a temperature of about 20°C to about 25°C.

[0088] Latex Comparative Example 1

[0089] A latex containing resin particles formed from the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 6.37 kilograms of Dowfax 2A1 (anionic surfactant) and 4096 kg of deionized water was prepared by mixing for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before being transferred to the reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated at a controlled rate to 80°C and held there. Separately, 64.5 kg of ammonium persulfate initiator was dissolved in 359 kg of deionized water. Separately, a monomer emulsion was prepared as follows: 3516.6 kg of styrene, 787.7 kg of butyl acrylate, 129.1 kg of beta-carboxyethyl acrylate (β-CEA), 30.1 kg of 1-dodecanethiol, 15.06 kg of ADOD (1,10-decanediol diacrylate), 85.1 kg of Dowfax 2A1 (anionic surfactant), and 2048 kg of deionized water were mixed to form an emulsion. One percent of the emulsion was then slowly fed into a reactor containing an aqueous surfactant phase at 80°C to form a "seed" while purging with nitrogen. The initiator solution was then slowly dosed into the reactor, and after 10 minutes, the remainder of the monomer emulsion was continuously fed at a rate of 0.5% per minute using a metering pump. After 100 minutes, half of the monomer emulsion was added to the reactor. At this point, 36.18 kilograms of 1-dodecanethiol was stirred into the monomer emulsion, which was continuously fed at a rate of 0.5% per minute. At this point, the reactor agitator was increased to 350 RPM. After all the monomer emulsion was charged to the main reactor, the temperature was held at 80°C for an additional 2 hours to complete the reaction. Full cooling was then applied, reducing the reactor temperature to approximately 35°C. The product was collected in a holding tank. After the latex was dried, the following properties were measured: M w =33,700, M n = 10,900 and the onset glass transition temperature (T g) was 58.6°C. T g was measured. For this measurement, 5-10 mg of the toner sample was placed in an aluminum pan, covered with a lid, and crimped shut. A reference pan and lid were also crimped shut. The sample was placed in the instrument, equilibrated at 0°C, then heated at a controlled heating rate to 150°C, then cooled to 0°C, and then heated at the same rate to 150°C. Heat flow data as a function of temperature was recorded. The glass transition temperature of the sample was determined where the onset of the step transition was reported for the second heat.

[0090] Weight average molecular weight (M w ), number average molecular weight (M n A Water Advanced Polymer Chromatography (APC) instrument was used to determine polymer molecular weight characteristics, including MW and polydispersity (MWD or PDI). The instrument is equipped with a series of separation columns and uses tetrahydrofuran (THF) solvent as the mobile phase. Approximately 25 mg of sample is dissolved in THF, filtered, and then an aliquot is injected into the instrument. The FID detector quantifies the number and mass of various polymer chains as they elute through the column. The instrument is calibrated with a series of polystyrene standards and used to determine the relative molecular weight characteristics of the analyzed samples.

[0091] Latex Comparative Example 2

[0092] A latex containing resin particles formed from the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 0.3352 kilograms of Calfax (anionic surfactant) and 476.9 kg of deionized water was prepared by mixing for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before being transferred to the reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated at a controlled rate to 80°C and held there. Separately, 1.9838 kg of ammonium persulfate initiator was dissolved in 14.96 kg of deionized water. Separately, a monomer emulsion was prepared as follows: 74.5767 kg of styrene, 24.7977 kg of butyl acrylate, 2.9849 kg of β-CEA, 48.11 kg of 1-dodecanethiol, 1.8991 kg of Dowfax 2A1 (anionic surfactant), and 46.9293 kg of deionized water were mixed to form an emulsion. Two percent of the monomer emulsion was then slowly fed into the reactor containing the aqueous surfactant phase at 80°C to form a "seed" while purging with nitrogen. The initiator solution was then slowly dosed into the reactor, and after 10 minutes, the remainder of the emulsion was continuously fed at a rate of 0.5% per minute using a metering pump. After all the monomer emulsion was dosed into the main reactor, the temperature was held at 80°C for an additional two hours to complete the reaction. Full cooling was then applied to reduce the reactor temperature to approximately 35°C. The product was collected in a holding tank. After the latex was dried, the following properties were measured: w = 55,000 ± 3,000, percent solids content is 41%, and T g The temperature was 55°C ± 3°C.

[0093] Latex Comparative Example 3

[0094] A latex containing resin particles formed from the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 605 grams of Dowfax 2A1 (anionic surfactant) and 387 kg of deionized water was prepared by mixing for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before being transferred to the reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated at a controlled rate to 80°C and held there. Separately, 6.1 kg of ammonium persulfate initiator was dissolved in 30.2 kg of deionized water. Separately, a monomer emulsion was prepared as follows: 311.4 kg of styrene, 95.6 kg of butyl acrylate, 12.21 kg of β-CEA, 2.88 kg of 1-dodecanethiol, 1.42 kg of ADOD (1,10-decanediol diacrylate), 8.04 kg of Dowfax 2A1 (anionic surfactant), and 193 kg of deionized water were mixed to form an emulsion. One percent of the monomer emulsion was then slowly fed into a reactor containing an aqueous surfactant phase at 80°C to form a "seed" while purging with nitrogen. The initiator solution was then slowly charged into the main reactor, and after 10 minutes, the remainder of the emulsion was continuously fed into the reactor containing the aqueous surfactant phase at a rate of 0.5% per minute using a metering pump. The temperature was maintained at 80°C for an additional 2 hours to complete the reaction. Full cooling was then applied to reduce the temperature to approximately 35°C. The product was collected in a holding tank. After drying a portion of the latex, the following properties were measured: w =35,419,M n =11,354 and T g was 51.0℃.

[0095] Latex Comparative Example 4

[0096] A latex containing resin particles formed from the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 605 grams of Dowfax 2A1 (anionic surfactant) and 387 kg of deionized water was prepared by mixing for 10 minutes in a stainless steel holding tank. The holding tank was then purged with nitrogen for 5 minutes before being transferred to the reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated at a controlled rate to 80°C and held there. Separately, 6.1 kg of ammonium persulfate initiator was dissolved in 30.2 kg of deionized water. Separately, a monomer emulsion was prepared as follows: 332.5 kg of styrene, 74.5 kg of butyl acrylate, 12.21 kg of β-CEA, 2.88 kg of 1-dodecanethiol, 1.42 kg of dodecanediol diarylate (ADOD), 8.04 kg of Dowfax 2A1, and 193 kg of deionized water were mixed to form an emulsion. One percent of the emulsion was then slowly fed into the main reactor containing the aqueous surfactant phase at 80°C to form a "seed" while purging with nitrogen. The initiator solution was then slowly dosed into the reactor, and after 10 minutes, the remainder of the emulsion was continuously fed at a rate of 0.5% per minute using a metering pump. After all the monomer emulsion was dosed into the reactor, the temperature was held at 80°C for an additional two hours to complete the reaction. Full cooling was then applied, reducing the reactor temperature to approximately 35°C. The product was discharged into a holding tank and dried to give a latex with the following molecular characteristics: w =33,700, M n = 10,900 and T g =58.6℃.

[0097] Latex Example 1: Synthesis of Styrene-Butyl Acrylate-Glycerol Formal Methacrylate Latex

[0098] In a 2 L Buchi reactor equipped with two P4 impellers, 0.57 g of Dowfax 2A1 (at 47% solids) was added to 518 g of deionized water (DIW). The reactor was deoxygenated by passing a stream of nitrogen through it during the reaction. The reactor was heated to 77 °C and the RPM was set to 350. Separately, in a 1 L glass vessel equipped with two P4 impellers, a monomer emulsion was prepared by mixing (at 400 rpm) 86.1 g of glycerol formal methacrylate, 344 g of styrene, 143.5 g of n-butyl acrylate, 17.2 g of b-CEA, 2.7 g of n-dodecyl mercaptan (NDM, formerly known as DDT), 9.81 g of Dowfax 2A1 surfactant (at 47% solids), and 265 g of DIW. 17.4 g of seeds were removed from the monomer emulsion and pumped into a 2 L reactor at 77 °C. An initiator solution prepared from 8.61 g of ammonium persulfate in 24.3 g of DIW was added over 20 min after the seed emulsion was added. The remaining monomer emulsion was fed into the reactor over 120 min. After adding half of the monomer emulsion, the RPM in the reactor was increased to 400 rpm. At the end of the monomer feed, the latex was held for an additional 2 hours and then cooled. The resulting D of 217 nm 50 A latex containing 43% percent solids by particle size was obtained. The T of the dried latex (resin particles) g The temperature was 56.2°C. The residual n-butyl acrylate monomer was 54.81 ppm, the residual styrene monomer was 37.1 ppm, and the residual glycerol formal methacrylate was 20.87 ppm. The weight average molecular weight M w is 52,574, and the number average molecular weight M n was 26,171.

[0099] Comparative Toner Example 1

[0100] 286.9 grams of Comparative Latex 3 (41.4 wt. % solids loading) and 60.49 grams of a wax emulsion containing refined paraffin wax C42 (FNP-0092®, available from Nippon Seiro) (30.50 wt. % solids loading) were added to 613.5 grams of deionized water in a vessel and stirred using an IKA Ultra Turrax® T50 homogenizer operating at 4,000 rpm. 64.1 grams of cyan pigment dispersion PB15:3 (available from Sun Chemical as Sun Pigment W51924) (17 wt. % solids loading) were then added to the reactor, followed by the dropwise addition of 36 grams of a flocculant containing 3.6 grams of a polyaluminum chloride mixture and 32.4 grams of a 0.02 molar nitric acid solution. Upon addition of the flocculant, the homogenizer speed was increased to 5,200 rpm, and the reactor contents were homogenized for an additional 5 minutes. The mixture was then heated at a rate of 1.0°C per minute to a temperature of 52°C and held at 52°C for a period of about 1.5 to about 2 hours, yielding cyan toner particles having a volume average particle size of 5 microns as measured by a Coulter Counter. During the heating period, the agitator was operated at about 250 rpm. Ten minutes after reaching the set temperature of 49°C, the agitator speed was reduced to about 220 rpm.

[0101] Following this step, 134.6 grams of Comparative Latex 4, having a solids loading of 41.6% by weight, was added to the reactor mixture and allowed to aggregate for an additional period of approximately 30 minutes at 51°C to yield cyan toner particles having a volume average particle size of approximately 5.7 microns as measured by a Coulter Counter. The pH of the reactor mixture was adjusted to pH 4.0 using 1.0 M sodium hydroxide solution added to 4.82 grams of ethylenediaminetetraacetic acid (EDTA) Versene™ 100, available from Dow, having a solids loading of 39% by weight. The reactor mixture was then heated to a temperature of 95°C at a rate of 1.0°C per minute. Following this, the reactor mixture was gently stirred at 95°C for 3 hours to allow the particles to coalesce and spheronize. After 1 hour of coalescence, the reactor pH was adjusted to pH 7.0, and the reactor mixture was gently stirred for the remaining 2 hours. The reactor heater was then turned off, and the reaction mixture was allowed to cool to room temperature at a rate of 1.0°C per minute. The resulting toner composition consisted of approximately 16.7 percent toner particles, 0.25 percent anionic surfactant, and approximately 82.9 percent water (all weights based on the total weight of the toner composition). The toner particles consisted of 58 percent by weight styrene / acrylate polymer resin (from Comparative Latex Example 3), approximately 28 percent by weight styrene / acrylate polymer resin (from Comparative Latex Example 4), approximately 5 percent by weight PB15:3 pigment, and approximately 9 percent by weight FNP-0092™ wax, and had a volume average particle size of approximately 5.7 microns and a geometric size distribution (GSD) of approximately 1.19. The toner particles were washed six times, the first at 63°C and pH 10, followed by three washes with deionized water at room temperature, one wash at 40°C and pH 4.0, and finally a final wash with deionized water at room temperature. The final measured aluminum concentration in the dried toner particles was 265 ppm as measured by Inductively Coupled Plasma Emission Spectroscopy (ICP).

[0102] Toner Example 1

[0103] 278 grams of the latex from Example 1 with a solids loading of 42.6% by weight, 75 grams of a wax emulsion containing a Fischer-Tropsch wax (Q436B® available from Cytech) with a solids loading of 30% by weight, and 43 grams of a cyan pigment dispersion (PB15:3 available from Sun Chemical) with a solids loading of 25.6% by weight were added to 630 grams of deionized water in a container and homogenized using an IKA Ultra Turrax® T50 homogenizer operating at 4,000 rpm. During homogenization, 36 grams of a flocculent mixture containing 3.6 grams of polyaluminum chloride mixture and 32.4 grams of 0.02 molar nitric acid solution were added dropwise. The mixture was then heated to a temperature of 52°C at a rate of 1.0°C per minute and held for a period of about 1.5 to about 2 hours, resulting in cyan toner particles with a volume average particle size of 5 microns as measured by a Coulter Counter. During the heating period, the agitator was at 225 rpm until 35°C was reached, at which point the agitator speed was reduced to approximately 200 rpm.

[0104] Following this step, 131.6 grams of the latex from Example 1 was added to the reactor mixture and allowed to aggregate for an additional period of approximately 60 minutes at 56°C to yield cyan toner particles having a volume average particle size of approximately 5.9 microns as measured by a Coulter Counter. The pH of the reactor mixture was adjusted to pH 4.0 using 1.0 M sodium hydroxide solution followed by 4.82 grams of ethylenediaminetetraacetic acid (EDTA) Versene™ 100, available from Dow, with a 39% solids loading by weight. The reactor mixture was then heated to a temperature of 95°C at a rate of 1.0°C per minute. Following this, the reactor mixture was gently stirred at 95°C for 3 hours to allow the particles to coalesce and spheronize. The reactor heater was then turned off and the reaction mixture was allowed to cool from 63°C to room temperature at a rate of 1.0°C per minute. The resulting toner composition consisted of approximately 16.7 percent toner particles, 0.25 percent anionic surfactant, and approximately 82.8 percent water (all weights based on the total weight of the toner composition). The toner particles consisted of 84 percent by weight styrene / acrylate polymer resin (from the latex of Example 1), approximately 5 percent by weight PB15:3 pigment, and approximately 11 percent by weight Q436B wax, and had a volume average particle size of approximately 5.9 microns and a geometric size distribution (GSD) of approximately 1.23. The particles were washed four times, the first at 63°C and pH 9, followed by one wash with deionized water at room temperature, one wash at room temperature and pH 4.0, and finally a final wash with deionized water at room temperature. The final aluminum content was 239.89 ppm and the sodium content was 192.96 ppm in the dried toner particles as measured by inductively coupled plasma emission spectroscopy (ICP). The T for the toner particles was g was 82.32°C, and the onset of decomposition was 355.8°C as determined by thermogravimetric analysis using a TA Instruments Q5000IR TGA system operated with argon gas.

[0105] The word "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Further, for the purposes of this disclosure, unless otherwise specified, "a" or "an" means "one or more."

[0106] Unless already included, all numerical values of parameters in this disclosure are preceded by the term "about," which means approximately. This encompasses the inherent variation in measuring the relevant parameter as understood by one of ordinary skill in the art. It also encompasses the exact value of the disclosed numerical value and any rounding of the disclosed numerical value.

[0107] The foregoing description of exemplary embodiments of the present disclosure has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure to the precise form disclosed, as modifications and variations are possible in light of the above teachings or may be acquired from practice of the present disclosure. The embodiments were chosen and described in order to explain the principles of the present disclosure and to enable those skilled in the art to utilize the disclosure in various embodiments, with various modifications suited to the particular uses contemplated. It is intended that the scope of the present disclosure be defined by the claims appended hereto and their equivalents. The present disclosure includes the following embodiments. (Embodiment 1) 1. A toner comprising toner particles, a colorant, and optionally a wax, wherein the toner particles comprise a resin comprising the polymerization product of a reactant comprising a dioxane / dioxolane monomer and a vinyl comonomer, wherein the dioxane / dioxolane monomer is an ester of (meth)acrylic acid with an alcohol comprising a dioxane moiety, an ester of (meth)acrylic acid with an alcohol comprising a dioxolane moiety, or both. (Embodiment 2) 2. The toner of embodiment 1, wherein the alcohol comprising a dioxane moiety or the alcohol comprising a dioxolane moiety is an acetal of a triol, a ketal of a triol, or a carbonate of a triol. (Embodiment 3) 3. The toner of embodiment 2, wherein the triol is glycerol or trimethylolpropane. (Embodiment 4) the dioxane / dioxolane monomer has Formula I or Formula II, JPEG0007725427000002.jpg75136 2. The toner of embodiment 1, wherein R is selected from the group consisting of hydrogen and methyl, R′ is selected from the group consisting of hydrogen and ethyl, and Z is selected from the group consisting of hydrogen, carbonyl groups, alkyl groups, aryl groups, and oxygen of alkoxy groups. (Embodiment 5) 2. The toner of embodiment 1, wherein the dioxane / dioxolane monomer is selected from the group consisting of glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate, isopropylidene glycerol (meth)acrylate, and combinations thereof. (Embodiment 6) 2. The toner of embodiment 1, wherein the dioxane / dioxolane monomer is glycerol formal (meth)acrylate. (Embodiment 7) 2. The toner of embodiment 1, wherein the dioxane / dioxolane monomer is present in the resin in an amount ranging from about 1% to about 50% by weight. (Embodiment 8) 2. The toner of embodiment 1, wherein the vinyl comonomer comprises an alkyl (meth)acrylate present in the resin in an amount of at least about 15% by weight. (Embodiment 9) 9. The toner of embodiment 8, wherein the alkyl (meth)acrylate is butyl (meth)acrylate. (Embodiment 10) 2. The toner of embodiment 1, wherein the reactants comprise two different types of said vinyl comonomers. (Embodiment 11) 11. The toner of embodiment 10, wherein the two different types of vinyl comonomers are styrene and alkyl(meth)acrylate. (Embodiment 12) 12. The toner of embodiment 11, wherein the alkyl (meth)acrylate is butyl (meth)acrylate. (Embodiment 13) 2. The toner of embodiment 1, wherein the reactants comprise three different types of said vinyl comonomers. (Embodiment 14) 14. The toner of embodiment 13, wherein the three different types of vinyl comonomers are styrene, alkyl (meth)acrylate, and vinyl comonomers containing a carboxylic acid group. (Embodiment 15) 15. The toner of embodiment 14, wherein the alkyl (meth)acrylate is butyl (meth)acrylate and the vinyl comonomer comprising a carboxylic acid group is beta-carboxyethyl acrylate. (Embodiment 16) 2. The toner of embodiment 1, wherein the toner particles have a volume average particle size D50 of about 2 μm to 10 μm. (Embodiment 17) 1. A toner comprising toner particles, a colorant, and optionally a wax, wherein the toner particles comprise a resin comprising the polymerization product of a reactant comprising a dioxane / dioxolane monomer, a vinyl comonomer, and an alkyl (meth)acrylate present in the resin in an amount of at least about 15% by weight, wherein the dioxane / dioxolane monomer is an ester of (meth)acrylic acid with an alcohol containing a dioxane moiety, an ester of (meth)acrylic acid with an alcohol containing a dioxolane moiety, or both. (Embodiment 18) 18. The toner of embodiment 17, wherein the alkyl (meth)acrylate is present in the resin in an amount of at least about 20% by weight. (Embodiment 19) 18. The toner of embodiment 17, wherein the dioxane / dioxolane monomer is glycerol formal (meth)acrylate. (Embodiment 20) 20. The toner of embodiment 19, wherein the vinyl comonomer is styrene and the alkyl (meth)acrylate is butyl (meth)acrylate.

Claims

1. 1. A toner comprising toner particles, a colorant, and optionally a wax, wherein the toner particles comprise a resin comprising the polymerization product of a reactant comprising a dioxane / dioxolane monomer and a vinyl comonomer, and the dioxane / dioxolane monomer is selected from the group consisting of glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate, isopropylidene glycerol (meth)acrylate, and combinations thereof.

2. 10. The toner of claim 1, wherein said dioxane / dioxolane monomer is glycerol formal (meth)acrylate.

3. 10. The toner of claim 1, wherein said dioxane / dioxolane monomer is present in said resin in an amount ranging from about 1% to about 50% by weight.

4. 10. The toner of claim 1, wherein said vinyl comonomer comprises an alkyl (meth)acrylate present in said resin in an amount of at least about 15% by weight.

5. 5. The toner according to claim 4, wherein the alkyl (meth)acrylate is butyl (meth)acrylate.

6. The toner of claim 1 , wherein the reactants include two different types of the vinyl comonomer.

7. 7. The toner of claim 6, wherein the two different types of vinyl comonomers are styrene and alkyl (meth)acrylate.

8. 8. The toner according to claim 7, wherein the alkyl (meth)acrylate is butyl (meth)acrylate.

9. The toner of claim 1 , wherein said reactants comprise three different types of said vinyl comonomers.

10. 10. The toner of claim 9, wherein the three different types of vinyl comonomers are styrene, alkyl (meth)acrylate, and vinyl comonomers containing a carboxylic acid group.

11. 11. The toner of claim 10, wherein said alkyl (meth)acrylate is butyl (meth)acrylate and said vinyl comonomer containing a carboxylic acid group is beta-carboxyethyl acrylate.

12. The toner particles have a volume average particle size D of about 2 μm to 10 μm 50 The toner of claim 1 , wherein

13. 1. A toner comprising toner particles, a colorant, and optionally a wax, wherein said toner particles comprise a resin comprising the polymerization product of a reactant comprising a dioxane / dioxolane monomer, a vinyl comonomer, and an alkyl (meth)acrylate present in the resin in an amount of at least about 15% by weight, said dioxane / dioxolane monomer being selected from the group consisting of glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate, isopropylidene glycerol (meth)acrylate, and combinations thereof.

14. 14. The toner of claim 13, wherein said alkyl (meth)acrylate is present in said resin in an amount of at least about 20% by weight.

15. 14. The toner of claim 13, wherein said dioxane / dioxolane monomer is glycerol formal (meth)acrylate.

16. 16. The toner of claim 15, wherein said vinyl comonomer is styrene and said alkyl (meth)acrylate is butyl (meth)acrylate.

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