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 through emulsion aggregation processes that generally encompass a wide range of desired properties. However, the emission of volatile organic compounds (VOCs) can be problematic in multifunction printers under certain conditions, for example, when using such toners in a closed space with limited air circulation or when running at high printing speeds for extended periods. To address this issue, residual monomer levels are kept low, processes for producing resins and toners are improved, and carbon filters are added to printers. [Overview of the project]

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

[0003] In one embodiment, a toner is provided comprising toner particles, a colorant, and optionally a wax, wherein the toner particles comprise a resin comprising a polymerization product of a reaction product comprising a dioxane / dioxolane monomer and a vinyl comonomer, and the dioxane / dioxolane monomer is an ester of (meth)acrylic acid with an alcohol containing the dioxane portion, an ester of (meth)acrylic acid with an alcohol containing the dioxane portion, or both.

[0004] Other key features and advantages of this disclosure will become apparent to those skilled in the art upon consideration of the modes for carrying out the invention described below and the appended claims. [Modes for carrying out the invention]

[0005] latex

[0006] In one embodiment, a latex is provided. Such a latex comprises resin particles synthesized from various monomers, forming a polymer material composed of resin particles. At least one type of monomer is used, which is an ester of (meth)acrylic acid with an alcohol containing a dioxane moiety or an alcohol containing a dioxolane moiety. (For example, the use of "(meth)" in (meth)acrylic acid refers to both acrylic acid and methacrylic acid.) In this disclosure, this type of monomer may be referred to as a "dioxane / dioxolane monomer." The term dioxane / dioxolane monomer encompasses both monomers that are esters of (meth)acrylic acid with an alcohol containing a dioxane moiety, monomers that are esters 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 the dioxane / dioxolane moiety may be a triol acetal, a triol ketal, or a triol carbonate. Exemplary triols include glycerol and trimethylolpropane. Triols may be unsubstituted or substituted. "Substituted" means that one or more bonds to carbon(s) or hydrogen(s) are replaced by bonds to non-hydrogen and non-carbon atoms. Dioxane / dioxolane monomers may 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 group, alkyl group, aryl group, and alkoxy group oxygen. Either or both types of monomers can be used in resin particles. [ka]

[0007] A carbonyl group refers to a C=O group, where Z is an oxygen atom covalently bonded to carbon via a double bond, thereby forming a carbonyl group between two oxygen atoms in a 5- or 6-membered ring.

[0008] Alkyl groups can be linear or branched. Alkyl groups can have 1 to 20 carbon atoms. This includes having 1 to 18 carbon atoms and 1 to 10 carbon atoms, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. Alkyl groups can be substituted or unsubstituted. Aryl groups can be monocyclic with one aromatic ring, e.g., benzene, or polycyclic with one or more fused rings. While aryl groups can be unsubstituted or substituted with respect to the alkyl group as described above, substituted aryl groups also include aryl groups in which the bond to hydrogen (or more) is replaced by a bond to an unsubstituted or substituted alkyl group as described above. Alkoxy groups refer to -O-alkyl groups.

[0009] Examples of 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 may 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 other dioxane / dioxolane monomers described in this paragraph) refers to either a dioxane isomer, a dioxolane isomer, or both. In other words, 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, hereinafter, styrene, acrylate, methacrylate, butadiene, and isoprene. Exemplary vinyl comonomers include, hereinafter, acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternary ammonium halides of dialkyl or trialkyl acrylamide or methacrylamide, vinyl pyridine, vinyl pyrrolidone, vinyl-N-methyl pyridinium chloride, and other acidic and basic such monomers. Exemplary vinyl comonomers include, hereinafter, 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. Combinations of a single type or different types of vinyl comonomers can be used. In an embodiment, at least two vinyl comonomers are used, including styrene and alkyl (meth)acrylate (e.g., methyl (meth)acrylate, ethyl (meth)acrylate), butyl (meth)acrylate) or combinations thereof. Thus, the alkyl group of the alkyl (meth)acrylate can have one or more carbons, two or more carbons, four or more carbons, or one to six carbons. In an embodiment, at least three vinyl comonomers are used, including styrene, alkyl (meth)acrylate, and a vinyl comonomer containing a carboxylic acid group. In an embodiment, the alkyl (meth)acrylate is n-butyl acrylate. In an embodiment, the third vinyl comonomer is β-CEA.

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

[0012] Chain transfer agents can be used to form 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. Carbon tetrabromide, carbon tetrachloride, and combinations thereof such as halogenated carbons can be used as chain transfer agents.

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

[0014] When forming a latex containing resin particles, various combinations of the above-mentioned monomers can be used in a monomer emulsion containing a solvent, an initiator (which can be included in the monomer emulsion as described herein or added separately in one or more individual steps during the polymerization process), and optionally one or more of a crosslinking agent, a chain transfer agent, and a surfactant. Water is generally used as the solvent, but water-soluble or water-miscible organic solvents (such as ethanol) can also be included.

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

[0016] Dioxane / dioxolane monomers may be used in monomer emulsions in amounts ranging from 1% to 50% by weight, 5% to 40% by weight, and 5% to 30% by weight. (where wt% is (total weight of dioxane / dioxolane monomer) / (total weight of monomer, crosslinking agent (if present), and chain transfer agent (if present) in the monomer emulsion) * (Refers to 100). Vinyl comonomers may be used in monomer emulsions in amounts ranging from 50-98% by weight, 60-90% by weight, and 65-85% by weight. (where wt% is (total weight of vinyl comonomer) / (total weight of monomer, crosslinking agent (if present), and chain transfer agent (if present) in the monomer emulsion) * (referring to 100). In embodiments in which multiple types of vinyl comonomers, for example two or three, are used, the first vinyl comonomer (e.g., styrene) may constitute, for example, 40% to 95% by weight of the total weight of the vinyl comonomer; the second vinyl comonomer (e.g., alkyl (meth)acrylate) may constitute, for example, at least 15% by weight, at least 30% by weight, and 5% to 60% by weight of the total weight of the vinyl comonomer; and the third vinyl comonomer (e.g., β-CEA) may constitute, for example, up to 10% by weight of the total weight of the vinyl comonomer. Other ranges include, for example, 50% to 80% by weight and 50% to 70% by weight for the first vinyl comonomer; for example, 10% to 50% by weight and 10% to 30% by weight for the second vinyl comonomer; and for example, 0.1% to 8% by weight and 0.1% to 5% by weight for the third vinyl comonomer. In the embodiments, alkyl (meth)acrylates as possible vinyl comonomers are present in the monomer emulsion in an amount of at least 15% by weight of the total weight of the monomer, crosslinking agent (if present), and chain transfer agent (if present). This includes 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 amounts ranging from a maximum of 20% by weight, 0.01% to 20% by weight, and 0.1% to 5% by weight. (where weight % is (total weight of crosslinking agent) / (total weight of monomer, crosslinking agent, and chain transfer agent (if present) in the monomer emulsion) * (Refers to 100).

[0018] If used, chain transfer agents may be present in the monomer emulsion in amounts of, for example, up to 10% by weight, 0.05% to 10% by weight, or 0.25% to 5% by weight. (where weight % is (total weight of chain transfer agent) / (total weight of monomer, crosslinking agent (if present), and chain transfer agent in the monomer emulsion) * (Refers to 100).

[0019] Initiators initiate polymerization reactions between various monomers in a monomer emulsion. Suitable examples of 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-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-(4-aminophenyl)-2-methylpropionamidine]tetrahydrochloride, 2,2'-azobis[2-methyl-N(phenylmethyl)propionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-2-propenylpropionamidine]dihydrochloride, and 2,2'-azobis[N-(2-hydroxy-ethyl)2-methylpropion 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-diazepine-2-yl)propane]dihydrochloride, 2,2'-azobis[2-( Examples include 3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidine-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 described above, initiators may be added separately at individual steps in the polymerization process. Initiators may be added as an initiator solution containing the initiator and a solvent, such as water. The amount of initiator used may range from, for example, 0.1% to 5% by weight (where wt% is (total weight of initiator) / (total weight of monomer in monomer emulsion)).* (Refers to 100.)

[0020] Surfactants can be used in monomer emulsions, which may be selected from anionic surfactants, cationic surfactants, nonionic surfactants, and combinations thereof. The amount may be, for example, up to 5% by weight, 0.01% to 5% by weight. (where wt% is (total weight of surfactant) / (total weight of monomer in monomer emulsion)) * (Refers to 100). Examples of anionic surfactants include sulfates and sulfonates such as sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate, and sodium dodecylnaphthalenesulfate; disulfonates; dialkylbenzenesulfates; acids such as palmitic acid; and NEOGEN or NEOGEN SC available from Daiichi Kogyo Seiyaku. Other suitable anionic surfactants include DOWFAX® 2A1, an alkyldiphenyl oxide 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, halogenated salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL® and ALKAQUAT® available from Alkaril Chemical Company, and SANISOL® (benzalkonium chloride) available from Kao Chemicals.

[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, and dialkylphenoxypoly(ethyleneoxy)ethanol. Surfactants commercially available from Rhone-Poulenc, such as IGEPAL CA-210(trademark), IGEPAL CA520(trademark), IGEPAL CA-720(trademark), IGEPAL CO-890(trademark), ANTAROX 890(trademark), IGEPAL CO-720(trademark), IGEPAL CO-290(trademark), IGEPAL CA-210(trademark), and ANTAROX 897(trademark), can be selected. Other 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 a technique may involve preparing a surfactant solution in a suitable reactor. In a separate vessel, a monomer emulsion having any of the above compositions can be prepared, for example, comprising a dioxane / dioxolane monomer, two or three vinyl comonomers, a chain transfer agent, and a surfactant. Aliquots 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. Additional amounts of monomer emulsion (e.g., the remaining amount) can be supplied to the reactor to grow the seeds to the desired size. The reaction conditions used during the steps, e.g., mixing, heating, etc., are selected to promote polymerization and provide resin particles having the desired properties. Exemplary reaction conditions are described in the following examples. Reaction conditions described in U.S. Patents 6,841,329 and 7,413,842 can also be used, each of which is incorporated herein by reference in whole.

[0024] The seed emulsion polymerization technique described above provides a latex containing 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 include, for example, filtration, drying, centrifugation, spray drying, freeze-drying, and the like.

[0025] The resin particles formed by the seed emulsion polymerization technique described above may be characterized by their composition. As stated above, the polymer material of the resin particles is the result of polymerization reactions between various combinations of monomers to form the polymerization product. For clarity, the composition of the polymer material / resin particles can be identified by referring to the monomers being polymerized and recognizing that the chemical forms of these monomers are generally altered as a result of the polymerization reaction. The polymerization product, and therefore the resin particles, may contain other components present in the emulsion described above. For example, initiators (or parts thereof, e.g., sulfate groups) may be incorporated into the beginning and end of the polymer chain. Similarly, crosslinking agents, when used, are generally incorporated into the polymer chain. Surfactants, when used, may entangle with the polymer chain and be embedded within the resin particles, for example, due to strong non-covalent bonding or adsorption.

[0026] In the embodiments, the resin particles comprise (or consist thereof) the polymerization product of a reaction comprising a dioxane / dioxolane monomer, a vinyl comonomer, an initiator, and optionally a crosslinking agent. Any of the dioxane / dioxolane monomers, vinyl comonomers, crosslinking agents, and initiators described herein may be used. In the embodiments, the resin particles comprise (or consist thereof) the polymerization product of a reaction comprising a dioxane / dioxolane monomer, two different vinyl comonomers, an initiator, and optionally a crosslinking agent. In the embodiments, the resin particles comprise (or consist thereof) the polymerization product of a reaction comprising a dioxane / dioxolane monomer, three different vinyl comonomers, an initiator, and optionally a crosslinking agent. In each of these embodiments, the monomers, crosslinking agents, and initiators may 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 may range from 1% to 50% by weight. As stated above, this weight percentage is calculated as (total weight of dioxane / dioxolane monomer) / (total weight of monomer, crosslinking agent (if present), and chain transfer agent (if present) in the resin particles). * It refers to 100.

[0027] In any of the embodiments referenced in the above paragraphs, one or more of the following modifications may be used: Glycerol formal methacrylate can be used as a dioxane / dioxolane monomer. Styrene, alkyl (meth)acrylates (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 a crosslinking agent.

[0028] Using a particular exemplary composition, the composition of the resin particles may also be specified as poly[(styrene)-ran-(n-butyl acrylate)-ran-(glycerol formal (meth)acrylate)-ran-(β-CEA)], including its crosslinked version. In this description, different chemical parts resulting from a polymerization reaction are identified by referring to the corresponding monomer in parentheses, where "ran" refers to the random incorporation of different monomers into the copolymer. Use of this description entails the presence of an initiator (or part thereof) of each copolymer chain and crosslinking via a crosslinking agent (if present).

[0029] In embodiments where certain monomers are excluded from forming resin particles, such monomers are not involved in the polymerization reaction for forming the polymer matrix of the resin particles. Therefore, in these embodiments, the resin particle composition may be described as being without (i.e., not containing) one or more of the following silyl ester monomers: vinyl-imidazolium monomer, urethane (meth)acrylate monomer, and triisopropylsilyl (meth)acrylate.

[0030] In an embodiment, the latex may be described as having no (i.e., not containing) resins / polymers other than those provided by the resin of the resin particles of the present invention. This includes no polyurethane, polyurethane (meth)acrylate, poly(meth)acrylate (other than the resin particles themselves), polyester, silyl ester copolymer, silyl (meth)acrylate polymer, or combinations thereof.

[0031] Since the resin / polymer that constructs the resin particles has already been polymerized, the latex itself is generally not curable, and thus has no (i.e., does not contain) initiator. This does not exclude the presence of a small amount of unreacted initiator or reacted initiator that can be incorporated into the polymer chains. Similarly, the latex may be described as having no (i.e., not containing) monomers.

[0032] In an embodiment, the latex may also be described as having no (i.e., not containing) bactericides / bacteriostatic agents such as medetomidine.

[0033] The water content of the latex can be at least 50% by weight. This includes at least 60% by weight and at least 70% by weight. These weight percentages refer to the weight of water compared to the total weight of the latex.

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

[0035] The resin particles have an initial glass transition temperature (T g ) may be characterized by. g The value can be measured as described in the following embodiment. In the embodiment, T g This range is 40°C to 90°C. This includes the ranges of 45°C to 85°C and 50°C to 75°C.

[0036] The polymer material (resin) of the resin particles was measured as described in the following examples, and its weight-average molecular weight (M) was determined accordingly. w ) and its number average molecular weight (M n ) may be characterized by M w This can range from 25,000 Daltons to 75,000 Daltons. This includes, for example, 30,000 Daltons to 70,000 Daltons and 40,000 Daltons to 60,000 Daltons. n This can range from 10,000 Daltons to 30,000 Daltons. This includes, for example, 15,000 Daltons to 25,000 Daltons and 20,000 Daltons to 30,000 Daltons.

[0037] toner

[0038] Toner containing toner particles can be formed using any of the latexes described above. 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. When preparing the toner, such waxes, colorants, and other additives can be used in a dispersion containing any of the solvents and surfactants described above.

[0039] wax

[0040] The wax can be combined with the latex described above when forming toner particles. A single type of wax or a combination of different types of wax can be used. The wax may be present in a total amount of about 3% to about 20% of the toner particles, including about 4% to about 20% by weight of the toner particles and about 5% to about 15% by weight of the toner particles.

[0041] Examples of waxes include alkylene waxes (such as alkylene waxes with 1 to 25 carbon atoms), polyethylene wax, polypropylene wax, paraffin wax, and Fischer-Tropsch wax (such as FNP-0092® available from Nippon Seiro, which contains Fischer-Tropsch wax with 42 carbon atoms). Polypropylene and polyethylene commercially available 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®; Viscol 550-P® commercially available from Eastman Chemical Products, Inc., low weight-average molecular weight polypropylene available from Sanyo Kasei KK; and similar waxes can be used. Commercial polyethylene is thought to have a molecular weight of approximately 1,000 to 5,000, and commercial polypropylene is thought to have a molecular weight of approximately 4,000 to 10,000.Examples of functionalized waxes that can be used include, for example, amines, amides, e.g., Aqua Superslip 6550™ and Superslip 6530™ available from Micro Powder Inc.; fluorinated waxes, e.g., Polyfluo 190™, Polyfluo 200™, Polyfluo 523XF™, Aqua Polyfluo 411™, Aqua Polysilk 19™, and Polysilk 14™ available from Micro Powder Inc.; mixed fluorinated amide waxes, e.g., Microspersion 19™ also available from Micro Powder Inc.; imides, esters, quaternary amines, carboxylic acids, or acrylic polymer emulsions, e.g., Joncryl 74™, 89™, 130™, 537™, and 538™, all available from SC Johnson Wax, as well as Allied Chemical, Petrolite Corporation, and SC Johnson Examples include chlorinated polypropylene and polyethylene, which are available from Wax. A single type or a combination of different types of wax can be used.

[0042] Coloring agents

[0043] Colorants 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. Examples of colorants include pigments, dyes, and mixtures thereof, such as mixtures of dyes, mixtures of pigments, and mixtures of dyes and pigments. Colorants may be added in an amount sufficient to impart the desired color, hue, and tint. For example, the colorant may be present in a total amount of about 1% to 25% by weight of the toner particles, including about 1% to 20% by weight of the toner particles or about 2% to 15% by weight of the toner particles.

[0044] Carbon black, available in forms such as furnace black and thermal black, is a suitable colorant. Carbon black can be used with one or more other colorants, such as cyan colorants, to produce desired hues.

[0045] Examples of cyanide pigments include copper tetra(octadecylsulfonamide) phthalocyanine, copper phthalocyanine colorants listed in the color index as CI74160, HELIOGEN BLUE L6900(trademark), D6840(trademark), D7080(trademark), D7020(trademark), PYLAM OIL BLUE(trademark), PYLAM OIL YELLOW(trademark), and PIGMENT BLUE(trademark) available from Paul Uhlich & Co., Inc., CI Pigment Blue (PB), PB15:3, PB15:4, Anthrazine Blue X-2137 identified as CI69810, and mixtures thereof.

[0046] Examples of magenta pigments include the diazo dye identified as CI26050, 2,9-dimethyl-substituted quinacridone, the anthraquinone dye identified as CI60710 and CIDispersed Red 15, CINQUASIA MAGENTA (trademark) available from EIDuPont de Nemours & Co., CISolvent Red 19, Pigment Red (PR) 122, PR 269, PR 185, and mixtures thereof.

[0047] Examples of yellow colorants include diarylylide yellow, 3,3-dichlorobenzidene acetoacetanilide, monoazo pigment identified as CI 12700 in the color index, CI Solvent Yellow 16, nitrophenylamine sulfonamide identified as Foron Yellow SE / GLN in the color index, LEMON CHROME YELLOW DCC 1026 (trademark) CI from Sanofi, NOVAPERM YELLOW FGL (trademark), 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. Examples include D0790 (BASF), Sunspers Yellow YHD 6001 (Sun Chemicals), SUCD-Yellow D1355 (BASF), Permanent Yellow FGL, Disperse Yellow, 3,2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxyacetanilide, and mixtures thereof.

[0048] Other colorants that may be used include: 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), Thermoplast NSD Red Scarlet (Aldrich), Lithol Rubine Toner (Paul Ulrich), Lithol Scarlet 4440, NBD 3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Ulrich), and 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 YellowExamples include FGL (Hoechst), Permanent 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 (BASF), Pigment Black K801 (BASF), and especially 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 Examples include 6020 and 6045 (Pigment Yellow 74), SUNSPERSE YHD 600 and 9604 (Pigment Yellow 14), and FLEXIVERSE LFD 4343 and LFD 9736 (Pigment Black 7). Other useful aqueous 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 surfactant before use.

[0050] Other useful colorants include, 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] Toner particles can be formed using various techniques, including the emulsion-aggregation (EA) process. In embodiments, the EA process involves agglomerating a mixture containing latex, a colorant, and optionally a wax, and then combining the agglomerated mixture. Any of the aforementioned latexes can be used, including a single type of latex or a combination of different types of latex, each containing different types of resin particles. The colorant and wax may be used as aqueous dispersions as described above. The mixture can be homogenized during the EA process, which can be accomplished by mixing at approximately 600 to 6,000 revolutions per minute.

[0053] Aggregation can be achieved by adding any suitable flocculant (coagulant) to the mixture. The flocculant may be, for example, a polyhalide such as polyaluminum chloride (PAC) or its corresponding bromide, fluoride, or iodide; a polyaluminum silicate such as polyaluminum sulfosilicate (PASS); or an inorganic cationic coagulant such as a water-soluble metal salt containing aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxyate, 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 mixtures thereof. The flocculant is used to control the T of the latex resin particles. g The flocculant can be added to the mixture at a temperature below [specified temperature]. The flocculant can 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 flocculant can be added in a solution of nitric acid or a similar acid. To control particle aggregation, the flocculant can be weighed into the mixture over time, for example, over a period of about 5 minutes to about 240 minutes. The addition of the flocculant can be carried out by continuous homogenization. After addition, the mixture can 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 when determined before formation, and the particle size can be monitored during the growth process. Samples are taken during the growth process, D 50 This can be analyzed, for example, with Nanotrac® 252. Aggregation can be carried out by maintaining the mixture at a high temperature to provide aggregated particles, or by slowly raising the temperature from, for example, about 40°C to about 100°C, and holding the mixture at this temperature for a certain period of time, for example, about 0.5 hours to about 10 hours, while maintaining stirring or homogenization. Once a predetermined desired particle size is reached, the growth process is stopped. D 50The particle size may be, for example, approximately 3 μm to 10 μm, approximately 3 μm to 8 μm, or approximately 3 μm to 6 μm.

[0055] Shell resin

[0056] In the embodiment, a resin coating may be applied to the aggregated particles (cores) after aggregation but before coalescing, and a shell may be formed thereon. The shell can be applied by using any of the latexes 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, for example, have different starting glass transition temperatures T g Values, different M w / M n They may differ from one another in terms of having a molecular weight, being crosslinked or uncrosslinked, 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 to a value of, for example, about 3 to about 10. Suitable pH control agents include various bases, such as alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, and combinations thereof. Chelating agents (metal ion sequestering agents) can also be added. Various suitable chelating agents include, for example, ethylenediaminetetraacetic acid (EDTA), salts of EDTA, tartaric acid, gluconal, hydroxyl-2,2'iminodisuccinic acid (HIDS), dicarboxylmethyl glutamic acid (GLDA), methyl glycidyl diacetic acid (MGDA), and hydroxydiethyliminodiacetic acid. Acids (HIDA), sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate, humic acid, fulvic acid; alkali metal salts of EDTA, gluconic acid, oxalic acid, polyacrylate, sugar acrylate, 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, hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, mixtures thereof, etc. can be used. Various suitable amounts of the chelating agent can be used, for example, in amounts of about 0.1% to 1% by weight of the toner particles, about 0.2% to 0.7% by weight of the toner particles, or about 0.3% to 0.5% by weight of the toner particles.

[0058] Fusion

[0059] Following the aggregation and coating of the shell (if desired), the particles are coalesced into the desired final shape, and the coalescing is, for example, a resin(s) used to form toner particles. g This is achieved by heating the mixture to a temperature of approximately 80°C to 110°C, which may be 0°C or higher. The specific choice of temperature depends on the resin used. The mixture may be stirred, for example, at approximately 100 rpm to 1,000 rpm. Coating may be carried out over a period of time, for example, from approximately 1 minute to approximately 10 hours. The particles may be coalesced until the desired roundness is achieved. During coalescing, the pH may be adjusted to a value of approximately 3 to approximately 10, for example, using pH control agents containing various acids such as nitric acid.

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

[0061] The toner particles include a single type of resin or a plurality of types of resins. The toner particles containing a plurality of types of resins may contain different relative amounts of different types of resins. In the embodiment, two different types of resins are used, where the first resin is present in an amount of, for example, 25% to 99% by weight of the toner particle, and the second resin is present in an amount of, for example, up to 35% by weight of the toner particle. This includes the first resin present in amounts of 30% to 80% and 40% to 70% by weight, and the second resin present in amounts of 10% to 50% and 15% to 40% by weight. In the embodiment, 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, in amounts of about 60% to 95% by weight of the toner particles, about 65% to 90% by weight of the toner particles, or about 75% to 85% by weight of the toner particles.

[0063] The composition of toner particles depends on the resin(s) used. Therefore, the composition of toner particles follows the above-mentioned characteristics for various resin particles.

[0064] Modifications of the exemplary toner preparation processes described above, including those described in U.S. Patents No. 6,841,329 and No. 7,413,842, can be applied, each of which is incorporated herein by reference in whole.

[0065] additives

[0066] Toners may further contain a variety of additives to enhance their properties. For example, a toner may contain charge additives 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 of U.S. Patents No. 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 whole), negative charge enhancing additives such as aluminum complexes, any other charge additives, and mixtures thereof.

[0067] Toner may contain surface additives. Examples of surface additives that may be added to toner particles after washing or drying include 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 about 0.1% to about 10% by weight of the toner. Examples of such additives are disclosed, for example, in U.S. Patents 3,590,000, 3,720,617, 3,655,374 and 3,983,045, each of which is incorporated herein by reference in whole. Other additives include zinc stearate and AEROSIL R972®, both available from Degussa. Coated silica of U.S. Patent No. 6,190,815 and U.S. Patent No. 6,004,714 (each of which disclosures are incorporated herein by reference in whole) can also be selected, for example, in amounts of about 0.05% to about 5% by weight of the toner, and these additives can be added during the aggregation process or blended into the formed toner particles.

[0068] In this disclosure, the terms “toner” and “toner composition” refer to these compositions configured for use in an electrophotographic printer to form an image with it. Thus, in addition to resins, colorants, present organic additives, and optionally waxes and others, toner may include any other components generally used in such compositions to form an object using a desired electrophotographic printer.

[0069] The toner of the present invention may be described as having no resin other than that provided by the resin of the resin particles of the present invention (i.e., not containing any other resin). This includes the absence of polyurethane, poly(meth)acrylate (other than the resin particles themselves), polyester, or combinations thereof. A single type of resin may be used. Similarly, the toner composition itself is generally not curable and therefore does not contain an initiator (i.e., does not contain any). This does not preclude the presence of small amounts of unused or used initiator from the resin particles that may be incorporated into the polymer chain of the resin particles. It should be noted that any other exclusions referenced above with respect to the resin particles and latex may apply to embodiments of the toner composition.

[0070] Toner characteristics

[0071] In this embodiment, the dried toner particles, excluding the external surface additive, have the following characteristics.

[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) Number-average geometric size distribution (GSDn) and / or volume-average geometric size distribution (GSDv) of 1.05 to 1.35, 1.15 to 1.30, or approximately 1.20 to 1.15.

[0074] (3) Roundness of 0.92-0.99, 0.94-0.97, or 0.95-0.96 (for example, when measured with Sysmex 3000).

[0075] (4) Starting glass transition temperature (T) 48℃~85℃, 50℃~90℃ or 52℃~85℃ g (For example, when measured with a differential scanning calorimeter).

[0076] Volume-average particle size D50 With respect to GSDv and GSDn, these characteristics can be measured using measuring instruments such as Nanotrac® 252, operated according to the manufacturer's instructions.

[0077] Both the latex and toner of the present invention may be characterized by their volatile organic compounds (VOCs). In embodiments, the VOC content is less than 500 ppm when 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 monomers, potential by-products of polymerization, and impurities derived from the starting monomers.

[0078] The toners of the present invention may be characterized by their residual aluminum and sodium levels when measured using inductively coupled plasma (ICP) as described in the following examples. The aluminum level may be less than 300 ppm, less than 275 ppm, or less than 250 ppm. The sodium level may be less than 250 ppm, less than 225 ppm, or less than 200 ppm.

[0079] Developer and carrier

[0080] The toner may be incorporated into a developer composition. The developer composition can be prepared by mixing the toner with known carrier particles, including coated carriers such as steel and ferrite. Such carriers are disclosed in U.S. Patents 4,937,166 and 4,935,326, the entirety of which is incorporated herein by reference. The carrier may be present in an amount of about 2% to 8% by weight of the toner. The carrier particles may also include a core having a polymer coating, such as polymethyl methacrylate (PMMA), in which a conductive component, such as conductive carbon black, is dispersed. Examples of 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 flexible containers such as vials, bottles, bags, or packages, to devices that perform functions beyond storage. Toner can also be incorporated into dedicated devices for delivering the same toner, for example, for the purpose of forming an image. Thus, specialized toner delivery devices can be utilized; see, for example, U.S. Patent No. 7,822,370. Such devices may include cartridges, tanks, reservoirs, etc., and may be replaceable, disposable, or reusable. Such devices may include storage sections; distribution or delivery sections, etc.; various ports or openings that allow toner to be added to and removed from the device; optional sections for monitoring the amount of toner in the device; and forming or molded sections that allow the device to be placed and seated, for example, in an imaging device. The toner in question may be included in a dedicated delivery device for recharging or replenishing toner in imaging device components, such as cartridges, that require replaceable or reusable toner (see, for example, U.S. Patent No. 7,817,944).

[0082] imaging

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

[0084] The imaging process includes, for example, preparing an image using an electrophotographic apparatus that includes 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 a toner composition described herein. The electrophotographic apparatus may include a high-speed printer, a black-and-white high-speed printer, a color printer, and the like.

[0085] Once an image is formed with toner / developer via a preferred developing method such as one of the methods described above, the image can then be transferred to an image-receiving medium such as paper. In embodiments, toner may be used for development in a developing apparatus utilizing a fuser roll member. The fuser roll member is a contact fusing device within the intent of those skilled in the art, which 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 toner fixing temperature, for example, to a temperature of about 70°C to about 160°C after or during melting on the image-receiving substrate.

[0086] The use of latex / resin particles in the present invention is not limited to providing toner. For example, latex can be used to provide latex coatings. In addition to water and any of the disclosed resin particles, latex coatings generally include a colorant. Any of the disclosed colorants may be used. Often, surfactants, such as any of the surfactants disclosed herein, are also included. Other possible additives include fillers such as inorganic particles (e.g., silica), dispersants, defoamers, wetting agents, viscosity modifiers, waxes, binders, and the like. These additives may be present in any amount to achieve the desired properties for the latex coating. Any of the above exclusions relating to latex and toner may also apply to embodiments of latex coatings. [Examples]

[0087] The following examples are provided to further define the various types of this disclosure. These examples are for illustrative purposes only and are not intended to limit the scope of this disclosure. Unless otherwise stated, proportions and percentages are given 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 produced by the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 6.37 kg of Dowfax 2A1 (anionic surfactant) and 4096 kg of deionized water was mixed in a stainless steel holding tank for 10 minutes. The holding tank was then purged with nitrogen for 5 minutes and transferred to a reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated to 80°C at a controlled rate and held therein. 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. Then, 1 percent of the above emulsion was slowly supplied at 80°C to a reactor containing an aqueous surfactant phase, forming a "seed" while purging with nitrogen. Next, the initiator solution was slowly added to the reactor, and after 10 minutes, the remainder of the monomer emulsion was continuously supplied 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 were added to the monomer emulsion with stirring, and the monomer emulsion was continuously supplied at a rate of 0.5% per minute. At this point, the reactor stirrer was increased to 350 RPM. After all the monomer emulsion was added to the main reactor, the temperature was maintained at 80°C for a further 2 hours to complete the reaction. Then, complete cooling was applied to lower the reactor temperature to approximately 35°C. The product was collected in a holding tank. After drying the latex, the following properties were measured: w =33,700, M n = 10,900 and the starting glass transition temperature (T gThe temperature was 58.6°C. Using a TA Instrument Discovery differential scanning calorimeter 2500, T g The following measurements were taken. For this measurement, 5-10 mg of toner sample was placed in an aluminum pan, covered with a lid, and sealed. A reference pan and lid were also sealed. The sample was placed in the instrument, equilibrated at 0°C, then heated to 150°C at a controlled heating rate, then cooled to 0°C, and then heated to 150°C at the same rate. Heat flow data as a function of temperature was recorded. The glass transition temperature of the sample was determined when the start of the step transition was reported for the second heat.

[0090] Weight average molecular weight (M w ), number average molecular weight (M n Water Advanced Polymer Chromatography (APC) instruments were used to determine the molecular weight properties of polymers, including polydispersity (MWD or PDI). The instruments were equipped with a series of separation columns and used tetrahydrofuran (THF) as the mobile phase. Approximately 25 mg of the sample was dissolved in THF, filtered, and then a portion was injected into the instruments. The FID detector quantified the number and mass of various polymer chains as they eluted through the columns. The instruments were calibrated with a series of polystyrene standards and used to determine the relative molecular weight properties of the analyzed samples.

[0091] Latex Comparative Example 2

[0092] A latex containing resin particles produced by the emulsion polymerization of styrene, n-butyl acrylate, and β-CEA was prepared as follows: A surfactant solution containing 0.3352 kg of Calfax (anionic surfactant) and 476.9 kg of deionized water was prepared by mixing in a stainless steel holding tank for 10 minutes. The holding tank was then purged with nitrogen for 5 minutes and transferred to a reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated to 80°C at a controlled rate and maintained 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. Then, 2 percent of the monomer emulsion was slowly supplied at 80°C to a reactor containing the aqueous surfactant phase, forming a "seed" while purging with nitrogen. Next, the initiator solution was slowly added to the reactor, and after 10 minutes, the remainder of the emulsion was continuously supplied at a rate of 0.5% per minute using a metering pump. After all the monomer emulsion was added to the main reactor, the temperature was maintained at 80°C for a further 2 hours to complete the reaction. Then, complete cooling was applied to lower the reactor temperature to approximately 35°C. The product was collected in a holding tank. After drying the latex, the following properties were measured: M w = 55,000 ± 3,000, the percentage solid content is 41%, T g The temperature was 55°C ± 3°C.

[0093] Latex Comparative Example 3

[0094] A latex containing resin particles produced by 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 in a stainless steel holding tank for 10 minutes. The holding tank was then purged with nitrogen for 5 minutes and transferred to a reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated to 80°C at a controlled rate and held therein. 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. Then, 1 percent of the monomer emulsion was slowly supplied at 80°C to a reactor containing the aqueous surfactant phase, forming a "seed" while purging with nitrogen. Next, the initiator solution was slowly added to the main reactor, and after 10 minutes, the remainder of the emulsion was continuously supplied to the reactor containing the aqueous surfactant phase at a rate of 0.5% per minute using a metering pump, and the temperature was maintained at 80°C for a further 2 hours to complete the reaction. Then, complete cooling was applied to lower 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: M w =35,419, M n =11,354 and T g The temperature was 51.0℃.

[0095] Latex Comparative Example 4

[0096] A latex containing resin particles produced by 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 in a stainless steel holding tank for 10 minutes. The holding tank was then purged with nitrogen for 5 minutes and transferred to a reactor. The reactor was then continuously purged with nitrogen while stirring at 100 RPM. The reactor was then heated to 80°C at a controlled rate and held therein. 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. Then, 1 percent of the emulsion was slowly supplied at 80°C to the main reactor containing the aqueous surfactant phase, forming a "seed" while purging with nitrogen. Next, the initiator solution was slowly added to the reactor, and after 10 minutes, the remainder of the emulsion was continuously supplied at a rate of 0.5% per minute using a metering pump. After all the monomer emulsion had been added to the reactor, the temperature was maintained at 80°C for a further 2 hours to complete the reaction. Then, complete cooling was applied to lower the reactor temperature to approximately 35°C. The product was released into a holding tank and dried to obtain a latex with the following molecular properties: M 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 2L Büch reactor equipped with two P4 impellers, 0.57g of Dowfax 2A1 (47% solids) was added to 518g of deionized water (DIW). The reactor was deoxygenated by passing a nitrogen stream 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 container equipped with two P4 impellers, a monomer emulsion was prepared by mixing together (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 called DDT), 9.81 g of Dowfax 2A1 surfactant (with 47% solids content) and 265 g of DIW. 17.4 g of seed was taken 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 minutes after the seed emulsion was added. The remaining monomer emulsion was supplied to the reactor over 120 minutes. 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 217 nm D 50 A latex containing 43% solids was obtained by particle size. The T of the dried latex (resin particles) g The temperature was 56.2°C. Residual n-butyl acrylate monomer was 54.81 ppm, residual styrene monomer was 37.1 ppm, and residual glycerol formal methacrylate was 20.87 ppm. Weight-average molecular weight M w It is 52,574, and the number average molecular weight M n The number was 26,171.

[0099] Toner Comparison Example 1

[0100] 286.9 grams of latex Comparative Example 3 with a solid content of 41.4 wt% and 60.49 grams of wax emulsion containing purified paraffin wax C42 (FNP-0092® available from Nippon Seiro) with a solid content of 30.50 wt% were added to 613.5 grams of deionized water in a container and stirred using an IKA Ultra Turrax® T50 homogenizer operating at 4,000 rpm. Subsequently, 64.1 grams of cyanide pigment dispersion PB15:3, available from Sun Chemical as Sun Pigment W51924 with a solid content of 17 wt%, were added to the reactor, followed by the dropwise addition of 36 grams of cottony mixture containing 3.6 grams of polyaluminum chloride mixture and 32.4 grams of 0.02 molar nitrate solution. When the cottony mixture was added, the homogenizer speed was increased to 5,200 rpm and the contents of the reactor were further homogenized for 5 minutes. Subsequently, the mixture was heated to a temperature of 52°C at a rate of 1.0°C per minute and held at 52°C for a period of approximately 1.5 to 2 hours to obtain cyan toner particles with a volume-average particle size of 5 microns as measured by a Coulter Counter. During the heating period, the stirrer was run at approximately 250 rpm. Ten minutes after reaching the set temperature of 49°C, the stirrer speed was reduced to approximately 220 rpm.

[0101] Following this step, 134.6 grams of Latex Comparative Example 4, with a solid content of 41.6 wt%, was added to the reactor mixture and allowed to aggregate at 51°C for a further period of approximately 30 minutes to obtain cyan toner particles with 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 by using a 1.0 M sodium hydroxide solution added to 4.82 grams of Dow-available ethylenediaminetetraacetic acid (EDTA) Versene® 100, with a solid content of 39 wt%,. The reactor mixture was then heated to a temperature of 95°C at a rate of 1.0°C per minute. Subsequently, the reactor mixture was gently stirred at 95°C for 3 hours to allow the particles to coalesce and spheroidize. One hour after coalescing, the pH of the reactor was adjusted to pH 7.0, and the reactor mixture was gently stirred for the remaining 2 hours. The reactor heater was then switched 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 (based on the total weight of the toner composition). The toner particles consisted of 58 wt percent styrene / acrylate polymer resin (from Latex Comparative Example 3), approximately 28 wt percent styrene / acrylate polymer resin (from Latex Comparative Example 4), approximately 5 wt percent PB15:3 pigment, and approximately 9 wt percent 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 wash was performed 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 latex from Example 1 with a solid content of 42.6 wt%, 75 grams of wax emulsion containing Fischer-Tropsch wax (Q436B® available from Cytech) with a solid content of 30 wt%, and 43 g of cyanide pigment dispersion (PB15:3 available from Sun Chemical) with a solid content of 25.6 wt% 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 cottony 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 to obtain cyanide toner particles with a volume-average particle size of 5 microns as measured by a Coulter Counter. During the heating period, the stirrer was run at 225 rpm until it reached 35°C, at which point the stirrer 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 at 56°C for a further period of about 60 minutes to obtain cyan toner particles with a volume-average particle size of about 5.9 microns as measured by a Coulter Counter. The pH of the reactor mixture was adjusted to pH 4.0 by using 4.82 grams of ethylenediaminetetraacetic acid (EDTA) Versene® 100, available from Dow, with a solid content of 39 wt% following a 1.0 M sodium hydroxide solution. The reactor mixture was then heated to a temperature of 95°C at a rate of 1.0°C per minute. Subsequently, the reactor mixture was gently stirred at 95°C for 3 hours to allow the particles to coalesce and spheroidize. The reactor heater was then switched 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 (based on the total weight of the toner composition). The toner particles consisted of 84 wt percent styrene / acrylate polymer resin (from the latex of Example 1), approximately 5 wt percent PB15:3 pigment, and approximately 11 wt percent 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 wash was performed 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 last measured aluminum content in the dry toner particles, as measured by inductively coupled plasma atomic emission spectroscopy (ICP), was 239.89 ppm, and the sodium content was 192.96 ppm. g The temperature was 82.32°C, and the onset of decomposition was 355.8°C, as measured by thermogravimetric analysis using a TA Instruments Q5000IR TGA system operated with argon gas.

[0105] The term “exemplary” is used herein to mean an example, case, or representation. Any embodiment or design described herein as “exemplary” is not necessarily construed as being preferable or advantageous to other embodiments or designs. Furthermore, for the purposes of this disclosure, unless otherwise specified, “a” or “an” means “one or more.”

[0106] Where not already included, all numerical values ​​of parameters in this disclosure are referred to by the term “approximately,” meaning approximate. This includes variations inherent in the measurement of the relevant parameters as understood by those skilled in the art. This also includes the exact values ​​of the disclosed numerical values ​​and the rounded values ​​of the disclosed numerical values.

[0107] The foregoing description of exemplary embodiments of the Disclosure is provided for illustrative and explanatory purposes only. It is not intended to be exhaustive or to limit the Disclosure to the exact form disclosed, and modifications and variations are possible in light of the above teachings or may be obtained from practices of the Disclosure. Embodiments are selected and described in order to illustrate the principles of the Disclosure and to enable those skilled in the art to utilize the Disclosure in various embodiments as a practical application of the Disclosure, and with various modifications suitable for the particular intended use. The scope of the Disclosure is intended to be defined by the claims and equivalents thereof appended herein.

Claims

**Claim 1** A toner comprising toner particles, a colorant, and optionally a wax, wherein the toner particles comprise a resin comprising a 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. **Claim 2** The toner according to claim 1, wherein the dioxane / dioxolane monomer is glycerol formal (meth)acrylate. **Claim 3** The toner according to claim 1, wherein the dioxane / dioxolane monomer is present in the resin in an amount in the range of about 1 wt% to about 50 wt%. **Claim 4** The toner according to claim 1, wherein the vinyl comonomer comprises an alkyl (meth)acrylate present in the resin in an amount of at least about 15 wt%. **Claim 5** The toner according to claim 4, wherein the alkyl (meth)acrylate is butyl (meth)acrylate. **Claim 6** The toner according to claim 1, wherein the reactant comprises two different types of the vinyl comonomer. **Claim 7** The toner according to claim 6, wherein the two different types of the vinyl comonomer are styrene and alkyl (meth)acrylate. **Claim 8** The toner according to claim 7, wherein the alkyl (meth)acrylate is butyl (meth)acrylate. **Claim 9** The toner according to claim 1, wherein the reactant comprises three different types of the vinyl comonomer. **Claim 10** The toner according to claim 9, wherein the three different types of the vinyl comonomer are styrene, alkyl (meth)acrylate, and a vinyl comonomer containing a carboxylic acid group. **Claim 11** The toner according to claim 10, wherein the alkyl (meth)acrylate is butyl (meth)acrylate and the vinyl comonomer containing the carboxylic acid group is beta-carboxyethyl acrylate. **Claim 12** The toner particles have a volume average particle diameter D of about 2 μm to 10 μm 50 The toner according to claim 1 **Claim 13** A toner comprising toner particles, a colorant and optionally a wax, wherein the toner particles comprise a resin comprising a 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, 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.

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

15. The toner according to claim 13, wherein the dioxane / dioxolane monomer is glycerol formal (meth)acrylate.

16. The toner according to claim 15, wherein the vinyl comonomer is styrene and the alkyl (meth)acrylate is butyl (meth)acrylate.

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