Organic additives and compositions containing the same

Abstract

To provide: compositions which may comprise a plurality of organic additive particles; and toner compositions and additive manufacturing compositions comprising the organic additive particles.SOLUTION: The organic additive particles comprise 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] Additives are often included in toner compositions and additive manufacturing compositions to adjust their properties. Silica, as well as other inorganic additives, are used as additives to improve flowability at high temperatures, triboelectric charging properties, and toner blocking. Several polymer additives have also been developed for such purposes. However, the properties of such additives have been somewhat limited by the properties of the monomers used to form the polymer additives. [Overview of the project]

[0002] Organic additives are provided that can be used in various compositions, including toner compositions and additive manufacturing compositions. The organic additives are polymer materials formed using dioxane / dioxolane monomers. The dioxane / dioxolane moieties present in these monomers impart useful properties to compositions containing the organic additives. For example, embodiments of the organic additives provide toner compositions with significantly improved blocking performance compared to existing polymer additives, without adversely affecting other properties such as electrostatic charge, aggregation, and sensitivity to humidity. Furthermore, embodiments of the organic additives exhibit significantly improved thermal stability compared to existing polymer additives.

[0003] In the embodiment, a composition is provided comprising a plurality of organic additive particles, the particles comprising polymerization products of a reaction product comprising dioxane / dioxolane monomer and vinyl comonomer, 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.

[0004] Toner compositions are also provided, in embodiments, which include toner particles, a colorant, and a plurality of organic additive particles, the particles comprising a polymerization product of a reaction product comprising dioxane / dioxolane monomer, vinyl comonomer, polyfunctional vinyl monomer, vinyl fluoride monomer, nitrogen-containing vinyl monomer, and additional vinyl monomer selected from the group consisting of combinations thereof, wherein the dioxane / dioxolane monomer comprises a plurality of organic additive particles comprising an ester of (meth)acrylic acid and an alcohol containing a dioxane moiety, an ester of (meth)acrylic acid and an alcohol containing a dioxolane moiety, or both thereof, and optionally a wax.

[0005] In embodiments, additive manufacturing compositions are also provided that include a polymer material, a metal material, or a combination thereof, and a plurality of organic additive particles, wherein the particles include a dioxane / dioxolane monomer and a vinyl comonomer, and the dioxane / dioxolane monomer is an ester of (meth)acrylic acid and an alcohol containing a dioxane moiety, an ester of (meth)acrylic acid and an alcohol containing a dioxolane moiety, or both thereof.

[0006] Other key features and advantages of this disclosure will become apparent to those skilled in the art upon consideration of the following drawings, modes for carrying out the invention, and the appended claims. [Modes for carrying out the invention]

[0007] Organic additives are provided, which can be used in various compositions in addition to, or instead of, inorganic additives such as silica, titania, and alumina, as well as other types of polymer additives. The organic additives are polymer materials in the form of small particles. The organic additives are formed by polymerizing various monomers. Using at least one type of monomer, the polymer material of the organic additive is formed, and the at least one type of monomer 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 "dioxane / dioxolane monomer." The phrase dioxane / dioxolane monomer encompasses monomers that are esters of (meth)acrylic acid with an alcohol containing a dioxane moiety, esters of (meth)acrylic acid with an alcohol containing a dioxolane moiety, or both. The dioxane moiety may be a 1,3-dioxane moiety, and the dioxolane moiety may be a 1,3-dioxolane moiety. Alcohols containing the dioxane / dioxolane moiety may be triols, ketals of triols, or carbonates of triols. Exemplary triols include glycerol and trimethylolpropane. Triols may be unsubstituted or substituted. "Substituted" means that one or more bonds to carbon or hydrogen are replaced by bonds to non-hydrogen and non-carbon atoms. Dioxane / dioxolane monomers may have the following formula I (dioxane) or II (dioxolane), where R is selected from hydrogen and methyl, R' is selected from hydrogen and ethyl, and Z is selected from hydrogen, carbonyl oxygen, alkyl, aryl, and alkoxy groups. Monomers of either or both types may be used in resin particles. [ka]

[0008] A carbonyl group refers to a C=O group, where Z is O covalently bonded to carbon via a double bond, thereby forming a carbonyl group between two oxygen atoms of a 5 or 6-membered ring. 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. An aryl group can be a monocyclic ring having one aromatic ring, for example, benzene, or a polycyclic ring having one or more fused rings. While aryl groups can be unsubstituted or substituted as described above with respect to alkyl groups, substituted aryl groups also include aryl groups in which the bond to hydrogen is replaced by a bond to the unsubstituted or substituted alkyl group described above. An alkoxy group refers to an -O-alkyl group.

[0009] Examples of dioxane / dioxolane monomers include glycerol formal (meth)acrylate, trimethylolpropane formal (meth)acrylate, and isopropylidene glycerol (meth)acrylate. A single type of different combination 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 the other dioxane / dioxolane monomers described in this paragraph) refers to either a dioxane isomer, a dioxolane isomer, or both; that is, all possibilities are encompassed by their names.

[0010] Vinyl comonomers are also used to form polymer materials for organic additives. Vinyl comonomers have a relatively high C / O ratio. The C / O ratio can be 3-8, 4-7, or 5-6. Vinyl comonomers can be aliphatic cyclo(meth)acrylates. Exemplary aliphatic cyclo(meth)acrylates include cyclohexyl methacrylate, cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, isobornyl methacrylate, isobornyl acrylate, benzyl methacrylate, and phenyl methacrylate. Different types of these vinyl comonomers, either individually or in combination, can be used. The aliphatic group of the cyclo(meth)acrylate may have three or more carbon atoms, four or more carbon atoms, five or more carbon atoms, or three to eight carbon atoms.

[0011] Polyfunctional vinyl monomers, i.e., polyfunctional vinyl monomers containing two or more vinyl polymerizable groups (e.g., 2, 3, 4), can be used to form polymer materials of organic additives, although in some embodiments, polyfunctional vinyl monomers are not required. Polyfunctional vinyl monomers achieve crosslinking within the organic additive. Polyfunctional vinyl monomers containing two or more vinyl groups can be used. Exemplary polyfunctional vinyl monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly(ethylene glycol) diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tri(propylene glycol) diacrylate, poly(propylene glycol) diacrylate, 2,2'-bis(4-(acrylooxy / diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and tri Examples include ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy / diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy / polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.Other exemplary polyfunctional vinyl monomers include bisphenol A ethoxylate diacrylate, bisphenol A ethoxylate dimethacrylate, bisphenol A dimethacrylate, bisphenol A ethoxylate diacrylate, methyl 2-(trifluoromethyl)acrylate, 10-decanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,4-phenylenedimethacrylate, pyromellitic acid dianhydride dimethacrylate, pyromellitic acid dianhydride glycerol dimethacrylate, and di Examples include (trimethylolpropane) tetraacrylate, diurethane dimethacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, glycerol 1,3-diglycerolate diacrylate, glycerol dimethacrylate, neopentyl glycol propoxylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxylate (1 EO / OH) methyl ether diacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, 1,4-cyclohexanedimethanol divinyl ether, 1,4-bis(4-vinylphenoxy)butane, and divinyl sulfone. A single type or combination of different types of polyfunctional vinyl monomers can be used.

[0012] Additional vinyl monomers can be used to form polymer materials of organic additives. However, in contrast to polyfunctional vinyl monomers, additional vinyl monomers may be monofunctional, having a single polymerizable vinyl group. Additional vinyl monomers may be selected from acrylic monomers, e.g., acrylates, acrylamides and methacrylamides, acrylic acids, acrylonitriles, bisphenol acrylics, fluorinated acrylics, and methacrylates; styrenes and styrene monomers functionalized by groups other than vinyl polymerizable groups; and vinyl esters and vinyl ethers.

[0013] Specific exemplary additional vinyl monomers include 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 3-(acrylamido)phenylboronic acid, (3-acrylamidopropyl)trimethylammonium chloride, 3-O-acryloyl-1,2:5,6-bis-O-isopropylidene-D-glucofuranose, N-acryloyl-L-valine, alkylacrylamide, 2-aminoethylmethacrylamide hydrochloride, N-(3-aminopropyl)methacrylamide hydrochloride, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N-dimethylacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N,N'-Hexamethylenebis(methacrylamide), N-Hydroxyethylacrylamide, N-(Hydroxymethyl)acrylamide, (4-Hydroxyphenyl)methacrylamide, 2-Hydroxypropylmethacrylamide, N-(Isobutoxymethyl)acrylamide, N-Isopropylacrylamide, N-Isopropylacrylamide, N-Isopropylmethacrylamide, Methacrylamide, N-(3-Methoxypropyl)acrylamide, N-Phenylacrylamide, N-(Triphenylmethyl)methacrylamide, N-[Tris (Hydroxymethyl)methyl]acrylamide, 4-acetoxyphenethyl acrylate, 6-acetylthiohexyl methacrylate, acrylic anhydride, acryloyl thiocarbamoyl rhodamine B, acryloyl chloride, 4-acryloylmorpholine, [2-(acryloyloxy)ethyl]trimethylammonium chloride, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, benzoyl acrylate, benzoyl 2-propyl acrylate, butyl acrylate, tert-butyl acrylate, 2-[[( Butylamino)carbonyl[oxy]ethyl acrylate, tert-butyl 2-bromoacrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, 2-(diethylamino)ethyl acrylate, di(ethylene glycol)ethyl ether acrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, ethyl acrylate, 2-ethyl acryloyl chloride, ethyl 2-(bromomethyl)acrylate, ethyl cis-(β-cyano)acrylate, ethylene glycol Dicyclopentenyl ether acrylate, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethyl acrylate, 2-ethylhexyl acrylate, ethyl 2-propyl acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate 96%, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, (2-isobutyl-2-methyl-1,3-Dioxolan-4-yl)methyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamide acrylate, methyl acrylate, methyl α-bromoacrylate, methyl 2-(bromomethyl)acrylate, methyl 2-(chloromethyl)acrylate, octadecyl acrylate, pentabromobenzyl acrylate, pentabromophenyl acrylate, pentafluorophenyl acrylate, poly(ethylene glycol)methyl ether acrylate, poly(propylene glycol) acrylate, epoxidized acrylate, 3-sulfopropyl acrylate, tetrahydrofurfuryl acrylate, 2-tetrahydropyranyl acrylate, 3,5,5-Trimethylhexyl acrylate, 10-Undecenyl acrylate, 4-Acetoxyphenethyl acrylate, 6-Acetylthiohexyl methacrylate, Acrylic anhydride, Acrylooxyethyl thiocarbamoyl rhodamine B, 4-Acryloylmorpholine 97%, [2-(Acryloyloxy)ethyl]trimethylammonium chloride, 2-(4-Benzyl-3-hydroxyphenoxy)ethyl acrylate, Benzyl acrylate, Benzyl 2-propyl acrylate, Butyl acrylate, tert-butyl acrylate, 2 -[[(butylamino)carbonyl]oxy]ethyl acrylate, tert-butyl 2-bromoacrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, 2-(diethylamino)ethyl acrylate, di(ethylene glycol)ethyl ether acrylate, 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl acrylate, ethyl acrylate, 2-ethyl acryloyl chloride, ethyl 2-(bromomethyl)acrylate, ethyl cis-(β-cyano)acrylate, ethylene glycol Col dicyclopentenyl, ethylene glycol methyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethyl acrylate, 2-ethylhexyl acrylate, ethyl 2-propyl acrylate, hexyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, isobutyl acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl acrylate Isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamide acrylate, methyl acrylate, methyl α-bromoacrylate, methyl 2-(bromomethyl)acrylate, methyl 2-(chloromethyl)acrylate, methyl 3-hydroxy-2-methylene butyrate, octadecyl acrylate, pentabromobenzyl acrylate, pentabromophenyl acrylate, 3-sulfopropyl acrylate, tetrahydrofurfuryl acrylate, 2-tetrahydropyranyl acrylate, 3,5,5-Trimethylhexyl acrylate, 10-Undecenyl acrylate, Acrylic acid, Acrylonitrile, Phenyl 2-(2-bromoisobutyryloxy)ethyl methacrylate, 2-(tert-butylamino)ethyl methacrylate, Butyl methacrylate, tert-butyl methacrylate, 3-Chloro-2-hydroxypropyl methacrylate, 3,3'-Diethoxypropyl methacrylate, 2-(Diethylamino)ethyl methacrylate, Diethylene glycol butyl ether methacrylate, Di(ethylene glycol)methyl ether methacrylate, 2-(diisopropylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-Ethoxyethyl methacrylate, Ethylene glycol dicyclopentenyl ether methacrylate, Ethylene glycol methyl ether methacrylate, Ethylene glycol phenyl ether methacrylate, 2-Ethylhexyl methacrylate, Ethyl methacrylate, Furfuryl methacrylate Methacrylate, glycidyl methacrylate, glycosyloxyethyl methacrylate, hexyl methacrylate, hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy-3-{3-[2,4,6,8-tetramethyl-4,6,8-tris(propylglycidyl ether)-2-cyclotetrasiloxanyl]propoxy}propyl methacrylate, isobutyl methacrylate, 2-isocyanatoethyl methacrylate, isodecyl methacrylate, lauryl methacrylate, N-hydroxysuccinimide methacrylate, 4-methacryloxyethyl trimellitic anhydride, methyl methacrylate, 2-(methylthio)ethyl methacrylate, mono-2,2-N-morpholinoethyl methacrylate, 1-naphthyl methacrylate, pentabromophenyl methacrylate, 2-hydroxyethyl methacrylate phosphate, poly(ethylene glycol) behenyl ether acrylate, poly(ethylene glycol) 2,4Examples include 6-tris(1-phenylethyl)phenyl ether methacrylate, poly(propylene glycol) methacrylate, 2-[2-(3-propa-1-en-2-ylphenyl)propan-2-ylcarbamoyloxy]ethyl methacrylate, propyl methacrylate, 1-pyrene methyl methacrylate, stearyl methacrylate, 3-sulfopropyl methacrylate, TEMPO methacrylate, tetrahydrofurfuryl methacrylate, triethylene glycol methyl ether methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, vinyl methacrylate, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate.

[0014] Other specific exemplary additional vinyl monomers include 4-acetoxystyrene, 4-benzhydrylstyrene, 4-benzyloxy-3-methoxystyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, α-bromostyrene, 4-tert-butoxystyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 3,4-dimethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, N,N-dimethylvinylbenzylamine, 4-(diphenylphosphine)styrene, 4-ethoxystyrene, 4-[N-(methylaminoethyl)aminomethyl]styrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 3-nitrostyrene, and 2,4,6-trimethylstyrene.

[0015] Other specific exemplary additional vinyl monomers include sodium 4-vinylbenzoate, 3-vinylaniline, 4-vinylaniline, 9-vinylanthracene, 4-vinylbenzocyclobutene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, vinylbenzyl chloride, 4-vinylbenzyl chloride, 4-vinylbenzyl(triphenyl)phosphonium chloride, 4-vinylbiphenyl, 2-vinylnaphthalene, vinylacetate, vinylbenzoate, 4-tert-butylvinylbenzoate, vinylchloroformate, vinyl cinnamate, vinyldecanoate, vinylneodecanoate, vinylneononanoate, vinylpivalate, vinylpropionate, vinylstearate, vinylvallate, 1,4-butanediol divinyl ether, 1,4-butanediol vinyl ether, butyl vinyl ether, tert-butyl vinyl ether This includes ethyl, 2-chloroethyl vinyl ether, 1,4-cyclohexanedimethanol vinyl ether, cyclohexyl vinyl ether, di(ethylene glycol) divinyl ether, di(ethylene glycol) vinyl ether, diethyl vinyl orthoformate, dodecyl vinyl ether, ethylene glycol vinyl ether, 2-ethylhexyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, N-ethyl-2-vinylcarbazole, ethyl vinyl sulfide, N-methyl-N-vinylacetamide, 9-vinylanthracene, 9-vinylcarbazole, N-vinylformamide, 2-vinylnaphthalene, vinylphosphonic acid, N-vinylphthalimide, 2-vinylpyridine, 4-vinylpyridine, 1-vinyl-2-pyrrolidinone, and vinylsulfonic acid.

[0016] Vinyl fluoride monomers also include 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorodecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate. Relate, 2,2,3,4,4,4-Hexafluorobutyl acrylate, 1,1,1,3,3,3-Hexafluoroisopropyl acrylate, 2,2,3,3,4,4,5,5-Octafluoropentyl acrylate, 2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate, Pentafluorophenyl acrylate, 2,2,3,3,3-Pentafluoropropyl acrylate, 2,2,3,3,3-Pentafluoropropyl methacrylate, 1H,1H,2H,2H-Pentafluorodecyl acrylate , 2,2,3,3-tetrafluoropropyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, 2,2,2-trifluoroethyl methacrylate, methyl 2-(trifluoromethyl)acrylate, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate, pentafluorophenyl methacrylate, 2-[(1' [1',1'-trifluoro-2'-(trifluoromethyl)-2'-hydroxy)propyl]-3-norbornyl methacrylate, 2,6-difluorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, pentafluorophenyl 4-vinyl benzoate, 2,3,4,5,6-pentafluorostyrene, 2-(trifluoromethyl)styrene, 3-(trifluoromethyl)styrene, 4-(trifluoromethyl)styrene, vinyl acetate, and other additional vinyl monomers may be used.

[0017] The additional vinyl monomer may contain a nitrogen-containing group, including such monomers disclosed above. For example, the additional vinyl monomer containing a nitrogen-containing group can be dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate or dibutylaminoethyl methacrylate.

[0018] When the additional vinyl monomer is used to form the polymer material of the organic additive, it can be of a single type or a combination of different types.

[0019] The selection of the types of dioxane / dioxolane monomers, vinyl comonomers, polyfunctional vinyl monomers (if present), additional vinyl monomers (if present), and combinations thereof depends at least in part on the desired properties of the organic additive. The selection of the relative amounts of the monomers (described below) also depends on the desired properties of the organic additive. Advantageously, the organic additive provides a greater degree of chemical diversity compared to the inorganic additive and thus results in a wider range of properties. Further, the dioxane / dioxolane moiety provides advantageous properties compared to existing polymer additives.

[0020] In embodiments, certain monomers may be excluded when forming the resin particles. Examples of the excluded monomers include one or more of vinyl-imidazolium monomers, urethane (meth)acrylate monomers, and silyl ester monomers, such as triisopropylsilyl (meth)acrylate.

[0021] Generally, organic additives are formed from selected monomers using seed emulsion polymerization. This technique involves the use of an emulsion comprising selected monomers, a solvent, an initiator (which may be included in the emulsion or added separately in a separate step), and optionally a surfactant. An amount of the emulsion (e.g., 0.5% - 10% of the total amount of the emulsion) is exposed to conditions that induce a polymerization reaction between the monomers to form seed particles composed of a polymeric material from which the organic additive is constituted. Then, an additional amount of the emulsion (e.g., the remaining amount) is supplied under conditions that further induce the polymerization reaction and grow the seed particles to a desired diameter. Emulsion polymerization can be carried out in any suitable reactor using any suitable conditions. Exemplary conditions are described in the following examples. However, variations in these conditions, such as different mixing rates, reaction times, reaction temperatures, etc., are encompassed to adjust the properties of the resulting organic additives.

[0022] Emulsion polymerization provides the organic additive as organic additive latex, i.e., particles dispersed in a solvent. Further processing steps can be used to, for example, recover the organic additive particles from the solvent. These processing steps include, for example, filtration, drying, centrifugation, spray drying, freeze drying, etc. Then, as further described below, the recovered organic additive particles can be added to any desired composition, such as a toner composition, an additive manufacturing composition, etc.

[0023] The recovered organic additive particles can be described as a dry powder. Such a composition can be described as not having (i.e., not containing) a resin / polymer other than those provided by the organic additive particles themselves. This includes not having polyurethane, polyurethane (meth)acrylate, poly(meth)acrylate (other than the organic additive particles themselves), polyester, silyl ester copolymer, silyl (meth)acrylate polymer, or combinations thereof.

[0024] Since the resins / polymers constituting the organic additive particles are already polymerized, the compositions themselves are generally not curable and therefore do not contain (i.e., do not contain) initiators. This does not rule out the presence of small amounts of unreacted or reacted initiators that may be incorporated into the polymer chain. Similarly, organic additive compositions may be described as having no monomers (i.e., not containing monomers).

[0025] In embodiments, the organic additive composition may also be described as not containing (i.e., not having) a fungicide / biocide such as medetomidine.

[0026] Water is commonly used as the solvent in emulsions, but other solvents such as acetone, ethyl acetate, methanol, and combinations thereof may also be included.

[0027] Initiators are used in emulsion polymerization processes to accelerate polymerization reactions. They may be present in (or added to) the emulsion in amounts of, for example, 0.1–8 weight percent or 0.2–5 weight percent of the total weight of the monomers. Different types of initiators can be used individually or in combination.

[0028] Suitable initiators include water-soluble initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate. Other water-soluble initiators, azoamidine compounds, e.g., 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, 2,2'-azobis[N-(2-hydroxy-ethyl)-2-methylpropionamidine]dihydrochloride [Ropionamidine]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 This product contains '-azobis[2-(3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, and 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride. A redox initiator may be used.

[0029] Surfactants are generally used in emulsions, but in this embodiment, surfactants are not required. Anionic, cationic, or nonionic surfactants can be used. They may be present in the emulsion in amounts, for example, 0.01 to 15 weight percent or 0.1 to 10 weight percent of the total weight of the monomer. A single type or combination of different types of surfactants can be used.

[0030] Anionic surfactants include sulfates and sulfonates such as sodium dodecylsulfate (SDS), also known as sodium lauryl sulfate (SLS), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfate, dialkylbenzenealkylsulfates, and sulfonates, and acids such as abietic acid available from Aldrich, and NEOGEN® and NEOGEN SC® available from Daiichi Kogyo Seiyaku Co., Ltd. Other suitable anionic surfactants include DOWFAX® 2A1 from Dow Chemical, and TAYCA POWER BN2060 from Teika Co., Ltd. (Japan), which is an alkyl diphonyl oxide disulfonate and / or branched sodium dodecylbenzenesulfonate.

[0031] Examples of cationic surfactants include ammonium, alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, and C 12 ,C 15 ,C 17 Examples include trimethylammonium bromide and combinations thereof. Other cationic surfactants include cetylpyridinium bromide, quaternary polyoxyethylalkylamine halogens, dodecylbenzyltriethylammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, and SANISOL (benzalkonium chloride) available from Kao Chemicals. A preferred cationic surfactant is SANISOL B-50 available from Kao Corp., which is mainly benzyldimethylalkonium chloride.

[0032] Examples of nonionic surfactants include alcohols, acids, and ethers. For example, polyvinyl alcohol, polyacrylic acid, metalrose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, 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 may be used. Surfactants commercially available from Rhone-Poulenc, such as IGEPAL CA-210(trademark), IGEPAL CA-520(trademark), IGEPAL CA-720(trademark), IGEPAL CO-890(trademark), IGEPAL CO-720(trademark), IGEPAL CO-290(trademark), IGEPAL CA-210(trademark), ANTAROX 890(trademark), and ANTAROX 897(trademark), may be used.

[0033] Organic additives formed by the emulsion polymerization techniques described above may be characterized by their compositions. As described above, the polymer material of an organic additive is the result of polymerization reactions between various combinations of monomers, forming polymerization products. For clarity, the composition of a polymer material / organic additive 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 products, and therefore the organic additives, may include other components present in the emulsion described above. For example, initiators (or parts thereof, e.g., sulfate groups) may be incorporated at the beginning of the polymer chain. Surfactants may entangle with the polymer chain and be embedded within the organic additive particles, for example, due to strong non-covalent bonds.

[0034] In embodiments, the organic additive comprises (or consists of) a polymerization product of a reaction comprising a dioxane / dioxolane monomer, a vinyl comonomer (e.g., an aliphatic cyclo(meth)acrylate monomer), and optionally one or more of a polyfunctional vinyl monomer, an additional vinyl monomer, and an initiator. Any of the dioxane / dioxolane monomers, vinyl comonomers, polyfunctional vinyl monomers, additional vinyl monomers, and initiators described herein may be used.

[0035] When using a specific exemplary composition, the composition of organic additive particles may also be identified as crosslinked poly[(glycerol formal (meth)acrylate)-ran-(cyclohexyl methacrylate)-ran-(dimethylaminoethyl methacrylate)]. In this description, different chemical parts resulting from the polymerization reaction are identified by referring to the corresponding monomers in parentheses, where "ran" refers to the random incorporation of different monomers into the copolymer. The use of this description includes the presence of initiators (or parts thereof) at the start and end of each copolymer, as well as crosslinking via polyfunctional monomers.

[0036] In embodiments where certain monomers are excluded from forming organic additive particles, such monomers do not participate in the polymerization reaction that forms the polymer matrix of the organic additive particles. Therefore, in these embodiments, the composition of the organic additive particles can be described as not having (i.e., not containing) one or more of the following: vinyl-imidazolium monomer, urethane-containing monomer (i.e., monomer containing a urethane group), and silyl ester monomer such as triisopropylsilyl (meth)acrylate.

[0037] In any of the embodiments referenced in the paragraph above, the dioxane / dioxolane monomer may be present in amounts of 1 to 50 weight percent of the total weight of the monomer. This includes, for example, 5 to 40 weight percent and 10 to 30 weight percent. If two or more types of dioxane / dioxolane monomers are used, these values ​​refer to the total amount of dioxane / dioxolane monomers. Other monomers (e.g., vinyl comonomers, polyfunctional vinyl monomers, and / or additional vinyl monomers) may be present in amounts of 50 to 99 weight percent of the total weight of the monomer. In any of these embodiments, the vinyl comonomer may be present in amounts of 50 to 99 weight percent of the total weight of the monomer. This includes, for example, 60 to 90 weight percent and 70 to 90 weight percent. If two or more types of vinyl comonomers are used, these values ​​refer to the total amount of vinyl comonomers. In any of these embodiments, the polyfunctional vinyl monomer, if present, may be present in amounts of up to 40 weight percent of the total weight of the monomer. This includes, for example, 8 to 40 weight percent and 10 to 30 weight percent. When one type of polyfunctional vinyl monomer is used, these values ​​refer to the total amount of the polyfunctional vinyl monomer. In any of these embodiments, additional vinyl monomers, if present, may be in an amount of up to 35 weight percent of the total weight of the monomers. This includes, for example, up to 20 weight percent, or 0.5 to 10 weight percent. When two or more types of additional vinyl monomers are used, these values ​​refer to the total amount of the additional vinyl monomers. As described above, amounts of initiators and optionally surfactants may also be present.

[0038] In any of the embodiments referenced in the above paragraphs, one or more of the following modifications may be used: Glycerolform methacrylate may be used as a dioxane / dioxolane monomer (or one of the dioxane / dioxolane monomers). Cyclohexyl methacrylate may be used as a vinyl comonomer (or one of the vinyl comonomers). Divinylbenzene may be used as a polyfunctional vinyl monomer (or one of the polyfunctional vinyl monomers). A monomer containing a nitrogen group may be present as an additional vinyl monomer (or one of the additional vinyl monomers) in an amount of 0.1 to 1.5 weight percent of the total weight of the monomers. The monomer containing a nitrogen group may be dimethylaminoethyl methacrylate.

[0039] Organic additives may be characterized by their diameter and morphology. As mentioned above, they are particulate. They are generally spherical, but this does not mean perfectly spherical, as some particles may have an elliptical, oval, or irregular shape. The particle size of organic additives is D 50 This may be reported as particle size, which refers to the diameter value in cases where 50% (by volume) of the particles in the sample have a diameter less than that value. In embodiments, the organic additive is in the range of 20 nm to 500 nm, 25 nm to 200 nm, 40 nm to 150 nm, or 40 nm to 100 nm. 50 It has a particle size. 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 diameter. 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, NIST polystyrene nanosphere control samples with diameters in the range of 15 mm to 150 mm can be used under the trademark name NIST Traceable Reference Material for Nanotrac Particle Size Analyzers, obtained from Microtrac.

[0040] Organic additives can be characterized by their thermal stability. Thermal stability can be quantified by the decomposition onset temperature of the organic additive. This onset temperature can be measured using a thermogravimetric analyzer as described in the following examples. In the examples, the onset temperature is at least 290°C, at least 295°C, at least 300°C, or in the range of 290°C to 360°C.

[0041] As described above, organic additives can be used in a variety of compositions, for example, compositions that generally contain inorganic additives such as silica, titania, or alumina. Exemplary such compositions include toners and additive manufacturing compositions, each of which is described further below. Organic additives (or organic additive latex) can be incorporated into / on / into the desired composition using a variety of techniques, including mixing, blending, spraying, and immersion. In embodiments, the organic additive is adsorbed onto the surface of particles of the desired composition, including forming a coating, layer, or film thereon. The amount of organic additive used generally depends on the desired properties for the composition. However, in embodiments, the organic additive is used in amounts ranging from 0.1 to 10 weight percent of the total weight of the desired composition. This includes, for example, 0.1 to 5 weight percent and 0.1 to 2 weight percent.

[0042] toner

[0043] Organic additives may be used in toner compositions (toners) containing toner particles. In such toner compositions, organic additive particles may be adsorbed onto the outer surface of the toner particles. The toner particles are formed from a resin, and the type of resin is not particularly limited. Exemplary resins, including polyester resins and styrene-acrylate resins, are described below. A single type or a combination of different types of resins may be used.

[0044] Crystalline resin

[0045] The resins used herein may be polyester resins formed by reacting a diol with a diacid (or diester) in the presence of an optional catalyst. Suitable organic diols for forming crystalline polyesters include aliphatic diols having about 2 to about 36 carbon atoms, including their structural isomers, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and combinations thereof. The aliphatic diol may be selected in an amount of, for example, about 40 to 60 mole percent of the resin, about 42 to 55 mole percent of the resin, or about 45 to 53 mole percent of the resin, and the second diol may be selected in an amount of about 0 to 10 mole percent of the resin, or about 1 to 4 mole percent of the resin.

[0046] Examples of organic diacids or diesters, including vinyl diacids or vinyl diesters, selected for the preparation of crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethyl itaconate, cis,1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid and mesaconic acid, their diesters or anhydrides. The organic diacid may be selected in an amount of, for example, about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, or about 45 to about 50 mole percent of the resin, and the second diacid may be selected in an amount of about 0 to about 10 mole percent of the resin.

[0047] Polycondensation catalysts that can be used to form crystalline (and amorphous) polyesters include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, and dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkylzincs, dialkylzincs, zinc oxides, stannous oxides, or combinations thereof. Such catalysts may be used in amounts of about 0.01 mole percent to about 5 mole percent, for example, based on the starting diacid or diester used to produce the polyester resin.

[0048] Examples of crystalline resins include polyester, polyamide, polyimide, polyolefin, polyethylene, polybutylene, polyisobutylate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, and mixtures thereof. Certain crystalline resins include poly(ethylene-adipate), poly(propylene-adipate), poly(butylene-adipate), poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate), poly(ethylene-succinate), poly(propylene-succinate), poly(butylene-succinate), poly(pentylene-succinate), poly(hexylene-succinate), poly(octylene-succinate), poly(ethylene-sebacate), poly(propylene-sebacate), poly(butylene-sebacate), poly(pentylene-sebacate), poly(hexylene-sebacate), and poly(octylene-sebacate). Polyester-based materials such as cate, poly(decylene-sebacate), poly(decylene-decanoate), poly(ethylene-decanoate), poly(ethylene-dodecanoate), poly(nonylene-sebacate), poly(nonylene-decanoate), copoli(ethylene-fumarate)-copoly(ethylene-sebacate), copoli(ethylene-fumarate)-copoly(ethylene-decanoate), copoli(ethylene-fumarate)-copoly(ethylene-dodecanoate), copoli(2,2-dimethylpropane-1,3-diol-decanoate)-copoly(nonylene-decanoate), poly(octylene-adipate), and mixtures thereof may also be used. Examples of polyamides include poly(ethylene-adipamide), poly(propylene-adipamide), poly(butylene-adipamide), poly(pentylene-adipamide), poly(hexylene-adipamide), poly(octylene-adipamide), poly(ethylene-succinimide), poly(propylene-sebacamide), and mixtures thereof.Examples of polyimides include poly(ethylene-adipimide), poly(propylene-adipimide), poly(butylene-adipimide), poly(pentylene-adipimide), poly(hexylene-adipimide), poly(octylene-adipimide), poly(ethylene-succinimide), poly(propylene-succinimide), poly(butylene-succinimide), and mixtures thereof.

[0049] In this embodiment, the crystalline polyester resin has the following formula (III). [ka] Each of a and b may be in the range of 1 to 12, 2 to 12, or 4 to 12, and furthermore, p may be in the range of 10 to 100, 20 to 80, or 30 to 60. In the embodiment, the crystalline polyester resin is poly(1,6-hexylene-1,12-dodecanoate), which can be produced by the reaction of dodecanediic acid with 1,6-hexanediol.

[0050] As described above, the disclosed crystalline polyester resin can be prepared by a polycondensation process in which a suitable organic diol is reacted with a suitable organic diacid / diester in the presence of a polycondensation catalyst. A stoichiometric equimolar ratio of the organic diol to the organic diacid may be used, but if the boiling point of the organic diol is about 180°C to about 230°C, an excess amount of diol such as about 0.2 to 1 molar equivalent of ethylene glycol or propylene glycol can be used and removed during the polycondensation process by distillation. The amount of catalyst used may vary and can be selected, for example, in amounts such as about 0.01 to about 1 or about 0.1 to about 0.75 molar percent of the crystalline polyester resin.

[0051] Crystalline resins or combinations of crystalline resins may be present in amounts of, for example, about 1% to 85% by weight of the toner, about 5% to 50% by weight of the toner, or about 10% to 35% by weight of the toner.

[0052] The crystalline resin may have various melting points, for example, about 30°C to about 120°C, about 50°C to about 90°C, or about 60°C to about 80°C. When measured by gel permeation chromatography (GPC), the crystalline resin may have a number average molecular weight (M n ), for example, of about 1,000 to about 50,000, about 2,000 to about 25,000, or about 5,000 to about 20,000, and a weight average molecular weight (M w ) of about 2,000 to about 100,000, about 3,000 to about 80,000, or about 10,000 to about 30,000 when determined by GPC. The molecular weight distribution (M w / M n ) of the crystalline resin may be, for example, about 2 to about 6, about 3 to about 5, or about 2 to about 4.

[0053] Amorphous resin

[0054] The resin may be an amorphous polyester resin formed by reacting a diol with a diacid or diester in the presence of an optional catalyst. Examples of diacids or diesters, including vinyl diacids or vinyl diesters, used for the preparation of amorphous polyesters include terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, dimethyl fumarate, dimethyl itaconate, cis, 1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, glutaric acid, glutaric acid Examples of dicarboxylic acids or diesters include adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedinioic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl phthalate, phthalic anhydride, diethyl phthalate, dimethyl succinate, dimethyl fumarate, dimethyl maleate, dimethyl glutarate, dimethyl adipate, dimethyl dodecyl succinate, and combinations thereof. The organic diacid or diester may be present in amounts, for example, about 40 to about 60 mole percent of the resin, about 42 to about 52 mole percent of the resin, or about 45 to about 50 mole percent of the resin.

[0055] Examples of diols that can be used to produce amorphous polyesters include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis(hydroxyethyl)-bisphenol A, bis(2-hydroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenediethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene, and combinations thereof. The amount of the selected organic diol may vary, and the organic diol may be present, for example, in amounts of about 40 to about 60 mole percent of the resin, about 42 to about 55 mole percent of the resin, or about 45 to about 53 mole percent of the resin.

[0056] Suitable examples of amorphous resins include polyester, polyamide, polyimide, polyolefin, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, and mixtures thereof.

[0057] Unsaturated amorphous polyester resins may be used as resins. Examples of such resins include those disclosed in U.S. Patent No. 6,063,827, which is incorporated herein by reference in its entirety. Exemplary unsaturated amorphous polyester resins include, but are not limited to, poly(propoxylated bisphenol cofmarate), poly(ethoxylated bisphenol cofmarate), poly(butyloxylated bisphenol cofmarate), poly(copropoxylated bisphenol coethoxylated bisphenol cofmarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol comareate), poly(ethoxylated bisphenol comareate), and poly(butyloxylated Examples include bisphenol comaleate, poly(copropoxylated bisphenol coethoxylated bisphenol comaleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol coitaconate), poly(ethoxylated bisphenol coitaconate), poly(butyloxylated bisphenol coitaconate), poly(copropoxylated bisphenol coethoxylated bisphenol coitaconate), poly(1,2-propylene itaconate), and combinations thereof.

[0058] Suitable polyester resins may be amorphous polyesters such as poly(propoxylated bisphenol A cofmarate) resin. Examples of such resins and processes for producing them are disclosed in U.S. Patent No. 6,063,827, the entirety of which is incorporated herein by reference.

[0059] Suitable polyester resins include amorphous acidic polyester resins. Amorphous acidic polyester resins may be any combination of propoxylated bisphenol A, ethoxylated bisphenol A, terephthalic acid, fumaric acid, and dodecenyl succinic anhydride, for example, the poly(propoxylated bisphenol-co-terephthalate-fumarate-dodecenyl succinate) system. Another amorphous acidic polyester resin that can be used is poly(propoxylate-ethoxylated bisphenol-co-terephthalate-dodecenyl succinic acid-trimellitic anhydride).

[0060] An example of a linear propoxylated bisphenol A fumarat resin that can be used as a resin is available from Resana S / A Industrias Quimicas (São Paulo, Brazil) under the trade name SPAMII. Other commercially available propoxylated bisphenol A fumarat resins that can be used include GTUF and FPESL-2 from Kao Corporation, Japan, and EM181635 from Reichhold, Research Triangle Park, NC.

[0061] Amorphous resins or combinations of amorphous resins may be present in amounts, for example, about 5 to about 95% by weight of the toner, about 30 to about 90% by weight of the toner, or about 35 to about 85% by weight of the toner.

[0062] Amorphous resins may have glass transition temperatures of approximately 30°C to 80°C, 35°C to 70°C, or 40°C to 65°C. The glass transition temperature can be measured using differential scanning calorimetry (DSC). When measured by GPC, amorphous resins may have M values ​​of, for example, approximately 1,000 to 50,000, 2,000 to 25,000, or 1,000 to 10,000. nWhen measured by GPC, for example, M values ​​of approximately 2,000 to 100,000, 5,000 to 90,000, 10,000 to 90,000, 10,000 to 30,000, or 70,000 to 100,000. w It may have.

[0063] One, two, or more resins may be used in the toner of the present invention. When two or more resins are used, the resins may be in any suitable ratio (e.g., by weight ratio), such as about 1% (first resin) / 99% (second resin) to about 99% (first resin) / 1% (second resin), about 10% (first resin) / 90% (second resin) to about 90% (first resin) / 10% (second resin). When the resins include a combination of amorphous and crystalline resins, the resins may be in a weight ratio of, for example, about 1% (crystalline resin) / 99% (amorphous resin) to about 99% (crystalline resin) / 1% (amorphous resin), or about 10% (crystalline resin) / 90% (amorphous resin) to about 90% (crystalline resin) / 10% (amorphous resin). In some embodiments, the weight ratio of the resin is about 80% to about 60% by weight of amorphous resin and about 20% to about 40% by weight of crystalline resin. In such embodiments, the amorphous resin may be a combination of amorphous resins, for example, a combination of two types of amorphous resins.

[0064] Other resins

[0065] Toner particles are not limited to polyester resins. Other resins may be used, such as resins formed from various combinations of monomers including styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, acrylamide, methacrylamide, dialkyl or trialkylacrylamide or methacrylamide, vinylpyridine, vinylpyrrolidone, and vinyl-N-methylpyridinium chloride. Examples of methacrylates include beta-carboxyethyl acrylate (β-CEA) and 2-carboxyethyl methacrylate. Other resins may be used, such as those disclosed in U.S. Patent No. 6,841,329 and U.S. Patent No. 7,413,842, each of which is incorporated herein by reference in whole. These references also provide exemplary processes for forming such resins.

[0066] Examples of resins include styrene acrylate, styrene butadiene, styrene methacrylate, and more specifically, poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly( (aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly( Poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-butadiene), Poly(propyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylonitrile),Examples include poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-beta-carboxyethyl acrylate), and combinations thereof. The polymers may be block, random, or alternating copolymers. The term "alkyl" as used in this paragraph may contain about 1 to about 12 carbon atoms, about 1 to about 10 carbon atoms, or about 1 to about 6 carbon atoms. In the resins described in this paragraph, various relative amounts of each monomer may be used as desired.

[0067] Similar to the above description of polyester resins, one, two, or more resins can be used to form toner particles. In embodiments where two or more resins are used, the resins may be in any preferred ratio (e.g., by weight ratio), such as about 1% (first resin) / 99% (second resin) to about 99% (first resin) / 1% (second resin), in embodiments about 4% (first resin) / 96% (second resin) to about 96% (first resin) / 4% (second resin), or about 50% (first resin) / 50% (second resin), although weight ratios outside these ranges may also be used.

[0068] Coloring agents

[0069] Various colorants may be included in the toner. The term "colorant" includes, for example, pigments, dyes, mixtures thereof, such as mixtures of dyes, mixtures of pigments, and mixtures of dyes and pigments. Colorants may be present in the toner in amounts such as, for example, about 0.1% to about 35% by weight, about 1% to about 20% by weight, or about 5% to about 15% by weight.

[0070] Examples of colorants include carbon blacks such as REGAL 330 (registered trademark) (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals), and Sunsperse Carbon Black LHD 9303 (Sun Chemicals); magnetites such as Mobay Magnetite MO8029 (trademark) and MO8060 (trademark); Columbia Magnetite; MAPICO BLACKS (trademark) and surface-treated magnetites, Pfizer Magnetites CB4799 (trademark), CB5300 (trademark), CB5600 (trademark), and MCX6369 (trademark); Bayer Magnetite, BAYFERROX 8600 (trademark), and 8610 (trademark); Northern Pigments Magnetite, NP-604 (trademark), and NP-608 (trademark); and Magnox Magnetite TMB-100 (trademark) or TMB-104 (trademark). Examples of colorants include pigments containing cyan, magenta, yellow, red, green, brown, blue, or mixtures thereof. Pigments are generally used as aqueous pigment dispersions.

[0071] Paliogen Violet 5100 and 5890 (BASF) Normandy Magenta RD-2400 (Paul Uhlrich) Permanent Violet VT2645 (Paul Uhlrich) Heliogen Green L8730 (BASF) Argyle Green XP-111-S (Paul Uhlrich) Brilliant Green Toner GR 0991 (Paul Uhlrich) Lithol Scarlet D3700 (BASF) Toluidine Red (Aldrich) Scarlet for Thermoplastics NSD PS PA(Ugine Kuhlmann of Canada)、Lithol Ruby Toner(Paul Uhlrich)、Lithol Scarlet 4440(BASF)、NBD 3700(BASF)、Good Red C(Dominion Color)、Royal Brilliant Red RD-8192(Paul Uhlrich)、Oracet Pink RF(Ciba). Geigy) Paliogen Red 3340, 3871 K (BASF), Lithol Fast Scarlet L4300 (BASF), Heliogen Blue D6840, D7080, K7090, K6910, and L7020 (BASF), Sudan Blue OS (BASF), Neopen Blue FF4012 (BASF), PV Fast Blue B2G01 (American Hoechst), Irgalite Blue BCA (Ciba Geigy), Paliogen Blue 6470 (BASF), Sudan II, III, and IV (Matheson, Coleman,Bell), Sudan Orange (Aldrich), Sudan Orange 220 (BASF), Paliogen Orange 3040 (BASF), Ortho Orange OR 2673 (Paul Uhlrich), Paliogen Yellow 152 and 1560 (BASF), Lithol Fast Yellow 0991 K (BASF), Paliotol Yellow 1840 (BASF), Novaperm Yellow FGL (Hoechst), Permanerit Yellow YE 0305 (Paul Uhlrich), Lumogen Yellow D0790 (BASF), Sunsperse Yellow YHD 6001 (Sun Chemicals), Suco-Gelb 1250 (BASF), Suco-Yellow D1355 (BASF), Suco Fast Yellow D1165, D1355 and D1351 (BASF), Hostaperm Pink Examples include E (trademark) (Hoechst), Fanal Pink D4830 (BASF), Cinquasia Magenta (trademark) (DuPont), Paliogen Black L9984 (BASF), Pigment Black K801 (BASF), Levanyl Black A-SF (Miles, Bayer), and combinations thereof.

[0072] Other suitable 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.

[0073] Specific examples of pigments include Sunsperse BHD 6011X (Blue 15 Type), Sunsperse BHD 9312X (Pigment Blue 15 74160), Sunsperse BHD 6000X (Pigment Blue 15:3 74160), Sunsperse GHD 9600X and GHD 6004X (Pigment Green 7 74260), Sunsperse QHD 6040X (Pigment Red 122 73915), Sunsperse RHD 9668X (Pigment Red 185 12516), Sunsperse RHD 9365X and 9504X (Pigment Red 57 15850:1), Sunsperse YHD 6005X (Pigment Yellow 83 21108), and Flexiverse YFD. Aqueous pigment dispersions available from Sun Chemicals, Heliogen Blue, including 4249 (Pigment Yellow 17 21105), Sunsperse YHD 6020X and 6045X (Pigment Yellow 74 11741), Sunsperse YHD 600X and 9604X (Pigment Yellow 14 21095), Flexiverse LFD 4343 and LFD 9736 (Pigment Black 7 77226), Aquatone, and combinations thereof; L6900 (trademark), D6840 (trademark), D7080 (trademark), D7020 (trademark), Pylam Oil Blue (trademark), Pylam Oil Yellow (trademark), Pigment Blue 1 (trademark), and Dominion Color, available from Paul Uhlrich & Company, Inc. Examples include Pigment Violet 1 (trademark), Pigment Red 48 (trademark), Lemon Chrome Yellow DCC 1026 (trademark), EDToluidine Red (trademark), Bon Red C (trademark), and Novaperm Yellow FGL (trademark), all available from Corporation, Ltd., Toronto, Ontario.Examples of magenta include 2,9-dimethyl-substituted quinacridone and anthraquinone dyes, identified in the color index as CI 60710, CI Dispersed Red 15, and diazo dyes, identified in the color index as CI 26050, CI Solvent Red 19. Exemplary examples of cyanides include copper tetra(octadecylsulfonamide) phthalocyanine, x-copper phthalocyanine pigment, listed in the color index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, and Anthrathrene Blue, identified in the color index as CI 69810, Special Blue X-2137. Exemplary examples of yellow include diarylylide yellow 3,3-dichlorobenzanilide, a monoazo pigment identified in the color index as CI 12700, CI Solvent Yellow 16; Foron Yellow SE / GLN, a nitrophenylamine sulfonamide identified in the color index as CI Dispersed Yellow 33; 2,5-dimethoxy-4-sulfonylide phenylazo-4'-chloro-2,5-dimethoxyacetoacetanilide; and Permanent Yellow FGL.

[0074] wax

[0075] Optionally, wax may be included in this toner. If wax is included, it may be present in an amount of, for example, about 1% to 25% by weight of the toner, or about 5% to 20% by weight of the toner.

[0076] When wax is used, the wax may include any of the various waxes used in emulsion agglomerating toners. Examples of waxes that can be selected include waxes having an average molecular weight of approximately 500 to 20,000, or approximately 1,000 to 10,000. Examples of waxes that can be used include polyolefins such as polyethylene containing linear and branched polyethylene wax, polypropylene containing linear and branched polypropylene wax, polymethylene wax, polyethylene / amide, polyethylene tetrafluoroethylene, polyethylene tetrafluoroethylene / amide, and polybutene wax, as commercially available from Allied Chemical and Petrolite Corporation; POLYWAX® polyethylene wax, as commercially available from Baker Petrolite; wax emulsions available from Michaelman, Inc. and Daniels Products Company; EPOLENE N-15®, as commercially available from Eastman Chemical Products, Inc.; and Sanyo Kasei KK.VISCOL 550-P™, a low weight-average molecular weight polypropylene available from [source], plant-based waxes such as carnauba wax, rice wax, candelilla wax, lacquer wax, and jojoba oil, animal-based waxes such as beeswax, microcrystalline waxes such as montan wax, ozokerite, ceresin, paraffin wax, and waxes derived from crude oil distillation, mineral waxes and petroleum-based waxes such as silicone wax, mercapto wax, polyester wax, and urethane wax, modified polyolefin waxes (such as carboxylic acid-terminated polyethylene wax or carboxylic acid-terminated polypropylene wax), higher fatty acids and higher alcohols such as Fischer-Tropsch wax, stearyl stearate, and behenyl behenate. Examples include ester waxes obtained from alcohol, ester waxes obtained from higher fatty acids such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetrabehenate, and monohydric or polyhydric lower alcohols, ester waxes obtained from higher fatty acids such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate, and triglyceryl tetrastearate, and polyhydric alcohol multimers, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes such as cholesteryl stearate. Examples of functionalized waxes that can be used include, for example, amines, amides, e.g., AQUA SUPERSLIP 6550™ and SUPERSLIP 6530™ available from Micro Powder Inc.; fluorinated waxes, e.g., POLYFLUO 190™, POLYFLUO 200™, POLYSILK 19™, and POLYSILK 14™ available from Micro Powder Inc.; mixed fluoramide waxes such as aliphatic polar amide functionalized waxes; and esters of hydroxylated unsaturated fatty acids, e.g., also available from Micro Powder Inc.Examples include MICROSPERSION 19(trademark), imides, esters, quaternary amines, carboxylic acids, or acrylic polymer emulsions available from SC Johnson Wax, such as JONCRYL 74(trademark), 89(trademark), 130(trademark), 537(trademark), and 538(trademark), all available from SC Johnson Wax, as well as chlorinated polypropylene and polyethylene available from Allied Chemical and Petrolite Corporation and SC Johnson Wax. Mixtures and combinations of the aforementioned waxes may also be used. The wax may be included, for example, as a release agent for the fixing machine rolls. In embodiments, the wax may be crystalline or amorphous.

[0077] Toner preparation process

[0078] To form this toner, any of the above resins can be provided as a latex, which can then be used as a raw material to form the toner, for example, by using emulsion aggregation (EA) and a coalescence process. Such a process may include agglomerating a mixture of the resin-containing latex, a colorant, and optionally a wax, and then coalescing the mixture. The colorant and wax may be provided in the mixture as separate aqueous dispersions.

[0079] Next, the mixture may be homogenized, which may be achieved by mixing at approximately 600 to 6,000 revolutions per minute. Homogenization may be achieved by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer.

[0080] The flocculant may be added to the mixture. Any suitable flocculant may be used. Suitable flocculants include, for example, aqueous solutions of divalent or polyvalent cationic materials. The flocculant may be, for example, a polyaluminum halide such as polyaluminum chloride (PAC), or an inorganic cationic flocculant such as the corresponding bromide, fluoride, or iodide, a polyaluminum silicate such as polyaluminum sulfosilicate (PASS), or 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, and copper sulfate, or a combination thereof. The flocculant may have a glass transition temperature (T) of the resin. g It can be added to the mixture at a temperature below 5°C. The flocculant may also be added to the mixture under homogenization conditions.

[0081] The flocculant may be added to the mixture in an amount of approximately 0% to 10% by weight of the total resin, approximately 0.2% to 8% by weight of the total resin, or approximately 0.5% to 5% by weight of the total resin.

[0082] The particles of the mixture may be aggregated until a predetermined desired particle size is obtained. The predetermined desired diameter refers to the desired particle size to be obtained when determined before formation, and the particle size is monitored during the growth process until such a particle size is reached. Samples may be taken during the growth process and analyzed for volume-average particle size, for example, with a Coulter Counter. Thus, aggregation may proceed by maintaining a high temperature or by slowly raising the temperature, for example, from about 30°C to about 100°C in the embodiment, from about 30°C to about 80°C in the embodiment, or from about 30°C to about 50°C in the embodiment. The temperature may be maintained for a period of about 0.5 hours to about 6 hours, or in the embodiment, about 1 hour to about 5 hours, with stirring to provide aggregated particles. Once the predetermined desired particle size is reached, a shell may be added. The volume-average particle size of the particles before the application of the shell may be, for example, about 3 micrometers (μm) to about 10 μm, about 4 μm to about 10 μm in the embodiment, or about 6 μm to about 9 μm.

[0083] Shell resin

[0084] In this embodiment, a resin coating may be applied to the aggregated particles after aggregation but before coalescing, and a shell may be formed on top of it. Any of the above-mentioned resins may be used for the shell.

[0085] The shell can be applied to the aggregated particles by using a shell resin in the form of latex, as described above. Such latex may be combined with the aggregated particles under conditions sufficient to form a coating on the aggregated particles. For example, shell formation on the aggregated particles may occur while heating to a temperature of about 30°C to about 80°C, or about 35°C to about 70°C. Shell formation may take place over a period of about 5 minutes to about 10 hours, or about 10 minutes to about 5 hours.

[0086] Once the desired diameter of the toner particles is achieved, the pH of the mixture may be adjusted to a value of about 3 to about 10, or in embodiments, about 5 to about 9, using a pH control agent, such as a base. pH adjustment may be used for freezing to stop toner growth. Suitable bases used to stop toner growth include any suitable bases such as alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof. In embodiments, a chelating agent such as ethylene diamine tetraacetic acid (EDTA) may be added to help adjust the pH to the desired value mentioned above. Other chelating agents may be used.

[0087] In this embodiment, the diameter of the core-shell toner particles (before coalescence) may be approximately 3 μm to 10 μm, approximately 4 μm to 10 μm, or approximately 6 μm to 9 μm.

[0088] Fusion

[0089] Following aggregation to a desired particle size and the application of an optional shell, the particles may then be coalesced into a desired final shape, which is done by heating the mixture to a temperature of, for example, about 45°C to about 99°C, about 55°C to about 99°C, or about 60°C to about 98°C (this temperature may be above the glass transition temperature of the resin used to form the toner particles). Heating may be continued, or the pH of the mixture may be adjusted (e.g., reduced) over a period of time to reach a desired circularity. This time may be about 1 hour to about 5 hours, or about 2 hours to about 4 hours. Various buffers may be used during coalescing. The total coalescing period may be about 1 to about 9 hours, about 1 to about 8 hours, or about 1 to about 5 hours. Stirring may be used during coalescing, for example, at about 20 rpm to about 1000 rpm, or about 30 rpm to about 800 rpm.

[0090] After aggregation and / or coalescence, the mixture may be cooled to room temperature. Cooling may be rapid or slow, as desired. A preferred cooling process may include introducing cold water into the jacket surrounding the reactor. After cooling, the toner particles may be sieved through a sieve of the desired size, filtered, washed with water, and then dried. Drying may be achieved by any preferred drying process, including, for example, freeze-drying.

[0091] For example, other toner preparation processes described in U.S. Patent Nos. 6,841,329 and 7,413,842 may be used, each of which is incorporated herein by reference in its entirety.

[0092] Other additives

[0093] As described above, these organic additives are also included in toners and may be used in addition to, or as a substitute for, the specific surface additives mentioned above, such as silica, titania, and alumina. The application of organic additives to toner particles may be carried out as described above.

[0094] However, in embodiments, the toner may also contain other optional additives. For example, the toner may contain positive or negative charge control agents. Surface additives may also be used, including metal oxides such as titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, tin oxide, strontium titanate, and mixtures thereof; metal salts and metal salts of fatty acids such as AEROSIL®, zinc stearate, calcium stearate, and magnesium stearate, and mixtures thereof; long-chain alcohols such as UNILIN 700, and mixtures thereof. These surface additives may be present in amounts of about 0.1% to about 5% by weight of the toner, or about 0.25% to about 3% by weight of the toner.

[0095] Toner characteristics

[0096] In the embodiment, the dried toner particles, excluding the external surface additive / organic additive, exhibit one or more of the following characteristics:

[0097] (1) Volume-average particle size of approximately 2.0 μm to approximately 24.0 μm, approximately 2.5 μm to approximately 10.0 μm, or approximately 3.0 μm to approximately 9.0 μm.

[0098] (2) Number-average geometric size distribution (GSDn) and / or volume-average geometric size distribution (GSDv) of approximately 1.05 to 1.30, 1.10 to 1.25, or 1.10 to 1.20,

[0099] (3) Circularity of approximately 0.92 to 1.00, approximately 0.95 to 0.99, or approximately 0.96 to 0.98.

[0100] The toner may exhibit excellent electrostatic properties under various relative humidity (RH) conditions, for example, in a low-humidity zone of 21.1°C / 10%RH (J zone) and a high-humidity zone of approximately 28°C / 85%RH (A zone). In the embodiment, toner particles containing the external surface additive / organic additive exhibit one or more of the following properties:

[0101] (4) A-zone charge-to-diameter ratio (Q / D) of approximately 4mm to 10mm, 5mm to 9mm, or 6mm to 8mm,

[0102] (5) A-zone charge-mass ratio (Q / M) of approximately 15 μC / g to approximately 40 μC / g, approximately 20 μC / g to approximately 35 μC / g, or approximately 25 μC / g to approximately 30 μC / g,

[0103] (6) J-zone charge-to-diameter ratio (Q / D) of approximately 9mm to 15mm, 10mm to 14mm, or 11mm to 13mm,

[0104] (7) J-zone charge-mass ratio (Q / M) of approximately 40 μC / g to 65 μC / g, approximately 45 μC / g to 60 μC / g, or approximately 50 μC / g to 55 μC / g.

[0105] These characteristics may be measured according to the techniques described in the following examples.

[0106] In the embodiment, toner particles containing the external surface additive / organic additive exhibit one or more of the following characteristics:

[0107] (8) Charge retention in Zone A after 24 hours in the range of approximately 50 percent to approximately 98 percent, approximately 60 percent to approximately 90 percent, or approximately 70 percent to approximately 80 percent.

[0108] (9) Charge retention in Zone A after 7 days in the range of approximately 65 percent to approximately 90 percent, approximately 70 percent to approximately 85 percent, or approximately 75 percent to approximately 80 percent.

[0109] (10) A degree of cohesion in the range of approximately 15 percent to 70 percent, approximately 25 percent to 60 percent, or approximately 35 percent to 50 percent.

[0110] (11) Initiation of blocking temperatures above approximately 50.0°C, above approximately 51.0°C, in the range of approximately 50.0°C to approximately 55.0°C, or between approximately 51.0°C and approximately 53.0°C.

[0111] These properties can be measured according to the techniques described in the following examples and using the surface additives described in the following examples.

[0112] Developer and carrier

[0113] 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 toner may be present in the carrier in amounts of about 1% to about 15% by weight, about 2% to about 8% by weight, or about 4% to about 6% by weight. 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.

[0114] Toner applications

[0115] The toner of the present invention can be used in various electrophotographic processes with various electrophotographic printers. Electrophotographic imaging processes include, for example, preparing an image in an electrophotographic printer comprising 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 any of the toners described herein. Electrophotographic printers may include high-speed printers, high-speed monochrome printers, color printers, and the like. Once an image is formed with the toner / developer, the image can then be transferred to an image-receiving medium such as paper. A fuser roll member may be used to fix the toner to the image-receiving medium by using heat and pressure.

[0116] In this disclosure, the phrases “toner” and “toner composition” refer to compositions used in electrophotographic printers and configured to form an image together. Thus, in addition to resins, colorants, present organic additives, and optionally selected waxes and others, toner may include any other components commonly used in such compositions to form an object using a desired electrophotographic printer. It should be noted that any other excluded organic additive particles and their latex referenced above may apply to embodiments of toner compositions.

[0117] additive manufacturing composition

[0118] Organic additives can also be used in additive manufacturing compositions. Additive manufacturing (also known as 3D printing) refers to several techniques for creating objects based on digital data representing those objects. The digital data is broken down into a series of two-dimensional (2D) cross-sections, and the object is created layer by layer. There are several additive manufacturing techniques based on the type of additive manufacturing composition (e.g., polymers, metals, or combinations thereof) and the form in which it is used (e.g., powder, pellets, wire, liquid). In embodiments, the additive manufacturing composition includes a polymer material (different from the organic additive), a metallic material, or a combination thereof. In embodiments, the polymer material or metallic material or a combination thereof is in the form of a powder. In such compositions, organic additive particles may be adsorbed onto the outer surface of the powder particles. The addition of the organic additive to such additive manufacturing compositions is described above.

[0119] In embodiments, the additive manufacturing composition includes a polymer material. Exemplary polymer materials include polyamide (PA), polyethylene (PE), polypropylene (PP), polyalkanoates, polyesters, polyaryl ether ketone (PAEK), polycarbonates, polyacrylates, polymethacrylates, polystyrene, polystyrene-acrylates, polyurethane (PU), thermoplastic polyurethane (TPU), polyether block amide (PEBA), polyalkylsiloxanes, fluorinated polymers, perfluoropolyether (PFPE) acrylates, and PFPE methacrylates, as well as copolymers thereof.Other exemplary polymer materials include polyamide 12 (PA12), polyamide 11 (PA11), polyamide 6 (PA6), polyamide 6,12 (PA6,12), low-density polyethylene, high-density polyethylene, polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polylactic acid (PLA), polyether ether ketone (PEEK), polyether ketone (PEKK); polyoxymethylene (POM), polymethyl methacrylate (PMMA), polystyrene (PS), and high-impact polystyrene. Examples include polystyrene (HIPS), polyacrylate, and polystyrene-acrylate, polyurethane (PU), polyacrylonitrile butadiene styrene (ABS), polyvinyl alcohol (PVA), polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), and combinations thereof.

[0120] In embodiments, the additive manufacturing composition includes a thermoplastic polymer. In addition to any thermoplastic polymers listed in the paragraph above, other examples of thermoplastic polymers include polyamides (e.g., nylon-6, nylon-12, etc.), polyurethanes, polyethylene, polypropylene, polyacetal, polycarbonate, polyethylene, or polybutylene terephthalate, glycol-modified polyethylene terephthalate or polybutylene terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polylactic acid, and other polyesters, polyethers, polyethersulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyarylene ethers, polyarylene sulfide, polysulfones, polyetherketones, polyaryletherketones (PAEK), polyamideimides, polyetherimides, polyether esters, polyether blocks and polyamide blocks (PEBA or polyether block amides). Examples include polymers, transplanted or untransplanted thermoplastic polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / alkyl (meth)acrylates, functionalized or unfunctionalized (meth)acrylic acid polymers, functionalized or unfunctionalized ethylene / vinyl monomer / alkyl (meth)acrylate terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / alkyl (meth)acrylate / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polybutadiene, polyisoprene, styrene block copolymers, polyacrylonitrile, silicones, and any combination thereof. Copolymers containing one or more of the above may also be used.Any of the aforementioned polymers may be thermoplastic elastomers and may include crystalline "hard" segments and amorphous "soft" segments.

[0121] Particularly preferred examples of thermoplastic polymers include polyamides such as nylon-6 or nylon-12, acrylonitrile butadiene styrene, polylactic acid, polyurethane, poly(arylene ether), polyaryl ether ketone, polycarbonate, polyimide, polyphenylene sulfide, poly(arylene sulfone), polyethylene terephthalate or polybutylene terephthalate or glycol-modified variants, and any combination thereof.

[0122] More specific examples of suitable polyamides include polycaproamide (nylon 6, polyamide 6, or PA6), poly(hexamethylene succinamide) (nylon 46, polyamide 46, or PA46), polyhexamethylene adipamide (nylon 66, polyamide 66, or PA66), polypentamethylene adipamide (nylon 56, polyamide 56, or PA56), polyhexamethylene sevacamide (nylon 610, polyamide 610, or PA610), polyundecaamide (nylon 11, polyamide 11, or PA11), polydodecaamide (nylon 12, polyamide 12, or PA12), and polyhexamethylene terephthalamide ( Examples include nylon 6T (polyamide 6T, or PA6T), nylon 10.10 (polyamide 10.10 or PA10.10), nylon 10.12 (polyamide 10.12 or PA10.12), nylon 10.14 (polyamide 10.14 or PA10.14), nylon 10.18 (polyamide 10.18 or PA10.18), nylon 6.10 (polyamide 6.10 or PA6.10), nylon 6.18 (polyamide 6.18 or PA6.18), nylon 6.12 (polyamide 6.12 or PA6.12), nylon 6.14 (polyamide 6.14 or PA6.14), semi-aromatic polyamides, and any combination thereof. Copolyamides may also be used. Examples of suitable copolyamides include, but are not limited to, PA11 / 10.10, PA6 / 11, PA6.6 / 6, PA11 / 12, PA10.10 / 10.12, PA10.10 / 10.14, PA11 / 10.36, PA11 / 6.36, PA10.10 / 10.36, and any combination thereof. Polyesteramides, polyether esteramides, polycarbonate esteramides, and polyether block amides, which may be elastomers, may also be used.

[0123] Examples of suitable polyurethanes include polyether polyurethanes, polyester polyurethanes, mixed polyethers and polyester polyurethanes, and any combination thereof. Suitable polyurethanes may include elastomeric polyurethanes prepared by condensation of isocyanates, polyols and chain extenders, where the polyol imparts flexibility to the polymer chains and typically constitutes soft segments. Examples of suitable polyurethanes include poly[4,4'-methylenebis(phenylisocyanate)-alt-1,4-butanediol / di(propylene glycol) / polycaprolactone], ELASTOLLAN® 1190A (a polyether polyurethane elastomer available from BASF), and any combination thereof.

[0124] Suitable polyesters are condensation reaction products formed from diacids and diols, or self-condensation reaction products of hydroxy acids such as lactic acid. Glycol-modified polyesters, such as glycol-modified polyethylene terephthalate or glycol-modified polybutylene terephthalate, may be particularly suitable. Glycol modification can provide desirable benefits such as light transmittance and flexibility of the polymer chain.

[0125] Suitable thermoplastic polymers may be elastomeric or non-elastomeric. Some of the aforementioned examples of thermoplastic polymers may be elastomeric or non-elastomeric depending on the specific composition of the polymer. For example, polyethylene, a copolymer of ethylene and propylene, may be elastomeric or independent of the amount of propylene present in the polymer.

[0126] Elastomer thermoplastic polymers generally fall into one of six classes: styrene-based block copolymers, thermoplastic polyolefin elastomers, thermoplastic vulcanized rubber (also called elastomer alloys), thermoplastic polyurethanes, thermoplastic copolyesters, and thermoplastic polyamides (typically block copolymers containing polyamides). Specific examples of elastomer thermoplastic polymers can be found in the Handbook of Thermoplastic Elastomers, 2nd edition, BMWalker and C., and in P. Rader, eds., Van Nostrand Reinhold, New York, 1988. Examples of suitable elastomeric thermoplastic polymers include elastomeric polyamides, polyurethanes, copolymers containing polyether blocks and polyamide blocks (PEBA or polyether block amides), methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block copolymers, polybutadiene, polyisoprene, styrene block copolymers, and polyacrylonitrile, and silicones. Examples of elastic styrene-based block copolymers include at least one block selected from the group consisting of isoprene, isobutylene, butylene, ethylene / butylene, ethylene-propylene, and ethylene-ethylene / propylene. More specific examples of elastic styrene-based block copolymers include poly(styrene-ethylene / butylene), poly(styrene-ethylene / butylene-styrene), poly(styrene-ethylene / propylene), poly(styrene-ethylene / propylene-styrene), poly(styrene-ethylene / propylene-styrene-ethylene-propylene), poly(styrene-butadiene-styrene), poly(styrene-butylene-butadiene-styrene), and any combination thereof.

[0127] In embodiments, polymer materials can be combined with nonpolymer materials, such as glass beads, mineral fillers, pigments, carbon black, carbon fibers, flame retardants, ceramic particles, silica particles, alumina particles, titania particles, and metal particles. With respect to metals, these may be metals, metal alloys, or combinations thereof. Exemplary metals and metal alloys include aluminum and aluminum alloys, stainless steel, tool steel, titanium and titanium alloys, copper and copper alloys, brass, cobalt-chromium (also known as cobalt-chromium) alloys, nickel-iron alloys, nickel-chromium superalloys, precious metals such as gold, platinum, palladium, silver, tantalum, rhenium, and niobium. Other exemplary metals / metal alloys include stainless steel metal powders, including 316L (low carbon), 17-4PH, hotworked, and maraging steel; AlSi 10 Mg and AlSi 12 Low-density aluminum alloys such as AlSi7Mg 0.6 6061 and 7075 series aluminum alloys; cobalt-chromium alloys including ASTM F75 CoCr; titanium alloys, e.g., Ti6Al4V and Ti6Al4V(ELI) (Ti6Al4V is a titanium alloy that is 6 percent aluminum and 4 percent vanadium); commercially available non-alloy titanium available in grades 1-4; nickel-chromium superalloys such as Inconel® 718 and Inconel® 625; and FeNi, also known as Invar® in the United States. 36 Alternatively, nickel-iron alloys such as 64FeNi; nickel-iron-cobalt alloys, such as Kovar®, a nickel-cobalt ferrous alloy with the same composition as Fernico 1.

[0128] Any of the above-mentioned metals and metal alloys can be used alone (i.e., without polymer materials) in additive manufacturing compositions.

[0129] Similar to the toner described above, the additive manufacturing composition may also include additional additives, including those described in the “Other Additives” section above, in the amounts specified in that section.

[0130] A additive manufacturing composition containing this organic additive can be used in any additive manufacturing system to perform any additive manufacturing technique, such as laser beam melting or selective laser sintering.

[0131] In this disclosure, the phrase “additive manufacturing composition” refers to a composition configured for use in an additive manufacturing system to form an object. Thus, in addition to polymer materials, metallic materials, present organic additives, and other optional additives, an additive manufacturing composition may include any other components commonly used in such compositions for forming an object using a desired additive manufacturing system. It should be noted that any other excluded organic additive particles and their latexes referred to above may apply to embodiments of additive manufacturing compositions.

[0132] In this disclosure, toner compositions and additive manufacturing compositions may be described as being initiator-free. This does not preclude the presence of small amounts of unused initiators from organic additive particles, or used initiators that may be incorporated into the polymer chains of organic additive particles. [Examples]

[0133] The following examples are provided to further define the various types of this disclosure. These examples are illustrative 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 approximately 20°C to approximately 25°C.

[0134] Example 1: Synthesis of an organic additive latex containing 15% glycerol formal methacrylate

[0135] In a 2 L Büch reactor equipped with two HE3 impellers, 3.75 g of sodium lauryl sulfate (SLS) surfactant (30% solid) was added to 816 g 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 450 rpm) 48 g of glycerol formal methacrylate, 190 g of cyclohexyl methacrylate (CHMA), 80 g of divinylbenzene (DVB), 2.57 g of dimethylaminoethyl methacrylate (DMAEMA), 9.18 g of SLS surfactant (30% solid) and 416 g of DIW. A fixed amount (37.2 g) of seed was taken from the monomer emulsion and pumped into a 2 L reactor at 77°C. An initiator solution prepared from 1.22 g of ammonium persulfate in 34.3 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. When half of the monomer emulsion had been added, the reactor rpm was increased to 450 rpm. At the end of the monomer supply, residual monomer was reduced at the end of the emulsion polymerization step using a post-treatment protocol of latex, heating to 77°C for 1 hour, followed by heating to 87°C for 2 hours and holding at 87°C for 2 hours. Similarly, the reactor rpm was further increased to 530 rpm. A product latex containing 20% ​​solid with a particle size of 84 nm was obtained. The final latex contained 91 ppm of residual CHMA and undetectable amounts of all residual monomers used, as measured by GC (gas chromatography).

[0136] Organic additive latex was spray-dried in a Yamato spray dryer using inlet and outlet temperatures of 190°C and 64°C, respectively. The final moisture content was <0.5%. The final dried organic additive was subjected to thermogravimetric analysis (TGA). A TA Instrument Q5000IR system operated with air as the gas was used. Approximately 10-15 mg of the sample was weighed into a TGA pan, and the pan was placed in the instrument. Using 100% air as the carrier gas, the sample was equilibrated at 35°C and then heated to 400°C at 5°C per minute. During this temperature profile, the weight loss of the sample was plotted as a function of temperature, and the first derivative was obtained to determine a specific endpoint. The reported data includes the weight loss rate and the decomposition onset temperature at 150°C. In this case, the measured decomposition onset temperature of the organic additive was 298°C.

[0137] Comparative Example 1: Synthesis of an organic additive latex that does not contain glycerol formal methacrylate

[0138] In a 300-gallon reactor equipped with two P4-type impellers and a condenser, 0.942 kg of SLS surfactant (30% solid) was added to 444 kg of deionized water (DIW). The reactor was deoxygenated by passing a nitrogen stream through it during the reaction, and the condenser was used. The reactor was heated to 77°C and the rpm was set to 59. Separately, in a 100-gallon reactor equipped with one P4-type impeller, a monomer emulsion was prepared by mixing 126 kg of CHMA, 42.45 kg of DVB, 1.358 kg of DMAEMA, 5.92 kg of SLS surfactant (30% solid), and 221.1 kg of DIW together (at 28 rpm). 0.369 kg of seed was taken from the monomer emulsion and pumped into the 300-gallon reactor at 77°C. An initiator solution prepared from 0.645 kg of ammonium persulfate in 7.045 kg of DIW was added over 15 minutes after the seed emulsion was added. The remaining monomer emulsion was supplied to a 300-gallon reactor over 120 minutes. When half of the monomer emulsion had been added, the reactor rpm was increased to 66 rpm. At the end of the monomer supply, the condenser was turned off. The latex underwent a post-treatment protocol at 77°C for 1 hour, followed by heating to 87°C for 2 hours and holding at 87°C for 1 hour to reduce residual monomer at the end of the emulsion polymerization step. During the post-treatment protocol, the pH of the latex was adjusted to ≥6.0 every 30 minutes using a 0.1 wt% NaOH solution. As a result, a latex containing 20% ​​solid particles with a particle size of 98 nm was obtained and filtered through a 25-micrometer filter bag. The final latex contained 194 ppm of residual CHMA and undetectable amounts of all residual monomers used, as measured by GC (gas chromatography).

[0139] Latex was spray-dried in a Yamato spray dryer using inlet and outlet temperatures of 190°C and 64°C, respectively. The final moisture content was <0.5%. The final dried comparative organic additive was subjected to TGA (thermogravimetric analysis). The decomposition onset temperature was measured at 270-285°C.

[0140] The remarkable increase in thermal stability of the organic additive in Example 1 compared to the organic additive in Comparative Example 1 is particularly surprising considering the similarity in chemical structure between glycerol formal methacrylate and cyclohexyl methacrylate, and the relatively small amount of glycerol formal methacrylate used compared to cyclohexyl methacrylate.

[0141] Example 2: Toner composition

[0142] Standard Xerox 700 parent cyan toner was blended with an additive package in a 10L Henschel (Reliance) mixer. However, in the additive package, the major additive silica X24 was replaced with either the organic additive of Example 1 at 1.05 pph or the organic additive of Comparative Example 1. The developers prepared this mixture with 5 pph toner and 30 g of Xerox 700 carrier.

[0143] Toner charging. Toner charging was collected by conditioning a sample for 3 days in a low-humidity zone (J zone) at 21.1°C / 10% relative humidity, and then conditioning another sample for 3 days in a high-humidity zone (A zone) at approximately 28°C / 85% relative humidity. The developer was charged in a Turbula mixer for 60 minutes.

[0144] The toner charge was measured in Q / D form, and the charge-to-diameter ratio was determined. Q / D was measured using a charge spectrograph with an electric field of 100 V / cm and visually measured as the midpoint of the toner charge distribution. The charge was reported as a millimeter value of displacement from the zero line (the mm displacement can be converted to femtocoulombs / micron (fC / μm) by multiplying by 0.092).

[0145] The toner charge was also measured as a charge-to-mass ratio (Q / M) determined by the total blow-off charge method, which measures the charge on a Faraday cage containing developer after the toner has been removed by blowing it off with an airflow. The Q / M ratio is obtained by weighing the cage before and after the blow-off and dividing the total charge collected in the cage by the mass of toner removed by the blow-off.

[0146] Toner charge retention. Developer samples (toner, additives, carrier) were conditioned in a 28°C / 85%RH A-zone environment for 3 days to achieve complete equilibration. The developer was charged by agitating the sample in a Turbula mixer for 2 minutes. The charge per unit mass of the sample was measured using the triboelectric blow-off method described above. The developer samples were then returned to the A-zone chamber at the idle position. The measurement of charge per unit mass was repeated after 24 hours and 7 days. Charge retention was calculated as a percentage of the initial charge from the charges after 24 hours and 7 days.

[0147] Toner Blocking. Toner blocking was determined by measuring toner aggregation at temperatures above room temperature. The measurement of toner blocking was completed as follows: A 2-gram developer sample was weighed into an open dish and conditioned in an environmental chamber with a specific high temperature and 50% relative humidity. After approximately 17 hours, the developer sample was removed and allowed to acclimate to ambient conditions for approximately 30 minutes. Each re-acclimatized developer sample was measured by sieving through two stacked pre-weighed mesh sieves (stacked as follows: 1000 μm on top, 106 μm on the bottom). The sieves were vibrated for approximately 90 seconds with an amplitude of approximately 1 mm using a Hosokawa flow tester. After vibration, the sieves were reweighed, and toner blocking was calculated as a percentage of the starting weight from the total amount of toner remaining on both sieves. Therefore, for a 2-gram developer sample, when A is the weight of the developer remaining on the upper 1000 μm sieve and B is the weight of the developer remaining on the lower 106 μm sieve, the toner blocking rate is calculated as blocking % = 50(A + B). The onset blocking temperature, defined as the temperature at which the measured toner aggregation begins to increase rapidly with temperature, was also measured.

[0148] [Table 1] Table 1. Results of charging, blocking, and aggregation.

[0149] As shown in Table 1 above, the charging performance of the toner containing the organic additive in Example 1 was almost identical to that of the toner using the organic additive in Comparative Example 1. However, the blocking performance was significantly improved by 1.3°C for the toner containing the organic additive in Example 1. This is particularly surprising considering the similarity between the chemical structures of glycerol formal methacrylate and cyclohexyl methacrylate, and the relatively small amount of glycerol formal methacrylate used compared to cyclohexyl methacrylate.

[0150] 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.”

[0151] 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.

[0152] 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

1. A composition comprising a plurality of organic additive particles, wherein the particles comprise a polymerization product of a reactant comprising a dioxane / dioxolane monomer and a vinyl comonomer, the 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, the vinyl comonomer being cyclohexyl methacrylate, the particles having a D50 particle size in the range of about 20 nm to about 500 nm, and the composition being in the form of a dry powder.

2. The composition according to claim 1, wherein the dioxane / dioxolane monomer is glycerol formal (meth)acrylate.

3. The composition according to claim 1, wherein the dioxane / dioxolane monomer is present in an amount of about 1 to about 50 weight percent of the total weight of the monomers in the particles, and the vinyl comonomer is present in an amount of up to about 85 weight percent of the total weight of the monomers in the particles.

4. The composition according to claim 1, wherein the reactant further comprises a polyfunctional vinyl monomer and an additional vinyl monomer selected from the group consisting of a vinyl fluoride monomer, a vinyl monomer containing a nitrogen-containing group, and combinations thereof.

5. A toner composition comprising: toner particles; a colorant; a plurality of organic additive particles, the organic additive particles comprising a polymerization product of a reactant comprising a dioxane / dioxolane monomer, a vinyl comonomer, a polyfunctional vinyl monomer, an additional vinyl monomer selected from the group consisting of a vinyl fluoride monomer, a vinyl monomer containing a nitrogen-containing group, and combinations thereof, the 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, the vinyl comonomer being cyclohexyl methacrylate; optionally a wax; wherein the organic additive particles have a D50 particle size in the range of about 20 nm to about 500 nm, and the toner composition is in the form of a dry powder.

6. A laminated molding composition comprising a polymer material, a metal material, or a combination thereof, and a plurality of organic additive particles, wherein the particles comprise a polymerization product of a reactant comprising a dioxane / dioxolane monomer and a vinyl comonomer, 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, the vinyl comonomer is cyclohexyl methacrylate, the organic additive particles have a D50 particle size in the range of about 20 nm to about 500 nm, and the composition is in the form of a dry powder. **Claim 7**: A composition comprising a plurality of organic additive particles, wherein the organic additive particles comprise a polymerization product of a reactant comprising a dioxane / dioxolane monomer and a vinyl comonomer, the reactant comprising glycerol formal (meth)acrylate as the dioxane / dioxolane monomer, an aliphatic cyclo (meth)acrylate as the vinyl comonomer, a polyfunctional vinyl monomer, a monofunctional vinyl monomer containing a nitrogen-containing group, and an initiator, the particles having a D50 particle size in the range of about 20 nm to about 500 nm, and the composition being in the form of a dry powder. **Claim 8**: The composition according to claim 7, wherein the glycerol formal (meth)acrylate is present in an amount of about 10 to about 30 weight percent of the total weight of the monomers in the particles, the aliphatic cyclo (meth)acrylate is present in an amount of about 50 to about 99 weight percent of the total weight of the monomers in the particles, the polyfunctional vinyl monomer is present in an amount of about 8 to about 40 weight percent of the total weight of the monomers in the particles, and the monofunctional vinyl monomer containing a nitrogen-containing group is present in an amount of about 0.1 to about 1.5 weight percent of the total weight of the monomers in the particles. **Claim 9**: The composition according to claim 8, wherein the particles are composed of the polymerization product of the reactant, and the reactant is composed of glycerol formal (meth)acrylate, the aliphatic cyclo (meth)acrylate, the polyfunctional vinyl monomer, the monofunctional vinyl monomer containing a nitrogen-containing group, and the initiator.

10. The aliphatic cyclo (meth) acrylate is cyclohexyl methacrylate, the polyfunctional vinyl monomer is divinylbenzene, and the monofunctional vinyl monomer containing the nitrogen-containing group is dimethylaminoethyl methacrylate. The composition according to claim 9.

11. The dioxane / dioxolane monomer is glycerol formal (meth) acrylate. The toner composition according to claim 5.

12. The dioxane / dioxolane monomer is glycerol formal (meth) acrylate. The laminated molding composition according to claim 6.

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