Crosslinked organic additive for waterborne coating compositions

Abstract

To provide waterborne coating compositions comprising organic additives that can replace silica.SOLUTION: Coating compositions are provided. A coating composition comprises: a solvent system comprising water; a crosslinked organic additive in the form of particles, the crosslinked organic additive comprising a polymerization product of reactants comprising a multifunctional vinyl monomer comprising two or more vinyl groups; a binder; and optionally, one or more of a colorant and a wax.SELECTED DRAWING: Figure 1

Description

[Background technology]

[0001] Water-based coating compositions are based on a variety of products, including paints and automotive finishes. Because they are water-based, they are generally more environmentally friendly and easier to apply compared to coating compositions based on organic solvents. The application and properties of water-based coating compositions depend on their components. While a wide variety of components may be used in water-based coating compositions, silica is a ubiquitous additive in such compositions. In fact, as one of the most abundant minerals in soil, silica is a natural choice of additive. Various types of silica are used to provide rheological control, reinforcement, scratch resistance, and gloss control. [Overview of the project]

[0002] This disclosure provides organic additives that can be used in aqueous coating compositions. The organic additives can be used as auxiliary components and, in embodiments, can completely replace silica in the aqueous coating composition. Illustrative benefits and advantages of the organic additives are described below. However, regardless of such benefits, this disclosure is at least in part based on the surprising discovery that the ability of organic additives to achieve certain properties, such as gloss control, actually surpasses that of silica. This is surprising because organic additives, consisting of organic chemicals, are chemically very different from silica, which consists only of Si and O.

[0003] A coating composition is provided. In an embodiment, the coating composition comprises a solvent system containing water, a crosslinking organic additive in the form of particles, the crosslinking organic additive comprising a polymerization product of a reaction containing a polyfunctional vinyl monomer containing two or more vinyl groups, a binder, and optionally one or more of a colorant and a wax. Methods for preparing and using the coating composition are also provided.

[0004] 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. [Brief explanation of the drawing]

[0005] Hereinafter, exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings.

[0006] [Figure 1] A schematic diagram of a substrate coated with a coating composition according to an exemplary embodiment is shown. [Modes for carrying out the invention]

[0007] Organic additives for use in aqueous coating compositions are provided. Coating compositions are also provided. In embodiments, the coating composition comprises water, organic additives, and binders. Other components that may be included in the coating composition are colorants, waxes, and combinations thereof. Each of these components is described below.

[0008] Organic additives are polymer materials in the form of small particles. Polyfunctional vinyl monomers (i.e., those containing two or more vinyl polymerizable groups (e.g., 2, 3, 4)) are used to form the polymer material of organic additives. 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 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, di(trimethylolpropane)tetraacrylate, diurethane dimethacrylate, 1,3-butanediol diacrylate, and 1,4-butanediol diacrylate. 1,3-Butanediol dimethacrylate, 1,4-Butanediol dimethacrylate, Poly(ethylene glycol) diacrylate, Glycerol 1,3-Diglycerolate diacrylate, Glycerol dimethacrylate, Tri(propylene glycol) diacrylate, 1,6-Hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, Neopentyl glycol diacrylate, Neopentyl glycol propoxylate, Pentaerythritol tetraacrylate, Pentaerythritol triacrylate, Poly(propylene glycol) diacrylate, Poly(propylene glycol) dimethacrylate, Trimethylolpropane (1 This includes EO / OH) methyl ether diacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-cyclohexanedimethanol divinyl ether, 1,4-bis(4-vinylphenoxy)butane, divinyl sulfone, and divinylbenzene. A single type or combination of different types of polyfunctional vinyl monomers can be used.

[0009] Generally, additional vinyl monomers are used to form organic additives. In contrast to polyfunctional vinyl monomers, the additional vinyl monomers may be monofunctional, having a single polymerizable vinyl group. Monomers that can be polymerized via emulsion polymerization may be used. These include acrylic monomers such as acrylates, acrylamides and methacrylamides, acrylic acids, acrylonitriles, bisphenol acrylics, fluorinated acrylics and methacrylates, as well as styrenes and styrene monomers functionalized in ways other than vinyl polymerizable groups, and vinyl esters and vinyl ethers.

[0010] 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-[Tri [(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 glyco 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, 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 glyco 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 96%, 2-hydroxy-3-phenoxypropyl acrylate, isobornyl acrylate, isobutyl acrylate, (2-isobutyl 1-2-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, Benzyl methacrylate, 2-(2-Bromoisobutyryloxy)ethyl methacrylate, 2-(tert-butylamino)ethyl methacrylate, Butyl methacrylate, tert-butyl methacrylate, 3-Chloro-2-hydroxypropyl methacrylate, Cyclohexyl 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-propylglycidyl ether)-2-cyclotetrasiloxanyl]propoxy}propyl methacrylate, isobornyl methacrylate, isobutyl methacrylate, 2-isocyanatoethyl methacrylate, isodecyl methacrylate, Uryl 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, phenyl methacrylate, 2-hydroxyethyl methacrylate phosphate, poly(ethylene glycol) behenyl ether acrylate, poly(ethylene glycol) 2,4It contains 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, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, and cyclohexyl methacrylate.

[0011] 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.

[0012] 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.

[0013] Fluorinated vinyl 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. Tacrylate, 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 monomers may be used.

[0014] The additional vinyl monomers may include nitrogen-containing groups, including such monomers disclosed above. For example, the nitrogen-containing vinyl monomers may be dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, or dibutylaminoethyl methacrylate.

[0015] The additional vinyl monomer may have acidic functional groups such as acrylic acid and methacrylic acid as disclosed above. For example, a vinyl monomer having an acidic functional group may be β-carboxyethyl acrylate (β-CEA).

[0016] Additional vinyl monomers may include sulfur-containing groups, including such monomers disclosed above. For example, vinyl monomers containing sulfur-containing groups may be styrene sulfonic acid, vinyl sulfonate, sulfoethyl methacrylic acid, sulfopropyl acrylic acid, styrene sulfonic acid, sulfoethyl acrylic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylene sulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, or 2-acrylamido-2-methyl-1-propanesulfonic acid.

[0017] The additional vinyl monomers used may be a single type or a combination of different types.

[0018] The selection of polyfunctional vinyl monomers and additional vinyl monomers depends at least in part on the desired properties (and amounts of monomers) of the coating composition. Organic additives offer a greater degree of chemical diversity compared to silica and therefore result in a wider range of properties for the coating composition. For example, monomer selection may be driven by the desire that the coating composition (or a coating formed therefrom) be hydrophobic (e.g., by using hydrophobic vinyl monomers such as styrene and alkyl methacrylate), oleophobic (e.g., by using oleophobic vinyl monomers such as fluorinated vinyl monomers), have a specific viscosity (e.g., by using a specific amount of monomers containing hydrogen-bonded moieties such as hydroxyl and glycol moieties), and have a specific hardness / scratch resistance (e.g., by using a relatively large amount of polyfunctional vinyl monomers).

[0019] The selection of vinyl monomers and their amounts may also be guided by the desire that the organic additives (i.e., the polymer material from which the organic additives are made) have a specific refractive index. Generally, homopolymers and copolymers based on the monomers disclosed herein have refractive indices in the range of 1.30 to 1.71. In contrast, silica additives used in aqueous coatings have a very limited range of refractive indices, 1.45 to 1.46. Thus, the use of the disclosed organic additives enables a much wider range of optical properties for coatings formed from the disclosed coating compositions. For example, the refractive index of the organic additive may be selected to match (i.e., be the same as) that of the binder in the coating composition (when cured). "Same" means within ±0.10, ±0.05, ±0.02, or ±0.01. This can improve the transparency of the resulting coating by reducing light scattering between the organic additive and the binder. As another example, the refractive index of the organic additive may be selected to provide a desired mismatch with the binder (when cured). This can reduce the gloss of the resulting coating by increasing light scattering. In embodiments, the disclosed refractive index values, where the discrepancy is at least 0.11, at least 0.2, at least 0.3, at least 0.4, or in the range of 0.11–0.4, may refer to a measurement of the refractive index at a specific wavelength of light, e.g., 633 nm. The wavelength selected for the refractive index measurement is suitable for the application of the coating. For example, to provide a highly transparent polymer film for visual inspection, as is typical for many coating applications, the selected wavelength is optimal for the visual range. The refractive index may be measured by any preferred method, using an ASTM standard appropriate for the particular material, or using a suitable commercially available refractometer. In embodiments, the refractive index may be measured by sequentially immersing an organic additive or binder (or a coating formed therefrom) in a standard fluid of a known refractive index and observing when the additive / binder is no longer visible in the standard fluid. Cargill refractive index liquids are an example of a set of standards that may be available.In other embodiments, standard fluids with different refractive indices can be prepared by mixing miscible fluids with known refractive indices, such as glycerol and water. However, determining whether the refractive indices of organic additives and binders are the same or different may involve different measurement techniques, as long as the comparative measurements are performed in the same manner.

[0020] The selection and amounts of vinyl monomers may also be guided by the desire to achieve compatibility with other components of the coating composition (e.g., binders) or to promote association between such components. This association may be covalent or non-covalent (e.g., hydrogen bonds, van der Waals bonds, etc.). Compatibility may be achieved by selecting vinyl monomers that are chemically inert to other components. Compatibility may be achieved by including an amount of the binder in the organic additive itself. Association may be achieved by selecting vinyl monomers that contain functional groups that form covalent or non-covalent bonds with components of the coating composition. For example, (meth)acrylic acid monomers and β-CEA are vinyl monomers that can form covalent bonds with certain components of the coating composition.

[0021] Various polymerization techniques can be used to form organic additives from selected vinyl monomers, including emulsion polymerization techniques. In emulsion polymerization, an emulsion is formed containing the selected vinyl monomers and generally a solvent and a surfactant. Initiators may be included in the emulsion (or added separately in a separate step). The emulsion is exposed to conditions that induce polymerization reactions between the vinyl monomers to form a polymer material in which the organic additive is composed. These conditions may include mixing for a certain period of time (e.g., 1 minute to 72 hours, 4 hours to 24 hours) at a specific temperature (e.g., 10°C to 100°C, 20°C to 90°C, 45°C to 75°C). An inert gas may be supplied during the polymerization reaction, for example, in nitrogen. Emulsion polymerization can be carried out in any suitable reactor.

[0022] Emulsion polymerization provides organic additive latexes, i.e., organic additives as particles dispersed in a solvent. This is generally an advantage over silica, for example, which generally requires additional steps, such as high shear, to disperse it and incorporate it into a coating composition. Organic additive latexes can be used, for example, to be added along with other components of the disclosed coating composition. However, additional processing steps can be used, for example, to recover the organic additive from the solvent. These processing steps include, for example, filtration, drying, centrifugation, spray drying, freeze drying, and the like.

[0023] Water is generally used as the solvent in the emulsion, but other solvents may be included, such as toluene, benzene, xylene, tetrahydrofuran, acetone, acetonitrile, carbon tetrachloride, chlorobenzene, cyclohexane, diethyl ether, dimethyl ether, dimethylformamide, heptane, hexane, methylene chloride, pentane, and combinations thereof.

[0024] As noted above, surfactants are generally used in emulsions comprising anionic, cationic, or nonionic surfactants. They can be present in the emulsion in an amount of 0.01 to 15 weight percent of the total weight of the vinyl monomers, or 0.1 to 10 weight percent of the total weight of the vinyl monomers. A single type or combination of different types of surfactants can be used.

[0025] Anionic surfactants include sulfates and sulfonates such as sodium dodecyl sulfate (SDS), also known as sodium lauryl sulfate (SLS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkylbenzene alkyl sulfate, and sulfonates, and acids such as abietic acid available from Aldrich, NEOGEN (trademark), NEOGEN SC (trademark), etc. available from Daiichi Kogyo Seiyaku Co., Ltd. Other suitable anionic surfactants include DOWFAX (trademark) 2A1 manufactured by Dow Chemical Company, alkyldiphenyloxide disulfonate, and / or TAYCA POWER BN2060 manufactured by Teika Corporation (Japan), which is a branched sodium dodecylbenzene sulfonate.

[0026] Examples of cationic surfactants include ammonium, alkylbenzyldimethylammonium chloride, dialkylbenzene alkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, and C 12 ,C 15 ,C 17 , trimethylammonium bromide, combinations thereof, and the like. Other cationic surfactants include cetylpyridinium bromide, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyltriethylammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, and SANISOL (benzalkonium chloride) available from Kao Chemicals. Suitable cationic surfactants include SANISOL B-50 available from Kao Corp., which is mainly benzyl dimethyl alkonium chloride.

[0027] 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.

[0028] Initiators are generally used in emulsion polymerization processes to accelerate polymerization reactions. They may be present (or added) to the emulsion in amounts of 0.1 to 8 weight percent of the total weight of vinyl monomers, or 0.2 to 5 weight percent of the total weight of vinyl monomers. Different types of initiators can be used individually or in combination.

[0029] Suitable initiators include water-soluble initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate, as well as organic water-soluble initiators comprising organic peroxides and azo compounds containing Vazo peroxides such as VAZO 64 (trademark), 2-methyl 2-2'-azobispropannitrile, VAZO 88 (trademark), and 2-2'-azobisisobutylamide anhydride. 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.

[0030] Organic additives formed by the emulsion polymerization techniques described above may be characterized by their compositions. As described above, the polymer material of the organic additive is the result of polymerization reactions between various combinations of vinyl monomers, forming polymerization products. For clarity, the composition of the polymer material / organic additive can be identified by referring to the vinyl 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 into the beginning and end 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 bonding.

[0031] In embodiments, the organic additive comprises (or consists of) a polymerization product of the reaction, comprising a polyfunctional vinyl monomer, an additional vinyl monomer, and optionally an initiator. Any of the polyfunctional vinyl monomers, additional vinyl monomers, and initiators described herein may be used. In any of these embodiments, the surfactant may be present in the organic additive, or, for example, embedded therein. Any of the surfactants described herein may be used. In any of these embodiments, the polyfunctional vinyl monomer may be present in an amount of 2 to 99 weight percent of the total weight of the solids (including the total vinyl monomer and surfactant (if present)). This includes 5 to 90 weight percent, 10 to 80 weight percent, and 25 to 70 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, the additional vinyl monomer may be present in an amount of 0 to 97 weight percent of the total weight of the solids. This includes 1 to 90 weight percent, 10 to 80 weight percent, and 25 to 70 weight percent. If two or more types of additional vinyl monomers are used, these values ​​refer to the total amount of the additional vinyl monomers. In any of these embodiments, the surfactant may be present in an amount of 0 to 10 weight percent of the total weight of the solids. This includes 0.1 to 8 weight percent and 1 to 6 weight percent.

[0032] In any of the embodiments referenced in the above paragraphs, one or more of the following modifications may be used: Divinylbenzene may be used as a polyfunctional vinyl monomer (or one of the polyfunctional vinyl monomers). Acrylates or methacrylates may be used as additional vinyl monomers (or one of the additional vinyl monomers). Fluorinated vinyl monomers (e.g., trifluoroethyl (meth)acrylate) may be used as additional vinyl monomers (or one of the additional vinyl monomers). Monomers containing sulfur groups may be used as additional vinyl monomers (or one of the additional vinyl monomers). Monomers containing nitrogen groups may be used as additional vinyl monomers (or one of the additional vinyl monomers) in amounts of 0.1 to 1.5 weight percent of the total weight of solids (as defined above). Monomers having acidic functional groups (e.g., acrylic acid, methacrylic acid, or β-CEA) may be used as additional vinyl monomers (or one of the additional vinyl monomers) in amounts of 0.1 to 10 weight percent of the total weight of solids.

[0033] Organic additives can be characterized by their size and shape. 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 fluorescent dye is D in the range of 20 nm to 500 nm, 25 nm to 200 nm, or 40 nm to 150 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 size. The signals are mathematically converted into particle size and particle size distribution. The analysis can be performed using an external probe or by inserting the probe into a fixed sample chamber. For the light scattering technology, 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.

[0034] For the same size, embodiments of organic additives provide a larger surface area compared to silica. For example, the Brunauer-Emmett-Teller (BET) value of approximately 65 nm silica particles is approximately 80 nm. 2 The particle size of the same organic additive, consisting of approximately 70% by weight of trifluoroethyl methacrylate and approximately 30% by weight of divinylbenzene, is approximately 120 m. 2 It has a BET value of / g. Furthermore, silica tends to aggregate, leading to a loss of surface area and / or a harmful increase in viscosity. Embodiments of organic additives are not plagued by such problems.

[0035] Organic additives may be characterized by their degree of crosslinking. The degree of crosslinking can be given by calculating the number of crosslinks per unit of vinyl monomer in the coating composition. In the case of an organic additive in which crosslinking is provided by using a difunctional vinyl monomer, this can be calculated using the following formula, where Mc is the molecular weight of the difunctional vinyl monomer, Xc is the weight fraction of the difunctional vinyl monomer to the total amount of vinyl monomers, sum is the sum of all vinyl monomers, i = 1 to n, where Mi is the molecular weight of vinyl monomer i, and Xi is the weight fraction of vinyl monomer i to the total amount of vinyl monomers.

number

[0036] For organic additives provided by using vinyl monomers with a functional value higher than 2, the degree of crosslinking can be calculated in the same manner, except that it is modified by a factor associated with the number of crosslinks formed. For example, for trifunctional vinyl monomers, since each trifunctional vinyl monomer creates 2 crosslinks, the crosslink density value must be multiplied by 2. Similarly, since quaternary vinyl monomers have three times the crosslink density of difunctional vinyl monomers, the crosslink density value must be multiplied by 3.

[0037] In this embodiment, the degree of crosslinking (crosslinking density value) is 0.03 to 0.60. This includes 0.05 to 0.50, 0.10 to 0.40, and 0.20 to 0.40.

[0038] Organic additives can be characterized by their gel fraction. The gel fraction can be measured as follows using a gravimetric technique. Dissolve the organic additive latex in toluene and then filter it by vacuum filtration. Dry and weigh the collection membrane and weigh the remaining material on the membrane for the retained gel percentage. An example of the detailed procedure is as follows. Weigh 0.04 g ± 0.001 g (W1) of the resin into a scintillation vial, add 20 mL of toluene to each vial, and shake for 4 hours. Place one glass filter (e.g., Whatman glass filter paper 4.25 cm type GF / a) and one Teflon filter (e.g., MSI Micro Teflon filter 47 mm type PTEF) in an aluminum pan and record the weight (W2). Set up a vacuum glass filter funnel, moisten the filter support with toluene, and place the Teflon filter with the shiny side down on the moistened filter pad. Place the glass filter on the Teflon filter. Remove the sample from the shaker and pour the solution from the vial onto the filter paper. Empty the contents of the vial, rinse the vial with 10 mL of toluene, and rinse the glass funnel with toluene. Remove the moistened filter paper, place it in an aluminum dish, and dry it overnight. Weigh the crucible (W3) and determine the percentage of toluene-insoluble matter. The calculation of the total toluene-insoluble matter is determined as follows: Total toluene-insoluble matter = [(W3) - (W2) / (W1)] * × 100. The percentage of total toluene-insoluble matter is the gel fraction.

[0039] In embodiments, the gel fraction is 40% - 100%, 40% - 90%, 50% - 95%, 75% - 99%, 80% - 100% or 90% - 100%.

[0040] Organic additives may be used in the coating composition in varying amounts, for example, depending on the desired properties of the coating formed therefrom. In embodiments, organic additives are present in the coating composition in amounts of 2–25 weight percent, 5–20 weight percent, and 2–10 weight percent of the total weight of the coating composition. This amount refers to the solid content of the organic additive (as opposed to the amount of organic additive latex). If different types of organic additives are used, this amount refers to the total amount of organic additives. Other components of the coating composition are described below.

[0041] Compared to silica, for example fumed silica having a density of 2.2 g / mL, the density of organic additives is significantly lower, covering a wider range, for example, 0.9 g / mL to 2.2 g / mL. This means that, in embodiments, smaller amounts of organic additives may be used compared to silica to provide reinforcing agents with the same properties, for example, dependent on volume fraction as opposed to weight fraction.

[0042] The coating composition contains water. However, water may be one component of a solvent system containing water-soluble or water-miscible organic solvents such as alcohols, ketones, glycols, glycol ethers, glycol ether esters, and N-methylpyrrolidone. A single type or a combination of different types of such solvents may be used. The coating composition generally contains a relatively large amount of water. In embodiments, the solvent system in the coating composition contains at least 50% water, at least 60% water, at least 70% water, or at least 80% water (by volume). The total amount of water-containing solvent in the coating composition may be, for example, in the range of 10 to 80 weight percent, 20 to 70 weight percent, or 30 to 60 weight percent of the total weight of the coating composition.

[0043] The coating composition also contains a binder. The term “binder” refers to a prepolymer that, when exposed to conditions that cause the prepolymer to cure, forms a cured polymer. These prepolymers may be monomers, oligomers, and / or polymers that undergo additional chemical reactions during curing, including the formation of covalent bonds (i.e., crosslinks) between prepolymers. However, these prepolymers may be oligomers and / or polymers in the form of particles that coalesce during curing (e.g., latex particle coalescence induced by the drying of capillary forces). Thus, in at least the embodiments, the binder refers to the prepolymers in their uncured state in the coating composition. In coating compositions, binders are generally not crosslinked, unlike crosslinked organic additives. However, such crosslinks may form during curing to form polymers from the binder / prepolymer.

[0044] It should be noted that certain organic additives are used in electrophotographic toners. However, this coating composition is not a toner, and the binder in this coating composition is not a toner particle. Furthermore, the function of the organic additives in electrophotographic toner is completely different from the function of the organic additives in this coating composition. Similarly, in this embodiment, the coating composition is not an aqueous inkjet ink composition, and the binder is not a resin or polymer found in such an aqueous inkjet ink composition.

[0045] A variety of binders can be used, including acrylic, melamine, polyester, polyacrylate, alkyd, epoxy, epoxy ester, polyol, polyisocyanate, polyurethane, silicone, silicate, vinyl propionate copolymer, vinyl acetate copolymer, acrylate methacrylate copolymer, styrene-butadiene copolymer, vinyl acetate, and polystyrene. A single type or a combination of different types of binders can be used. In embodiments, the binder includes styrene-butadiene copolymer, acrylic, alkyd, polyvinyl acetate, polystyrene, or a combination thereof. The total amount of binder in the coating composition may range, for example, from 20 to 88 weight percent of the total weight of the coating composition. This includes 30 to 80 weight percent and 40 to 60 weight percent.

[0046] The coating composition may contain a colorant. The colorant is generally a pigment, but dyes and combinations thereof can be used. Examples of suitable pigments include black, cyan, magenta, and yellow pigments. The pigment may be organic or inorganic particles. A suitable inorganic pigment is carbon black (further described below). However, other inorganic pigments such as cobalt blue (CoO-Al2O3), chrome yellow (PbCrO4), iron oxide, and titanium dioxide may be preferred. Suitable organic pigments include, for example, azo pigments such as diazo pigments and monoazo pigments, polycyclic pigments (e.g., phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green), perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, pyrantron pigments, and quinophthalone pigments), insoluble dye chelates (e.g., basic dye type chelates and acid dye type chelates), nitro pigments, nitroso pigments, and anthantron pigments such as PR168. Representative examples of phthalocyanine blue and green include copper phthalocyanine blue, copper phthalocyanine green, and their derivatives (pigment blue 15, pigment green 7, and pigment green 36). Representative examples of quinacridone include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42. Representative examples of anthraquinone include Pigment Red 43, Pigment Red 194, Pigment Red 177, Pigment Red 216, and Pigment Red 226. Representative examples of perylene include Pigment Red 123, Pigment Red 149, Pigment Red 179, Pigment Red 190, Pigment Red 189, and Pigment Red 224.Representative examples of thioindigoids include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Representative examples of heterocyclic yellows include Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 90, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 155, and Pigment Yellow 213. Such pigments are commercially available in powder or press cake form from many suppliers, including BASF Corporation, Engelhard Corporation, and Sun Chemical Corporation. Examples of usable black pigments include carbon pigments. These include carbon black, graphite, vitreous carbon, charcoal, and combinations thereof. Such carbon pigments can be manufactured by various known methods, such as the channel process, contact process, furnace process, acetylene process, or thermal process, and are commercially available from such suppliers, including Cabot Corporation, Columbian Chemicals Company, Evonik, and EIDuPont de Nemours and Company.Suitable carbon black pigments include MONARCH® 1400, MONARCH® 1300, MONARCH® 1100, MONARCH® 1000, MONARCH® 900, MONARCH® 880, MONARCH® 800, MONARCH® 700, CAB-O-JET® 200, CAB-O-JET® 300, CAB-O-JET® 450, REGAL®, and BLACK. Examples of pigments include, but are not limited to, those manufactured by Cabot, such as PEARLS®, ELFTEX®, MOGUL®, and VULCAN® pigments; pigments manufactured by Columbia, such as RAVEN® 5000 and RAVEN® 3500; and pigments manufactured by Evonik, such as Color Black FW200, FW2, FW2V, FW1, FW18, FW5160, FW5170, Special Black 6, Special Black 5, Special Black 4A, Special Black 4, PRINTEX® U, PRINTEX® 140U, PRINTEX® V, and PRINTEX® 140V. Other pigments include CAB-O-JET 352K, CAB-O-JET 250C, CAB-O-JET 260M, CAB-O-JET 270Y, CAB-O-JET 465M, CAB-O-JET 470Y, and CAB-O-JET 480V (available from Cabot Corporation). Examples of special effect pigments include pigments from Silverline Manufacturing such as ECKART America Corporation STAPA UCP pigments, SILBERCOTE AquaPellet, and STARBRITE Reveal AQ, and pigments from New Brook International, including Sun Chemical's Benda-Lutz COMPAL WS aluminum pigment, bismuth vanadate, fluorescent agents, phosphorescent materials, iron oxides, lithon, metals (aluminum and bronze), mica-like iron oxides, and Pigmentan® (magnesium-based) pigments.

[0047] Suitable dyes include anionic dyes, cationic dyes, nonionic dyes, and zwitterionic dyes. Specific examples of suitable dyes include food colorings such as Black No. 1, Black No. 2, Red No. 40, Blue No. 1, and Yellow No. 7, FD&C dyes, acid black dyes (No. 1, 7, 9, 24, 26, 48, 52, 58, 60, 61, 63, 92, 107, 109, 118, 119, 131, 140, 155, 156, 172, 194), and acid red dyes (No. 1, 8, 32, 35, 37, 52, 57, 92, 115, 119, 154, 249, 254, 256), Acid Blue Dye (No. 1, 7, 9, 25, 40, 45, 62, 78, 80, 92, 102, 104, 113, 117, 127, 158, 175, 183, 193, 209), Acid Yellow Dye (No. 3, 7, 17, 19, 23, 25, 29, 38, 42, 49, 59, 61, 72, 73, 114, 128, 151), Direct Black Dye (No. 4 , 14, 17, 22, 27, 38, 51, 112, 117, 154, 168), Direct Blue Dye (No. 1, 6, 8, 14, 15, 25, 71, 76, 78, 80, 86, 90, 106, 108, 123, 163, 165, 199, 226), Direct Red Dye (No. 1, 2, 16, 23, 24, 28, 39, 62, 72, 236), Direct Yellow Dye (No. 4, 11, 12, 27, 28, 33, 34, 39, 50, 58, 86, 1 Examples include reactive dyes such as 00, 106, 107, 118, 127, 132, 142, 157), reactive red dyes (No. 4, 31, 56, 180), reactive black dye (No. 31), and reactive yellow dye (No. 37), as well as anthraquinone dyes, monoazo dyes, diazo dyes, phthalocyanine derivatives including various phthalocyanine sulfonate salts, aza(18)annulene, formazan copper complexes, and triphenodioxazine.

[0048] The total amount of colorant in the coating composition may be, for example, in the range of 0 to 10 weight percent of the total weight of the coating composition. This includes 0.1 to 10 weight percent and 0.1 to 5 weight percent.

[0049] The coating composition may contain wax. Examples of waxes include paraffin wax, polyethylene wax, polypropylene wax, microcrystalline wax, polyolefin wax, montan ester wax, and carnauba wax. Waxes having a melting point in the range of about 50°C to about 150°C may be used. Examples include Michelman (e.g., Michem Lube 103DI, 124, 124P, 135, 156, 180, 182, 190, 270R, 368, 511, 693, 723, 743, 743P, and 985, and Michem Emulsion) Nanoscale wax emulsions (e.g., diameters of 1000 nm or less, 500 nm or less, or 100 nm or less) based on carnauba wax and paraffin wax may be used, including those from 24414, 34935, 36840, 41740, 43040, 43240, 44730, 47950, 48040M2, 61355, 62330, 66035, 67235, 70750, 71150, 71152, 91735, 93235, 93335, 93935, and 94340. Aquacer 2500, Aquacer 507, Aquacer 513, Aquacer 530, Aquacer 531, Aquacer 532, Aquacer 535, Aquacer 537, Aquacer Waxes from Byk, including 539 and Aquacer 593, may also be used.

[0050] The total amount of wax in the coating composition may be, for example, in the range of 0 to 10 weight percent of the total weight of the coating composition. This includes 0.1 to 10 weight percent and 0.1 to 5 weight percent.

[0051] additives

[0052] The coating composition may contain additives (different from organic additives). For example, inorganic particles may be used as additives containing oxide particles. The particles may be spherical (spherical is defined above). The particles are in the range of 10 nm to 500 nm. 50 It may have a particle size. Various oxides can be used, such as silica, titania, zirconia, alumina, iron oxide, copper oxide, tin oxide, boron oxide, cerium oxide, thallium oxide, tungsten oxide, titanate, and combinations thereof. Mixed oxides such as aluminosilicate, borosilicate, and aluminoborosilicate, and combinations thereof, can be used. Regarding silica, see D above. 50 Particle size may refer to primary particles (as opposed to aggregates and agglomerates formed from such particles). Various types of silica can be used, including silica gel, precipitated silica, fumed silica, and combinations thereof. Oxide particles can be functionalized (e.g., via hydrophobic surface treatment) or defunctionalized. A single type or combination of different types of inorganic particles can be used. Embodiments of the coating composition include inorganic particles, while other embodiments do not include inorganic particles in the coating composition. Embodiments do not include silica in the coating composition.

[0053] The total amount of inorganic particles in the coating composition may be, for example, in the range of 0 to 20 weight percent of the total weight of the coating composition. This includes 0.1 to 10 weight percent and 0.1 to 5 weight percent.

[0054] Other additives that may be included in the coating composition include those that accelerate the curing of the binder. Such additives include catalysts and curing agents. Specific types of catalysts and curing agents may be selected based on the type of binder. Each of these types of additives may be present in the coating composition in an amount of, for example, 0 to 10 weight percent of the total weight of the coating composition. This includes amounts of 0.1 to 10 weight percent and 0.1 to 5 weight percent.

[0055] Other additives that may be included in the coating composition include biocides, fungicides, stabilizers, acids or bases, phosphates, carboxylates, sulfites, amine salts, pH adjusters such as buffers, metal ion sequestering agents such as EDTA (ethylenediamine tetraacetic acid), defoamers, and wetting agents. Each of these types of additives may be present in the coating composition in amounts ranging from 0 to 10 weight percent of the total weight of the coating composition, for example. This includes amounts ranging from 0.1 to 10 weight percent and 0.1 to 5 weight percent.

[0056] In the embodiments, the coating composition comprises (or consists of) a solvent system, an organic additive, a binder, and optionally one or more of a colorant, a wax, and an additive. In the embodiments, the coating composition comprises (or consists of) a solvent system, an organic additive, a binder, a colorant, and optionally one or more of a wax and an additive. In any of these embodiments, a single type or different types of each component may be used. In any of these embodiments, the components may be selected from any of the solvent systems, organic additives, binders, colorants, waxes, and additives disclosed herein. However, in the embodiments, the additive is not silica, or the additive is not inorganic particles. In any of these embodiments, the amounts of the components may be used as described above.

[0057] A coating composition can be formed by combining and mixing desired components in desired amounts. Components can be provided in solid form, such as organic additives, waxes, etc., and can be added as a dispersion of solids in a solvent (e.g., water), such as by adding organic additives as organic additive latex. Specific components of a coating composition may be provided together as a binder formulation, for example, comprising a solvent system, a binder, and optionally one or more of colorants, waxes, and additives. In such embodiments, an organic additive (or organic additive latex) may be added to this binder formulation in desired amounts and mixed. A variety of commercially available binder formulations can be used. For example, commercially available paints were used as binder formulations in the following embodiments. Commercially available binder formulations may contain silica. In embodiments, the same binder formulation is used, except that silica is omitted.

[0058] Coating compositions can be used in various industries to provide coatings to machinery, vehicles (e.g., automobiles), floors, walls, etc. As shown in Figure 1, one of the coating compositions can be applied to the surface 102 of a substrate 100 to form a coating 104 thereon. The substrate 100 is not particularly limited and depends on the components of the application and coating composition, e.g., the type of binder. Exemplary substrate materials include metal, glass, plastic, and wood. Various application techniques can be used, for example, diffusion, painting, brushing, wiping, spraying, and dipping. Although not shown in Figure 1, a second substrate may be placed on the coating 104. In such embodiments, the coating 104 may function to bond the two substrates together.

[0059] In any environment in which it is to be used, and in any application, the coating composition (or the coating formed therefrom) will generally cure to form a cured coating. (The term "cured coating" distinguishes it from "coating," which refers to the layer of the coating composition after it has been applied to the substrate.) As described above, curing is induced by curing conditions. Since this curing may involve the formation of crosslinks, the cured coating may be crosslinked. The curing conditions then depend on the components of the coating composition, e.g., the type of binder. For example, curing can be induced by heating for a certain period of time, exposure to water (e.g., in the case of silicone), and the addition of a curing agent. In other embodiments, simply exposing the coating to ambient conditions (e.g., air at room temperature and atmospheric pressure) for a certain period of time is sufficient to induce curing.

[0060] In addition to the organic additives and coating compositions described above, coatings, cured coatings, and coated substrates are also included in this disclosure. [Examples]

[0061] 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.

[0062] The organic additive latex was formed as follows: In a 3000-Gal reactor equipped with two HE3-type impellers and a condenser, 26.3 kg of sodium lauryl sulfide (SLS) surfactant (30% solid) was added to 5711 kg of deionized water (DIW). The reactor was deoxygenated by passing a nitrogen stream through it during the reaction, and the condenser was also used. The reactor was heated to 77°C and the rpm was set to 65. Separately, in a 2000-Gal reactor equipped with two HE3-type impellers, a monomer emulsion was prepared by mixing 1659 kg of cyclohexyl methacrylate (CHMA), 559 kg of divinylbenzene (DVB), 17.9 kg of dimethylaminoethyl methacrylate (DMAEMA), 64.3 kg of SLS surfactant (30% solid) and 2913 kg of DIW together (at 100 rpm). 261 kg of seed from the monomer emulsion was pumped into a 3000-Gal reactor at 77°C. An initiator solution was prepared from 8.5 kg of ammonium persulfate (APS) in 240 kg of DIW, and this solution was added to the 3000-Gal reactor over 20 minutes. The remaining monomer emulsion was then supplied to the 3000-Gal reactor over 120 minutes. At the end of the monomer supply, the condenser was turned off and the rpm was further increased to 75 rpm. 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 process. 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 19.7% solid particles with a particle size of 87 nm was obtained and filtered through a 25-micrometer filter sieve.

[0063] In a 250ml bottle, 55g of the above organic additive latex was added to 109g of paint. Therefore, a 10% organic additive solid was added to yellow latex paint (Sherwin Williams Promar200 Zero VOC-colour L1 Blue, N1 Raw Umber, Y1 Yellow with eggshell gloss) to form a coating composition. The coating composition was brushed onto heavily coated paper to form a coating. Two sheets of heavily coated paper were prepared using this composition. The coated paper was dried under ambient conditions. A control composition (without organic additives) was also brushed onto the heavily coated paper. Two sheets of heavily coated paper were prepared in this way, along with the control composition. Gloss was measured for each sheet at a 75° angle. To measure gloss, a Novo-Gloss triple-angle glossometer from Rhopoint Instruments, measuring at a 75° angle, was used to collect the data shown in Table 1 below. In this table, "S" refers to measuring gloss in the same direction as the brushing application, and "P" refers to brushing perpendicular to the brushing application. The two pages measured for the control are labeled Control Sheet 1 and Control Sheet 2, and the two pages measured with the organic additive are labeled Coating Composition Sheet 1 and Sheet 2 with Organic Additive. Four measurements were taken for each page in the "S" and "P" directions, and these are the data in the first four rows of the table.

[0064] [Table 1]

[0065] Surprisingly, the gloss measurements showed that the organic additive was able to significantly reduce gloss compared to the control composition. This was surprising for an eggshell finish, as commercially available water-based paints already have relatively low gloss. Further reduction in gloss was not expected.

[0066] Abrasion rate tests were performed on each of the coating compositions having control sheet 1 and organic additive sheet 1 using the Taber abrasion rate test. For the Taber abrasion rate test, a Taber Rotary Abrader, Model 5130 was used together with a CS-10 abrasion wheel. The environment for the test was 22.1°C and 8.7% relative humidity (RH). The load was 500 grams, consisting of an external weight of 250 grams and an arm weight of 250 grams. The CS10 roll was new and prepared by 50 cycles of resurfacing on an S-11 disc. The preparation procedure was performed twice for the new wheel. Before the test, the sample was placed in the holder several times to ensure that the sample plate fitted and removed any excess coating. The test piece was weighed, placed on the abrasive, and locked in place. The wheel and vacuum nozzle were lowered, and the cycle was set to 100. Before weighing the test sample, 100 test cycles were performed, the sample was removed, and light brushing was performed on both sides. The process is repeated for 500 cycles, with 100 cycles of execution and weighing of the test specimen. After 500 cycles, a single 50-cycle resurfacing of the wheel on an S-11 disc is performed. The test is then repeated for up to 1000 cycles. The Taber wear index abrasive indicates the wear rate and is calculated by measuring the weight loss in milligrams per 1000 cycles of wear. A lower wear index indicates better wear resistance. Taber wear index, TWI = (AB) * The formula is 1000 / C, where A = milligram weight of the specimen before abrasion, B = milligram weight of the specimen after abrasion, and C = number of test cycles. At each 100-cycle point, the coating composition with organic additive sheet 1 showed less abrasion than control sheet 1. At the end of 100 cycles, the Taber abrasion index was 67.1 for control sheet 1, and 56.2 for the coating composition with organic additive sheet 1, an improvement of approximately 16%. These results were also surprising, as this commercially available paint is already optimized for improved abrasion and scratch resistance. Such an improvement in the abrasion resistance of a paint coating was not expected.

[0067] 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.”

[0068] 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.

[0069] 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. 1. A coating composition comprising: a solvent system comprising water; a crosslinked organic additive in the form of particles, the crosslinked organic additive comprising the polymerization product of a reactant comprising a multifunctional vinyl monomer containing two or more vinyl groups, the particles having a D50 particle size in the range of 20 nm to 500 nm; A binder; Optionally, one or more of a colorant and a wax.

2. The coating composition of claim 1 , wherein the reactants further comprise an additional monofunctional vinyl monomer.

3. The coating composition of claim 1 , wherein the binder is in its uncured state.

4. 10. The coating composition of claim 1, wherein the crosslinked organic additive has a refractive index that matches the binder in its cured state.

5. 10. The coating composition of claim 1, wherein the crosslinked organic additive has a refractive index in its cured state that is mismatched by at least about 0.11 from the binder.

6. 10. The coating composition of claim 1, wherein the crosslinked organic additive is characterized by a gel fraction ranging from about 40% to about 100%, the crosslinked organic additive is characterized by a degree of crosslinking ranging from about 0.03 to about 0.60, or both.

7. The coating composition of claim 2 , wherein the additional monofunctional vinyl monomer comprises a functional group capable of covalently bonding to the binder in its cured state.

8. The coating composition of claim 7, wherein the additional monofunctional vinyl monomer has acid functionality.

9. 9. The coating composition of claim 8, wherein the additional monofunctional vinyl monomer is (meth)acrylic acid, beta-carboxyethyl acrylate, or a combination thereof.

10. The coating composition of claim 1 , wherein the bridged organic additive comprises a surfactant embedded within the particles.

11. The composition of claim 1 , wherein the coating composition is a paint.

12. The coating composition of claim 1 , wherein the coating composition is silica-free.

13. The coating composition of claim 1 , wherein the multifunctional vinyl monomer comprises divinylbenzene.

14. The coating composition of claim 2 , wherein the additional monofunctional vinyl monomer is selected from acrylic monomers.

15. The coating composition of claim 14 , wherein the acrylic monomer comprises a (meth)acrylate.

16. The coating composition of claim 2 , wherein the additional monofunctional vinyl monomer comprises a nitrogen-containing group or a sulfur-containing group.

17. A paint comprising: a solvent system comprising water; a crosslinked organic additive in the form of particles, the crosslinked organic additive comprising the polymerization product of reactants including a multifunctional vinyl monomer containing two or more vinyl groups, the reactants consisting of cyclohexyl methacrylate, divinylbenzene, dimethylaminoethyl methacrylate, and an initiator; A binder; A paint comprising a colorant.

18. The coating of claim 17, wherein the cross-linked organic additive comprises the polymerization product of the reactants and a surfactant, the surfactant being embedded within the particles, and the coating is silica-free.

19. The coating composition of claim 1, wherein the D 50 particle size is from 40 nm to 150 nm.

20. The coating composition of claim 1, wherein the reactants consist of cyclohexyl methacrylate, divinylbenzene, dimethylaminoethyl methacrylate, and an initiator.

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