Patent Application
20090143502
Aqueous dispersions containing hydrophobic materials that are useful as reduced volatile organic content may be utilized as a coating, a stain, a resin, a polymer, or an additive. Specifically, the aqueous dispersion may contain one or more of a carboxyalkyl cellulose ester, such as carboxymethyl cellulose acetate butyrate, a fluorosurfactant, such as a polyoxetane fluorosurfactant or a fluoroaliphatic polymeric ester based surfactant, a water dispersible resin, and optionally, a C-11 ketone and/or surfactant.
The invention provides an aqueous dispersion of a hydrophobic material that may be utilized as a stain, resin, coating, polymer, or an additive.
In one embodiment of the invention, the aqueous dispersion comprises a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion optionally includes C-11 ketone. In yet another embodiment of the invention, the aqueous dispersion optionally includes a surfactant.
In a second embodiment of the invention, the invention is directed to a method for dispersing a hydrophobic material in water, comprising: (a) dissolving a carboxyalkyl cellulose ester and a fluorosurfactant in a compatible solvent; (b) adding the hydrophobic material; (c) neutralizing the carboxyalkyl cellulose ester with a base; and (d) adding water, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises optionally dissolving C-11 ketone with the carboxyalkyl cellulose ester and fluorosurfactant in a compatible solvent. In yet another embodiment of the invention, the method additionally comprises optionally including a surfactant with the carboxyalkyl cellulose ester and fluorosurfactant in a compatible solvent.
In a third embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In yet another embodiment, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In a fourth embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition comprises optionally includes a surfactant.
In a fifth embodiment of the invention, the aqueous dispersion comprises a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion optionally includes a surfactant.
In a sixth embodiment of the invention, the invention is directed to a method for dispersing a hydrophobic material in water, comprising (a) dissolving a carboxyalkyl cellulose ester and a water dispersible resin in a compatible solvent; (b) adding the hydrophobic material; (c) neutralizing the carboxyalkyl cellulose ester and water dispersible resin to some percent neutralization with a base; and (d) adding water, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises dissolving a fluorosurfactant with the carboxyalkyl cellulose ester and the water dispersible resin in a compatible solvent. In yet another embodiment of the invention, the method optionally comprises dissolving C-11 ketone with the carboxyalkyl cellulose ester, the water dispersible resin, and fluorosurfactant in a compatible solvent. In still yet another embodiment of the invention, the method optionally comprises adding a surfactant with the carboxyalkyl cellulose ester, the water dispersible resin, and fluorosurfactant in a compatible solvent.
In a seventh embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In an eighth embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In a ninth embodiment of the invention, the invention is directed to a method of dispersing hydrophobic materials into water comprising (a) charging the water dispersible resin to the mixing vessel, (b) adding the hydrophobic material, (c) neutralizing the water dispersible material to the appropriate percent neutralization with a base; and (d) adding water, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises dissolving a fluorosurfactant with the water dispersible resin. In yet another embodiment of the invention, the method optionally comprises dissolving C-11 ketone with the water dispersible resin and fluorosurfactant in a compatible solvent. In still yet another embodiment of the invention, the method optionally comprises adding a surfactant to the water dispersible resin and fluorosurfactant in a compatible solvent.
In a tenth embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a water dispersible resin and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In an eleventh embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a water dispersible resin and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In a twelfth embodiment of the invention, the invention is directed to a dispersant system comprising a carboxyalkyl cellulose ester and a fluorosurfactant, wherein the dispersant system is capable of dispersing a hydrophobic material. In another embodiment of the invention, the aqueous dispersant system optionally includes C-11 ketone. In yet another embodiment of the invention, the aqueous dispersant system optionally includes a surfactant.
Various embodiments of the invention are described below. Any of the embodiments of the invention may be used alone, or may be taken in various combinations. Some of the combinations according to the invention may be used to formulate coating compositions having unexpected properties in view of the state of the art, and are intended to be encompassed within the scope of the invention. Additional objects and advantages of the invention are discussed in the detailed description that follows, and will be obvious from that description, or may be learned by practice of the invention. It is to be understood that both this summary and the following detailed description are exemplary and explanatory only, and are not intended to restrict the scope of the invention.
The accompanying figures, which are incorporated herein and form a part of the specification, illustrate the present invention and, together with the description, further serve to explain the principles of the invention and to enable a person skilled in the pertinent art to make and use the invention.
The invention provides an aqueous dispersion of a hydrophobic material that may be utilized as a stain, resin, coating, polymer, or an additive.
In one embodiment of the invention, the aqueous dispersion comprises a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material.
The term “aqueous dispersion” is intended to encompass compositions containing an aqueous phase (e.g., water) as a continuous phase within which is dispersed a solid, liquid or polymeric phase. This solid, liquid, or polymeric phase becomes the discontinuous phase of the composition.
The term “hydrophobic material” is intended to encompass hydrophobic resins and moieties that can be incorporated into aqueous compositions of the invention that result in dispersions that may be utilized as a stain, resin, coating, polymer, or an additive.
The term “aqueous coating composition” is intended to encompass compositions containing an aqueous phase (e.g., water) that are applied to substrates.
Suitable carboxyalkyl cellulose esters for the invention are selected from a group consisting of carboxymethyl cellulose butyrate, carboxymethyl cellulose propionate, carboxymethyl cellulose acetate butyrate, and carboxymethyl cellulose acetate propionate. In one embodiment of the invention, the dispersion comprises certain esters of carboxy (C1-C3 alkyl) cellulose such as those taught in U.S. Pat. Nos. 5,668,273; 5,994,530; and 7,026,470 B2, and WO 01/35719.
In another embodiment, the carboxylmethyl cellulose ester of the invention comprises a carboxymethyl cellulose acetate butyrate “CMCAB”, having a degree of substitution of carboxymethyl of about 0.20 to about 0.75, a degree of substitution per anhydroglucose unit of hydroxyl from about 0.10 to about 0.70, and a degree of substitution per anhydroglucose unit of butyryl of about 0.10 to about 2.60 and a degree of substitution per anhydroglucose unit of acetyl of about 0.10 to about 1.65, and having an inherent viscosity of about 0.20 to about 1.70 dL/g, as measured in a 60/40 (wt/wt) solution of phenol/tetrachloroethane at 25° C. In yet another embodiment, the CMCAB has a degree of substitution carboxymethyl of about 0.25 to about 0.35, a degree of substitution per anhydroglucose unit of hydroxyl from about 0.10 to about 0.70, and a degree of substitution per anhydroglucose unit of butyryl of about 0.10 to about 2.60 and a degree of substitution per anhydroglucose unit of acetyl of about 0.10 to about 1.65, and having an inherent viscosity of about 0.20 to about 1.70 dL/g, as measured in a 60/40 (wt/wt) solution of phenol/tetrachloroethane at 25° C. In yet another embodiment, the CMCAB has a degree of substitution per anhydroglucose unit of hydroxyl of about 0.10 to about 0.70, butyryl of about 1.10 to about 2.55, and acetyl of about 0.10 to about 0.90.
Incorporation of the fluorosurfactant in the dispersant system results in improved dispersion processing, reduced foaming characteristics, improved dispersion appearance and stability, and decreased dispersion particle size. Suitable fluorosurfactants include, but are not limited to, one or more of polyoxetane fluorosurfactants and fluoroaliphatic polymeric esters. In one embodiment, these fluorosurfactants may be short chain, (four carbons or less). Examples of suitable polyoxetane fluorosurfactants include, but are not limited to, those described in WO2002/092660, WO2003/051959, WO2006/065752, WO2001/048051, and U.S. Pat. Nos. 6,403,760 and 6,660,828. In particular, WO2006/065752 discloses short chain fluorinated polyether block copolymers which result in small micelle particle size, a property which is beneficial in the current invention. More specifically, WO2006/065752 discloses block copolymers that include a first polyether block having a pendant alkoxyfluoroalkyl group and a second polyether block substantially devoid of pendant alkoxyfluoroalkyl groups. Other suitable polyoxetane fluorosurfactants include commercially available products such as PolyFox™ PF-151N, PolyFox™ PF-159, PolyFox™ PF-154N, and PolyFox™ PF-3320 (Omnova Solutions, Fairlawn, Ohio). Other fluorinated surfactants useful for the invention include, but are not limited to, commercially available fluoroaliphatic polymeric esters such as the FC-4430, FC-4432, and FC-4434 (3M Company, Minneapolis, Minn.).
The aqueous dispersion of the present invention includes a hydrophobic material. Examples of suitable hydrophobic materials that may be used include, but are not limited to, one or more of a wax, a silicone, a silicone wax, a fluorocarbon, a UV absorber, a photoinitiator, a chlorinated polyolefin, a nonchlorinated polyolefin, a hydroxy-functional polymer, a silanol modified polyol, an acrylic, a polyester, a polyether, an acrylate-functional resin, an acrylated acrylic, an acrylated polyester, an acrylated polyether, an acrylated polyurethane, an acrylated epoxy, an amine-modified acrylated acrylic, an amine-modified polyester, an amine-modified polyether, an unsaturated polyester, an allyl-functional polymer, styrene allyl alcohol, a non-water soluble polyol, an air-oxidizable initiator/crosslinker, a phenoplast resin, a hydrocarbon resin, a polyvinyl butyral resin, a polybutadiene resin, a modified polybutadiene resin, an aminoplast resin, an oil, a fat, a fatty acid, a resin derived from an oil, fat, or fatty acid, a plasticizer, a hydroxyl-terminated polybutadiene resin or derivative thereof, a maleic-modified resin, an ethylene vinyl acetate copolymer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, an acrylic copolymer, an alkyd resin, a modified alkyd resin including styrene, vinyl toluene and urethane-modified alkyds, a fluorinated acrylic, and an aliphatic or aromatic hydrocarbon resin.
Additionally, oils and fats and resins derived therefrom can be used as part of the hydrophobic moiety of the invention. Examples of suitable oils and resins derived therefrom include, but are not limited to, those described in Bailey's Industrial Oil and Fat Pioducts, Volume 1, 4th ed., Swern, D., ed., John Wiley & Sons, New York, N.Y. Other hydrophobic moieties that may be dispersed with the invention include defoamers (e.g., silicone), antioxidants, waxes, colorants, pigments, dyes, dispersants, UV absorbers, light stabilizers, catalysts, crosslinkers, biocides, flow and leveling agents, wetting agents, sunscreens, and water repellants.
Still other hydrophobic moieties that can be incorporated into the aqueous dispersions, coating compositions, and additives according to the invention include the resins and additives described in WO 2004/030801, such as, for example, different types of silicones, waxes, chlorinated polymers, polyols/hydroxyl functional polymers, unsaturated and UV-curable resins and oligomers, photoinitiators, additives stabilizers, and aminoplast and phenoplast resins.
In another embodiment of the invention, the aqueous dispersion optionally includes C-11 ketone. An example of one suitable C-11 ketone is CAS number 71808-49-6.
In another embodiment of the invention, the aqueous dispersion optionally includes a surfactant. Examples of suitable surfactants include, but are not limited to, one or more nonionic surfactants, such as acetylenic glycol based surfactants, polyalkylene glycol ethers, aliphatic alcohol ethoxylates, alkylphenol ethoxylates, tristyrylphenol ethoxylates, block copolymers such as ethoxylated polyoxypropylenes, the nonionic ADEX brand of surfactants (Rhodia, Polymer System Specialties, Cranbury, N.J.) and surfactant blends such as Carbowet DC01 (Air Products and Chemicals, Allentown, Pa.). Other surfactants useful for the invention include those mentioned in Rosen, M. J., Surfactants and Interfacial Phenomena, 3rd ed., John Wiley & Sons, New York, N.Y.; (2004) and Möbius, D., et al., Surfactant: Chemistry, Interfacial Properties, Applications (Studies in Interface Science), Bk&CD-Rom edition, Elsevier Science BV, Amsterdam, The Netherlands (2001).
In a second embodiment of the invention, the invention is directed to a method for dispersing a hydrophobic material in water, comprising: (a) dissolving a carboxyalkyl cellulose ester and a fluorosurfactant in a compatible solvent; (b) adding the hydrophobic material; (c) neutralizing the carboxyalkyl cellulose ester with a base; and (d) adding water with sufficient agitation, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises optionally dissolving C-11 ketone with the carboxyalkyl cellulose ester and fluorosurfactant in a compatible solvent.
In another embodiment of the invention, the method additionally comprises optionally including a surfactant with the carboxyalkyl cellulose ester and fluorosurfactant and/or C-11 ketone in a compatible solvent. Examples of typical solvents useful for the invention include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, 2-propoxy-ethanol, 2-butoxyethanol, ethyl 3-ethoxypropionate, 2-butanone, methanol, ethanol, propanol, isopropyl alcohol, butanol, 2-ethyl-hexanol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tertiary butyl acetate, ethyl ether, propyl ether, propyl glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene butyl ether, dipropylene glycol ether, dipropylene glycol methyl ether, ethylene glycol, ethylene glycol butyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ethyl ether, ethylene glycol ethyl ether, ethylene glycol 2-ethylhexyl ether, ethylene glycol methyl ether, ethylene glycol phenyl ether, 1-methyl-2-pyrrolidinone, ethylene glycol diacetate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethyl ether, propylene glycol butyl ether, propylene glycol dimethyl ether, propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol phenyl ether, propylene glycol propyl ether, tripropylene glycol ethyl ether, triethylene glycol, tri(ethylene glycol) dimethyl ether, and mixtures thereof. Other suitable solvents include those listed in Wypych, G., ed., Handbook of Solvents, ChemTec Publishing, Ontario, Canada (2001) and Swaraj, P., Surface Coatings Science and Technology, 2nd ed. John Wiley & Sons, New York, N.Y. (1996). Other volatile inert solvents typically used in coating compositions may also be used in the aqueous dispersions of the present invention, as will be apparent to one of ordinary skill in the art. Typically, the amount of solvent will be adjusted to dissolve and/or suspend the various components of the composition in a uniform liquid suspension or liquid. Typically, the amount of solvent will be kept as low as possible in order to keep the volatile organic compound “VOC” of the composition as low as possible.
In a third embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
The aqueous dispersions of the present invention may be utilized in a coating, a stain, a resin, a polymer, or an additive. Illustrative coatings that can utilize the composition of the invention include wood coatings such as, e.g., stains, seal coat/sealers, topcoats, wiping stains, glazes, and fillers. Examples of other coatings include paper coatings, cardboard coatings, paints (e.g., house paints), primers, architectural coatings, industrial coatings, maintenance coatings, general metal-type coatings, paper coatings including textile treatments, plastic coatings such as primers, base coats, top coats, antigraffiti coatings, UV coatings, and adhesion promoters, and polishes. Other suitable coatings that may include the aqueous coating compositions of the invention can be found in Flick, E. W., Paint & Ink Formulation Database, William Andrew Publishing, Norwich, N.Y. (2005), Lambourne, R. and Strivens, T. A., eds., Paint and Surface Coatings: Theory and Practice, 2nd ed., 1999; William Andrew Publishing, Norwich, N.Y. (1999), and Wicks, Z. W., et al., eds., Organic Coatings: Science and Technology, 2nd ed., John Wiley & Sons, New York, N.Y. (1999).
In a fourth embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a carboxyalkyl cellulose ester, a fluorosurfactant, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In yet another embodiment of the invention, the aqueous coating composition optionally includes a surfactant.
In a fifth embodiment of the invention, the aqueous dispersion comprises a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion optionally includes a surfactant.
The use of the water dispersible resin in place of all or a portion of the carboxyalkyl cellulose ester is advantageous in that its use results in dramatically reduced volatile organic compounds (“VOCs”).
Suitable water dispersible resins for use in the aqueous dispersion of the invention include, but are not limited to, one or more olefinic copolymers.
In one embodiment, the olefinic copolymer is one or more of hydroxyl functional acrylics or polyesters having hydrophilizing functionality. U.S. Pat. No. 5,466,745 discloses olefinic copolymers with an average molecular weight of about 1000 to about 50000, an acid number of from about 15 to about 150 mg KOH/g resin, and an amount of hydroxyl groups of from about 2.5 wt % to about 6 wt % (on a 100% solids basis). Fiori, D, et al., in “The Effect of Particle Size Distribution on the Performance of Two-Component Water Reducible Acrylic Polyurethane Coatings Using Tertiary Polyisocyanate Crosslinkers,” Journal of Coatings Technology 72 (2000) further describe olefinic copolymers that are useful for the invention.
In a sixth embodiment of invention, the invention is directed to a method for dispersing a hydrophobic material in water, comprising (a) dissolving a carboxyalkyl cellulose ester and a water dispersible resin in a compatible solvent; (b) adding the hydrophobic material; (c) neutralizing the carboxyalkyl cellulose ester and water dispersible resin to some percent neutralization with a base; and (d) adding water with sufficient agitation, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises dissolving a fluorosurfactant with the carboxyalkyl cellulose ester and the water dispersible resin in a compatible solvent. In yet another embodiment of the invention, the method optionally comprises dissolving C-11 ketone with the carboxyalkyl cellulose ester, the water dispersible resin, and fluorosurfactant in a compatible solvent. In yet another embodiment of the invention, the method optionally comprises adding a surfactant with the carboxyalkyl cellulose ester, the water dispersible resin, and fluorosurfactant in a compatible solvent.
In a seventh embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In an eighth embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a carboxyalkyl cellulose ester, a water dispersible resin, and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In a ninth embodiment of the invention, the invention is directed to a method of dispersing hydrophobic materials into water comprising (a) charging the water dispersible resin to the mixing vessel, (b) adding the hydrophobic material, (c) neutralizing the water dispersible material to the appropriate percent neutralization with a base; and (d) adding water with sufficient agitation, so as to invert the resulting mixture from a solvent continuous phase to an aqueous continuous phase. In another embodiment of the invention, the method additionally comprises dissolving a fluorosurfactant with the water dispersible resin. In yet another embodiment of the invention, the method optionally comprises dissolving C-11 ketone with the water dispersible resin and fluorosurfactant in a compatible solvent. In still yet another embodiment of the invention, the method optionally comprises the addition of a surfactant with the water dispersible resin and fluorosurfactant in a compatible solvent.
In a tenth embodiment of the invention, the invention is directed to an aqueous coating composition comprising an aqueous dispersion comprising a water dispersible resin and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the composition additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the composition optionally includes a surfactant.
In an eleventh embodiment of the invention, the invention is directed to an article coated with an aqueous coating composition comprising a water dispersible resin and a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition additionally comprises a fluorosurfactant. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In still yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
In a twelfth embodiment of the invention, the invention is directed to a dispersant system comprising a carboxyalkyl cellulose ester and/or a water dispersible polymer, and a fluorosurfactant, wherein the dispersant system is capable of dispersing a hydrophobic material. In another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes C-11 ketone. In yet another embodiment of the invention, the aqueous dispersion of the aqueous coating composition optionally includes a surfactant.
A person of ordinary skill in the art will be routinely able to adjust the amounts of the various components of the dispersant system to achieve the desired final aqueous dispersion. Exemplary amounts of the various components are as follows.
In one embodiment, the concentration of the carboxyalkyl cellulose ester in the aqueous dispersion ranges from about 0 to about 30%. In another embodiment, the concentration of the carboxyalkyl cellulose ester in the aqueous dispersion ranges from about 0.1% to about 20%. In yet another embodiment, the concentration of the carboxyalkyl cellulose ester in the aqueous dispersion ranges from about 0.4% to about 8%.
In one embodiment, the concentration of the water dispersible resin in the aqueous dispersion ranges from about 0 to about 60%. In another embodiment, the concentration of the water dispersible resin in the aqueous dispersion range from about 0 to about 30%. In yet another embodiment, the concentration of the water dispersible resin in the aqueous dispersion ranges from about 1% to about 10%.
In one embodiment, the concentration of the fluorosurfactant in the aqueous dispersion ranges from about 0 to about 30%. In another embodiment, the concentration of the fluorosurfactant in the aqueous dispersion ranges from about 0 to about 20%. In yet another embodiment, the concentration of the fluorosurfactant ranges from about 0-to about 6%.
Optionally, the aqueous dispersion contains C-11 ketone and/or surfactant. In one embodiment, the concentration of C-11 ketone in the aqueous dispersion ranges from about 0 to about 30%. In another embodiment, the concentration of C-11 ketone in the aqueous dispersion ranges from about 0 to about 12%. In yet another embodiment, the concentration of C-11 ketone in the aqueous dispersion ranges from about 0 to about 6%. In one embodiment, the concentration of surfactant in the aqueous dispersion ranges from about 0 to about 10%. In another embodiment, the concentration of surfactant in the aqueous dispersion ranges from about 0 to about 5%. In yet another embodiment, the concentration of surfactant in the aqueous dispersion ranges from about 0 to about 2%.
The balance of the particular composition consists of the hydrophobic material, solvents, including water, and miscellaneous additives such as stabilizers and/or rheology modifiers that will be readily apparent to those of ordinary skill in the art.
The following examples are illustrative, but not limiting, of the methods of the present invention. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which are obvious to those skilled in the alt, are within the spirit and scope of the invention.
All patents and publications cited herein are fully incorporated by reference herein in their entirety.
Example 5 may be used as is or reduced with water under agitation to make baths as shown below in Examples 8 and 9 to impart water and oil repellency to substrates.
A bath of the Example 2 dispersion was prepared by placing 68.83 grams of Example 2 dispersion into a 600 ml beaker. The mixture was stirred and then 79.38 grams of deionized water was added. The mixture was again stirred. The mixture had a creamy foam on the surface that was removed. The balance of the sample looked good.
4.95 grams of 100% cotton was dipped into the bath and squeezed by hand. The resultant wet cotton weighed 12.50 grams. The wet cotton was cured at 80° C. for 15 minutes. After a 2 hour recovery period, a water drop was placed on the treated cotton. Initial wicking of the water took place within 10 seconds, with complete wick occurring after about 6 minutes for one drop.
6.13 grams Repearl MF crosslinker was added to the remainder of the bath. After stirring, a piece of cotton weighing 4.87 grams was dipped into the bath and squeezed. The resultant wet cotton weighed 12.68 grams. The wet cotton was cured at 132° C. for 20 minutes. After a 2 hour recovery period, a drop of water was place on the cured cotton. Initial wicking of the water took place after 3 minutes 10 seconds, while a final wicking took place after 4 minutes.
Example 7 may be used as is or reduced with water under agitation to make baths as shown below in Examples 8 and 9 to impart water and oil repellency to substrates.
Example 12 was further evaluated by Hamby Textile Research Laboratory (Raleigh, N.C.) by pad application. The results of the study showed a 0 rating for oil and water repellency (i.e., no repellency).
Examples 10-19, above, illustrate the difficulty in making a uniform, stable dispersion that produces a grit free film and that can be further reduced with water to provide improved water and oil repellency to various substrates utilizing aqueous dispersions of only carboxyalkyl cellulose esters.
Thus, it has been found that the combination of carboxyalkyl cellulose ester, such as carboxymethyl cellulose acetate butyrate, in combination with a fluorosurfactant, such as the polyoxetane fluorosurfactant PolyFox PF-151N, provides a method of easily dispersing very hydrophobic materials, such as perfluorinated acrylic polymers, to produce stable, uniform dispersions that produce grit free films.
The aqueous dispersion containing carboxyalkyl cellulose esters and fluorosurfactant may be further reduced with water and coated onto a substrate, such as 100% cotton, to provide coated substrates with outstanding water and oil repellency.
Further, it has been found that decreased dispersion particle size, improved dispersion stability, and improved dispersion drawdown appearance may be obtained utilizing carboxyalkyl cellulose esters, such as carboxymethyl cellulose acetate butyrate, a polyoxetane fluorosurfactant, such as PolyFox PF-151N, and a C-11 ketone (Kesolv 184), when dispersing particularly difficult items such as a mineral spirits solution of perfluorinated acrylic polymer, particularly when the batch sizes are increased.
Examples 20-23 were further evaluated by making a 1.5 mil draw down with a bird bar and by evaluation of dispersion particle size under the microscope. The following table details the draw down results.
BYK 348 is a Polyether modified poly-dimethyl-siloxane available from BYK-Chemie, Wallingford, Conn.
An aqueous UV formulation was made with TAW 10-3. First, the amount of triethylamine (“TEA”) in TAW 10-3 as supplied was determined utilizing Calculation 1.
The amount of TEA in TAW 10-3 as supplied may also be determined utilizing Calculation 2.
Then, the composition of TAW 10-3 was adjusted as detailed in the table below.
The TAW 10-3 can be utilized to disperse a UV resin thus making an aqueous UV Resin Formula. A clear film is produced indicating compatibility in the system.
An aqueous UV formulation was made with TAW 10-3. Since the TAW 10-3 is pre-neutralized with TEA, the triethanolamine (“TEOA”) was left out.
The sample separated into two phases with a clear liquid top and solid white bottom. The sample was remade trying three different approaches. First, the neutralization was decreased to 80% with the addition of TEOA and the solids were reduced to ≈45% by adding water and EB, while keeping the VOC at 3.5%. The second sample was made as the first, but PF151N was left out. In the third sample, the CMCAB Solution (see Example 43 below) replaced the EB added to the first approach raising the VOC to ≈4%. The amount of TEOA added was adjusted to compensate for the CMCAB acid equivalents.
The addition of the CMCAB solution to the UV resin utilizing the TAW 10-3 improves the appearance of the resin.
To a portion of the dispersions of Example 36, photoinitiator, water, and additives were added to evaluate the samples for cure and appearance. A 20 RDS DD was made on Form N2A of each sample. The DDs were placed in the Low Relative Humidity Box ≈47° C. and 9% RH under air at 100 L/min and allowed to flash for 20 minutes. The DDs were then cured by 4 passes through the UV Curing Unit at 25-fpm, with a 300-WPI Hg lamp with an elliptical reflector.
The table below details these formulations and the results of the DDs.
There was some separation in the dispersions of Example 37A and Example 37B, but they stirred back together easily. The dispersion of Example 37C did not separate.
The calculation to determine the amount of TEOA to add to reduce the neutralization to 80% is shown in Calculation 3 below.
To evaluate the particle size of the dispersions of Example 37, the samples were cut 1/100 with DI water as detailed in the table below. These samples were then placed on a microscope slide and examined with transmitted light at 400× magnification. The images of the sample are shown as
The addition of PolyFox PF-151N to the dispersion utilizing the TAW 10-3 and the CMCAB solutions results in decreased dispersion particle size.
To the dispersion of Example 37F, Rhoplex CL-204 and Alberdingk AC-2538 were added 1:1 to determine compatibility. DDs were made and cured as stated above. The table below details the formulations and the results.
The dispersion of Example 37C was placed in a 50° C. oven for 4 days to evaluate stability. The sample separated into two phases with a liquid top and semi-solid bottom. The sample was re-stirred and the pH and viscosity were measured. A 20 RDS DD was made as stated above. The table below details the results.
Improvement in dispersion stability is required.
Samples were made evaluating various polymers (see Table 1 below). The polymers with 100% NVM were dissolved in MAK to 60% solids and then added to the dispersion. The samples were then crosslinked with Bayhydur XP-7063, NCO:OH 1.1:1.0. A 3 mil DD on Leneta Form 7B was made of both the dispersion and the crosslinked sample. The DDs were air-dried overnight and then evaluated for cure and appearance. MEK double rubs were performed on the DDs of the crosslinked samples 10 days later. Tables 2-12 detail the formulations of the samples.
Example 41YY was remade adding Shamrock 395 N5 1:1 on TAW 10-3 solids as shown below in Table 10.
A formulation of Example 41PP (see Table 6) was made, dissolving the Irgacure 819 in monomer and oligomer as shown below in Table 11.
This sample was dispersed in the formulation of Example 41EEE (see Table 12 below) and a sample with Cytec TAW 10-4 and a sample with a mixture of 65% methyl amyl ketone and 35% CAB 551.2 were also made. These formulas are detailed in Table 12. Example 41FFF was UV cured by 1 pass through the UV Curing Unit under a 300 WPI gallium lamp with a parabolic reflector at 352 mJ/cm2.
The dispersion stability, dispersion DD, crosslinked DD, and MEK rubs for the aqueous acrylic dispersions of Example 41 are shown below in Table 13.
The samples with SAA 100 (Example 41EE) and Irgacure 819 in TPGDA and Ebecryl 3700 (Example 41HHH) gave the best results in terms of giving a clear, dry film with excellent MEK Resistance. Overall, the SAA 100 dispersion (Example 41AA) was the best because it remained stable for over seven months whereas the Irgacure 819 dispersion (Example 41FFF) remained stable for only two weeks.
We then evaluated the oven aged sample versus the non oven aged sample for let down with water and sprayability. The results are shown in the following table.
A 2 component antigraffiti coating was made by mixing 300 grams Example 48 dispersion with 147.42 grams of Tolunate HDT-LV2 Polyisocyanate crosslinker from Rhodia in a mixing vessel. To this mixture was added 44.51 grams of DI water under agitation. The sample was mixed for approximately 2 minutes, and the mixed coating spray applied onto Form WK chart from Leneta company. The coating was allowed to air dry. The resulting crosslinked coating was tack free after 4 days, and resists wetting by a permanent marker after 8 days, with complete marker clean up with MEK in that same time period. Other tests show that improved dry times can be obtained with alternative polyisocyantes (an example being Rhodocoat X EZ-M 501, a product of Rhodia, Cranbury, N.J.), and addition of catalysts to the system. The above example merely serves as one of the many examples of the outstanding antigraffiti results possible with the dispersion presented, and as one of the many examples of both the breadth of types of hydrophobic materials that can be dispersed utilizing the invention and the breadth of types of the many coatings that may be obtained therefrom from the invention.
This application claims the benefit of U.S. Provisional Patent Application No. 60/697,538, filed Jul. 11, 2005, herein incorporated by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US06/27012 | 7/11/2006 | WO | 00 | 1/11/2008 |
| Number | Date | Country | |
|---|---|---|---|
| 60697538 | Jul 2005 | US |
