WO2005047358A1 - Compositions aqueuses de revetement hydrophobe et oleophobe, procedes et utilisations - Google Patents

Compositions aqueuses de revetement hydrophobe et oleophobe, procedes et utilisations Download PDF

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Publication number
WO2005047358A1
WO2005047358A1 PCT/US2004/037545 US2004037545W WO2005047358A1 WO 2005047358 A1 WO2005047358 A1 WO 2005047358A1 US 2004037545 W US2004037545 W US 2004037545W WO 2005047358 A1 WO2005047358 A1 WO 2005047358A1
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Prior art keywords
coating
polymer
composition
oleophobic
functionality
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PCT/US2004/037545
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English (en)
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Robert T. Sobieski
Guillermina C. Garcia
Barry Rosenbaum
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Omnova Solutions Inc.
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Publication of WO2005047358A1 publication Critical patent/WO2005047358A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the invention relates to aqueous coating compositions. More specifically, the invention relates to aqueous hydrophobic and oleophobic coating compositions comprising fluorinated polymer.
  • BACKGROUND Water repellency and stain resistance are important properties for many materials, and especially for textile materials. Thus, various types of water repellant, oil repellant and stain resistant coatings have been provided in the prior art.
  • hydrophobic as used herein means that the coating is water repellent and resists removal by washing.
  • oleophobicity as used herein means that the coating is resistant to attack and removal by oils.
  • the two terms can be combined herein with reference to the term “repellent.”
  • stain resistant as used herein means that the coating exhibits high stain release.
  • the property of being cleanable is particularly desirable when the substrate is a textile substrate.
  • a repellent coating is capable of being formed as an aqueous system for ease of processing and to reduce release of volatile organic solvents into the environment.
  • US Patent Nos. 6,465,565 and 6,465,566 relate to anionic waterborne polyurethane dispersions that are formed in the presence of polyfluorooxetane oligomers, polymers, or copolymers so that the polyfluorooxetanes are incorporated in the polyurethane.
  • the anionic water borne polyurethane dispersions are disclosed to be blended with vinyl ester monomers, such as various acrylates, and subsequently polymerized by radiation, for example ultraviolet light, to form a commingled blend of at least two different types of polymers.
  • U.S Patent No 6,391,807 discloses a polymer composition comprising a fluorochemical oligomeric compound and a thermoplastic or thermoset polymer.
  • the polymer composition is useful in preparing shaped articles such as fibers and films, which have desirable oil- and water repellency properties.
  • Many conventional repellant polymers contain C 8 F 17 esters that are currently under scrutiny because they have been found to be bio-accumulative. It would be desirable to prepare a stain repellent and/or stain resistant coating system that performs well, and reduces or eliminates the amount of C 8 F 17 esters used in the system. It is further desirable to provide coating compositions that provide excellent stain release and cleanability properties.
  • an aqueous coating composition for preparation of hydrophobic and oleophobic coatings comprises at least one polymeric component comprising highly fluorinated functionality, wherein the coating composition comprises less than an amount of non-fugitive surfactant that would deleteriously affect the oleophobic or hydrophobic properties of a coating made from the coating composition when in place on a substrate.
  • an aqueous coating composition for preparation of hydrophobic and oleophobic coatings comprises at least one polymeric component comprising highly fluorinated functionality, wherein the coating composition comprises a fugitive surfactant in an amount so that the ultimate coating in place on the substrate comprises less than an amount of surfactant that would deleteriously affect the oleophobic or hydrophobic properties of the coating.
  • the coating composition comprises a fugitive surfactant in an amount so that the ultimate coating in place on the substrate comprises less than an amount of surfactant that would deleteriously affect the oleophobic or hydrophobic properties of the coating.
  • aqueous coating compositions for preparation of hydrophobic and oleophobic coatings comprising a film- forming polymer comprising at least one pendent fluoro-containing functionality; and a non-film-forming polymer comprising at least one pendent highly fluorinated functionality.
  • a polymer is considered to be film-forming if it is capable, when cast as a two mil film on a glass substrate under coalescing conditions, to form a self supporting film.
  • some polymeric materials such as waxes may coalesce to form a layer having a continuous appearance on the surface thereof when cast on glass, the resulting coating cannot be removed in a sheet form from the substrate as a self-supporting film.
  • the film-forming polymer comprises pendent fluoroalkoxyalkyl functionality
  • the non-film-forming polymer comprises pendent perfluoroalkyl ester functionality
  • the coating composition comprises a film-forming polymer that is a C 4 F fluoroalkoxyalkyl modified polyurethane polymer, and a non-film-forming polymer that is a perfluoroalkyl acrylic co-polymer.
  • the composition also includes a film- forming oleophobic polymer, such as a polyacrylic polymer.
  • the compositions of this aspect of the present invention are substantially surfactant free.
  • the polymeric components of the composition comprises a blend of about 20 to about 98 percent by weight of a polymer comprising at least one pendent fluoroalkoxyalkyl functionality and about 2 to about 80 percent by weight of an oleophobic polymer.
  • the coating composition comprises a C 4 F fluoroalkoxyalkyl modified polyurethane polymer in combination with a polyacrylic co-polymer.
  • the compositions of this aspect of the present invention are substantially surfactant free.
  • compositions of the present invention surprisingly provide coatings on substrates that exhibit excellent hydrophobicity and oleophobicity.
  • Substrates coated with compositions as described herein exhibit excellent stain resistance properties, and provide surprising stain release during conventional cleaning operations.
  • Compositions of the present invention in particular provide durable coatings that are capable of remaining on the substrate to which they are applied in ordinary use conditions, and preferably are sufficiently durable to provide effective repellency and/or release properties upon repeated washings.
  • the coating compositions of the present invention can provide effective stain release and/or stain repellency properties when applied at a temperature less than about 110°F (about 43 °C).
  • coating compositions of the present invention can provide exceptional performance while being applied under ambient temperature conditions.
  • the coating compositions of the present invention can be surprisingly effective even when applied in aftermarket applications, such as by a wholesaler, dealer or the consumer.
  • These properties are preferably achieved by compositions comprising a very low overall fluorine content, and can provide cost and manufacturing advantages as compared to previous fluorine-containing coating compositions. Methods of making and method of using these coating compositions and coatings are also provided.
  • copolymer encompasses both oligomeric and polymeric materials, and encompasses polymers incorporating two or more monomers.
  • monomer means a relatively low molecular weight material (i.e., generally having a molecular weight less than about 500
  • Daltons having one or more polymerizable groups.
  • Oligomer means a relatively intermediate sized molecule incorporating two or more monomers and generally having a molecular weight of from about 500 up to about 10,000 Daltons.
  • Polymer means a relatively large material comprising a substructure formed two or more monomeric, oligomeric, and/or polymeric constituents and generally having a molecular weight greater than about 10,000 Daltons.
  • the present invention contemplates that the ultimate coating in place on a substrate comprises little or no surfactant, so that the amount of any surfactant present in the coating in place on the substrate would not deleteriously affect the oleophobic or hydrophobic properties of the coating.
  • the resulting coating can be obtained in any appropriate manner of providing a coating that has low or no surfactant content.
  • the coating composition is originally formulated to contain low or no non-fugitive surfactant content in the composition.
  • an aqueous stain release coating composition is provided comprising at least one polymeric component comprising highly fluorinated functionality, wherein the coating composition comprises less than about 0.25 phr, and more preferably less than about 0.1 phr, of non-fugitive surfactant.
  • the coating composition is substantially free of non-fugitive surfactant.
  • a surfactant is considered to be present in an amount that deleteriously affects the oleophobic properties of a coating made from the coating composition when in place on a substrate when the coating containing the surfactant has an Oil Repellency Test score of 3 A or less, and a like coating that does not contain surfactant (i.e. a control coating composition) has an Oil Repellency Test score of greater than 3 A.
  • an amount of surfactant is considered to be an amount that deleteriously affects the hydrophobic properties of a coating made from the coating composition when in place on a substrate when the coating containing the surfactant has a Hydrophobicity Test score of 3 A or less, and a like coating that does not contain surfactant has a Hydrophobicity Test score of greater than 3 A.
  • the Oil Repellency Test and the Hydrophobicity Test are described in more detail in the Example and Test Methodology section below.
  • a surfactant is a molecule that contains both hydrophobic and hydrophilic components, and therefore is at least partially soluble in both organic and aqueous solvents.
  • a surfactant is semi-soluble in both organic and aqueous solvents.
  • a surfactant will lower the surface tension of water.
  • a fugitive surfactant is defined as a molecule that is not bonded to the polymer of the coating is sufficiently volatile that the surfactant is volatilized during the coating process or during drying or storage, so that the resulting coating, when evaluated after 7 days of conventional product storage conditions, has less than about 10% of the fugitive surfactant as originally present in the coating composition still present in the coating.
  • the resulting coating when evaluated after 7 days of conventional product storage conditions, has substantially none of the fugitive surfactant as originally present in the coating composition still present in the coating.
  • a surfactant that is not bonded to a polymer of the coating is considered to be non-fugitive if, seven days after formation of the coating, more than about 10% of the surfactant as originally present in the coating composition is still present in the coating.
  • Evaluation of the presence of fugitive or non-fugitive surfactant can be carried out using conventional chemical analysis techniques. The formulation of low surfactant content or surfactant free compositions is particularly facilitated by preparation of some or all polymer starting materials by solvent polymerization, rather than emulsion polymerization.
  • Solvent polymerization is a polymerization process in which the monomers and the polymerization initiators are dissolved in a non-monomeric liquid solvent at the beginning of the polymerization reaction.
  • the solvent is later removed in a solvent exchange process, for example, by forming salts in an aqueous medium.
  • Solvent polymerization has fallen into substantial disfavor in industry due to the use of solvents in the manufacturing process that could potentially be released to the environment, or which could create waste disposal issues.
  • the reaction process as described herein preferably is carried out under controlled conditions that enable reclamation of solvents used in the reaction process.
  • solvent polymerization processes are readily capable of providing polymers in a manner that does not introduce surfactants to the coating composition.
  • the polymers that result from the polymerization process can be tailored to be substantially free of functionalities that can have an affinity to staining material, such as hydrophilic pendent end groups.
  • preferred solvent polymerization processes are controlled single phase polymerizations, which generally result in a more uniform molecular composition of the polymer. Additionally, these processes can provide a greater degree of control of the hydrophilic and hydrophobic characteristics of the ultimate polymer.
  • the coating composition can be formulated to contain a fugitive surfactant that is subsequently removed from the coating composition or the coating by volatilization (i.e. release to the environment or recaptured) during the coating process, by a post-coating surfactant removal process (such as heating or gas impingement to sweep away surfactant), or during conventional storage by gradual volatilization of the surfactant.
  • a fugitive surfactant that is subsequently removed from the coating composition or the coating by volatilization (i.e. release to the environment or recaptured) during the coating process, by a post-coating surfactant removal process (such as heating or gas impingement to sweep away surfactant), or during conventional storage by gradual volatilization of the surfactant.
  • Examples of preferred surfactants as defined herein include N-methyl pyrrolidone, and lower alkyl glycol ethers such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol phenyl ether, ethylene glycol n-butyl ether acetate, diethylene glycol n-butyl ether acetate, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol n-propyl ether and mixtures thereof.
  • lower alkyl glycol ethers such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol pheny
  • the composition comprises a fugitive surfactant such as amine oxide.
  • a fugitive surfactant such as amine oxide. It has surprisingly been found that limiting the amount of surfactant present in the final coating to little or no surfactant has most significant impact when the perfluorinated functionality contains predominantly, and preferably only perfluorinated chains having less than eight carbon atoms, more preferably six or less, and most preferably four or less carbon atoms. While not being bound by theory, it is believed that longer chain perfluorinated functionality can have sufficient steric "reach" and/or repellant activity to overwhelm the oil and or water attracting effect of the surfactant present in the coating.
  • Shorter chain perfluorinated functionality in contrast, is believed to have less steric "reach" and/or repellant activity, and does not overwhelm the oil and or water attracting effect of the surfactant present in the coating.
  • materials that cause stains on surfaces can be attracted to surfactants in a coating, and stain repellent and/or stain resistant coatings that contain small amounts or no surfactant can be more effective for that reason.
  • surfactants While not being bound by theory, it alternatively or additionally is believed that surfactants will tend to discourage migration of pendent fluoro side groups from within the matrix of a coating to the surface of a coating.
  • the fluorinated functionalities of the polymer in the coating can be at least partially embedded within the coating itself, and therefore are not available at the surface of the coating to repel or resist staining materials that can come in contact with the surface of the coating.
  • longer chain perfluorinated functionalities can have sufficient steric "reach” to overwhelm the surfactant and migrate to the surface of the coating.
  • Shorter chain perfluorinated functionalities are believed to have less steric "reach," and do not overwhelm the surfactant and migrate to the surface of the coating.
  • Various polymer components can be particularly identified as providing advantageous properties when used in the compositions of this embodiment of the present invention.
  • a preferred low surfactant content or substantially surfactant free composition comprises a polymeric component comprising highly fluorinated functionality is a polymer comprising at least one pendent fluoroalkoxyalkyl functionality.
  • the polymeric component comprising highly fluorinated functionality is a polyurethane polymer.
  • the polymeric component comprising highly fluorinated functionality is a polymer comprising at least one pendent fluoroalkyl ester functionality.
  • the polymeric component comprising highly fluorinated functionality is a polyacrylic polymer.
  • the coating composition further comprises an additional polymer that does not contain a fluorinated functionality.
  • aqueous coating compositions for preparation of hydrophobic and oleophobic coatings comprising a film-forming polymer comprising at least one pendent fluoro-containing functionality; and a non-film-forming polymer comprising at least one pendent highly fluorinated functionality.
  • the film-forming polymer comprises pendent fluoroalkoxyalkyl functionality
  • the non-film-fo ⁇ ng polymer comprises pendent perfluoroalkyl ester functionality.
  • the coating composition comprises a film-forming polymer that is a C 4 F fluoroalkoxyalkyl modified polyurethane polymer, and a non-film-forming polymer that is a perfluoroalkyl acrylic co-polymer.
  • the composition also includes a film- forming oleophobic polymer, such as a polyacrylic polymer.
  • the compositions of this aspect of the present invention are substantially surfactant free. While not being bound by theory, it is believed that the film-forming polymer comprising at least one pendent fluoro-containing functionality provides a durable coating on the substrate that additionally provides stain repellent and/or stain release properties.
  • Addition of a non-film-forming polymer comprising at least one pendent highly fluorinated functionality to this coating composition provides a final coated substrate with significantly enhanced stain repellent and/or stain release properties.
  • This non-film-forming polymer surprisingly exhibits excellent adhesion to the substrate, it is believed due to the commonality of fluorine functional groups on both the film-forming polymer, which acts as an anchoring medium, and the non- film-forming polymer, which is highly compatible with the like functionalities in the formed film.
  • a fluorinated polymer that forms a film as defined herein and is not as effective in repelling and/or releasing stains as desired may be augmented with extremely low levels of non-film-forming fluorinated polymers at fractions of conventional non-film-forming fluorinated polymer use levels, to provide a coating that exhibits exceptional stain repellent and/or stain release performance.
  • a particularly effective fluorinated functionality for stain repellent and/or stain release applications are polymers comprising C 8 F 17 perfluoroalkyl functionalities. These functionalities, however, are under scrutiny because certain potential degradation products of these polymers can be persistent in certain systems and can also be bioaccumulative.
  • the present invention provides a system whereby these very effective fluorinated functionalities may be used at very low levels, while still achieving stain repellent and/or stain release properties previously obtainable only when using high amounts of C 8 F 17 perfluoroalkyl functionalities.
  • the determination of whether a polymer is a film- forming polymer or a non-film-forming polymer can be carried out experimentally if the properties of the polymer are not known.
  • a polymer to be evaluated is cast as a two mil film on a glass substrate using appropriate coating techniques, such as use of a wire wound rod, meyer bar, or other coating methods, under conditions to form a two mil coating layer (i.e.
  • This layer is then removed from the substrate in a single sheet, if possible, to demonstrate whether the polymer will form a self supporting film. Removal of the layer may be carried out by any appropriate technique, such as edge lifting using a spatula and the like, and peeling the layer from the substrate.
  • a non- film forming polymer typically will fracture or scrape off in pieces, and therefore will not be in the form of a self supporting film.
  • Preferred film forming polymers will have sufficient cohesive strength to form a film that not only is self supporting, but preferably exhibits sufficient cohesive properties to have a stress at break tensile strength of at least about 300 psi, and more preferably at least about 1000 psi, measured in a manner as described below. If the polymer forms a film, preferably it does so at a temperature of from about 25°C to about 100°C, and more preferably from about 35°C to about 75°C. It will be understood that the actual temperature of film formation of certain film fo ⁇ ning polymer can be modified by incorporation of material that will act as a coalescent for the polymer.
  • fluoropolymers that contain a high amount of fluorine, and particularly that contain fluorine functional portions that exhibit steric hindrance relative to association with other polymers are non-film-forming polymers.
  • non-film-forming polymers include those with a high amount of C8 perfluorinated functionality.
  • Commercially available examples of such polymers include Zonyl 8412 from DuPont, and X-Cape® GFC from OMNOVA Solutions, Inc.
  • film forming polymers comprising at least one pendent fluoro- containing functionality typically have lower amounts of fluorine, and/or particularly contain fluorine functional portions that exhibit little or no steric hindrance relative to association with other polymers.
  • non-film-forming polymers examples include those with a low amount of C8 perfluorinated functionality.
  • fluorine-containing film-forming polymers comprise have shorter chain perfluorinated functionalities such as C6, C4 or C2 perfluorinated functionality.
  • the film-forming polymer contributes a total fluorine content of from about 0.1 to about 7% by weight to the composition, and the non-film-forming polymer contributes a total fluorine content of from about 0.1 to about 6% by weight to the composition solids.
  • the film-forming polymer contributes a total fluorine content of from about 2 to about 4% by weight to the composition, and the non-film-forming polymer contributes a total fluorine content of from about 1 to about 3% by weight to the composition solids.
  • the film- forming polymer preferably comprises from about 70 to about 95% by weight of the composition, and the non-film-forming polymer comprises from about 5 to about 30% by weight of the composition.
  • the film-forming polymer preferably is a polyurethane polymer comprising at least one pendent fluoroalkoxyalkyl functionality.
  • the fluoroalkyl portion of the pendent fluoroalkoxyalkyl functionality comprises from 1 to about 20 carbon atoms and the oxyalkyl portion of the fluoroalkoxyalkyl functionality comprises from 1 to about 4 carbon atoms. More preferably, the fluoroalkyl portion of the pendent fluoroalkoxyalkyl functionality comprises from 1 to about 4 carbon atoms and the oxyalkyl portion of the fluoroalkoxyalkyl functionality comprises 1 carbon atom.
  • the non-film-forming polymer preferably is a polymer comprising at least one pendent fluoroalkyl ester functionality.
  • the non-film-forming polymer is a polyacrylate polymer comprising at least one pendent fluoroalkyl ester functionality.
  • the alkyl of the fluoroalkyl ester functionality has a mean carbon chain length of 8.
  • the alkyl of the fluoroalkyl ester functionality has a mean carbon chain length of 2 to 7, and more preferably of 4 to 6.
  • the polymeric components of the composition comprises a blend of about 20 to about 98 percent by weight of a polymer comprising at least one pendent fluoroalkoxyalkyl functionality and about 2 to about 80 percent by weight of an oleophobic polymer.
  • the coating composition comprises a fluoroalkoxyalkyl modified polyurethane polymer (preferably comprising C 4 F 9 fluoroalkoxyalkyl functionalities) in combination with a polyacrylic co-polymer.
  • compositions of this aspect of the present invention are substantially surfactant free. While not being bound by theory, it is believed that high repellency polymers, such as polymers comprising at least one pendent fluoroalkoxyalkyl functionality have limited cohesive and adhesive strength, which inherently can be detrimental to the overall durability of the coating. Augmentation of these polymers with an oleophobic polymer as defined herein surprisingly enhances durability of the resulting coating while simultaneously enhancing stain release and/or stain repellency properties.
  • the pendent fluoroalkoxyalkyl functionalities of the fluoropolymer tend to orient to the surface of the coating composition as the coating is cured, thereby presenting more fluoro functionality at the surface than would be presented in a homogeneous polymer composition.
  • the polymeric components of the composition preferably comprises from about 50 to about 85 percent by weight of the polymer comprising at least one pendent fluoroalkoxyalkyl functionality and from about 15 to about 50 percent by weight of the oleophobic polymer.
  • the fluoroalkyl portion of the pendent fluoroalkoxyalkyl functionality comprises from 1 to about 20 carbon atoms (more preferably from 1 to about 8 carbon atoms, and most preferably from 1 to about 4 carbon atoms) and the oxyalkyl portion of the fluoroalkoxyalkyl functionality comprises from 1 to about 4 carbon atoms (and more preferably 1 carbon atom).
  • the polymer comprising at least one pendent fluoroalkoxyalkyl functionality is a polyurethane polymer. More preferably, the polymer comprising at least one pendent fluoroalkoxyalkyl functionality comprises: i) at least one repeat unit derived from a fluorooxetane, ii) at least one repeat unit derived from a polyol intermediate, and iii) at least one repeat unit derived from a polyisocyanate.
  • the polymer comprising at least one pendent fluoroalkoxyalkyl functionality and the oleophobic polymer are formulated to be coreacted during coating and/or cure of the coating composition after application to a substrate. While not being bound by theory, it is believed that this co-reaction enhances the durability of the coating on the substrate, while simultaneously permitting desired orientation of fluoro functionality to the surface of the coating prior to fixing of the coating matrix.
  • the composition preferably comprises a crosslinking agent selected from an aziridine, a carbodimide, an epoxy, an isocyanate or a melamine-fo ⁇ naldehyde.
  • the fluorinated polymers to be used in the compositions of the invention may be made using materials and synthesis techniques well known in the art.
  • a film-forming polymer or a non-film forming polymer can be prepared by selection of components having the desired steric and functional properties to facilitate coalescence or to discourage coalescence as desired in a manner generally known to the skilled artisan, and now particularly apparent in view of the present teachings for selection in particular of the desired fluoro-containing functionality for particular polymer performance.
  • the fluoropolymer preferably has a fluorine content of from about 1 to about 40% by weight of the polyurethane polymer. In one aspect of the present invention, the fluoropolymer comprises from about 1 to about 5% fluorine.
  • the fluoropolymer comprises from about 5% to about 40% fluorine, more preferably from about 10 to about 35% fluorine and most preferably from about 25 to about 30 % fluorine. While such high fluorine content can be unacceptably expensive for use in conventional fluorinated polymers, in embodiments of the present invention wherein the fluoropolymer is blended with at least one non-fluoropolymer oleophobic polymer, the overall composition surprisingly benefits from use of polymers having this high fluorine content. Because the fluoropolymers are provided in a composition together with oleophobic polymer, the actual total fluorine content is effectively reduced when coated on an intended substrate.
  • the final coating composition comprises less than about 10% fluorine by weight, and more preferably from about 1 to about 6% fluorine by weight based on total solids of the coating composition.
  • the total fluorine content of the coating composition as provided herein is about the same or less than the fluorine content of previously described fluorine- containing polymers, the hydrophobic, oleophobic and stain resistance properties are superior. It is particularly surprising that compositions having a fluorine content of from about 1 to about 6% fluorine by weight based on total solids of the coating composition would exhibit such superior hydrophobic and hydrophilic properties.
  • the proximity of fluorine functionalities to each other on the fluoropolymer can enhance the effectiveness of these compositions relative to the hydrophobic, oleophobic and stain resistance properties or alternatively that the fluorine functionalities are preferentially oriented to the surface of the coating prior to and/or during the cure of the coating.
  • at least one of the fluoropolymers in the composition comprises perfluorinated or highly fluorinated functionalities, wherein pendent fluorinated groups have a carbon chain length of equal to or less than four carbons.
  • Such short chain fluorinated moieties have been shown to have low bioaccumulation in living organisms.
  • the fluorinated polymer comprises a plurality of pendent fluoroaliphatic groups ("R f groups"), the loci of the fluorine being essentially in the R f groups.
  • R f is a stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic.
  • R f preferably contains at least about 2 to about 6 carbon atoms.
  • R f preferably contains at least about 6 to about 20 carbon atoms, and most preferably about 4 to about 14 carbon atoms.
  • R f can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic, alkylene groups.
  • R f is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms.
  • catenary heteroatoms means heteroatoms (for example, nitrogen, oxygen, or sulfur) that replace one or more carbon atoms of a group in a manner such that the heteroatom is bonded to at least two carbon atoms of the group.
  • the terminal portion of the R f group preferably contains a fully fluorinated terminal group.
  • This terminal group preferably contains at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 --, (CF 3 ) 2 CF ⁇ , or the like.
  • Perfluorinated aliphatic groups are the most preferred embodiments of R f .
  • the fluoroaliphatic group R f is linked to the polymer backbone by a linking group such as a covalent bond, divalent alkylene, or a group that can result from the condensation reaction of a nucleophile such as an alcohol, an amine, or a thiol with and electrophile, such as an ester, acid halide, isocyanate, sulfonyl halide, sulfonyl ester, or can result from a displacement reaction between a nucleophile and leaving group.
  • Linking groups contain from 1 to about 20 carbon atoms and can optionally contain catenary oxygen, nitrogen, sulfur, or silicon-containing groups or a combination thereof.
  • prefe ⁇ ed linking groups include straight chain, branched chain, or cyclic alkylene, arylene, aralkylene; oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, urylene, and combinations thereof such as sulfonamidoalkylene.
  • the highly fluorinated or perfluorinated functionality is provided to the polymer by reaction of reactive monomers comprising highly fluorinated or perfluorinated functionality with other monomers to form the desired polymer.
  • Examples of such reactive monomers comprising highly fluorinated or perfluorinated functionality and methods for the preparation thereof are known and disclosed, e.g., in U.S. Pat. No. 2,803,615 (Ahlbrecht et al.) and U.S. Pat. No. 2,841,573 (Ahlbrecht et al.).
  • Examples of such compounds include general classes of fluorochemical monomers such as acrylates, methacrylates, vinyl ethers, and allyl compounds containing fluorinated sulfonamido groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, fluorochemical thiols, and the like.
  • non-fluoro monomers comprising highly fluorinated or perfluorinated functionality are reacted with non-fluoro monomers to form the desired polymer.
  • Prefe ⁇ ed non-fluoro monomers can optionally be selected from alkyl acrylate esters, vinyl acetate, styrene, alkyl vinyl ethers, alkyl methacrylate esters, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and N-vinylpy ⁇ olidone.
  • Alkyl acrylate ester monomers useful in the invention include straight-chain, cyclic, and branched-chain isomers of alkyl esters containing C 1-50 alkyl groups.
  • alkyl acrylate esters include: methyl acrylate, ethyl acrylate, n-propyl acrylate, 2-butyl acrylate, iso-amyl acrylate, n- hexyl acrylate, heptyl acrylate, n-octyl acrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, and tetradecyl acrylate.
  • the fluoropolymer comprises pendent fluorinated groups linked to the polymer through an ether linkage.
  • the fluoropolymer comprises perfluoroalkoxy alkyl functionalities.
  • the fluoropolymer is a polyurethane copolymer having fluoroalkoxyalkyl functionality.
  • Particularly prefe ⁇ ed polymers include fluorinated oxetane co- or ter- polymers prepared by OMNOVA Solutions, as described in U.S. Pats. No. 5,650,483; 5,668,250; 5668,251; and 5,663,289.
  • the fluorinated alkyl groups i.e.
  • the fluoroalkyl portion of the fluoroalkoxyalkyl functionality are the same or different and, independently, on each repeat unit, preferably is a linear or branched fluorinated alkyl of 1 to about 20 carbon atoms, more preferably from about 1 to about 8 carbon atoms, and most preferably from about 1 to about 4 carbon atoms, with a minimum of 25%, 50%, 75%, 85%, 90%, or 95%, or 100% (perfluoronated), of the non-carbon atoms of the alkyl being fluorine atoms.
  • the alkyl groups i.e.
  • the alkyl linking portion of the fluoroalkoxyalkyl functionality are the same or different and, independently, on each repeat unit, preferably is a linear or branched alkyl of 1 to about 20 carbon atoms, more preferably from about 1 to about 8 carbon atoms, more preferably from about 1 to about 4 carbon atoms, and most preferably is a methylene linking group.
  • various amounts of polyfluorooxetane oligomers, polymers, or copolymers which have one or two fluorinated side chains, or a copolymer thereof made from various cyclic comonomers can be reacted along with aqueous carboxylic acid dispersants, and with a polyol intermediate such as various polyesters, or polycarbonate polyols or other polyol intermediates, to form a polyurethane generally utilizing an excess of a polyisocyanate during an in-situ bulk polymerization.
  • cyclic comonomers examples include oxiranes (for example, epichlorohydrin), monomers having a four member cyclic ether group such as oxetane, and monomers having a five member cyclic ether group such as tetrahydrofuran.
  • a prefe ⁇ ed fluoropolymer is a polyurethane polymer comprising pendent fluoroalkoxyalkyl functionality that comprises i) at least one repeat unit derived from a fluorooxetane, ii) at least one repeat unit derived from a polyol intermediate, and iii) at least one repeat unit derived from a polyisocyanate.
  • the polyurethane polymer comprises a dispersant functionality bonded to the polymer to assist in dispersion of the polymer in water.
  • the dispersant functionality bonded to the polymer is an anionic dispersant functionality bonded to the polymer, and most preferably the dispersion moiety is carboxylic acid functionality.
  • the polyfluorooxetane oligomers, polymers, or copolymers can be pre-reacted with two or more units of a dicarboxylic acid such as adipic acid to form an acid terminated polyfluorooxetane.
  • This compound can be reacted with the polyol intermediate (such as a polyester) or desirably monomers forming the polyol intermediate (e.g. diacids and diols which form a polyester) to yield a polyfluorooxetane-polyol copolymer (e.g. a polyfluorooxetane-ester copolymer), which then can be mixed and reacted with the polyisocyanate along with the carboxylic acid dispersant.
  • a neutralizing agent such as a tertiary amine reacts with the acid group of the carboxylic acid dispersant to form a salt, which renders the polyurethane dispersible in subsequently added water.
  • the polyfluorooxetane is generally prepared by utilizing a monoalcohol or a diol having from 1 or 2 to about 40, desirably from about 1 or 2 to about 18, and preferably from about 1 to about 10 carbon atoms as an initiator.
  • monohydric alcohols include the various aliphatic alcohols such as the paraffinic alcohols, for example methyl alcohol, ethyl alcohol, propyl alcohol, etc., or the olefmic alcohols, for example vinyl alcohol, allyl alcohol, and the like.
  • alicyclic alcohols such as cyclohexanol and the like can also be utilized, as well as various aromatic or alkyl substituted aromatic alcohols such as benzyl alcohol, phenol, and the like.
  • Various heterocyclic alcohols can also be utilized such as furfuryl alcohol, and the like.
  • halogenated alcohols and especially fluoroalcohols are desired such as trifluoroethanol, heptafluorobutanol, and the like.
  • prefe ⁇ ed monohydric alcohols include benzyl alcohol, trifluoroethanol, heptafluorobutanol, and allyl alcohol.
  • Suitable diols include ethylene glycol, propylene glycol, and the like with butanediol being prefe ⁇ ed.
  • the oxetane monomer used to form the polyfluorooxetane generally has the structure 1A 0— (CH 2 )— Rf
  • the repeat unit of a polyfluorooxetane polymer derived from the oxetane monomer 1 A or IB with a monoalcohol initiator respectively has the formula
  • the repeat unit derived from the oxetane monomer 1A or IB will be the same as set forth above respectively in formula 2A and formula 2B but the oligomer or polymer thereof will have the formula
  • n is the same or different and, independently, on each repeat group, is an integer of from 1 to about 5 and preferably 1 or 2
  • R is hydrogen or an alkyl of 1 to about 6 carbon atoms and preferably is methyl
  • each R f is the same or different and is as defined above.
  • R 1 is derived from the alcohol initiator and has from 1 to about 40 carbon atoms and is an aliphatic, an alicyclic, an aromatic, an alkyl substitute aromatic, a heterocyclic, or a halogenated derivative thereof.
  • the total number of carbon atoms is from about 1 to about 18.
  • the amount of the fluorooxetane monomers utilized is sufficient to yield a degree of polymerization (DP) of from about 2 to about 150 or 250, desirably from about 3 to about 50, and preferably from about 12 to about 25.
  • DP degree of polymerization
  • Such polyfluorooxetanes are generally available from OMNOVA Solutions Inc., Fairlawn Ohio, as for example, PolyFox 6320 and PolyFox 6520, i.e.
  • the fluorooxetane monomer starting materials are prepared by a synthetic route such as reacting a reactive oxetane starting material, such as a bromomethyl methyl oxetane (BrMMO), with a fluorinated alcohol to provide the desired fluoroalkoxyalkyl oxetane monomer.
  • a reactive oxetane starting material such as a bromomethyl methyl oxetane (BrMMO)
  • BrMMO bromomethyl methyl oxetane
  • an aryl sulfonate derivative of hydroxyalkyl oxetane is reacted with a fluorinated alkoxide to form the fluoroalkoxyalkyl oxetane monomer as described in US 5,674,951 at column 7, lines 37 to column 8, line 15.
  • the fluorooxetane monomers can also be copolymerized with a variety of monomers having epoxy (oxirane) functionality such as epichlorohydrin, propylene oxide, ethylene oxide, butyl glycidylether, and perfluorooctyl propylene oxide; monomers having a 4-membered cyclic ether group such as trimethylene oxide, 3,3- bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, and, 3,3- bromomethyl(methyl) oxetane; monomers having a 5 membered cyclic ether group such as tefrahydrofuran, tetrahydropyran, and 2-methyltetrahydrofuran; and the like.
  • epoxy oxirane
  • monomers having a 4-membered cyclic ether group such as trimethylene oxide, 3,3- bis(chloromethyl)oxetane, 3,
  • Still other suitable monomers include 1,4-dioxane, 1,3-dioxane as well as trioxane and epsilon-caprolactone.
  • the copolymerization reaction is carried out generally under the same conditions as the polymerization of the fluorooxetane monomers set forth hereinabove.
  • the amount of the comonomer is from about 1% to about 90% by weight, desirably from about 1.5% to about 50% by weight, and preferably from about 2% to about 10% by weight based upon the total weight of the one or more comonomers and the fluorooxetane monomers.
  • the one or more polyfluorooxetane oligomers, polymers, or copolymers can have an acid group on the end thereof in lieu of the above-noted one or two hydroxyl groups. That is, the oligomer, polymer, or copolymer can be reacted with a dicarboxylic acid to form a half ester wherein one of the carboxylic acid groups is reacted with the polyfluorooxetane hydroxyl group, and the remaining group is an acid group. This acid terminated polyfluorooxetane then can be reacted, along with the carboxylic acid dispersant and the polyol intermediate with the one or more polyisocyanates.
  • Suitable dicarboxylic acids generally contain from 2 to 20 carbon atoms with from about 4 to about 15 carbon atoms being prefe ⁇ ed such as succinic acid, glutaric acid, adipic acid, maleic acid, and the like.
  • the polyurethane is preferably made in situ. That is the following reactants or components are reacted with one or more polyisocyanates: the one or more of the hydroxyl terminated (or acid terminated) polyfluorooxetane oligomers or polymers or copolymers, the one or more polyol intermediates, and the one or more hydroxyl terminated carboxylic acid dispersants.
  • the net result is a polyurethane polymer containing moieties or segments (i.e.
  • the polyol intermediate is generally a polyether polyol, preferably a polythioether polyol, a polyacetal polyol, a polyolefin polyol, an organic polyol, preferably a polycarbonate polyol, or preferably a polyester polyol, or combinations thereof, desirably having primary hydroxy groups and having a number average molecular weight of from about 400 to about 15,000 and desirably from about 2,000 to about 9,000.
  • the polyether polyols generally are derived from monomers containing from
  • polystyrene resin examples include polyoxypropylene or polyoxy ethylene diols and triols, poly(oxyethylene-oxypropylene) diols and triols, and the like.
  • Polythioether polyols which can be used include products obtained by condensing monomers such as thiodiglycol either alone or with other glycols, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarboxylic acids.
  • Polyacetal polyols which can be used include those prepared by reacting monomers, for example, glycols such as diethylene glycol, triethylene glycol and hexanediol with formaldehyde. Suitable polyacetals can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers. Organic polyols having molecular weights below 400 can also be used in the preparation of the prepolymers particularly include those made from monomers such as diols and triols and mixtures thereof, but higher functionality polyols can be used.
  • Examples of such lower molecular weight monomers include ethylene glycol, diethylene glycol, tetraethylene glycol bis(hydroxyethyl) terephthalate, cyclohexane dimethanol, furan dimethanol, glycerol, neopentyl glycol and the reaction products, up to molecular weight 399 of such polyols with propylene oxide and/or ethylene oxide.
  • the prefe ⁇ ed polycarbonate polyols which can be used include products obtained by reacting monomers such as diols having from 2 to 10 carbon atoms such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethyene glycol or tetraethylene glycol with diaryl carbonates having from 13 to 20 carbon atoms, for example diphenyl carbonate, or with phosgene.
  • the prefe ⁇ ed polyester polyols are typically formed from the condensation of monomers such as one or more polyhydric alcohols having from 2 to 18 carbon atoms with one or more polycarboxylic acids or their anhydrides having from 2 to 14 carbon atoms.
  • suitable polyhydric alcohols include the following: ethylene glycol, propylene glycol such as 1,2- propylene glycol and 1,3 -propylene glycol, glycerol; pentaerythritol; trimethylolpropane; 1,4,6-octanetriol; butanediol; pentanediol; hexanediol; dodecanediol; octanediol; chloropentanediol, glycerol monoallyl ether; glycerol monoethyl ether, diethylene glycol; 2-ethylhexanediol-l,4; cyclohexanediol-1,4; 1,2,6-hexanetriol; neopentyl glycol; 1,3,5-hexanetriol; l,3-bis-(2- hydroxyethoxy)propane and the like.
  • Cyclic ethers with desirably 2 to 18 carbon atoms can be used instead, but they are more expensive to use.
  • polycarboxylic acids include the following: phthalic acid; isophthalic acid; terephthalic acid; tetrachlorophthalic acid; maleic acid; dodecylmaleic acid; octadecenylmaleic acid; fumaric acid; aconitic acid; trimellitic acid; tricarballylic acid; 3,3'-thiodipropionic acid; succinic acid; adipic acid; malonic acid, glutaric acid, pimelic acid, sebacic acid, cyclohexane-l,2-di carboxylic acid; 1,4- cyclohexadiene-1 ,2-dicarboxylic acid; 3-methyl-3,5-cyclohexadiene-l ,2- dicarboxylic acid and the conesponding acid anhydrides, acid chlorides and acid esters such as phthalic an
  • Polyesters from lactones can also be used.
  • Prefe ⁇ ed polyol intermediates include polyesters as prepared from the reaction between adipic acid or phthalic acid or isomers thereof with glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexamethylene glycol, trimethylolpropane, or trimethylolethane.
  • polyester intermediates include poly(ethylene adipate)glycol, poly(diethylene adipate)glycol, ⁇ oly(ethylene/propylene adipate)glycol, poly(propylene adipate)glycol, ⁇ oly(butylenes adipate)glycol, poly(neo ⁇ entyl adipate)glycol, poly(hexamethylene adipate)glycol, ⁇ oly(hexamethylene/neopentyl adi ⁇ ate)glycol, and the like.
  • the hydroxyl terminated carboxylic acid dispersant can generally be any organic compound which contains one or more carboxy groups and two or more hydroxyl groups such as a carboxyl group containing diol or triol. Generally, such compounds can contain a total of from about 4 to about 24 carbon atoms with from about 4 to about 8 carbon atoms being prefe ⁇ ed. A prefe ⁇ ed carboxy containing diol is 2,2-dimethylol propionic acid. If desired, the carboxy containing diol or triol can be incorporated into a polyester by reaction with a dicarboxylic acid before being incorporated into the polyurethane prepolymer. Useful compounds include the fumarate polyether glycols described in U.S. Pat. No.
  • carboxy-containing compounds include aminocarboxylic acids, for example lysine, cystine and 3,5-diaminobenzoic acid.
  • the one or more polyisocyanates which are utilized generally have the formula R(NCO) n where n is an integer of 2, 3 or 4 with approximately 2 being prefe ⁇ ed. However, it is to be understood that since combinations of various polyisocyanates can be utilized, the equivalent amount of isocyanate can vary and often n is not an integer.
  • R is an aliphatic having from about 2 to about 20 carbon atoms with from about 6 to about 15 carbon atoms being prefe ⁇ ed, an aromatic including an alkyl substituted aromatic having from about 6 to about 20 carbon atoms with from about 6 to about 12 carbon atoms being prefe ⁇ ed, or combinations thereof.
  • Aliphatic diisocyanates are prefe ⁇ ed inasmuch aromatic diisocyanates tend to yellow.
  • polyisocyanates examples include hexamethylene diisocyanate, 2,2,4-and/or 2,4,4-trimethyl hexamethylene diisocyanate, p- an m- tetramethyl xylene diisocyanate, methylene bis(4-cyclohexyl isocyanate) (hydrogenated MDI), 4,4- methylene diphenyl isocyanate (MDI) mixtures of MDI with polymeric MDI having an average isocyanate functionality of from about 2 to about 3.2, p- and m-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI) and adducts thereof, and isophorone diisocyanate (IPDI).
  • hexamethylene diisocyanate 2,2,4-and/or 2,4,4-trimethyl hexamethylene diisocyanate
  • p- an m- tetramethyl xylene diisocyanate
  • diisocyanates prepared by capping low molecular weight compounds, that is less than 300, such as epsilon-caprolactam, butanone oxime, phenol, etc., with diisocyanates. Any combination of polyisocyanates can be employed. Prefe ⁇ ed polyisocyanates include aliphatic diisocyanates such as IPDI, MDI, hexamethylene diisocyanate, and the like.
  • the equivalent weight ratio of the one or more diisocyanates to the total of the one or more polyol intermediates, as well as to the one or more polyfluorooxetane oligomers, polymers, or copolymers, as well as the one or more hydroxyl terminated carboxylic acid dispersants can be from about 0.8 to about 5.0, and desirably from about 0.9 to about 1.8.
  • the amount of the one or more hydroxyl containing compounds can vary widely with respect to each other.
  • the equivalent weight ratio of the one or more polyol intermediates to the one or more polyfluorooxetane oligomers, polymers, or copolymers is from about 2 or 5 to about 100 or 200, and, desirably from about 15 or 20 to about 35 or 50.
  • the weight of the at least one hydroxyl terminated carboxylic acid dispersant is from about 1% to about 15%, desirably from about 2% to about 10%, and preferably from about 3% to about 8% based upon the total weight of all of the polyol intermediates.
  • the reaction conditions of forming the polyurethane are generally known to the art and to the literature and include a reaction temperature of from about 40° C. to about 160° C, desirably from about 55° C.
  • Catalysts are desirably utilized and include conventional compounds such as dibutyl tin dilaurate, stannous octoate, diazobicyclo (2.2.2) octane (DABCO), Zn ACAC, tin octoate, and the like.
  • the amount of catalyst is small, generally from about 0.005 to about 0.2 parts by weight per 100 parts by weight of the urethane forming monomers.
  • Suitable solvents can be utilized such as N-methyl-py ⁇ olidone, toluene, and the like.
  • the various polyols that is the polyfluorooxetane oligomer, polymer, or copolymer, the hydroxyl terminated carboxylic acid dispersant, and the polyol intermediate can be all added at once and reacted with the diisocyanates, they can be reacted separately.
  • the one or more polyol intermediates and/or the one or more polyfluorooxetane oligomers, polymers, or copolymers can be reacted with the one or more diisocyanate, and then subsequently the acid dispersant can be reacted with the diisocyanate, and the like.
  • the one or more polyurethanes are converted into an aqueous solution or dispersion.
  • a neutralizing agent is added to the polyurethane solution to fo ⁇ n a salt of the hydroxyl containing carboxylic acid dispersant.
  • Neutralizing agents include an inorganic base, ammonia, amine, and the like. When amine neutralizing agents are utilized, a number of amine groups therein can generally range from about 1 to about 3 or 4 and the total number of carbon atoms can range from about 2 or 3 to about 12.
  • Inorganic bases include sodium hydroxide and potassium hydroxide, while the amines, in addition to ammonia include trimethylamine, triethylamine and dimethylethanolamine.
  • the neutralizing agents can be used in either substoichiometric or excess quantities. Accordingly, the stoichiometric ratio can generally vary from about 0.9 to about 1.2 and preferably from about 1.0 to about 1.05 based upon the equivalent weight of the neutralizing agent to the equivalent weight of the acid dispersant. Use of the neutralization agent changes the dispersant into a salt thereby generally rendering the polyurethane dispersible in water.
  • the amount of water generally used to form the aqueous polyurethane dispersion is preferably such that the solid content of the solution is generally from about 20 or 30 to about 65, and preferably from about 35 to about 50 percent by weight. While optional, it is desirable to chain extend the various above noted polyurethanes after neutralization.
  • the chain extender can be a polyol, an amino- alcohol, ammonia, a primary or secondary aliphatic, alicyclic, aromatic, arylaliphatic, or heterocyclic amine, especially a diamine, hydrazine or a substituted hydrazine..
  • chain extenders useful herein include ethylene diamine, diethylene triamine, triethylehe tetramine, propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, piperazine, 2-methyl piperazine, phenylene diamine tolylene diamine, xylylene diamine, tris(2-aminoethyl)amine, 3,3'-dinitrobenzidine, 4,4'-methylenebis (2-chloroaniline), 3,3'dichloro-4,4'-bi- phenyl diamine, 2,6-diaminopyridine, 4,4'-diaminophinylmethane, methane diamine, m-xylene diamine and isophorone diamine.
  • the chain extension can be conducted at elevated, reduced or ambient temperatures. Convenient temperatures are from about 5° to 95° C, preferably from about 35° C. to about 65° C.
  • the amount of chain extender can vary greatly but is generally from about 0.5 to about 2.0 parts by weight for every 100 parts by weight of the formed polyurethane. .
  • the above formed and chain extended compounds are preferably anionic aqueous polyurethane particles dispersed in water and such dispersions generally have low viscosities, i.e. less than 500 centipoise, and desirably from about 60 to about 400 centipoise, and preferably from about 120 to about 300 centipoise.
  • an oleophobic polymer can be provided in combination with a polyfluorinated polymer as described herein.
  • a polymer is considered to be an oleophobic polymer if it has an Oil Contact Angle of greater than 30 degrees when the oil is n-hexadecane. More preferably, the oleophobic polymer has an Oil Contact Angle of greater than 50 degrees, and most preferably greater than 65 degrees when the oil is n-hexadecane.
  • the Oil Contact Angle is determined by casting the polymer to be evaluated for suitability for use as the oleophobic polymer to form a continuous coat on a surface.
  • the contact angle of a drop of n-hexadecane is determined using a conventional contact angle measurement protocol.
  • Oleophobic polymers suitable for use in the present coating compositions are readily identifiable by the artisans in the coating industry, and generally comprise those polymers having functional groups that are polar in nature. Examples of such polymers include polymers comprising acid functionality in an acid number preferably higher than 40. Prefe ⁇ ed such polymers include acrylate polymers formed from monomers comprising acid functionality, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
  • the oleophobic polymer to be used in the coating composition is a carboxylic acid functional polymer that is a copolymer prepared from polymerization of one or more unsaturated aliphatic carboxylic acids and esters, with one or more other reactive monomers such as acrylamide, acrylonitrile, vinyl chloride, allyl chloride, vinyl acetate, and ethylenically unsaturated groups such as ethenyl and 2-propenyl. Ter- and higher polymers can also be used.
  • the unsaturated aliphatic carboxylic acids of this copolymer are preferably, for example, one or more of acrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-bromoacrylic acid, 3- bromoacrylic acid, methacrylic acid, itaconic acid, maleic acid, glutaconic acid, aconitic acid, citraconic acid, mesaconic acid, fumaric acid, tiglic acid and maleic anhydride.
  • additional reactive functionality can be introduced into the polymer during the polymer formation process.
  • acrylate polymers comprising sulfonate functionality can be formed during the polymerization process, wherein the polymerization reaction is initiated using a persulfate, such as sodium, ammonium or fe ⁇ ous persulfates.
  • the sulfonate functionality typically is provided as end groups on the acrylate copolymer.
  • Prefe ⁇ ed oleophobic polymers are solution polymerized (meth)acrylic polymers (i.e. acrylic and/or methacrylic polymers) having an acid number of at least about 40, and more preferably of at least about 50.
  • a particularly prefe ⁇ ed embodiment comprises oleophobic polymer comprising one or more of the solvent borne acrylic copolymers (subsequently dispersed in water in accordance with the present invention) available from NoveonTM company under the name "Carboset.”
  • a particularly prefe ⁇ ed oleophobic copolymer is Carboset 552.
  • the polymer of the aqueous coating composition is an acrylonitrile polymer.
  • the oleophobic polymer is an acrylonitrile /(meth)acrylate co-polymer emulsion. Most preferably, these polymers comprise about 35-50 percent acrylonitrile in the copolymer.
  • such polymers include Rhoplex 1691 polymer, commercially available from Rohm & HassTM company; Hycar 1571 polymer from NoveonTM company and MorFlo 155 polymer from OMNOVA Solutions Inc.
  • the fluoropolymer can be optionally crosslinked, either before or after addition of the oleophobic polymer.
  • the oleophobic polymer can comprise reactive groups, so that the fluoropolymer and/or the oleophobic polymer can be crosslinked to each other. Crosslinking can be carried out in any conventional manner.
  • crosslinking agents can be added to the aqueous solution such as various aziridines, carbodimides, epoxies, melamine- formaldehyde, or polyisocyanates, or the like.
  • Preferred examples of crosslinking agents are amino crosslinking resins, including for example, urea resins, and aminoplast resins such as the (alkoxyalkyl) aminotriazine compounds derived from melamine, glycoluril, benzoguanamine, acetoguanamine, formoguanamine, spiroguanamme and the like.
  • Aminoplast resins are based on the condensation products of formaldehyde, with an amino- or amido- group carrying substance.
  • Condensation products obtained from the reaction of alcohols and formaldehyde with melamine, urea or benzoguanamine are most common and prefe ⁇ ed herein.
  • condensation products of other amines and amides can also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanadines, guanamines and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines.
  • Some examples of such compounds are N,N'- dimethyl urea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, glycoluril, ammeline, 2-chloro-4,6-diamino-l,3,5-triazine, 6-methyl-2,4-diamino- 1,3,5-triazine, 3,5- diaminotriazole, triaminopyrimidine, 2-mercapto4,6- diaminopyrimidine and 3,4,6-tris(ethylamino)-l ,3,5-triazine.
  • aldehyde employed is most often formaldehyde
  • other similar condensation products can be made from other aldehydes, such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural and glyoxal.
  • the aminoplast resins can contain methylol or other alkylol groups, and in most instances, at least a portion of these alkylol groups are etherified by a reaction with an alcohol.
  • Any monohydric alcohol can be employed for this purpose, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others, as well as, benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of glycols, and halogen-substituted or other substituted alcohols, such as 3-chloropropanol and butoxyethanol.
  • Commonly employed aminoplast resins are substantially alkylated with methanol or butanol. In one example, the amino resin is an alkylated melamine resin.
  • the amino resin is a methylated melamine resin such as hexamethoxy methyl melamine (HMMM).
  • the amino resin is HMMM that is modified with styrene allyl alcohol.
  • Such amino resins are commercially available.
  • ResimeneTM resins available from Solutia Inc., such as ResimeneTM747 (HMMM), or ResimeneTM 797 (styrene allyl alcohol modified HMMM) may be used.
  • Other ResimeneTM resins include ResimeneTM CE- 7103 and ResimeneTM 717.
  • Prefe ⁇ ed crosslinking agents include the melamine formaldehyde crosslinking agents, such as Resimene 735 commercially available from Solutia Inc., St. Louis, MO.
  • Alternative prefe ⁇ ed crosslinking agents include the urea formaldehyde crosslinking agents, such as GP®2981 commercially available from Georgia-Pacific Corporation, Atlanta, GA.
  • flattening agents are particulate materials with average particle sizes in the range of 3-12 microns.
  • flattening agents include various urea-formaldehydes, various silicas such as precipated silica and fumed silica, talc, alumina, or calcium-carbonate, and the like.
  • suitable urea-formaldehyde flattening agents include Pergopak
  • silica flattening agents include Syloid 7000, Syloid C-907 (a synthetic amorphacylica wherein the surface is treated with a hydrocarbon-type wax) from W. R. Grace of Maryland.
  • the amount of such flattening agents will depend on the amount of initial gloss and the desired flatness desired. Generally speaking, the amount of such flattening agents is from about 0.1 to about 10 parts by weight, and preferably from about 0.5 to about 4 parts by weight based upon the total weight of the solids of the coating composition.
  • Coating compositions of the present invention can be prepared in any manner as will now be apparent to the skilled artisan.
  • Prefe ⁇ ed fonnulations of the present invention comprise one or more polymer(s), high boiling co-solvents (typically incorporated as diluents in a polyurethane dispersion, such as n-methyl py ⁇ olidone), and a fugitive surfactant.
  • the fugitive surfactant is primarily used to reduced surface tension of the formulation and allow wetting of the substrate, and is thermally converted to a non-flammable gas in the drying/curing stage of processing.
  • the order of addition can be an important aspect of the formulation in that a careful balance of compatibilities of material are preferably maintained to prevent "crashing" of the system.
  • the formulations are preferably dilute (e.g. on the order of 1-4% solids) to provide control of dry coating weight through control of wet pick up of material on the substrate to be coated.
  • a substrate that is coated in a manner to provide a 75% wet pick up rate based on weight of the substrate with a coating composition at 3% total solids will provide a 2.3% dry coating weight of the fabric based on weight of the substrate.
  • the fabrics used in our experimentations were simple woven polyester / polyester-cotton blends that are particularly suitable for such types of evaluations.
  • Coating compositions as described herein can be applied by any appropriate technique, such as by brush application, spraying, or casting by various techniques, such as dip coating, doctor blade, gravure printing or other method of application.
  • the coating is applied as a continuous and uniform coating.
  • the coating composition is dried after application at an elevated temperature, such as from about 60°C to about 250°C.
  • an optional crosslinking agent may be incorporated in the composition, with crosslinking of one or more polymers of the coating composition after application to a substrate.
  • one or more polymers of the coating composition is crosslinked during the drying step.
  • the coating composition is applied by any appropriate technique (such as discussed above) at ambient temperature (ie. At conventional room temperature such as less than about 110°F (about 43 °C)).
  • ambient temperature ie. At conventional room temperature such as less than about 110°F (about 43 °C)
  • coating compositions of the present invention can provide exceptional performance while being applied under these conditions, which provides superior repellent and/or release properties without the need for expensive or bulky plant equipment to be used in the coating operation.
  • the coating compositions of the present invention can be surprisingly effective even when applied in aftermarket applications, such as by a wholesaler, dealer or the consumer.
  • Coating compositions of the present invention may advantageously be provided in small, non-industrial quantities for use specifically in small production facilities or by the consumer.
  • Prefe ⁇ ed embodiments of the present invention include provision of the coating composition in a packaged container having a capacity of less than 20 liters, less than about 6 liters, or less than about 2 liters.
  • the coating composition of the present invention is applied as a second coating on a substrate, so that the pendent fluorine functionalities of the fluorine-containing polymer are available on the surface of the article to be coated for maximum hydrophobic and repellent effect.
  • the first coating on an article to be coated is a composition comprising an oleophobic polymer that does not contain fluorine functionality, and most preferably a polymer selected from a polyurethane that does not contain fluorine functionality, to form a first layer.
  • a second composition comprising a fluorine-containing polymer as described herein is then applied to the first layer.
  • the second composition comprising a fluorine-containing polymer also contains an oleophobic polymer, and most preferably the oleophobic polymer of the first coating is the same polymer as to be used in the second coating composition.
  • the polymers of the first layer are preferably selected to provide a balance of ease of film forming under manufacturing conditions, together with durability of the resultant layer.
  • the polymers of the first layer are preferably selected to provide acceptable hand of the final substrate.
  • the hand of the substrate is the aesthetic feel of the substrate, as determined by simple touching of the substrate or by comparing the rigidity of a coated substrate with that of an uncoated substrate.
  • rigidity may be tested by crumpling the substrates by hand or comparing the relative stiffness of coated and uncoated substrates. If the coating cracks when crumpled or if the coated substrate is significantly more rigid than an uncoated one, the coating does not provide a soft hand.
  • the relative hand characteristics of a material can be readily determined by persons of ordinary skill in the fabric art, and unequivocal relative acceptability of hand characteristics may be determined by trained three member panels of evaluators.
  • the properties of the first layer can also be affected by mixing polymers having a relatively low glass transition temperature (“soft polymers”) with polymers of relatively high glass transition temperatures (“hard polymers”).
  • soft polymers polymers having a relatively low glass transition temperature
  • hard polymers polymers having a relatively high glass transition temperatures
  • the polymer components of the first layer are selected to balance the characteristics of the resulting coating, so that the a film is formed under processing conditions while at the same time the final first layer coating is hard enough to be durable under conditions of use. In general, hard polymers are more durable and more stain resistant.
  • Soft polymers generally exhibit more affinity to certain substrates (especially to fabrics) due to greater conformation to the surface of the substrate, and tend to readily coalesce under convenient processing conditions to form a film.
  • Prefe ⁇ ed soft polymers have a glass transition temperature of below about 30°C, and preferably from about -30°C to about 10°C.
  • Prefe ⁇ ed hard polymers have a glass transition temperature of above about 100°C, and more preferably from about 120°C to about 180°C.
  • the composition of the first layer is a blend of soft and hard polymers comprising about 5% to about 95% of soft polymers and about 95% to about 5% of hard polymers by weight, and more preferably about 10% to about 45% of soft polymers and about 55% to about 90% of hard polymers by weight.
  • the composition of the first layer comprises about 20 to about 35% of soft polymers and about 65 to about 80% of hard polymers by weight.
  • the polymers of the first layer are predominantly aliphatic in nature. Aromatic functional groups can raise stability and/or discoloration issues in certain environments, and therefore can be less desirable.
  • Polymers are preferably selected from water dispersible polymers, such as acrylate and/or methacrylate (jointly refened to as "(meth)acrylate”) copolymers, urethanes, polyesters, polyethers, polycarbonates and hybrids of one or more of these polymers.
  • Polymers useful for the present invention can be formed from copolymerized monomers having a combination of monomers that result in a copolymer having characteristic properties.
  • the Tg and other properties of the copolymer can be tailored to the desired properties by incorporation of various selected monomeric compounds during the polymerization process.
  • soft monomers are preferably incorporated to impart flexibility and toughness to the copolymer, and so that the resulting copolymer exhibits the desired low Tg property.
  • Monomers can be characterized as "soft" monomers or "hard” monomers by consideration of the Tg of the conesponding homopolymers made from the designated monomer.
  • a monomer is considered to be a "soft” monomer if the conesponding homopolymer has a Tg of less than about 25°C.
  • a monomer is considered to be a "hard” monomer if the conesponding homopolymer has a Tg of more than about 25°C.
  • Polymers of the first layer coating composition are selected to provide the desired chemical functionalities for providing affinity to a selected fabric substrate and for reactivity to the fluoropolymer of the second layer.
  • prefened functionalities include hydroxyl and/or carboxyl groups.
  • a prefe ⁇ ed first layer of the present invention comprises a (meth)acrylate copolymer as one of the polymers of the composition.
  • (Meth)acrylate copolymers can be formulated to provide a desired Tg, and also can be provided with useful functionality both for providing affinity to a selected fabric substrate and for reactivity to the fluoropolymer of the second layer.
  • Monomer selection is important for performance of the layer on the fabric, particularly in applications where the fabric is expected to be exposed to substantial UV radiation, such as direct sunlight, and particularly outdoors.
  • substantial UV radiation such as direct sunlight, and particularly outdoors.
  • vinyl toluene and styrene can lead to yellowing if added in large amounts (e.g. greater than 20%).
  • the soft monomer is typically soft monomeric acrylic or methacrylic acid ester of an alkyl alcohol containing a single hydroxyl, the alcohol being further described as having from 2 to about 14 carbon atoms when the soft monomer is an acrylic acid ester, and about 7 to 18 carbon atoms when the soft monomer is a methacrylic acid ester.
  • acrylic acid esters for use as the soft monomer include the esters of acrylic acid with non-tertiary alcohols such as ethanol, 1 -butanol, 2- butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l -butanol, 1-hexanol, 2- hexanol, 2-methyl- 1-pentanol, 3 -methyl- 1-pentanol, 2-ethyl-l butanol, 3,5,5- trimethyl- 1-hexanol, 3-heptanol, 1-octanol, 2-octanol, iso-octyl alcohol, 2-ethyl-l - hexanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol and the like.
  • non-tertiary alcohols such as ethanol, 1 -butanol, 2- butanol, 1-pent
  • suitable methacrylic acid esters for use as the soft monomer include the esters of methacrylic acid with non-tertiary alcohol such as 3-heptanol, 1-octanol, 2-octanol, iso-octyl alcohol, 2-ethyl- 1-hexanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-octadecanol and the like.
  • non-tertiary alcohol such as 3-heptanol, 1-octanol, 2-octanol, iso-octyl alcohol, 2-ethyl- 1-hexanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-octadecanol and the like.
  • monomers that can be used for the soft monomer component are monomers having the requisite Tg values including dienes, such as butadiene and isoprene; acrylamides, such as N-octylacrylamide; vinyl ethers, such as butoxyethylene, propoxyethylene and octyloxyethylene; vinyl halides, such as 1,1-dichloroethylene; and vinyl esters such as vinyl versatate, vinyl caprate and vinyl laurate.
  • the copolymer can comprise a single type of soft monomer or can comprise two or more different soft monomers.
  • a hard monomer of the copolymer is typically a monomeric methacrylic acid ester of an alkyl alcohol containing a single hydroxyl.
  • the alcohol contains from 1 to about 6 carbon atoms, and preferably 1 to about 4 carbon atoms.
  • suitable monomers for use as the hard monomer include the esters of methacrylic acid with non-tertiary alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1- butanol, 2-butanol, 1-pentanol, 2-pentanol and 3-pentanol.
  • monomers having the requisite Tg values include methacrylates having a structure other than delineated above, such as benzyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate; methacrylamides, such as N-t- butylmethacrylamide; acrylates, such as isobornyl acrylate; acrylamides, such as N- butylacrylamide and N-t-butylacrylamide; diesters of unsaturated dicarboxylic acids, such as diethyl itaconate and diethyl fumarate; vinyl nitriles, such as acrylonitrile, and methacrylonitrile; vinyl chloride; vinyl esters, such as vinyl acetate and vinyl propionate; and monomers containing an aromatic ring such as styrene; alpha- methyl styrene and vinyl toluene. It is to be understood that the copomers having a structure other than delineated above, such as
  • the low Tg polymer comprises about 20-40% butyl acrylate, about 30-
  • Hard polymers are preferably selected for their durability and stain resistant properties.
  • the hard polymers are hard enough to withstand conventionally applied forces used for removal of stains from fabric substrates in the field of use of the particular fabric to be treated.
  • the hard polymer is selected to be hydrolytically stable under conventionally applied cleaning solutions or anticipated staining materials to which the fabric substrates' are expected to be exposed in the field of use of the particular fabric to be treated.
  • the hard polymers are preferably hydrolytically stable to prolonged exposure (e.g. 24 hours) to a conventionally applied alkaline cleaning solution, such as Formula 409® cleaner, and to a dilute acid solution such as vinegar having 5% acidity.
  • Prefe ⁇ ed hard polymers include selected polyurethane polymers, and particularly polyurethane/poly carbonate polymers. Prefened commercially available polymers include WF 41-035 from Stahl, USA.
  • the coating compositions of the present invention are useful as a coating such as a layer, film, or membrane to coat, either directly or indirectly, a substrate.
  • the substrate can be generally any surface in need of treatment to assist in repelling water or oil materials, particularly in repelling stains.
  • Prefe ⁇ ed such surfaces include fabrics and sheet substrates, including flexible film substrates.
  • Prefe ⁇ ed materials to be treated by the coating compositions of the present invention include plastic such as polyvinyl chloride, nylon, polyester, polyolefin, polyurethane, polycarbonate, polystyrene, a polyacrylic such as polyacrylate, and the like, as well as combinations thereof.
  • Plastics may be provided as various fibers woven into various articles and especially carpet fibers such as nylon fibers, polyolefin fibers, polyacrylic fibers, polyester fibers, and the like, and combinations thereof.
  • Plastics also include plastic wall covering such as films made from polyvinyl chloride.
  • Other substrates include paper or wood containing articles such as paper sheets, cardboard, corrugated paper or cardboard, and the like.
  • Wood containing articles include wood such as oak, maple, other hard woods or soft woods, particle board, pressed board, fiber board, laminated wood, and the like as well as combinations thereof.
  • Metals generally include any type of metals such as iron, steel, aluminum, copper, brass, and the like as well as combinations thereof.
  • the coatings of this invention provide excellent stain repellency and/or stain release properties. Additionally, the coatings preferably have good resistance to moisture, good abrasion resistance, good chemical resistance, low coefficient of friction values, and in certain embodiments remain flexible at temperatures of use.
  • Oleophobicity and Hydrophobicity As noted above, oleophobicity of coatings and materials is determined by conducting an Oil Repellency Test. This test is carried out in accordance with AATCC test 118-97 to evaluate the resistance of the substrate to oily liquids. This is a test comprising evaluation of the surface tension of the fabric using a selected series of liquid hydrocarbons having varied surface tensions. Oil repellency is graded by identifying the highest numbered test liquid that does not wet the fabric surface.
  • a coating or material is considered to be oleophobic if the oil repellency of a continuous coating has a score of at least 3 A.
  • Prefe ⁇ ed materials or coatings that are desirably oleophobic have a test score of at least 4, and more preferably at least 5.
  • a Hydrophobicity Test as conducted in accordance with the present disclosure is similar to the test protocol of the AATCC Test Method 188-1997. Instead of using hydrocarbon materials, however, graduated solutions of isopropyl alcohol and water were prepared having increasing relative proportions of isopropyl alcohol.
  • the scale for performance runs from 1 to 9, with "1" being 100% water, i.e. highest surface tension least likely to wet the fabric substrate, and "9” being 20% water/80% isopropyl alcohol, i.e. very low surface tension and most likely to wet the surface.
  • test liquids Specific identification of the test liquids is set forth in Table X.
  • a fabric coated with a coating of the present invention preferably exhibits a dynamic spray rating evaluation that is greater than about 60%, more preferably greater than about 70, and most preferably greater than about 80% as measured in accordance with AATCC test method 22-1989.
  • Elongation at Break Tensile Strength Evaluation of the properties of the film-forming polymer is carried out by providing cured film samples as Dumbbell shape specimens for testing in an Instron testing machine model 1120 having a gauge length of 40 mm. The testing is carried out under the ASTM D882 test protocol at about 25°C, at a rate of 1.0 mm/min. Six tests of each film are taken, and the mean value of elongation at break is calculated using the highest three measurement values.
  • a coating composition is prepared by mixing the following components in order under mild agitation: 1. X-Cape® GFC solution, a perfluoroacrylic copolymer high solids emulsion commercially available from OMNOVA Solutions Inc. 2. Water in quantity sufficient to dilute the emulsion to a final polymer content in the coating composition of 3% by weight. 3. Amine oxide fugitive surfactant (commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight. The composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • EXAMPLE 2 (Comparative) A coating composition is prepared by mixing the following components in order under mild agitation: 1. WF41-035 resin, an aliphatic polycarbonate-based polyurethane polymer commercially available from Stahl (USA) Inc. 2. Water in quantity sufficient to dilute the resin to a final resin content in the coating composition of 3 % by weight. 3. Amine oxide fugitive surfactant (commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight. The composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • EXAMPLE 3 (Comparative) A coating composition is prepared by mixing the following components in order under mild agitation: 1.
  • a polymer resin that is prepared from an aliphatic polycarbonate-based polyurethane polymer wherein 5% of the diol components of the polyurethane polymer is substituted by C 4 F fluoroalkoxyalkyl functionalities derived from polyfiuorinated oxetane reactants, as described in US Patent Nos. 6,465,565 and 6,465,566. This polymer is designated herein as Polyurethane/PolyFox5% polymer.
  • Water in quantity sufficient to dilute the resin to a final resin content in the coating composition of 3% by weight.
  • Amine oxide fugitive surfactant commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight. The composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • a coating composition is prepared by mixing the following components in order under mild agitation: 1.
  • a polymer resin blend composition comprising Polyurethane/PolyFox5% polymer resin component and an acrylonitrile-based resin component commercially available as Hycar® 26138 resin from Noveon Inc; wherein the two resin components are present as a 50/50 (w/w) blend.
  • the Hycar® 26138 resin comprises surfactant.
  • Water in quantity sufficient to dilute the resin blend composition to a final resin blend content in the coating composition of 3% by weight.
  • Amine oxide fugitive surfactant commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight.
  • the composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • a coating composition is prepared by mixing the following components in order under mild agitation: 1.
  • a polymer resin blend composition comprising Polyurethane/PolyFox5% polymer resin component and a polyacrylic acid resin commercially available as K-752 resin from Noveon Inc; wherein the two resin components are present as a 50/50 (w/w) blend.
  • Water in quantity sufficient to dilute the resin blend composition to a final resin blend content in the coating composition of 3% by weight.
  • Amine oxide fugitive surfactant commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight.
  • the composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • a coating composition is prepared by mixing the following components in order under mild agitation: 1.
  • a polymer resin blend composition comprising Polyurethane/PolyFox5% polymer resin component and a polyacrylic acid resin commercially available as K-732 resin from Noveon Inc; wherein the two resin components are present as a 50/50 (w/w) blend.
  • Water in quantity sufficient to dilute the resin blend composition to a final resin blend content in the coating composition of 3% by weight.
  • Amine oxide fugitive surfactant commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight.
  • the composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • a coating composition is prepared by mixing the following components in order under mild agitation: 1.
  • a polymer resin blend composition comprising Polyurethane/PolyFox5% polymer resin component and a polyacrylic acid resin commercially available as Carboset® 552 resin from Noveon Inc; wherein the two resin components are present as a 50/50 (w/w) blend.
  • Water in quantity sufficient to dilute the resin blend composition to a final resin blend content in the coating composition of 3% by weight.
  • Amine oxide fugitive surfactant commercially available as NRW-3 from OMNOVA Solutions, Inc. in quantity sufficient to provide final surfactant content in the coating composition to 0.5% by weight.
  • composition is mixed to assure an adequate dispersion of the materials and to provide a homogeneous solution.
  • Each of the above formulations is then pad applied to 1 ft x 3 ft textiles samples of polyester cloth via submergence and then nipped at an adequate pressure, experimentally determined, to afford the conect wet and dry pick-ups.
  • the coated textile samples were then placed in an oven at 300°F for 10 minutes before being air dried overnight.
  • Stain resistance/Cleanability A layer is considered to be stain resistant if when a staining material wets onto the surface of a substrate having a stain resistant coating, the staining material is more easily removed from the substrate by conventional cleaning techniques than from a like substrate without the stain resistant coating.
  • stain removal evaluation tests are common in the fabric industry, and can include controlled application of cleaning substances, optionally in a predetermined sequential format, to evaluate the ease of removing certain staining materials, such as mustard, blood, and so forth. While this test is somewhat subjective in nature, it provides excellent identification of trends in stain resistance and cleanability to assist in identification of superior treatment compositions.
  • Stain testing was performed following the following procedure: Textile samples of Examples 1-7 as indicated were labeled for exposure to various staining compositions.
  • the staining compositions are antifreeze coolant, grape juice, soy sauce, used motor oil, wine, coffee, brake fluid, and Mazola corn oil.
  • one drop of each staining composition was placed on the textile samples and allowed to sit for lhr.
  • one drop of each staining composition was placed on the textile samples and allowed to sit for 24 hrs. After the indicated residence time, the samples were rinsed with tap water, evaluated and numerically scored 0 to 5 to indicate the strength of the stain.
  • the rating scale was as follows:
  • coating compositions comprising a fluorinated polymer provide a degree of stain resistance and recleanability.
  • the stain resistance and recleanability is not particularly enhanced when the composition comprises surfactant, as shown in Comparative Example 4.
  • Addition of an additional polymer in the composition provides enhancement of stain resistance and recleanability, as shown in Examples 5 and 6.
  • These polymers comprise sufficient acid functionality to have limited oleophobicity.
  • Example 7 shows even more enhancement of stain resistance and recleanability when the coating composition is provided with a highly hydrophobic polymer that additionally is substantially free of surfactant. All percentages and ratios used herein are weight percentages and ratios unless otherwise indicated.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des compositions aqueuses de revêtement qui comprennent des polymères fluorés présentant d'excellentes propriétés antitaches et de résistance aux taches. Dans une forme de réalisation, les compositions comprennent peu ou pas de tensioactif. Dans une autre forme de réalisation, les compositions renferment un mélange de polymère filmogène qui comprennent au moins une fonctionnalité disponible contenant un fluoro ; et un polymère non filmogène comprenant au moins une fonctionnalité disponible à forte teneur en fluor. Dans une autre forme de réalisation encore, les compositions comprennent un mélange d'environ 20 à environ 98 pour cent en poids d'un polymère comprenant au moins une fonctionnalité fluoroalcoxyalkyle disponible et d'environ 2 à environ 80 pour cent en poids d'un polymère oléophobe. Des articles revêtus et des procédés sont également décrits.
PCT/US2004/037545 2003-11-11 2004-11-10 Compositions aqueuses de revetement hydrophobe et oleophobe, procedes et utilisations WO2005047358A1 (fr)

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US7947097B2 (en) 2006-12-21 2011-05-24 Saint-Gobain Abrasives, Inc. Low corrosion abrasive articles and methods for forming same
US8287611B2 (en) 2005-01-28 2012-10-16 Saint-Gobain Abrasives, Inc. Abrasive articles and methods for making same
US8435098B2 (en) 2006-01-27 2013-05-07 Saint-Gobain Abrasives, Inc. Abrasive article with cured backsize layer
WO2013081892A1 (fr) * 2011-11-30 2013-06-06 U.S. Coatings Ip Co. Llc Composition de revêtement
US8628596B2 (en) 2005-01-28 2014-01-14 Saint-Gobain Abrasives, Inc. Method of forming structured abrasive article
ITVA20120051A1 (it) * 2012-12-20 2014-06-21 Lamberti Spa Poliuretani antimacchia
US8883288B2 (en) 2007-08-03 2014-11-11 Saint-Gobain Abrasives, Inc. Abrasive article with adhesion promoting layer
US20140364542A1 (en) * 2011-11-30 2014-12-11 Axalta Coating Systems Ip Co., Llc Clear coat coating composition
WO2016057072A1 (fr) * 2014-10-07 2016-04-14 Qed Labs Inc Procédés de modification de la surface de matériaux
US9688866B2 (en) 2013-12-27 2017-06-27 Industrial Technology Research Institute Method of manufacturing hydrophobic antifouling coating material and method of forming hydrophobic antifouling coating film
CN112457762A (zh) * 2020-12-10 2021-03-09 中国科学院长春应用化学研究所 一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法
US11306414B2 (en) 2014-01-17 2022-04-19 Qed Labs Inc. Articles with improved flame retardancy and/or melt dripping properties

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WO1993001349A1 (fr) * 1991-07-10 1993-01-21 Minnesota Mining And Manufacturing Company Compositions impermeables a l'eau et aux huiles aqueuses
US5668250A (en) * 1992-07-10 1997-09-16 Aerojet-General Corporation Polyether coprepolymers formed from mono-substituted fluorinated oxetane monomers and tetrahydrofuran
EP1038919A1 (fr) * 1999-03-25 2000-09-27 Ausimont S.p.A. Compositions conférant des propriétés oléophobes et hydrophobes
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Cited By (16)

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Publication number Priority date Publication date Assignee Title
US8628596B2 (en) 2005-01-28 2014-01-14 Saint-Gobain Abrasives, Inc. Method of forming structured abrasive article
US8287611B2 (en) 2005-01-28 2012-10-16 Saint-Gobain Abrasives, Inc. Abrasive articles and methods for making same
US8435098B2 (en) 2006-01-27 2013-05-07 Saint-Gobain Abrasives, Inc. Abrasive article with cured backsize layer
US7947097B2 (en) 2006-12-21 2011-05-24 Saint-Gobain Abrasives, Inc. Low corrosion abrasive articles and methods for forming same
US8883288B2 (en) 2007-08-03 2014-11-11 Saint-Gobain Abrasives, Inc. Abrasive article with adhesion promoting layer
US20140329934A1 (en) * 2011-11-30 2014-11-06 Axalta Coating Systems Ip Co., Llc Coating composition
WO2013081892A1 (fr) * 2011-11-30 2013-06-06 U.S. Coatings Ip Co. Llc Composition de revêtement
CN104204018A (zh) * 2011-11-30 2014-12-10 涂层国外知识产权有限公司 涂料组合物
US20140364542A1 (en) * 2011-11-30 2014-12-11 Axalta Coating Systems Ip Co., Llc Clear coat coating composition
ITVA20120051A1 (it) * 2012-12-20 2014-06-21 Lamberti Spa Poliuretani antimacchia
WO2014095300A1 (fr) 2012-12-20 2014-06-26 Lamberti Spa Polyurethanes inhibant la coloration
US9688866B2 (en) 2013-12-27 2017-06-27 Industrial Technology Research Institute Method of manufacturing hydrophobic antifouling coating material and method of forming hydrophobic antifouling coating film
US11306414B2 (en) 2014-01-17 2022-04-19 Qed Labs Inc. Articles with improved flame retardancy and/or melt dripping properties
WO2016057072A1 (fr) * 2014-10-07 2016-04-14 Qed Labs Inc Procédés de modification de la surface de matériaux
US10131757B2 (en) 2014-10-07 2018-11-20 Qed Labs, Inc. Methods for surface modification of materials
CN112457762A (zh) * 2020-12-10 2021-03-09 中国科学院长春应用化学研究所 一种高附着力的含氟疏水聚氨酯透明防护涂料及其制备、使用方法

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