WO1998028368A1 - Aqueous fluorochemical compositions - Google Patents
Aqueous fluorochemical compositions Download PDFInfo
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- WO1998028368A1 WO1998028368A1 PCT/US1997/023677 US9723677W WO9828368A1 WO 1998028368 A1 WO1998028368 A1 WO 1998028368A1 US 9723677 W US9723677 W US 9723677W WO 9828368 A1 WO9828368 A1 WO 9828368A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- This invention relates to water-based, fluorine-containing coating compositions comprising organic and inorganic materials. Coatings comprising the cured compositions exhibit both low surface energy properties and abrasion resistance.
- the present invention has filled a void by providing a low surface energy, hard coating system with improved abrasion resistance.
- the coating system integrates a fluorine-containing, crosslinkable organic polymeric surfactant and surface-modified, colloidal inorganic microparticles.
- this invention provides a water-based composition
- a water-based composition comprising an aqueous solution, emulsion, or dispersion of: (a) a water-soluble or water-dispersible polymer or oligomer having at least one anionic moiety which is capable of reacting with an oxazoline or oxazine moiety; (b) a water-soluble or water-dispersible polymer or oligomer having at least one oxazoline or oxazine moiety; and (c) a sol comprising a colloidal dispersion of surface- modified, inorganic microparticles in liquid.
- At least one of components (a) , (b) , and (c) has at least one fluoroaliphatic moiety, and either polymer or oligomer (a) or (b) (or both) can further contain at least one silyl moiety.
- the term "surface-modified” refers to microparticles which have either polymeric or non-polymeric, surface-attached organic moieties, which are preferably reactive with functional group (s) on component (a) and/or component (b) .
- the sol (c) preferably comprises an aqueous dispersion of polymer- grafted silica microparticles.
- this invention provides a coating comprising the cured composition, which comprises crosslinked polymer (e.g., containing at least one amide-ester crosslink moiety derived from the reaction of carboxyl groups with oxazoline or oxazine moieties) having colloidal, surface-modified, inorganic microparticles integrated therein, and a coated article comprising the coating.
- crosslinked polymer e.g., containing at least one amide-ester crosslink moiety derived from the reaction of carboxyl groups with oxazoline or oxazine moieties
- the coating compositions can be used to provide a low surface energy hard coat to protect surfaces of essentially any kind (e.g., poly (vinyl chloride) , polycarbonate, polyester, nylon, metals (either painted or bare), glass, wood, stone, etc.).
- the good abrasion resistance properties will protect such surfaces from physical damage, and the low surface energy properties will provide easily cleanable and possibly antigraffiti properties.
- the coating can also be used as a low adhesion backsize for adhesives.
- the significant difference of the present invention over related technologies is the incorporation of colloidal, surface-modified, inorganic microparticles into the coating composition.
- the previous organic polymer-based coating systems have been transformed into organic-inorganic composite compositions.
- the finished coatings therefore become much more abrasion-resistant and are more durable in protective applications.
- the antigraffiti and release properties of the coating systems are also not degraded despite the incorporation of the high surface energy, hydrophilic, colloidal, surface-modified, inorganic microparticles, even with compositions containing a lower weight percentage of fluorine in many cases.
- the coating compositions of the invention exhibit improved dispersion stability and, upon dry-down, provide coatings which generally exhibit better abrasion resistance coupled with better low surface energy properties (as measured by water contact angles or by the pen test defined below) .
- anionic means capable of forming anions in aqueous media.
- copolymers or “polymers” includes polymers and oligomers .
- the anionic moiety-containing polymers useful in this invention preferably have an average of more than two reactive ionic moieties per polymer chain.
- the anionic moiety-containing polymers have an average of more than one fluoroaliphatic moiety per polymer chain.
- Such polymers include those described, for example, in U.S. Patents 5,382,639, 5,294,662, 5,006,624 and 4,764,564 supra .
- Useful anionic moieties include carboxy and mercaptan moieties, which can be reacted with bases to obtain carboxylate and mercaptide salts. At lower pH values, these moieties become essentially nonionic.
- the particularly preferred anionic moiety is carboxylate.
- the carboxylate anionic polymer can be utilized in the water-based compositions of this invention as its ammonium salts.
- the anionic moiety-containing polymers, polymer component, or surfactant, useful in the present invention can be prepared, for example, by the addition polymerization of one or more ethylenically unsaturated carboxy-containing monomers (e.g., acrylic acid, methacrylic acid, and esters thereof such as 2- carboxyethyl acrylate) with one or more ethylenically unsaturated comonomers (e.g., acrylic esters, vinyl ethers, or styrenic monomers) .
- the comonomers can be further substituted with fluorine.
- the carboxy- containing monomer is preferably acrylic acid or 2- carboxyethyl acrylate.
- oxazine or oxazoline polymers or oligomers useful in the present invention can be prepared by the addition polymerization of an oxazine- or oxazoline-containing ethylenically unsaturated monomer, such as 2-isopropenyl-2-oxazoline (IPO) and those represented by the general structures:
- Ri is an unsaturated organic radical capable of addition polymerization, such as 1, 2-ethylenic unsaturation.
- P ⁇ is an isopropenyl group.
- R 2 is independently hydrogen, halogen, or a substituted organic radical, preferably R 2 is hydrogen.
- the oxazoline- or oxazine-containing polymers useful in the present invention preferably have an average of more than two oxazoline or oxazine moieties per polymer chain.
- aziridine group- containing oligomers can be utilized in place of the oxazoline- or oxazine-containing polymers or oligomers, provided that shelf stability or one-part formulation is not required.
- the aliphatic moiety of the aliphatic radical-containing monomer can be a monovalent aliphatic or alicyclic moiety, preferably saturated. It can be linear, branched, cyclic, or combinations thereof. It can contain catenary, i.e., in-chain, heteroatoms bonded only to carbon atoms, such as oxygen, divalent or hexavalent sulfur, or nitrogen.
- the aliphatic moiety has from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
- the fluoroaliphatic moiety of the fluoroaliphatic radical-containing monomer can be a fluorinated, stable, inert, preferably saturated, non-polar, monovalent aliphatic or alicyclic moiety. It can be straight chain, branched chain, cyclic, or combinations thereof. It can contain catenary heteroatoms, bonded only to carbon atoms, such as oxygen, divalent or hexavalent sulfur, or nitrogen. A fully-fluorinated moiety is preferred but hydrogen or chlorine atoms can be present as substituents, provided that not more than one atom of either is present for every two carbon atoms.
- the moiety has at least about 3 carbon atoms, preferably from about 3 to about 20 carbon atoms, and most preferably from about 4 to about 10 carbon atoms.
- the terminal portion of the moiety is a perfluorinated moiety which preferably contains at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 -, (CF 3 ) 2 CF-, F 5 SCF 2 -, or the like.
- the polymers useful in this invention i.e., those having at least one anionic moiety (the surfactant component) , or those having at least one oxazoline or oxazine moiety (the cross-linking component) , can optionally contain at least one silyl moiety.
- the silyl moiety can be formed on one or both of the polymers by a compound which can be represented by the formula
- X is a group reactive to radical polymerization, such as an unsaturated acrylate or methacrylate radical or a mercapto group
- R is alkylene of 1 to about 10 carbon atoms
- R' is hydrogen or alkyl of 1 to about 3 carbon atoms
- R' ' is selected from the group consisting of lower alkyl groups having from 1 to about 4 carbon atoms and phenyl
- a is an integer of 0 to 2 (preferably, 0) .
- the silyl moiety can be incorporated either in the polymer chain, using, for example, a trialkoxysilylalkyl acrylate or methacrylate, or at the terminal end of the polymer chain via a chain transfer agent, using, for example, a trialkoxysilylalkyl mercaptan, preferably mercaptopropyltrimethoxysilane (MPTS) .
- a chain transfer agent using, for example, a trialkoxysilylalkyl mercaptan, preferably mercaptopropyltrimethoxysilane (MPTS) .
- MPTS mercaptopropyltrimethoxysilane
- the silyl moiety is attached to the surfactant component, the anionic moiety-containing polymer.
- UV absorbers e.g., NORBLOCTM 7966 ( ( (2- (2' -) hydroxy- 5-methacryloyloxyethylphenyl) -2H-benzotriazole) ; available from Noramco Inc.) .
- Inorganic microparticles suitable for use in the compositions of the invention are colloidal in size (e.g., having an average particle diameter in the range of from about 2 nanometers (2 millimicrons) to about 200 nanometers.
- Colloidal silica is generally most preferred, but other colloidal metal oxides, e.g., colloidal titania, colloidal alumina, colloidal zirconia, colloidal vanadia, colloidal chromia, colloidal iron oxide, colloidal antimony oxide, colloidal tin oxide, and mixtures thereof (with each other and/or with colloidal silica) , can also be utilized.
- the colloidal microparticles can comprise essentially a single oxide such as silica or can comprise a core of an oxide of one type (or a core of a material other than a metal oxide) on which is deposited an oxide of another type.
- the microparticles can range in size (average particle diameter) from about 2 nanometers to about 200 nanometers, preferably from about 5 nanometers to about 100 nanometers, more preferably from about 20 nanometers to about 75 nanometers.
- size average particle diameter
- the use of microparticles larger than about 75 nanometers may provide a final crosslinked coating which is translucent or even opaque, in contrast to the transparent coatings generally provided by the use of smaller particles.
- the colloidal microparticles be relatively uniform in size (have a substantially monodisperse size distribution or a polymodal distribution obtained by blending two or more substantially monodisperse distributions) and remain substantially non-aggregated (substantially discrete) , as microparticle aggregation can result in precipitation, gellation, or a dramatic increase in sol viscosity and can reduce both adhesion to substrate and optical clarity.
- a particularly desirable class of microparticles for use in preparing the compositions of the invention includes sols of inorganic microparticles (e.g., colloidal dispersions of inorganic microparticles in liquid media) , especially sols of amorphous silica.
- Such sols can be prepared by a variety of techniques and in a variety of forms which include hydrosols (where water serves as the liquid medium) , organosols (where organic liquids are used) , and mixed sols (where the liquid medium comprises both water and an organic liquid). See, e.g., the descriptions of the techniques and forms given in U.S. Patent Nos. 2,801,185 (Her) and 4,522,958 (Das et al.), as well as those given by R. K. Her in The Chemistry of Silica, John Wiley & Sons, New York (1979) .
- silica hydrosols are generally most preferred for use in preparing the compositions of the invention. Such hydrosols are available in both acidic and basic forms and in a variety of particle sizes and concentrations from, e.g., Nyacol Products, Inc. in Ashland, Maryland; Nalco Chemical Company in Oakbrook, Illinois; and E. I. duPont de Nemours and Company in Wilmington, Delaware. Concentrations of from about 2 to about 50 percent by weight of silica in water are generally useful.
- silica hydrosols can be prepared, e.g., by partially neutralizing an aqueous solution of an alkali metal silicate with acid to a pH of about 8 or 9 (such that the resulting sodium content of the solution is less than about 1 percent by weight based on sodium oxide) .
- Other methods of preparing silica hydrosols e.g., electrodialysis, ion exchange of sodium silicate, hydrolysis of silicon compounds, and dissolution of elemental silicon are described by Her, supra.
- Sols of surface-modified microparticles suitable for use in the compositions of the invention include sols of polymer-grafted microparticles.
- polymer-grafted microparticles are microparticles having linear or branched polymer chains covalently bonded to the microparticle (through surface-attached coupling agent).
- a sol is prepared first and then combined with the other components (a) and (b) of the composition.
- Such a sol can also be prepared in the presence of component (a) and/or component (b) or in the presence of the monomeric starting materials used for preparing component (a) and/or component (b) .
- the latter procedure can result in the surface attachment (e.g, grafting) of component (a) and/or component (b) to the microparticles, thereby providing a one-component or two-component composition (i.e., a three-component composition, as described above, wherein the same material serves as more than one of the three components) .
- the resulting sol can be mixed with additional amounts of component (a) and/or component (b) , if desired.
- Preparation of the sol generally requires that at least a portion of the surface of the inorganic microparticles be modified by chemical reaction (or strong physical interaction) with a coupling agent.
- silica microparticles can be treated with hydrolyzable, chain transfer group- containing organosilanes under conditions such that silanol groups on the surface of the particles chemically bond with hydrolyzed silane groups to produce covalent silicon-oxygen-silicon bonds.
- silica (or other metal oxide) particles can also be treated with other chemical compounds, e.g., hydrolyzable, chain transfer group-containing organotitanates, which are capable of attaching to the surface of the particles by a chemical bond (covalent or ionic) or by a strong physical bond, and which comprise at least one functional group, e.g., -CH 2 SH, -CH 2 NH 2 , etc., which can function as a chain transfer site for free radical polymerization.
- chemical compounds e.g., hydrolyzable, chain transfer group-containing organotitanates, which are capable of attaching to the surface of the particles by a chemical bond (covalent or ionic) or by a strong physical bond, and which comprise at least one functional group, e.g., -CH 2 SH, -CH 2 NH 2 , etc., which can function as a chain transfer site for free radical polymerization.
- Y is a chain transfer group (preferably, a moiety selected from the group consisting of mercapto, amino- containing, oxygen-containing, and halogen-containing groups; more preferably, mercapto)
- R is a divalent group selected from the group consisting of alkylene groups having from 1 to about 12 carbon atoms and arylene groups having from about 6 to about 12 carbon atoms
- X is a hydrolyzable group (preferably, a group selected from the group consisting of halogen, alkoxy groups having from 1 to about 12 carbon atoms and optionally containing from 1 to about 11 ether oxygen atoms, acyloxy, amino, and alkylamino)
- R 1 is selected from the group consisting of lower alkyl groups having from 1 to about 4 carbon atoms and phenyl
- a is an integer of 0 to 2 (preferably, 0) .
- hydrolyzable, chain transfer group-containing organosilanes include 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltriethoxysilane,
- a hydrosol e.g., a silica hydrosol
- a mixed sol e.g., a mixed silica sol, wherein the liquid medium comprises an aqueous solution of at least one preferably water-soluble organic solvent such as methanol, ethanol, acetone, tetrahydrofuran, ethylene glycol, l-methyl-2-pyrrolidinone, isopropanol, propoxyethanol, or the like
- an organosol e.g., a silica organosol, where the organic liquid medium comprises benzene, toluene, propoxyethanol, l-methyl-2- pyrrolidinone, dimethyl formamide, isopropanol, ethylene glycol, or the like
- coupling agent s
- Heat (and agitation) can be applied to facilitate reaction.
- concentration and/or pH of the sol may require adjustment to enhance the stability (and minimize the viscosity) of the sol during reaction with the coupling agent and, later, with monomer.
- Coupling agent can generally be used in an amount such that at least a portion of the surface of the microparticles is modified sufficiently to enable effective graft polymerization (upon combination with monomer and initiator) .
- the amount of coupling agent is selected to be, e.g., from about 1 x 10 " " to about 7 x 10 "3 , preferably from about 2 x 10 -4 to about 3 x 10 ⁇ ⁇ and more preferably from about 3 x 10 "4 to about 2 x 10 "3 millimoles of coupling agent per square meter of microparticle surface area.
- the resulting mixture • can be agitated and maintained at a temperature of, e.g., from about 20°C to about 100°C, preferably from about 50°C to about 100°C (e.g., for about one to about 24 hours) to enable the reaction (or other interaction) of the coupling agent with chemical groups on the surface of the microparticles.
- This provides a colloidal dispersion of inorganic microparticles which have surface-attached or surface-bonded organic groups.
- One or more free-radically polymerizable, ethylenically-monounsaturated monomers can then be added to the resulting colloidal dispersion of surface-modified microparticles.
- small amounts of one or more free-radically polymerizable, ethylenically- polyunsaturated monomers can also be added to provide a degree of crosslinking, if desired.
- Monomer (s) should generally be added in an amount greater than the molar equivalent of coupling agent utilized. For example, from about 0.001 to about 0.10 mole of monomer (s) per gram Si0 2 can be utilized.
- the resulting mixture (which can include surfactant to enable graft polymerization of water-insoluble monomer in an aqueous medium) can be purged of oxygen, an effective amount of a thermally- or radiation-activatable free radical initiator can be added, and the mixture can then be heated (to a temperature sufficient to decompose the free radical source, e.g., from about 20°C to about 130°C) or can be irradiated to effect polymerization of the monomer.
- a temperature sufficient to decompose the free radical source e.g., from about 20°C to about 130°C
- Suitable monomers for use in preparing the polymer-grafted microparticles are free-radically polymerizable, ethylenically-unsaturated monomers (or monomer mixtures) .
- Useful monomers include, for example, ethylenically-unsaturated acids and anhydrides; ethylenically-unsaturated macromers; ethylenically- unsaturated, substituted and unsubstituted esters, amides, and nitriles; vinyl monomers; vinylidene monomers; other olefinic monomers such as styrene, ethylene, tetrafluoroethylene, and hexafluoropropene; fluorochemical-containing acrylates and methacrylates; and heterocyclic monomers.
- Representative monomers include, for example, carboxyethyl acrylate; acrylic acid; methacrylic acid; itaconic acid; citraconic acid; aconitic acid; maleic acid; maleic anhydride; fumaric acid; crotonic acid; cinnamic acid; oleic acid; vinyl sulfonic acid; vinyl phosphonic acid; alkyl, cycloalkyl, and fluoroalkyl- containing esters of the foregoing acids, where the alkyl, cycloalkyl, and fluoroalkyl groups have from 1 to about 18 carbon atoms (such as, for example, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, 3- sulfopropyl, acetoxyethyl, cyanoethyl, hydroxyethyl, and hydroxypropyl acrylates and methacrylates) ;
- Particularly useful monomers include, for example, carboxyethyl acrylate, isopropenyl oxazoline, alkyl acrylates and methacrylates having from 1 to about 18 carbon atoms, acrylic acid, methacrylic acid, itaconic acid, fluorochemical-containing acrylates and methacrylates, and mixtures thereof.
- Monomers which are not soluble in the liquid medium can be solubilized by the addition of solubilizing organic liquid and/or surfactant in an amount sufficient to provide solution or emulsification of the monomers.
- Useful free radical initiators include inorganic and organic peroxides, hydroperoxides, persulfates, azo compounds, redox systems (e.g., a mixture of K2S2O8 and Na2S2 ⁇ 5) , and free radical photoinitiators such as those described by K.K. Dietliker in Chemistry _& Technology of UV _& EB Formulation for Coatings, Inks & ⁇ Paints, Volume 3, pages 276-298, SITA Technology Ltd., London (1991).
- Representative examples include hydrogen peroxide, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, and azobis (isobutyronitrile) (AIBN) .
- AIBN azobis (isobutyronitrile)
- Polymerization of the ethylenically- monounsaturated monomer (s) provides a colloidal dispersion of polymer-grafted microparticles.
- the microparticles have linear or branched polymer chains covalently bonded to surface-attached coupling agent. If desired, two or more sequential grafting polymerization reactions can be carried out.
- monomer (s) can be selected so as to optimize the dispersion stability and the final properties of the resulting coatings.
- sols of microparticles which, unlike the above-described polymer-grafted microparticles, have been surface-modified by treatment only with one or more non-polymeric coupling agents.
- Such inorganic microparticles have surface-attached or surface-bonded organic moieties derived from the reaction of the coupling agent (s) with, e.g., silanol groups on the surface of the microparticles.
- a sol is prepared first and then combined with the other components (a) and (b) of the composition.
- such a sol can also be prepared by carrying out the surface modification in the presence of component (a) and/or component (b) .
- the coupling agent (s) are selected so as to not only be capable of chemically reacting (or strongly physically interacting) with chemical groups on the surface of the microparticles, but also preferably to be capable of chemical reaction with component (a) and/or component (b) .
- Preferred coupling agents thus comprise at least one functional group, e.g., mercapto, amino, epoxy, carboxy, or oxazolinyl, etc., which can react with carboxy, mercapto, oxazolinyl, or oxazinyl group (s) on component (a) and/or component (b) .
- Representative examples of useful coupling agents include 3- mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
- the surfactant polymer component, crosslinking polymer component, and sol of surface- modified microparticles can be combined in any order and manner of combination by direct mixing using any conventional means such as mechanical agitation, ultrasonic agitation, stirring, and the like.
- the sol can be added to the combined polymer formulation, i.e., a mixture of the surfactant polymer component and the crosslinking polymer component, or prior to formulation to either the surfactant polymer component or the crosslinking polymer component.
- the crosslinking component and/or the surfactant component are added to the sol while maintaining the pH of the mixture at values greater than 8 to avoid precipitation of one or more of the components.
- Sol can be added in an amount sufficient to impart the degree of abrasion resistance desired for a particular application, while maintaining the desired surface energy characteristics.
- the coating formulation contains from about 1 to about 70 weight percent inorganic oxide, preferably from about 5 to about 40 weight percent.
- the coating compositions of the invention can contain additional components such as fillers.
- additional components such as fillers.
- the compositions can contain dyes; inorganic, non-colloidal fillers such as tin oxide, titanium dioxide, alumina, or alumina- coated silica; non-colloidal silica (e.g., fumed silica); carbon black; and/or organic fillers.
- the coating compositions can be cured at elevated and room temperatures, e.g., from about 20 to about 125°C.
- elevated temperatures e.g., 50°C to 125°C
- the cured coatings are transparent, translucent, or opaque, depending on the size of the microparticles and whether additional components such as fillers have been incorporated.
- the cured coatings are resistant to solvents and water, and have excellent abrasion resistance without sacrificing their very low surface energy (10-15 dynes/cm) properties.
- the coating compositions of this invention can be applied to a wide variety of substrates to impart abrasion resistance, solvent resistance, and corrosion resistance, as well as to impart release characteristics to the surface.
- the type of substrates that can be coated in accordance with this invention include rigid and flexible substrates such as: plastics, glass, metal, wood, paper, and ceramics.
- soft substrates such as plastics can be rendered abrasion resistant and mar resistant by the practice of this invention.
- Representative examples include: lenses used in ophthalmic spectacles, sunglasses, optical instruments, illuminators, watch crystals, and the like; plastic window glazing; signs and decorative surfaces such as wallpaper and vinyl flooring.
- Metal surfaces can be rendered resistant to corrosion by the practice of this invention, whereby the brilliance of polish can be maintained on decorative metal strips and mirrors.
- the coating compositions can be colored by addition of dyes and pigments and applied to surfaces as a paint.
- the coating composition can be applied as a protective coating on aircraft (in deicing wings), as automotive polish, as automotive topcoat, and as automotive transit coating; can be used on carpet, concrete, fishing line, formica, medical surfaces, siding, sinks, showers, textiles, vinyl flooring, and wallcovering; and can be used in food release, mold release, adhesive release, and the like.
- compositions of this invention can be applied to a substrate using any conventional technique.
- the composition can be brushed
- - li or sprayed e.g., as an aerosol
- the substrate can be immersed in the coating composition or can be spin-coated.
- knife- or bar-coat the substrate it is preferable to knife- or bar-coat the substrate to ensure uniform coatings.
- the coating compositions of the present invention can be applied to a substrate in any desired thickness. It has been found that coatings as thin as a few microns offer excellent abrasion resistance and low surface energy. However, thicker coatings (e.g., up to about 20 microns or more) can be obtained by applying a single thicker coating or by applying successive layers of the coating to the substrate. The latter can be done by applying a layer of the coating composition to the substrate and then drying without extensive curing, for example, by heating the coated substrate for about one minute at about 75°C. Successive layers of the coating can then be applied to dried, but uncured, coatings. This procedure can be repeated until the desired coating thickness is obtained.
- thicker coatings e.g., up to about 20 microns or more
- the latter can be done by applying a layer of the coating composition to the substrate and then drying without extensive curing, for example, by heating the coated substrate for about one minute at about 75°C. Successive layers of the coating can then be applied to dried, but uncured, coatings
- the precursor polymers such as for example the surfactant component polymer and the crosslinking component polymer were prepared essentially as described in U.S. Patent Nos. 5,382,639, 5,294,662, 5,006,624, and 4,764,564 cited above.
- the coating compositions were prepared, applied to a polyethylene terephthalate film substrate, cured, and evaluated for low surface energy properties and abrasion resistance performance. The test methods utilized are described below:
- the abrasion resistance of the coatings was determined by measuring the resulting % haze of a film sample using ASTM D-1044-90 on a Teledyne Tabor Abrasor with a 500 g load and a pair of CS-10F Calibrasers. The lower the resulting percent haze, the higher the abrasion resistance of the coating.
- the resulting coatings were also tested for water contact angle by essentially the method described by Zisman, W.A., in "Contact Angle, Wettability, and Adhesion," Advances in Chemistry, Series 43, American Chemical Society, Washington, D.C. (1964) .
- An ESCA test comprised evaluating the samples for surface fluorine content using a 1/4 inch by 1/4 inch portion of the coated sample using a Fison F InspectorTM ESCA analyzer. The sample was scanned from 0 electron volts to 1100 electron volts, and the results were averaged for four scans.
- the temperature control was adjusted to 70°C and heating continued at that temperature for about 2.5 hours.
- the cooling condenser was replaced by a distillation condenser, and isopropanol was distilled from the reaction mixture.
- the resulting polymer was neutralized by addition of aqueous ammonia and water until the solution was basic.
- This WXF Formulation was allowed to sit at room temperature for about 1-2 days after which it was then coated onto a primed polyethylene terephthalate film with a #30 Mayer rod to a coating thickness of about 10-12 microns. The resulting coating was then heated in a oven at 120°C for 30 min. The finished film was transparent and resistant to solvents and water.
- aqueous dispersion of colloidal silica (LudoxTM AS-40 hydrosol, 100 g solids) was diluted with deionized water to give 800 g total.
- N- methylpyrrolidinone 108 g
- CX-WS-300TM crosslinker (14.4 g solids) .
- a 3.2 g sample of the resulting mixture was vacuum fractionated (150°C, 0.06 torr) using a Kugelrohr apparatus to give 2.43 g of a clear, colorless distillate of a silane coupling agent (6- (2-oxazolinyl) -4-thiaheptyltrimethoxysilane) having the formula (CH 3 0) 3 SiCH 2 CH 2 CH 2 SCH 2 C (Me) C 3 H 4 N0, where -C 3 H 4 N0 represents an oxazolinyl group.
- a silane coupling agent (6- (2-oxazolinyl) -4-thiaheptyltrimethoxysilane) having the formula (CH 3 0) 3 SiCH 2 CH 2 CH 2 SCH 2 C (Me) C 3 H 4 N0, where -C 3 H 4 N0 represents an oxazolinyl group.
- FX-13TM/carboxyethyl acrylate (CEA) copolymer solution (0.245 g solids, 0.68 mmol of neutralized carboxylic groups, prepared essentially as in Comparative Example 1), followed by addition of N-methylpyrrolidinone (1.0 g) .
- the resulting combination was then mixed with "WXF Formulation" (4.1 g solids) to yield a final coating formulation with 25 weight % Si0 2 by solids.
- the formulation was then coated and evaluated essentially as described in Comparative
- Example 1 The results of testing are shown in Table 1.
- the resulting solution was purged with nitrogen for about 3 min. and heated to initiate polymerization. As the resulting reaction became exothermic, the temperature was adjusted to 75°C and heating was continued at that temperature for about 4 hours. The cooling condenser was replaced by a distilling head, and isopropanol was distilled from the reaction mixture. The resulting polymer was neutralized by addition of aqueous ammonia and water until the solution was basic.
- VAZO- 50TM initiator (2, 2' -azobis (2-amidinopropane) dihydrochloride, about 0.02 g) was added to the suspension after 8 hours.
- the isopropanol and some of the water were evaporated at 60°C under reduced pressure to provide 106 g of a translucent suspension.
- the solids content (23.1 weight %) was measured by drying a small sample in a forced air oven at 105°C. Since the content of silica should be 18.9 weight % in the suspension, the poly (IPO) content was calculated to be 4.2 weight %. The conversion of IPO to poly (IPO) was therefore about 55%. Elemental analysis: C: 8.8, H: 1.5, N: 0.2.
- the ratio of IPO to Si0 2 was 1:4.5 by weight .
- Example 7 A suspension of "Si0 2 -g-poly (CEA) , 5:1" (10.0 g solids, 11.6 mmol of carboxylic acid groups) was mixed with crosslinker CX-WS-300TM (1.67 g solids, 12.7 mmol of oxazoline groups) to produce a sample of "PIPO/Si0 2 -g- poly(CEA), 5:1". Part of this sample (1.0 g solids, 0.71 g Si0 2 ) was mixed with "WXF Formulation" (1.75 g solids) to yield a final coating formulation with 26 weight % Si0 2 by solids. This formulation was then evaluated essentially as described in Comparative Example 1. The test results are shown in Table 1.
- Example 8 A suspension of "Si0 2 -g-poly (CEA) , 5:1" (10.0 g solids, 11.6 mmol of carboxylic acid groups) was mixed with crosslinker CX-WS-300TM (1.67 g solids, 1
- the above-described suspension (10.5 g solids, average particle size: 20 nm, ) was mixed with FX-13TM acrylate (15.0 g, available from the 3M Company), carboxyethyl acrylate (10.0 g) , AIBN (0.40 g) , and isopropanol (40.0 g) .
- the resulting suspension was purged with nitrogen for about 5 min. and heated to 70°C for 3 hours.
- the isopropanol was then removed from the suspension under reduced pressure, and the suspension was neutralized with ammonia and then further diluted with water to 21.5 weight % solids. A clear suspension was obtained.
- a suspension of MPTS-f-Si0 2 (0.25 mmol/g Si0 2/ prepared essentially as described above) in N- methylpyrrolidinone (50.0 g solids Si0 2 with 79 g N- methylpyrrolidinone, average particle size: 20 nm) was mixed with FX-13TM acrylate (70.0 g) , acrylic acid (30.0 g) , AIBN (0.40 g) , and isopropanol (70.0 g) .
- the resulting suspension was purged with nitrogen for about 5 min. and heated to 70°C for 7 hours.
- the isopropanol was then removed from the suspension under reduced pressure and neutralized with ammonia to basic. A milky but stable suspension was obtained.
- Alumina-coated silica sol (Nalco 1056TM hydrosol, 30 weight % solids, 350 g) was mixed with mercaptopropyltrimethoxysilane (0.52 g, 2.7 mmol) and water (350 g) . After adjusting the pH to 3.6 with acetic acid, the dispersion was heated overnight at 80°C for 16 hours, and an additional 350 g of water was then added to yield a MPTS- functionalized, alumina-coated silica dispersion at 15 weight % solids. Part of this prepared dispersion (13.3 g) was diluted with water to 20 g, and 10 weight % aqueous acrylic acid (80 g) was added.
- the resulting dispersion was heated to 65°C, degassed with nitrogen, and t- butylhydroperoxide added (0.11 g, 70 weight % solution from Aldrich) .
- the resulting combination was then purged with nitrogen and heated at 70°C overnight, and the pH was then adjusted to 9 with ammonium hydroxide.
- the resulting suspension was very viscous, so an additional 50 g of water was added to give 4 weight % total solids.
- Example 11 To the coating formulation described in Example 11 (1.0 g solids) was added "WXF/AA Formulation" (Comparative Example 2, 1.68 g solids) to yield a fluorochemical-containing formulation (10.5 weight % solids, 2.5 weight % Si0 2 (Al 2 0 3 ) based on solids). The formulation was then evaluated essentially as described in Comparative Example 1. The test results are shown in Table 1. Table 1
- One-half of the surface area of a 1 ft X 1 ft square sample of vinyl flooring was coated with a water-based coating composition of this invention (prepared essentially as in Example 8, having 21.7 weight % silica and 16.6 weight % fluorine content) and cured at room temperature. The remaining one-half of the surface area was left uncoated.
- One-half of the surface area of a second sample of vinyl flooring was coated with the same coating composition and cured at 120°C for three hours.
- the initial gloss of the coated vinyl samples was measured using a Minolta Gloss Meter at 60 degrees from the plane of the sample, sampling at randomly determined areas in the coated and uncoated areas of the vinyl.
- the samples were then subjected to a walk-on test in which approximately 60,000 people walked though the test site area containing the two samples and the gloss of the soiled samples determined as before. Because the uncoated portions of both vinyl samples were identical in appearance, the gloss was measured on one. Next, the samples were cleaned with soap and water and the gloss of the cleaned samples measured again. The average measured gloss for these samples is reported in Table 2.
- the samples were treated with common staining materials for a prescribed period of time (indicated below) and then wiped with a dry cloth. If a stain persisted, the sample was then wiped with a solution of dish detergent, followed by wiping with isopropanol if necessary.
- the staining materials were as follows:
- the coating composition of the present invention provided improved protection of surfaces against staining, relative to an uncoated surface.
- the coating composition allowed stains to be removed more completely and under less rigorous conditions than for the uncoated sample.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002274973A CA2274973A1 (en) | 1996-12-20 | 1997-12-17 | Aqueous fluorochemical compositions |
JP52902798A JP2001507071A (en) | 1996-12-20 | 1997-12-17 | Aqueous fluorochemical composition |
EP97952581A EP0946650A1 (en) | 1996-12-20 | 1997-12-17 | Aqueous fluorochemical compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/771,786 | 1996-12-20 | ||
US08/771,786 US5760126A (en) | 1996-12-20 | 1996-12-20 | Aqueous fluorochemical compositions and abrasion-resistant coatings therefrom |
Publications (1)
Publication Number | Publication Date |
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WO1998028368A1 true WO1998028368A1 (en) | 1998-07-02 |
Family
ID=25092969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/023677 WO1998028368A1 (en) | 1996-12-20 | 1997-12-17 | Aqueous fluorochemical compositions |
Country Status (5)
Country | Link |
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US (1) | US5760126A (en) |
EP (1) | EP0946650A1 (en) |
JP (1) | JP2001507071A (en) |
CA (1) | CA2274973A1 (en) |
WO (1) | WO1998028368A1 (en) |
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CN104877089A (en) * | 2015-05-08 | 2015-09-02 | 中山职业技术学院 | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion |
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- 1997-12-17 EP EP97952581A patent/EP0946650A1/en not_active Withdrawn
- 1997-12-17 WO PCT/US1997/023677 patent/WO1998028368A1/en not_active Application Discontinuation
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CA2274973A1 (en) | 1998-07-02 |
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US5760126A (en) | 1998-06-02 |
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