United States Patent (19) 11) Patent Number: 4,617,057 Plueddemann 45) Date of Patent: Oct. 14, 1986

54 OIL AND WATER REPELLENT COATING COMPOST ONS OTHER PUBLICATIONS N. L. Jarvis et al. in Contact Angle, Wettability and Ad (75) Inventor: Edwin P. Plueddemann, Midland, hesion, pp. 317-331, American Chemical Society, Wash Mich. ington, D.C. (1964). 73 Assignee: Dow Corning Corporation, Midland, Primary Examiner-Amelia B. Yarbrough Mich. Attorney, Agent, or Firm-James E. Bittell 21 Appl. No.: 741,642 57 ABSTRACT An oil and water repellent coating composition is dis 22 Filed: Jun. 4, 1985 closed. The composition comprises a blend of an ami 51) Int. Cl...... CO9K 3/18 noorganosilane, a perfluorinated organic compound 52 U.S.C...... 106/2 and a resin selected from the group consisting of colloi 58) Field of Search ...... 106/2; 8/115.54 dal inorganic-based siloxane resin, poly (dialkylsilox ane)-monoorgano substituted silisesquioxane block co 56) References Cited polymer, acrylic polymer and copolymer, ethylene U.S. PATENT DOCUMENTS vinyl acetate latex and styrene-butadiene latex. The silane and perfluorinated organic, combined, constitute 3,317,629 5/1967 Quaal ...... 260/827 from 0.1% to 10% by weight of the total resin solids in 3,681,266 8/1972 Domba ...... 260/25 a solution or suspension of the blend. A method of coat 4,070,152 1/1978 Pentz ...... 8/115.6 ing a smooth substrate or treating a fabric to render the 4,410,563 10/1983 Richter et al...... 427/08 respective surface oleophobic and hydrophobic is fur FOREIGN PATENT DOCUMENTS ther disclosed. 142958 8/1983 Japan ...... 3/18 147483 9/1983 Japan ... 15 Claims, No Drawings 4,617,057 1. 2 Jarvis et al. (Contact Angle, Wettability, and Adhesion, p. OIL AND WATER REPELLENT COATING 317, American Chemical Society, Washington, D.C., COMPOSITIONS 1964) that only certain combinations of fluorinated or ganic compounds and (extending) polymers result in This invention relates to the field of protective coat 5 low energy surfaces. Moreover, this reference teaches ings. More specifically, this invention relates to hydro that a critical balance of organophilic/organophobic phobic and oleophobic coating compositions which character (i.e., the precise solubility/insolubility bal impart water and oil repellent properties to substrates ance of the fluorinated compound in the polymer) is coated therewith. These substrates, in turn, may com required of the modifying fluorinated compound if the prise hard, smooth forms such as metal, glass or 10 modified polymer combination is to produce a uniform, as well as fabrics of various types. clear, high quality film, in addition to low surface en ergy. It is therefore recognized in the art that there is no BACKGROUND OF THE INVENTION a priori way to determine how much of, and indeed, Many industrial applications of materials require the which of the many available fluorinated organic com surfaces of these products to possess hydrophobic and 5 pounds, or other low surface energy modifiers, can be oleophobic character for both aesthetic as well as prac successfully combined with a given polymer to produce tical reasons. Coated glass cloth, employed in pre-fab the desired hydrophobic/oleophobic character while ricated air-supported structures such as sports stadia, maintaining a uniform, high quality surface. for example, should have an oil repellent surface so as to prevent unsightly dirt accumulation. High voltage elec 20 SUMMARY OF THE INVENTION trical insulators, likewise, must be hydrophobic and This invention relates to an oil and water repellent "self-cleaning' in contaminated environments such that coating composition, comprising: surface dirt and moisture, and therefore undesirable arc (a) a resin selected from the group consisting of col tracking, are kept to a minimum. Furthermore, many loidal inorganic-based siloxane resin, poly(dialkylsilox coatings, such as those applied to optics, mirrors, wind 25 ane)-monoorgano substituted silisesquioxane block co shields, solar collectors, and greenhouses, must retain polymer, acrylic polymer and copolymer, ethylene clarity to be efficient light transmitters, and therefore vinyl acetate latex and styrene-butadiene latex, also have to be "self-cleaning' (e.g., as by rainfall) rela (b) an aminoorganosilane of the general formula tive to the uncoated surfaces. Finally, as yet another illustration of the utility of low surface energy coatings, 30 the treatment of various fabrics for water repellency and stain resistance (i.e., oleophobicity) has become a Ri R3 Rn, major commercial success. It is known in the coating arts to employ silicones to wherein R is selected from the group consisting of achieve hydrophobic surfaces and treated fabrics. Like 35 hydrogen, alkyl of one to four carbon atoms or wise, perfluorinated organic coatings and fabric treat ments are known to confer oleophobic properties. In deed, these two classes of materials have been effec -R'OR)- tively combined in U.S. Pat. No. 4,410,563 to coat opti Rn, cal glass surfaces as well as in U.S. Pat. No. 3,681,266 to treat fabrics. R2 is an alkylene group of two to four carbon atoms, Unfortunately, the perfluorinated organic com R3 is hydrogen or alkyl of one to four carbon atoms, R. pounds are quite costly and therefore not suitable for is an alkylene group of three to four carbon atoms, R. many applications in which oleophobic surfaces would and R6 are alkyl groups of one to four carbon atoms otherwise prove desirable. Such disadvantage was par 45 each, n is zero to four and m is zero or one; and tially overcome by U.S. Pat. No. 3,317,629, wherein (c) a perfluorinated organic compound of the general fluoroalkylsiloxanes were "extended' with acrylic pol formula: ymers and used to treat a variety of fabrics to obtain hydrophobic and oleophobic character. In a similar RY fashion, U.S. Pat. No. 4,070,152 employs a copolymer 50 of a maleic-anhydride copolymer, a fatty acid amine wherein Rf is a straight or branched perfluoroalkyl and an aminoorganopolysiloxane as an extender for group of four to 18 carbon atoms and Y is selected from fluorinated "textile treating resins.” It discloses im the group consisting of -COOH, -COOR, wherein R proved oil and water repellency and better retention of is alkyl or alkoxyalkyl of one to six carbon atoms and repellency after laundering and dry cleaning relative to 55 wherein the combined amount of the aminoorganosi use of the textile treating resins alone. Still further ex lane and the perfluorinated organic compound com amples of this general concept are provided by Japanese prises between about 0.1 and about 10 percent by Pat. Nos. 142,958/83 and 147,483/83 which combine a weight of said resin and the mole ratio of the perfluori perfluoroalkyl-containing silane and a silane coupling nated organic compound to the sum of primary and agent with water-glass and colloidal silica, respectively, 60 secondary amine group(s) in the aminoorganosilane is for use as a water and oil repellent agent for glass sur fixed between about 0.33 and about 1.0. faces. Although such attempts to reduce the expense of DETAILED DESCRIPTION OF THE fluorinated treating resins have been successful in that INVENTION less of the costly ingredient is required to achieve the 65 It has been discovered that, when certain polymers or same extent of surface modification, complex and costly resins are modified with relatively small quantities of a reaction schemes are sometimes required to produce the perfluorinated organic compound and an aminoor disclosed components. Furthermore, it is known from ganosilane, compositions result which exhibit excellent 4,617,057 3 4 water and oil repellency when employed in bulk, as most preferred aminosilane. Other suitable aminosilanes coatings or as fabric treating resins. One aspect of the include invention, therefore, teaches "extending' or diluting fluorinated organic compounds with certain less expen sive polymers and resins, thereby producing hydropho- 5 bic and oleophobic coating and fabric treating composi tions which are less costly than these compounds alone, or in combination with, an amino-functional silane. Alternatively, the invention discloses the modification of the particular polymers or resins within its scope with the fluorinated organic compounds and amino functional silanes so as to impart hydrophobic and oleo phobic character to the surfaces of these polymers or resins, without attendant untoward effects upon other properties. 15 The invention may be practiced by simply blending The aminoorganosilanes are well known in the art and the three components, at room temperature, either in are typically formed by the reaction of chloroalkylalk solution or suspension, and using that solution or sus oxysilanes with organic amines. For example, the bis pension to coat a substrate or treat a fabric. The order of structures, including formula III above, have been de blending is not critical, so that, for example, the resin 20 scribed in U.S. Pat. No. 4,448,694 and are formed by and silane may be blended together and then the perflu heating the respective amine with the appropriate chlo orinated compound added, or the resin and the perfluo roalkylalkoxysilane in a 1:2 molar ratio. The resultant rinated compound may be blended together and then aminoorganosilanes are generally not pure species and the silane added. In the preferred, as well as most con several side products coexist with the main component. venient, embodiment, a mixture of the perfluorinated 25 Generally either unpurified reaction products or more organic compound and aminoorganosilane may be pre purified portions of the main species can be employed pared (in solution or suspension) and an appropriate for the purposes of this invention. portion thereof used to modify the particular polymer The perfluorinated organic compound employed, or resin. Pre-reaction of the modifying components (i.e., also well known in the art, may be selected from the formation of the perfluoroalkyl amidoalkylsilane) is not 30 group having the general formula necessary for the operation of this invention. The aminoorganosilanes employed may be selected from the group having the general formula wherein Rf is a straight chain or branched perfluori nated alkyl group of four to 18 carbon atoms, six to 12 carbons being preferred and seven to nine carbons being k is Rn, most preferred. Examples of Rf would include C18F37-, C12F25-, CoF19-, C8F17-, C7F15-, wherein R is selected from the group consisting of C6F13- and CF9-. Y is either a carboxy (-COOH) hydrogen, alkyl of one to four carbon atoms such as 40 or an ester (-COOR) moiety wherein R is alkyl, alk methyl, ethyl, propyl, isopropyl, butyl, iso-butyl or oxyalkyl or hydroxyalkyl, of one to eight carbon atoms, methyl being preferred. Other usable R groups include ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, -R'OR)- heptyl, octyl, 2-ethylhexyl, 2-hydroxypropyl, and 2 Rn, 45 methoxyethyl. The carboxy, or ester, group is capable of reacting R2 is an alkylene group of two to four carbon atoms with the aminoorganosilane component to form a per such as ethylene, propylene or butylene, R3 is hydrogen fluoroalkylamidosilane. This reaction has been shown or alkyl of one to four carbon atoms, R is an alkylene to occur slowly in the case of the carboxy compound group of 3 to 4 carbon atoms such as trimethylene or 50 (R. E. Banks, and their Derivatives, Old tetramethylene, R5 and R6 are alkyl groups of one to bourne Press, London, 1964). According to R. D. four carbon atoms each, such as methyl, ethyl, propyl Chambers ( in Organic Chemistry, J. Wiley, or butyl, n is zero to four and m is zero or one. Preferred London, 1973), however, the reaction with perfluoroal aminoorganosilanes are: kyl esters is quite facile. It results in an exothern even at 55 room temperature and is completed by brief heating to 80 C. In any event, the reaction does not constitute a necessary pre-condition to the operability of the current invention. In fact, when the amidosilane reaction prod and uct of C7F15COOH or C9F19COOH with Z-6020 (R) 60 was formed by refluxing the reactants in xylene, it was found to be a viscous oil, insoluble in all common sol (III) vents tried and could not be used according to the cur rent invention. Contrarily, equimolar dispersions of wherein Me is CH3- and Et is CH3CH2-. these fluoroalkyl acids and Z-6020 (R) in water were The N-beta-aminoethyl-gamma-aminopropyltrime 65 found to be stable for about one year and could be thoxysilane (formula I, above) is produced under the employed in such a salt form to modify the water-based trade name Z-6020 (R) by the Dow Corning Corpora polymers or resins within the scope of the current in tion, Midland, Michigan, U.S.A., and represents the vention. It is, of course, recognized that reactions can 4,617,057 5 6 occur between the aminoorganosilane and the perfluo the aminoorganosilane component is intentionally left roalkyl acid, during subsequent drying and/or curing of out of the compositions, poorer retention of oleo the resins of the current invention. phobicity is observed. Furthermore, without the ami As was explicitly recited in the "Background of the noorganosilane component, coatings on glass slides Invention' section, supra, and as will be readily appre 5 retract into "islands' so that uniform surface coverage ciated by those skilled in the art, a critical balance of is not attainable, even though the suspension, before solubility/insolubility of the modifying components in coating, is clear. All the compositions within the scope the polymer or resin is required in order to impart the of this invention result in uniform, cured coatings which desired surface hydrophobicity and oleophobicity while retain the hard, abrasion resistant surface characteristics retaining other advantageous properties of the polymer 10 of the unmodified resins. or resin. This result can only be achieved when specific Poly(dialkylsiloxane)-monoorgano substituted silses fluorinated organic compound, aminoorganosilane and quioxane block copolymers, hereinafter referred to as extending polymer or resin are combined in a particular "block copolymers,' are room temperature curable ratio. The specific preferred compositions and ratios of through, e.g., alkoxy functionality. The block copoly modifying components was determined for the individ 5 mers comprise poly(diorganosiloxane) and monoor ual polymers or resins within the scope of this inven ganosilsesquioxane units. The block copolymer may be tion. In each case, the preferred molar ratio of perfluori "capped' with alkoxy functionality and is generally nated organic compound to the total of primary and applied from toluene or xylene solution. These block secondary amine group(s) in the aminoorganosilane was copolymers may be effectively employed for junction found to be 1:2, although ratios may range between 1:1 20 coating and encapsulation of components in the elec and 1:3 within the scope of the invention. Between tronics industry. They also find utility in the coating of about 0.1% and about 10% by weight, based on resin glass cloth for such applications as air-supported struc solids, of the combined amount of aminoorganosilane tures, greenhouses and semi-enclosed architectural tents and perfluorinated organic compound is effective, for, e.g., shopping centers. The latter applications take while about 1% to 2% is preferred. 25 advantage of the material's relatively low degree of dirt The class of materials referred to as "colloidal inor pick-up from airborne contamination; this allows a fair ganic-based siloxane resin' comprises an acidic disper retention of light transmission and pleasing aesthetics sion of colloidal silica and hydroxylated silsesquioxane after long-term outdoor exposure. Nevertheless, the in an -water medium. More specifically, these soiling resistance is not equal to that of, e.g., Teflon (E) pigment-free aqueous coating compositions comprise a 30 (E. I. Du Pont de Nemours, Wilmington, Delaware, dispersion of colloidal silica in lower aliphatic alcohol U.S.A.) and improvements for the above-mentioned water solution of the partial condensate of a silanol of applications, as well as others, are desirable. Detailed the formula R7Si(OH)3. R7 is selected from the group descriptions of the block copolymers and their method consisting of alkyl radical of 1 to 3 inclusive carbon of preparation may be found in U.S. Pat. Nos. 3,639,155, atoms, the vinyl radical, the 3,3,3-trifluoropropyl radi 35 3,629,228, and 4,508,887, which are hereby incorpo cal, the gamma-glycidoxypropyl radical and the gam rated by reference. ma-methacryloxypropyl radical. At least 70 weight Excellent oleophobic and hydrophobic coatings, percent of the silanol is CH3SiOH)3. The compositions moisturecured on glass slides, are obtained by blending contain from 10 to 50 weight percent solids, consisting perfluoroalkyl acid in combination with aminoorganosi essentially of 10 to 70 weight percent colloidal silica and lane into a block copolymer composed of 70 mole per 30 to 90 weight percent of the partial condensate. Fi cent poly(dimethylsiloxane) and 30 mole percent phe nally, the compositions contain sufficient acid to pro nylsilsesquioxane units and capped with methyldime vide a pH in the range of 3.0 to 6.0. Detailed descrip thoxysiloxane end blocks. An attendant result of this tion, and method of preparation, of these compositions modification is significant augmentation of adhesion of may be found in U.S. Pat. No. 4,027,073 which is hereby 45 the coating to the glass surface. Other ratios of the incorporated by reference. blocks of the block copolymer can be employed and a These resins have found great utility as clear or tinted range of about 40 to about 75 mole percent of the poly(- protective coatings, particularly for plastic substrates, diorganosiloxane) component is within the scope of this wherein they impart hard, abrasion-resistant surfaces to, invention. The poly(diorganosiloxane) block may also for example, optical elements such as spectacles. Al 50 include polymers of phenylmethylsiloxane, methylvin though coatings derived from these resin suspensions ylsiloxane and diethylsiloxane. The silisesquioxane block are somewhat hydrophobic, presumably due to the may further comprise tolyl, xylyl, propyl, methyl, vinyl monoorganosilsesquioxane component, modification or ethyl substituted silsesquioxanes. Other siloxane end according to the current invention is desirable to blocking (capping) units may comprise ethyldimethoxy, achieve oleophobic surfaces as well. Such modification 55 methyldiethoxy, methylethoxymethoxy, propyldime would enhance the coating's utility in applications thoxy, butyldimethoxy and phenyldimethoxy. where dirt pick-up, staining or smudging were of con Acrylic polymers are well known in the art. These cern. Examples would include plastic windshields, ap are produced by polymerization of acrylic ester mono pliance protective coatings, electrical insulators and mers such as methylmethacrylate, for example. Copoly cover plates for solar cell modules. mers with other monomers, such as methyl acrylate, Modification of the colloidal inorganic-based siloxane ethyl acrylate, acrylonitrile and styrene, have been re resin suspensions was achieved with addition of either ported. These polymers and copolymers may be either the preferred fluor alkyl acids or esters and aminoor or thermosetting, depending on formula ganosilane. Coatings are typically cured on glass or tion and processing. Furthermore, these polymers and plastic substrates for about 15 minutes at 150° C. One 65 copolymers are known in the form of bulk plastic, solu advantage of the present invention is that coated sub tion and dispersion (e.g., latex). strates retain the oleophobic surface characteristics Like the above-mentioned siloxane block copoly even after soaking in water for extended periods. When mers, the cured films resulting from thermosettable 4,617,057 7 8 acrylic copolymer latices are hydrophobic but not oleo ally used with melamine resin cross linkers of the form phobic. Oleophobic character was readily imparted according to the current invention by blending with such acrylic latices, the and aminoorganosilane. The materials were cured, typically at 80 C. for about two hours, on a plastic substrate, prior to evaluation of surface properties. Generally, the term "thermosettable acrylics' as used herein includes an acrylic polymer or copolymer hav ing reactive functional groups which are capable of 10 reacting between themselves to effect a cross-linkage thereof. These materials are described, for example, in wherein X is U.S. Pat. No. 4,353,965. The term, thermosettable acrylics, also includes acrylic polymers or copolymers CH2OCH3 5 having a reactive functional group to which there is ceN added an appropriate cross-linking agent which reacts N with the functional group to effect cross-linking. The CH2OCH3 term, thermosettable acrylics, still further includes a mixture of two or more polymers containing cross-link Cure of these resins is effected through functionality able functional reactive groups. These polymers may be 20 pendant on the acrylic copolymer, according to, e.g.,

CH2OCH3 -(melamine resin)-N-CH2OCH3 -- HO (acrylic copolymer) -Ge. (acrylic copolymer)-OCH2N-(melamine resin)-N-CH2-O-(acrylic copolymer) -- CH3OH CH3OCH2 CH2OCH3 acrylic polymers or copolymers having reactable, cross-linkable, functional groups thereon, or at least one In addition to the latices discussed, solvent-based of the polymers may be an acrylic polymer or copoly acrylic copolymers, such as Rohm and Haas mer having a reactive functional group and the other Acryloid (R) AT-51, were equally amenable to modifica- " polymer or copolymer may be one or more other types tion with addition of a blend of perfluorinated com of known polymers having functional groups which are pound and aminoorganosilane. Cured in like fashion to reactive with the acrylic functional group to provide 35 the acrylic latices supra, the films from such composi the thermoset product as a result of cross-linking. tions were clear and adhered well to and The needed functional group in the acrylic copoly poly(methylmethacrylate) substrates. mer, which is the foundation of the thermosettable Excellent oleophobic character was imparted to fab acrylic polymer, is provided by employing in the copo rics treated with certain polymer latices which were lymerization a monomer which supplies the needed first modified with blends of perfluorinated compound reactive functional group into the polymer chain. Usu and aminoorganosilane. Latices which provided oleo ally, this copolymerizable functional group-supplying phobic fabrics included acrylic, ethylene-vinyl acetate monomer will be present in small amounts, that is, on (EVA) and styrene-butadiene (SB) copolymers. An the order of 25 weight percent or less, and typically, example of a thermoplastic acrylic polymer latex is between about 1 and 20 percent of the monomer mass 45 Rhoplex (R) AC-235 (Rohm and Haas, Philadelphia, which is polymerized. Exemplary of these functional Pennsylvania, U.S.A.). EVA copolymers are thermo group-supplying monomers are glycidyl acrylate, glyci plastic polymers, which may contain from about 5 to 50 dyl methacrylate, allyl glycidyl ether, dimethylamino percent by weight of vinyl acetate randomly copoly ethyl methacrylate, vinyl pyridine, tert-butyl-aminoeth merized with ethylene under high pressure, and are well yl-methacrylate, maleic anhydride, itaconic anhydride, 50 known in the art. An example of such an EVA copoly allyl alcohol, monoallyl ethers of polyols, hydroxyethyl mer is ELVACE (R)-1875 (Reichhold Chemicals, Inc., methacrylate, hydroxypropyl methacrylate, hydroxy Dover, Delaware, U.S.A.). SB copolymers, also well propyl acrylate, acrylamide, methacrylamide, male known in the art, are random copolymers of styrene mide, N-methylolacrylamide, N-(isobutoximethyl)a- with butadiene. An example of this latex type is DL233 crylamide, vinyl isocyanate, allyl isocyanate. Usually 55 (Dow Chemical Co., Midland, Michigan, U.S.A.). the other monomer which will be polymerized along These modified latex compositions may be applied to with the monomer supplying the functional group is a any natural or synthetic fabric such as cotton, wool, lower (C1-C3) alkyl acrylic ester or mixtures thereof, , , Dacron, glass or various blends e.g. methyl acrylate, ethyl acrylate, methyl methacry thereof. Fabrics are rendered relatively non-staining late, ethyl methacrylate, or mixtures thereof, in an 60 when treated with the above-described compositions amount ranging between about 75 parts to about 99 and dried. A typical dry cycle on 65/35 polyester/cot parts and, more typically, between about 80 parts to ton fabric is preferably about 30 minutes at 90° C. when about 97 parts. the treatment consists of dipping in a 15% total solids Suitable thermosettable acrylic copolymer latices are modified latex. the water dispersions of commerce: Rhoplex (RAC868, 65 latex (e.g., Spensol (R), an emulsified Rhoplex (R) 604 and Acrysol (RWS-12 (Rohm and Haas thermoplastic polyurethane manufactured by the Spen Co., Philadelphia, Pennsylvania, U.S.A.). These are cer Kellog Division of Textron, Inc., Buffalo, New described as thermosetting acrylic copolymers, gener York, U.S.A.) did not lend itself to modification accord 4,617,057 10 ing to the instant invention and fabric treated with this composition was only moderately hydrophobic and EXAMPLE 2 oleophobic. This illustrates the lack of precise balance The perfluorinated ester from Example 1A, was of solubility/insolubility needed for this invention. blended in equimolar amounts with N-beta-aminoethyl Likewise, attempts at modification of a one-part curable gamma-aminopropyltrimethoxysilane (Dow Corning rubber composition suitable for coating high voltage Z-6020 (R)) (i.e., 1:2 mole ratio of perfluorinated ester to insulators, based on ketoxime-functional poly(dimethyl total primary and secondary amine groups in the silane) siloxane) and filled with hydrated alumina, failed to in methanol solution (50%). This solution was then produce an oleophobic surface while maintaining a added in varying amounts, as indicated in the first col quality coating. O umn of Table I, to a colloidal inorganic-based siloxane The coating compositions of this invention can be resin suspension, the preparation and full description of employed to coat solid or fabric substrates. Solid sub which is essentially disclosed in Example 1 of U.S. Pat. strates may include, for example, metal, glass, ceramic No. 4,027,073. or plastic items. which may be coated include The modified resin mixtures were employed to knife polycarbonate, , poly(methylmethacrylate) 15 coat thin films onto substrates of glass, polymethyl and poly(vinylchloride), for example. Metals which methacrylate and polycarbonate. The coatings were may be coated include steel, aluminum, brass, copper, cured in an air oven at 150 C. for 15 minutes. The cured bronze, iron and lead, for example. Representative fab films were optically clear and retained the desirable rics, which may be treated with the compositions of this abrasion resistance of unmodified resin films, i.e., they invention, inlcude cotton, wool, nylon, rayon, cellulose 20 could not be scratched by No. 0000 steel wool. In order acetate, dacron and glass, for example. to assess the hydrophobic/oleophobic character of the The following examples are illustrative only and coatings, a semi-quantitative test was employed should not be construed as limiting the invention which whereby uniform drops of water, or liquid hydrocarbon is set forth in the appended claims. All compositions are of low molecular weight, were applied to the cured in weight percent based on solids content, except where 25 surfaces and the drop diameter measured. This diameter noted. is inversely proportional to contact angle of the liquid substrate interface and therefore an inverse indication of EXAMPLE 1. wettability; i.e., a small diameter drop results when the Perfluoroalkyl esters were prepared from the corre surface is not wetted by the liquid applied, while a large sponding carboxylic acids and the indicated co-react 30 drop, or liquid "spreading,” is observed when the liquid ants by heating at reflux in a stirred flask, equipped with wets the surface. Table I summarizes the observations a water trap, for the indicated time. using water to test for hydrophobicity and a series of A. 5.41 g of C9F19COOH, 20.0 g of CH3CH(OH)C- three hydrocarbon fluids, C7 through C16, to determine H2OCH3, and 25.0 g toluene were mixed in a flask. The oleophobicity of the test surface. The effect of as little reactants were refluxed for 1 hour and 0.2 ml water was 35 as 0.4% of the perfluorinated ester-aminosilane blend recovered in the trap to provide a clear solution which was detectable but modification with about 2% of the contained 0.01 mole of the ester in 50 g of solution. blend was preferred, while increasing the blend content B. 41.4 g of C7F15COOH, 20.0 g ofisoproponol, 40.0 beyond 2% offered no significant advantage in this test. g of toluene and 0.1 g of toluenesulfonic acid were For comparison purposes, 2% of the amide reaction mixed in a flask. The reactants were refluxed for 4 hours product of lauric acid with N-beta-aminoethyl-gamma and 2 ml of an aqueous layer was recovered in the trap. aminopropyltrimethoxysilane was mixed with the resin The residual clear solution contained 0.1 mole of ester suspension, tested on glass and found not to offer signifi in 100 g solution. cant improvement with respect to hydro C. 41.4 g of C7F15COOH, 20.0 g of trimethylortho phobicity/oleophobicity relative to an unmodified resin formate and 40.0 g of methanol were mixed in a flask. 45 coating. TABLE I Modification of a colloidal inorganic-based siloxane resin with perfluoroalkylester/ aminoorganosilane blend. (Liquid drop diameter given in millimeters) SUBSTRATE Percent modifier blend Glass Poly(methylmethacrylate) Polycarbonate (based on solids) H2O C16 C10 C7 H2O C16 C10 C, H2O C16 C10 C7 8 6 5 5 5 5 6 5 5 4. 6 5 5 5 2 5 4. 5 4 5 5 5 4. 5 5 5 5 0.4 4. 8 9 10 5 5 7 8 S One 5 8 0. S 5 S S S 5 7 10 S 2 percent lauarmide of 5 8 S S N-beta-aminoethyl-gamma aminopropyltrimethoxy silane S = the liquid spread C16 = hexadecane C10 = decane C = heptane

The reactants were refluxed for 4 hours. Analysis by 65 EXAMPLE 3 gas-liquid chromatography indicated about 83% methyl The perfluorinated acids C7F15COOH and ester formation and 17% residual acid. C9F19COOH, as well as the respective methyl esters, 4,617,057 11 12 were blended with Dow Corning Z-6020 (R), N-beta aminoethyl-gamma-aminopropyltrimethoxysilane in TABLE III Modification of a colloidal inorganic-based siloxane resin equimolar ratios, as in Example 2. These blends were with C7F15COOH and N-beta-aminoethyl-gamma-amino added to the colloidal inorganic-based siloxane resin propyltrimethoxysilane: Effect of order of mixing. suspension of Example 2 at levels of 1 and 2% based on (Liquid drop diameter given in millimeters). solids. A coating of each composition was applied to Order of glass, cured and tested, all in accordance with Example addition H2O Hexadecane Decane Heptane i-PA 2. Silane added to 5 5 7 8 12 Table II shows that, at these levels, the perfluoralkyl resin, then 10 CF15COOH acids and esters were essentially equivalent in imparting CF5COOH 5 12 hydrophobicity and oleophobicity to the modified resin added to resin, surface, with the composition containing 2% modifying then silane blend being slightly preferred. The last three columns C7F15COOH 6 O added to silane, represent measurements performed after immersion of then resin the coatings in room temperature water for a period of 15 1 hour and are an indication of relative permanence of i-PA = Isopropanol the surface modifications. Resin modified with only CgF19COOH (i.e., no Z-6020 (R)) was more easily EXAMPLE 5 leached by water and resulted in reduced permanence versus modification with the corresponding blend (i.e., 20 Toluene solutions (70% solids) of a room temperature with Z-6020 (R)). Moreover, even though the fluoroal vulcanizable block copolymer of (70 mole percent poly kyl acid-modified resin suspensions retained clarity, dimethylsiloxane with about 35 siloxy units per block, films of these compositions on glass retracted into "is and 30 mole percent phenyl silisesquioxane, endblocked lands' which prevented uniform coverage. This indi with methyldimethoxysiloxy units) were prepared ac cated that, without the aminoorganosilane component, 25 cording to methods essentially disclosed in Example 1 the fluoroalkyl acids were too incompatible with the of U.S. Pat. No. 4,508,887. The catalyst used to couple colloidal inorganic-based siloxane resin. As in Example poly(dimethylsiloxane) blocks to phenyl silisequioxane l, an amide was formed from the amino-silane and blocks was changed to a combination of 0.0026% iron lauric acid; this composition resulted in a hydrophobic, octoate and 0.018% concentrated hydrochloric acid, but not oleophobic, coating when the resin was modi 30 both weight percents based on total resin solids. These fied at a 2% level: block copolymer solutions were modified with 1% of TABLE I Modification of a colloidal inorganic-based siloxane resin with perfluoroalkylester/amino-silane and perfluoroalkyl acid/aminoorganosilane blends. (Liquid drop diameter given in millimeters). Perfluoro Compound Percent Initial Surface After soaking 1 hr. in H2O with amino-silane Added H2O Decane Heptane iPA H2O Heptane iPA C7 acid 2 5 5 5 6 5 8 8 C7 ester 2 5 5 5 6 5 8 9 C9 acid 2 4. 5 5 5 5 10 7 Cg ester 2 4. 5 6 6 5 12 10 C7 acid only (no silane) 7 6 8 10 6 S 12 Cg acid only (no silane) 5 6 8 7 6 S 12 C7 acid (with amino-silane) 6 6 7 7 5 S 11 C7 ester (with amino-silane) 6 6 7 8 5 S 11 C9 acid (with amino-silane) 5 6 6 6 6 10 8 C9 ester (with amino-silane) 5 7 10 7 5 S 9 S = spread i-Pa = Isopropanol the fluoroalkyl acid (or ester)/aminoorganosilane blends described in Example 3. The solutions were EXAMPLE 4 50 coated onto glass microscope slides and allowed to moisture cure in ambient air. The colloidal inorganic-based siloxane resin em Table IV compares water and hydrocarbon drop ployed in Examples 2 and 3 was mixed with diameters, as described in Example 2, of an unmodified C7F15COOH and N-beta-aminoethyl-gamma-amino control block copolymer surface with three modified propyltrimethoxysilane, the latter two components 55 films. While the control exhibited only a hydrophobic being maintained at a 1:1 molar ratio, as in Example 3. surface, all modified films were hydrophobic and oleo Order of mixing the ingredients was varied such that phobic. Furthermore, a significant improvement in ad the total modification level, based on resin solids, was hesion of the coatings to the glass slide was observed maintained at 2%. The modified resin blends were with the modified compositions. coated onto polycarbonate sheets and cured at 100 C. 60 for 30 minutes each. Table III summarizes drop diame TABLE IV Modification of a poly(dimethylsiloxane)-phenyi ter results for these blends, using the same formalism as silsesquioxane block copolymer with perfluoroalkyl acid/ in the previous two examples. It can be seen that results aminoorganosilane and perfluoroalkyl ester/aminoorgano are relatively insensitive to the order of mixing-resin, silane blends. (Liquid drop diameters given in millimeters). perfluorinated acid and N-beta-aminoethyl-gamma 65 Adhesion aminopropyltriemthoxysilane, although adding the % - Biend H2O C16 C10 C i-PA to Glass blend of the latter two components to the resin is pre None 5 10 O S S v. poor ferred. 1% silane/ 6 4. 4. 5 6 good 4,617,057 13 14 for use with water-borne nitrogen (melamine and urea) TABLE IV-continued resins. Modification of a poly(dimethylsiloxane)-phenyl silsesquioxane block copolymer with perfluoroalkyl acid/ Rhoplex (R) AC-604 is a thermosetting acrylic emul aminoorganosilane and perfluoroalkyl ester/aminoorgano sion, with self-contained crosslinker, a total solids con silane blends. (Liquid drop diameters given in millimeters). 5 tent of 46%, a pH (as packed) of 10.0 and a dry density Adhesion of 0.101 gals/1b. % - Blend H2O C16 C10 C7 i-PA to Glass Acrysol (R) WS-12 is a colloidal dispersion with a CoF9COOH total solids content of 30%, a pH (as packed) of 8.2, a 1% silane/ 5 5 6 6 8 excellent dry density of 0.103 gals/1b and is recommended for air CF15COOH O dry (as supplied) or baking finishes (crosslinked with 1% silane/ 4 6 6 7 8 good C7F15COOCH3 melamine resin). S = spread To each of the above mixtures of acrylic resins and Cl6 = hexadecane silane modified crosslinker, was added 2% (based on Clo - decane solids) of an equimolar blend (as in Example 3) of N C = heptane 15 beta-aminoethyl-gamma-aminopropyltrimethoxysilane i-PA = isopropanol (Z-6020 (R)) and CoF19COOH in the form of a 10% solution in methanol. These dispersions were coated EXAMPLE 6 onto polycarbonate sheets, cured for 2 hours at 80° C. This example is presented for comparison purposes 20 and tested for wettability as in the previous examples. only and is not within the scope of the instant invention. All films were optically clear. A one part, curable, soft, silicone rubber coating, The liquid drop diameter measurements, Table VI, suitable for application to high voltage insulators to indicate hydrophobic surfaces in these cases, but the prevent arc tracking thereof, consisting of a naphthol degree of oleophobicity obtained was somewhat less spirits dispersion (78% solids) of ketoxime-functional 25 than with the colloidal inorganic-based siloxane resin of polydimethylsiloxane fluid of a viscosity of about Example 2, when similarly modified. This offers further 10,000 cp, about 40% hydrated alumina and an evidence of the critical relationship between blend com organotin curing catalyst (0.25% dibutyl tin di-2-ethyl position, modification level and ultimate surface charac hexoate), was modified with equimolar blends of N ter. beta-aminoethyl-gamma-aminopropyltrimethoxysilane 30 TABLE VI and CoF19COOH, as in Example 3. Wettability of Modified Acrylic Polymers on When applied to glass slides, the silicone rubber coat Polycarbonate Substrate. ing containing 1% of the blend severely retracted, pro Diameter of drops (mm) ducing a "pock marked' surface of incompatible drop Acrylic hexa- hep- 2-B lets. Addition of only 0.05% of the blend did result in a 35 Polymer Modifier H2O decane decane tane Ethanol uniform cured film but no change in surface hydropho Siloxane silane/ 6 5 5 5 - resin CgFigCOOH bicity or oleophobicity was detected versus an unmodi of Ex. 2 fied control coating. These results are summarized in Rhoplex Z-6020 (R) + 7 6 8 9 S Table V. AC 868 C9F19COOH Rhoplex Z-6020 (R) -- 5 5 7 7 S TABLE V AC 604 C9F9COOH Modification of a soft silicone rubber coating Acrysol Z-6020 (R) + 5 7 8 10 S composition with a C9F19COOH/Aminoorganosilane WS-12 C9F19COOH blend. (Liquid drop diameters given in millimeters). S = spread Drop Diameter 45 % Blend H2O C16H34 C10H22 C7H14 EXAMPLE 8 One 5 9 O 2 0.05 5 9 9 12 Acroloid (RAT-51 (Rohm and Haas) is described as a 1.0 5 7 6 9 solvent-based thermosetting with a total "spotty; poor surface quality 50 solids content of 50% in a 78% xylene/22% butanol solution having a viscosity in the range of 1,070-2,265 cps. The resin has hydroxyl functionality and is de EXAMPLE 7 signed to cure via a self-contained melamine cross A silane-modified crosslinker was prepared by cold linker. This resin was diluted to 10% solids with blending 5 parts gamma-glycidoxypropyltrimethoxysi 55 CH3CH(OH)CH2OCH3(Dowanol (R) PM, Dow Chem lane (Dow Corning Z-6040 (R)) with 95 parts of a me ical Co., Midland, Michigan, U.S.A.) and 1% of an thylol-functional melamine resin (CYMEL(R) 370, equimolar blend of N-beta-aminoethyl-gamma-amino American Cyanamid, Wayne, New Jersey, U.S.A.) propyltrimethoxysilane and CoF19COOH was added according to U.S. Pat. No. 4,231,910. Thirty parts of thereto, as in Example 3. This mixture was coated onto this blend was mixed with 100 parts each, based on 60 polycarbonate and polymethylmethacrylate sheets, solids, of three commercially available (Rohm and Haas dried and cured for 2 hours at 80 C.; the resulting films Co.; Philadelphia, Pennsylvania, U.S.A) water disper were optically clear and had good adhesion to the poly sions of thermosetting acrylic resins which were predi carbonate substrate. luted to 10% solids. The resins employed in this exam The composition containing both fluoroalkyl acid ple are described as follows. Rhoplex (R) AC-868 is a 65 and aminoorganosilane provided excellent hydro thermosetting acrylic emulsion, without crosslinker, phobic/oleophobic surfaces (Table VII). A similar having a total solids content 50%, a pH (as packed) of composition, containing only the fluoroalkyl acid, was 8.8, a dry density of 0.1099 gals/1b and is recommended marginally hydrophobic (Table VII), and not ole 4,617,057 15 16 phobic, when a coating cured on polycarbonate sheet greatest repellency. The test is completely described in was tested. the Manual of AATCC, Volume 48 Edition 1972. Re sults of the water and oil repellency tests, summarized TABLE VII in Table VIII, indicate excellent oleophobicity was Wettability of Modified Acrylic Films 5 imparted to the fabric when the modified acrylic, ethy Film on Polycarbonate Substrate lene-vinyl acetate and styrene-butadiene latices were Adduct to AT-51 Diameter of drops (mm) used as treatments. Modified polyurethane latex did not 1% based Hexa- hep- 2-B result in improved water and oil repellency and is only on solids H2O decane decane tane Ethanol included in this example for comparison purposes. Silane/C9F9COOH 4.5 6 6 6 8 O C9F19COOH, no silane 7 2 S S re TABLE VIII Film on Poly(methyl Water, Alcohol and Oil Repellency of Polyester/ methacrylate) substrate Cotton Fabrics Treated with Modified Polymer Latices. Silane/C9F9COOH 6 6 7 7 9 Water Oil Repellency 2-B Ethanol S = spread Latex Repellency Rating Resistance 15 Polyurethane Fair 2 No (Spensol) EXAMPLE 9 Acrylic Poor 8 No (AC-235) An equimolar blend of C7F15COOH and N-beta EVA Good 8 No aminoethyl-gamma aminopropyltrimethoxysilane (as in (Elvace-1875) Example 3) was added to four commercial thermoplas 20 SBR Good 7 Yes tic organic polymer latices (6% level each, based on (DL-233) latex solids). The resulting mixtures were diluted with water to a total solids content of 15% and used to in pregnate (by dipping) 65/35 polyester/cotton fabric EXAMPLE 10 samples which were subsequently dried for 30 minutes 25 Two perfluoroalkyl acids were blended with gamma at 90° C. in an air oven. aminopropyl triethoxysilane and bis-trimethoxysilyl The polymer latices employed in this example are propyl-tetraethylenepentamine, the latter made accord described above and additionally as follows: ing to Example 2, U.S. Pat. No. 4,448,694. Each blend Spensol (R) is a thermoplastic polyurethane emulsion was diluted with water to a total solids content of 2%. supplied by spencer Kellog Division of Textron, Inc., 30 This dispersion was employed to treat 65 cotton/35 Buffalo, New York, U.S.A. polyester fabric by dipping. Treated samples were dried Acrylic latex Rhoplex (R) AC-235 is a thermoplastic for 5 minutes at 80 C. and the water, alcohol and oil acrylic copolymer emulsion produced by Rohm and repellency ratings were determined according to the Haas, Philadelphia, Pennsylvania, U.S.A. methods of Example 9. Good to excellent oil and water ELVACE (R)-1875 is an ethylene-vinyl acetate 35 repellency of the treated fabrics was obtained. (Table (EVA) copolymer latex produced by Reichhold Chem IX). icals, Inc., Dover, Delaware, U.S.A. It is described as a If the blends of Table IX are mixed with the acrylic, "high' ethylene content EVA copolymer water-based ethylene-vinylacetate and styrene-butadiene rubber emulsion having a solids content of 55%, pH of 4.5 and latices of Example 9 at about 6% based on latex solids, a density of 8.9 pounds/gallon. 40 and used to treat fabrics as described in Example 8, Styrene-butadiene (SB) DL233, manufactured by the similar improvements in oil repellency would ensue. TABLE IX Water, Alcohol and Oil Repellency of Cotton/Polyester Fabrics treated with Perfluoroalkyl acid/Aminoorganosilane Blends. Aminofunctional Perfluoro- Acid Water Oil Repellency 2-B Ethanol silane (1 mole) alkyl Acid Ant. Repellency Rating Repellency prehydrolyzed C7F15COOH mole yes 7 H2NCH2)3SiOEt)3 Silane A CgF19COOH 2 mols yes 8 yes Silane B C7F15COOH 2 mols yes 7 O Silane A is a bis-trimethoxysilylpropyl substituted tetraethylene pentamine. "Molar amount of perfluoroalkyl acid component per one mole of aminosilane in blend. Dow Chemical Co., Midland, Michigan, U.S.A., is a water-based carboxylated styrene-butadiene copolymer emulsion having a solids content of 50%, pH of 6.0, 55 That which is claimed is: particle size of 1600 to 1900 A and viscosity of less than 1. An oil and water repellent coating composition, 300 cps. comprising: The fabrics treated with the above-described latices (a) a resin, selected from the group consisting of colloi were evaluated with respect to water and alcohol (2-B dal inorganic-based siloxane resin, poly(dialkylsilox ethanol) repellency on a qualitative basis. This involved 60 ane)monoorgano substituted silisesquioxane block observation of relative absorption of each liquid by the copolymer, acrylic polymer and copolymer, ethy treated fabric samples. Additionally, oil repellency was lene-vinyl acetate latex and styrene-butadiene latex, determined according to the American Association of (b) an aminoorganosilane of the general formula Textile Chemists and Colorists (AATCC) Standard Test Method 118-1972. Briefly, this procedure ranks the oil repellency of textiles by determining which of a 65 Hi-R-R-OR)- series of hydrocarbon oils of increasing surface tension does not wet the fabric, a rating of 8 indicating the 4,617,057 17 18 wherein R is selected from the group consisting of 4. A composition in accordance with claim 3 wherein said perfluoroalkyl group, Rf has seven to nine carbon hydrogen, alkyl of one to four carbon atoms or atOS. 5. A composition in accordance with claim 1 wherein said perfluoroalkyl group, Rf, has seven to nine carbon R'OR)- atOnS. 6. A composition in accordance with claim 4 wherein said resin is a colloidal inorganic-based siloxane resin. R2 is an alkylene group of two to four carbon atoms, 7. A composition in accordance with claim 6 wherein R3 is hydrogen or alkyl of one to four carbon atoms, O said blend of perfluorinated organic compound and R“is an alkylene group of three to four carbon atoms, aminoorganosilane constitutes 1 to 3% by weight of R5 and R6 are alkyl groups of one to four carbon said resin. 8. A composition in accordance with claim 4 wherein atoms each, n is zero to four and m is zero or one; and said resin is a block copolymer of poly(dimethylsilox (c) a perfluorinated organic compound of the general 15 ane) and phenylsilsesquioxane. formula: 9. A composition in accordance with claim 8 wherein said resin is a block copolymer of about 70 mole percent poly(dimethylsiloxane) and about 30 mole percent phe nylsilsesquioxane which has been capped with methyl wherein Rf is a perfluoroalkyl group of four to 18 dimethoxysiloxy groups. 10. A composition in accordance with claim 9 carbon atoms and Y is selected from the group con wherein said blend of perfluorinated organic compound sisting of -COOH, -COOR, wherein R is alkyl, and aminoorganosilane constitute from 1% to 2% by alkoxyalkyl or hydroxyalkyl of one to eight carbon weight of said resin solids. atoms; 25 11. A composition in accordance with claim 4 wherein the combined amount of the aminoorganosi wherein, said resin is a thermosetting acrylic polymer or lane and the perfluorinated organic compound com copolymer. 12. A composition in accordance with claim 4 prises between about 0.1 and about 10 percent by wherein said resin is a thermoplastic acrylic polymer or weight of said resin and the molar ratio of the perfluo 30 copolymer. rinated organic compound to the sum of primary and 13. A composition in accordance with claim 4 secondary amine group(s) in the aminoorganosilane is wherein said resin is a thermoplastic ethylene-Vinyl fixed between about 0.33 and about 1.0. acetate copolymer latex. 2. A composition in accordance with claim.1 wherein 14. A composition in accordance with claim 4 said aminoorganosilane is N-beta-aminoethyl-gamma 35 wherein said resin is a thermoplastic styrene-butadiene copolymer latex. aminopropyltrimethoxysilane. 15. The method of applying the composition of claim 3. A composition in accordance with claim 2 wherein 1 to a solid or fabric substrate, whereby an oil and water said perfluoroalkyl group, Rf, has six to twelve carbon repellent surface coating is provided to said substrate. atoms. 40 s: 1

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