MXPA98002647A - Additives of fluorourethane for coating compositions dispersed in a - Google Patents

Abstract

Fluorourethane additives are described for water dispersible coating compositions comprising the reaction product of. (1) at least one diisocyanate, or polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula R10- (R2) k-YH, in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and in which R10 is a C1-C18 alkyl, a C1-C18 omega-alkenyl radical, or C1-C18 omega-alkenoyl; R2 is CnH2n- optionally crowned at the end with - [OCH2C (R4) H] p-, - [OCH2C (CH2Cl) H] p- or -C (R5) (R6) (OCH2C [CH2Cl] H) p-, where R4, R5 and R6 are the same or different , and they are H or a C 1 -C 6 alkyl radical, n is from 0 to 12, p is from 1 to 50, Y is O, S or N (R 7), wherein R 7 is H or C 1 -C 6 alkyl; and k is 0 or 1, and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate

Description

FLUOROURETHANE ADDITIVES FOR COATING COMPOSITIONS DISPERSED IN WATER FIELD OF THE INVENTION This invention relates to the substituted perfluoroalkyl diisocyanates or diisocyanates which are extended by partial reaction with water. Such compounds are used as additives for water dispersible coating compositions to reduce the swelling of wood substrates and to provide dirt resistance, oil repellency and improved cleaning ability for dry coating. This invention also relates to coating compositions containing such additives, and dry coatings formed from such coating compositions.

BACKGROUND OF THE INVENTION Water-dispersible coating compositions provide better advantages over solvent-based paints, such as non-flammability, solvent costs, and interest REF .: 26994 environmental on the evaporation of volatile organic compounds during the manufacture and application. Conventional water-dispersible, water-dispersible coating compositions use, as the binder or film-forming component, an emulsion, latex, or suspension of a resin, wax, or other film-forming material. For example, in conventional paints, a resin is used. Such resins are commonly formed of acrylic ester copolymers (acrylic emulsion or latex paints) or vinyl acetate, vinyl chloride, or vinyl butyral polymers or copolymers (vinyl emulsions or latex paints), although other film forming materials emulsi fied or suspended can be used. Such different formulations are well known to those skilled in the art. Paint emulsions are described by W. M. Morgans in "Outlines of Paints Technology". 3rd Edition, Halstead Press (John Wiley &Sons, Inc., New York NY, 1990). During application, the water evaporates, leaving a matrix of pigment and polymer particles interspersed with minor components. The coating is formed as particles attached to a continuous film incorporating the pigment. While such water dispersible coating compositions have good protective and decorative properties and can provide reasonable water repellency, they have little or no oil repellency. This lack of oil repellency can lead to the problem of dirt. In particular, such drying coatings show poor oil repellency in contact with angled measurements, dirt cleaning, and these have poor dirt resistance. Additionally, water dispersible coatings tend to cause swelling of wood substrates, potentially decreasing the quality of the dry finish. W093 / 17165 describes as soil release agents for textiles, the alkoxypolyoxyalkylene fluorocarbamates containing urea bonds, prepared by reacting a polyisocyanate, a fluorochemical reagent, a water-soluble hydrophilic reagent, and a reagent containing an active hydrogen group , and then extending further with water. There is no description of the use of these compounds as additives for water-dispersible coating compositions for hard surfaces. Kirchner, in U.S. Patent No. 5,414,111, discloses the compounds that contain polo fluoronitrogen, for example, formed by reacting an isocyanate trimer with fluorinated alcohols and then further spreading the reaction product with water. Such products are applied to fibrous substrates to impart water, oil, and dirt repellency and / or soil release properties for such substrates. There is no description of the use of these compounds as additives for water dispersible coating compositions to improve soil resistance and improve the improved cleaning ability. On the other hand, fluorinated surfactants are shown as rheology modifiers in paint films, but not as additives to improve soil resistance and cleaning ability for water dispersible coating compositions. Recently, it has been found that the cleaning ability of flat urethane finishes can be improved by applying a LUDOX coating (a colloidal silica label available from E. I. du Pont de Nemours and Company, Wilmington DE) to the dry surface. This approach has two shortcomings, 1) it is required that the surface be painted twice and 2) it is removed with dirt. It is preferred that the agent that improves the cleaning ability can be applied together with the paint and that it retains its effect after washing. It is highly desirable that it be capable of providing effective costs, durable dirt resistance and cleaning ability to water dispersible coating compositions by the addition of an aqueous emulsion of such an oil repellent additive to the conventional water dispersible coating.

BRIEF DESCRIPTION OF THE INVENTION The present invention comprises a polyfluorourethane compound which is the product of the reaction of: (1) at least one diisocyanate, (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate, (3) at least one compound of the formula Rio- (R2) k * -YH in an amount sufficient to react with 5% to 80% of the groups isocyanate in the diisocyanate, wherein Rio is a Ci-Cia alkyl, an Ci-Cis omega-alkenyl radical, or Ci-Ciß omega-alkenoyl radical; R2 is -CnH2n- optionally end-capped by - [OCH2C (R) H] p-, - [OCH2C (CH2C1) H] p-, or -C (R5) (R6) (OCH2C- [CH2C1] H] p- wherein R4, R5 and Re are the same or different and are H or an alkyl radical of Ci-Cß, n is 0 to 12, and p is 1 to 50; Y is O, S, or N (R7) wherein R7 is H or C6-C6 alkyl, and k is 0 or 1, and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate.The present invention further comprises a compound of polyfluoro-urethane which is the product of the reaction of: (1) at least one polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule, (2) at least one fluorochemical compound which contains minus one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 33% of the isocyanate groups in the polyisocyanate, (3) at least one compound of the formula Rio- (R2) k-YH in an amount of sufficient to react with 5% to 80% of the isocyanate groups in the polyisocyanate and wherein R10 is a Ci-Ciß alkyl, an omega-alkene radical of Ci-Ciß, or omega-alquenoi of i-Ciß; R2 is -CnH2n- optionally end-capped by - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p-, or -C (R5) (Re) (OCH2C [CH2C1] H] p - wherein R4, R5 and R6 are the same or different and are H or an alkyl radical of C? _6, n is 0 to 12, p is 1 to 50, and is O, S, or N (R7) wherein R7 is H or d-C6 alkyl, and k is 0 or 1, and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the polyisocyanate The present invention further comprises a composition of water-dispersible coating, improved, and the dry coating derived therefrom, comprising an emulsion, latex, or suspension of film-forming material dispersible in an aqueous medium, wherein the improvement comprises the incorporation into the aqueous medium of a compound of polyfluorourethane which is the product of the reaction of: (1) at least one diisocyanate, or polyisocyanate or a mixture of polyisocyanates containing at least three groups of isocyanate per molecule, (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least a compound of the formula R? o- (R2) k-YH in a sufficient quantity to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and wherein R10 is a Ci-Ciß alkyl, a omega-alkenyl radical of CL-C? s, or omega-alkenei of Ci-Cis; R2 is -CnH2n- optionally end-capped by - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p-, or -C (R5) (R6) - (OCH2C [CH2C1] H] p- wherein R4, R5 and e are the same or different and are H or an alkyl radical of C? -C6, n is 0 to 12, p is 1 to 50, Y is O, S, or N (R7), wherein R7 is H or C6-C6 alkyl, and k is 0 or 1, and optionally 4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate. The present invention further comprises both a method for reducing the swelling of a wood substrate when it is covered with the improved water dispersible coating composition and a method for improving the cleaning ability and oil repellency of a surface that has been deposited on the wood. same as a dry coating composition comprising the improved water dispersible coating composition described above.

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises polyfluorourethane compounds, water dispersible coating compositions containing polyfluorourethane compounds and dry coatings derived from such compositions. Such compounds are formulated as aqueous emulsions and are added to conventional water-dispersible coating compositions, such as paints and finishes, used on various substrates. For wood substrates the compounds reduce the swelling of the wood when they are coated with a water-dispersible coating composition. Dry coatings of such modified water-dispersible coating compositions provide dirt resistance, oil repellency and improved cleaning ability to substrate surfaces. The poly fluorourethane compounds (hereinafter "polyfluorourethane additives" or "polyurethane compounds") of the present invention are categorized based on the use of diisocyanate or polyisocyanate (hereinafter, the isocyanate reagent) as a reactant in its preparation as follows: 1) compounds prepared by reacting one or more diisocyanates (the isocyanate reagent), a fluorochemical compound containing one or more Zerewitinoff hydrogens (hereafter, the luorochemical reactant f) in an amount sufficient to make reacting with 5% to 80% of the isocyanate groups, a compound of the formula (Rio) - (R2) ~ YH (hereinafter, the non-fluorinated reagent), and optionally water; and 2) compounds prepared by reacting one or more polyisocyanates (the isocyanate reagent), a fluorochemical compound containing one or more Zerewitinoff hydrogens (fluorochemical reactant) in an amount sufficient to react with 5% to 33% of the isocyanate groups, a non-fluorinated reagent of the formula (Rio) - (R2) k-YH, and optionally water. The luorourethane polif additives used in the improved coating compositions and dry coating compositions of the present invention comprise both categories of the above luorourethane polyf compounds plus an additional group of compounds. This additional group comprises compounds prepared by reacting a polyisocyanate (the isocyanate reagent), a fluorochemical reagent in an amount sufficient to react with 5% to 80% of the isocyanate groups, a non-fluorinated reagent of the formula (Rio) - ( R2) k-YH, and optionally water. By the term "water-dispersible coating compositions", as used herein, means coating surfaces proposed for the decoration or protection of a substrate, essentially comprising an emulsion, latex, or suspension of a diesable film-forming material. in an aqueous phase, and optionally containing surfactants, protective colloids and thickeners,. pigments and pigments expanders, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents for pH control, binding aids, and other ingredients. Water-dispersible coating compositions are exemplified by, but not limited to, pigmented coatings such as latex paints, pigment-free coatings such as wood sealers, dyes, and finishes, coating compositions for masonry and cement, and asphalt based emulsions. in water For latex paints, the film-forming material is an acrylic acrylate latex polymer, 1-acrylic vinyl, vinyl, or a mixture thereof. Such water-dispersible coating compositions are described by C. R. Martens in "Emulsion and Water-Soluble Paints and Coatings" (Reinhold Publishing Corporation, New York NY, 1965). Conventional air-dried water-dispersible coating compositions are used, such as the binder or film-forming component, an emulsion comprising polymers or methyl methacrylate, butyl acrylate, and methacrylic acid in an aqueous solvent (available as RHOPLEX from Rohm & Haas Company, Philadelphia PA), vinyl acrylic, methacrylic, butylacrylate, and methacrylic acid (available as ROVACE 9100 from Rohm &Haas Company) or UCAR (available from Union Carbide, Danbury CT). The optional partial reaction of diisocyanates or polyisocyanates with water is referred to as "diisocyanate extension" and the reaction product is referred to as an "extended diisocyanate". Methods for extending the diisocyanates are well known in the art. As an example, Wagner in US Pat. No. 3,124,605 describes methods for extending 1-methybenzene-2,4-diisocyanate by reacting it with one-half the molar proportion of water to produce tri-N, N ' , N "- (3-isocyanato-4-methyl phenyl) biuret A" hydrogen Zerewitinoff "is an active hydrogen that will react with a methylmagnesium halide (Grignard reagent) to release methane.The reaction is quantifiable by the method of Zerewitinoff et al. al., wherein an organic compound containing an active hydrogen such as -OH, -COOH and the like, is reacted with a methylmagnesium halide to release methane.The volumetric measurement of methane allows a quantitative estimation of the active hydrogen content of the methane. The primary amines provide 1 mole of methane when they react in the cold, usually 2 moles when heated (Organic Chemistry by Paul Karrer, English Translation published by Elsevier, 1938, page 135). For the purposes of this invention, it is assumed that a primary amine provides an active hydrogen as defined by Zerewitinoff et al. A hydrogen Zerewitinoff reacts with isocyanate groups to form urethanes.

The dry water dispersible coating composition of the present invention comprises a coating composition containing at least one poly fluoromethane additive as defined above, which is allowed to dry for 7 days under normal environmental conditions of about 21 ° C. (70 ° F) and approximately 50% relative humidity. The polyfluorourethane additives of this invention are prepared from (1) an isocyanate reagent, (2) a fluorochemical reagent, (3) a non-fluorinated reagent and optionally (4) water. The poly fluorourethane additives are prepared in a suitable solvent, converted to an aqueous emulsion, and a mixture in a water dispersible coating composition in an amount sufficient to provide a dry coating containing from about 100 to about 20,000 μg / g. of fluorine. Dry coatings have increased their resistance to dirt, increasing oil repellency, and improved cleaning ability. The reagents and catalysts used to make the polyurethane compounds, the preparation and emulsification processes and the use and application of the polyurethane additives in water dispersible coating compositions are described sequentially in the following. Any diisocyanate or polyisocyanate having three or more isocyanate groups can be used as the main isocyanate reagent for the purposes of this invention. For example, one can use homopolymers of hexamethylene diisocyanate having the formula: wherein x is an integer equal to or greater than 1, preferably between 1 and 8. Due to its commercial availability, mixtures of such hexamethylene diisocyanate homopolymers are preferred for the purposes of this invention. Also of interest are the diisocyanate hydrocarbon trimers-isocyanurate derivatives which may be represented by the formula: wherein R p is a divalent hydrocarbon group, preferably aliphatic, alicyclic, aromatic or arylaliphatic. For example, R:? is hexamethylene, toluene or cyclohexylene, preferably the first. Other polyisocyanates useful for the purposes of this invention are those obtained by reacting three moles of toluene diisocyanate with 1,1-t-ris (hydroxymethyl) ethane or 1,1,1-tris- (hydroxymethyl) propane. The isocyanurate trimer of toluene diisocyanate and that of isocyanate of 3-isocyanatomethyl-3,4,4-trimethyl-cyclohexyl are other examples of polyisocyanates useful for the purposes of this invention, such as metin-tris- (phenylisocyanate). Also useful for the purposes of this invention is the polyisocyanate. which has the formula: Suitable, commercially available diisocyanates are exemplified by DESMODUR H (1,6-hexamethylene diisocyanate, HMDI) DESMODUR W (bis [4-isocyanatocyclohexyl] methane, PICM), MONDUR TD (a mixture of toluene diisocyanate isomers, specifically 2, -di socianato-1-metilbenzene and 1,3-diisocyanato-2-methylbenzene, TDI), MONDUR M (4,4'-diisocyanatodiphenylmethane, MDI), and isophorone diisocyanate (5-isocyanato-l- (isocianatomet il) -1 , 3, 3-trimethylcyclohexane, IPDI) each available from Aldrich Chemical Co. Milwaukee Wl. Suitable preformed, commercially available diisocyanates are exemplified by DESMODUR 3200 and DESMODUR N-100 (hexamethylene diisocyanate homopolymers) available from Bayer Corporation, Pittsburgh PA, both probably prepared by the process described in U.S. Patent No. 3,124,605 for provide mixtures of mono-, bis-, tetra-, and derivatives of higher order. Also suitable is DESMODUR 3300 (a trimer of hexamethylene derived from isocyanurate), and CYTHANE 3160 (an glycerol based on isocyanate) available from American Cyanamid, Stanford CT. The typical properties of such compounds are as follows: Properties Equivalent weight Content in% Typical average of NCO DESMODUR N-100 191 22.0 DESMODUR N-3200 181 23.2 The typical NCO content of Desmodur N-100 is close to that registered for an International Report of SRI (Isocyanates ID No., July 1983, Page 279) homopolymers of hexamethylene diisocyanate with the following composition: Product Composition% by weight Hexamethylene diisocyanate 0 .1 Monobiuret 44 .5 Bisbiuret 17 .4 Trisbiuret 9, .5 Tetrabiuret 5. .4 Derivatives of higher molecular weight 23. .1 Content of NCO 21., 8 Based on their equivalent average weight and NCO content, the comparatives bis, tris, tetra, etc., content of DESMODUR N-3200 must be less than that of product N-100. DESMODUR N-3300 is an isocyanurate trimer derived from hexamethylene diisocyanate of the formula wherein Ri2 is hexamethylene. A wide variety of fluorochemical compounds can be used as the second or luorochemical reactant as large as each luorochemical compound containing at least two carbon atoms and each carbon atom contains at least two fluorine atoms. For example, the fluorochemical compound can be represented by the formula: wherein Rf is a monovalent aliphatic group containing at least two carbon atoms, each of which contains at least two fluorine atoms; R is a divalent organic radical; k e s 0 or 1; and X is -O-, -S-, or -N (R:) -, in which Ri is H, an alkyl group containing 1 to 6 carbon atoms or a group Rf-Rk. In a more specific embodiment, the luorochemical compound f that contains an individual functional group that can be represented by the formula Rf-Rk-R2-X-H where Rf and k are as defined in the above; R is a divalent radical: -CmH2mSO-, "C H2mS02" '-S ° 2N (R3) "' S ° 2N (R3) - '° -O0N (R3), wherein m is 1 to 22 and R3 is H or a divalent alkyl group of 1 to 6 carbon atoms, R2 is a linear divalent hydrocarbon radical, -CnH2n-, which is optionally crowned at the end with R4 CH C1 I I (OCH2CH) p-, - (OCH2CH) p-,! -C- (OCH2CH) p- I I Rg CK2C1 wherein n is 0 to 12, p is 1 to 50; R4, R5 and R6 are the same or different and are H or an alkyl group containing from 1 to 6 carbon atoms: X is O, S, or N (R7) is H, an alkyl group containing 1 to 6 atoms of carbon, or a group Rf-Rk-R2-. More particularly, Rf is a fully fluorinated linear or branched aliphatic radical of 3 to 20 carbon atoms, which can be interrupted by an oxygen atom. In a preferred embodiment, the luorochemical compound f can be represented by the formula: Rf- (CH2) q-X-H wherein X is O, S, or N (R7), wherein R7 is H, an alkyl group containing 1 to 6 carbon atoms, or a group RE-Rk-R2-, f is a mixture of groups perfluoroalkyl, CF3CF2 (CF;) r wherein r is 2 to 18; and q is 1, 2 or 3. In a more particular embodiment, Rf is a mixture of the perfluoroalkyl groups, CF3CF2 (CF2) r; and r is 2, 4, 6, 8, 10, 12, 14, 16 and 18. In a preferred embodiment, r is predominantly 4, 6 and 8. In another preferred embodiment, r is predominantly 6 and 8. The first preferred embodiment it is commercially available more easily and for the next less expensive, while the latter can provide improved properties. Representative fluoroaliphatic alcohols that can be used for the purposes of this invention are: CSF (2s +?) (CH2) t-OH, (CF3) 2CFO (CF2CF2) uCH2CH20H, CsF (2s +?) CON (R?) - (CH2) t-OH, CsF (2s +?) S02N (R8 ) - (CH2) t-OH and R9 CsF (2s + 1) S02N (Rβ) -C (OCH 2 CH-) OH I R 9 (CH 2 C 1) V wherein s is 3 to 14; t is 1 to 12; u is 1 to 5; each of R8 and R9 is H or an alkyl group containing from 1 to 6 carbon atoms. In another embodiment, the fluorochemical compound can be represented by the formula: H (CF2CF2) wCH2OH, where w is 1-10. The last luorochemical compound f is prepared by reacting tetrafluoroethylene with methanol. Providing yet another compound such as 1, 1, 1, 2, 2, 2-hexaf luorosispropanol having the formula: CF3 (CF3) CHOH.

Suitable fluorinated alcohols of the second reactant with the structure RfCH2CH2 HH where Rf is a C2-C20 perfluorocarbon is exemplified by, but not limited to, perfluoroalkyl ethanols commercially available as ZONYL BA and BA-N Fluorotelomer Intermediate from EI Du. Pont de Nemours and Company, Wilmington DE. The ZONYL BA and the BA-N contain alpha-f luoro-omega- (2-hydroxyethyl) - poly (difluoromet ilene) in the form of a mixture of the compounds of the series of homologs of the formula F (CF2CF2) n (CF2CF2) OH, contained in this one for n = 2, BA contains 1 ° or -2%, BA-N contains < 1% for n = 3, BA contains 27% - 34%, BA-N contains 3% - 8% for n = 4, BA contxene 29% - 34%, BA-N contains 45% - 50% for n = 5 , BA contains 17% - 21%, BA-N c has 28% - 33% for n = 6, BA contains 6% - 9%, BA-N contains 8% - 13% for n = 7, BA contains 2% - 5%, BA-N contains 1% - 6% for n = 8, BA contains 1% - 2%, BA-N contains 1% - 8% Suitable fluorinated thiols of the structure RfCH2CH2SH wherein Rf is a C2.C20 perfluorocarbon of the second reagent, is exemplified by LODYNE 924, commercially available from Ciba-Geigy, Ardsley NY. Suitable fluorinated sulfonamides of the structure RfS02N (CH2CH3) CH2CH2OH, wherein Rf is a perfluoro group of C2 to C20, is exemplified by FLUORAD FC-10 available from 3M Company, Minneapolis MN.

In another embodiment, the water-modified phuuorochemical carbamates can be prepared by the sequential catalytic reaction of DESMODUR N-100, DESMODUR N-3200, or DESMODUR N-3300, (homopolymers of hexamet and lendi isocyanate available from Bayer Corporation, Pittsburgh, PA) or mixtures thereof, with a stoichiometric deficiency of a perfluoroalkyl compound containing a functional group, then with a fluorinated reagent as described in the following, and then with water. The third or non-fluorinated reagent used to prepare the polyfluoro compounds of the present invention and the polyurethane additives used in the coating of the present invention comprise a non-fluorinated organic compound containing an individual functional group. Usually between about 1% to about 60% of the isocyanate groups of the polyisocyanate are reacted with at least one of such non-fluorinated compound. For example, said non-fluorinated compound can be represented by the formula: (R? O) - (R2) k-YH wherein Rio is an alkyl group of C.-C? 8, an omega-alkenyl radical of Ci-Ciß, or an omega-alkenoyl of C? -C18; R2 is a divalent linear hydrocarbon radical, -CnH2n-, which is optionally end-capped by R4 CH2C1! I - (OCH2CH) p-, -. { OCH2CH) p-, O I -C- (OCH2CH) p- R? CH2C1 wherein R4, R5 and R6 are the same or different and are H or an alkyl group of 1 to 6 carbon atoms; n is 0 to 12, and p is 1 to 50; Y is 0, S, or N (R7), in which R7 is H, or an alkyl group containing 1 to 6 carbon atoms, and k is 0 or 1. For example, the non-fluorinated compound may be an alkanol or a monoalkyl or ether or monoalkenyl ester of a polyoxyalkylene glycol. Particular examples of such compounds include stearic alcohol, monomethyl ether or polyoxyethylene glycol, polyalkylene glycol monoallyl or methalyl ether, and monometacrylic or polyoxyethylene glycol acrylic acid ester. In one embodiment, the polyfluoro-urethane additives used in the coatings of the invention are prepared by reacting: (1) at least one diisocyanate, or polyisocyanate or mixtures of polyisocyanates containing at least three isocyanate groups per molecule with (2) ) at least one fluorochemical compound containing per molecule (a) a single functional group having one or more hydrogen atoms Zerewitinoff and (b) at least two carbon atoms each of which contain at least two carbon atoms fluorine; and (3) at least one non-fluorinated reagent as described above. After that, the remaining isocyanate groups can optionally be reacted with water to form one or more urea linkages or can be reacted completely with the second and d reagents previously described to form urea, carabamate, or carbamate linkages. Usually between about 40% and about 95% of the isocyanate groups will have to be reacted before the water optionally reacts with the diisocyanate or polyisocyanate. In other words, the amount of water is generally sufficient to react with from about 5% to about 60% of the isocyanate groups in the diisocyanate or polyisocyanate. Preferably, between about 60% and 95% of the isocyanate groups have been reacted before the water optionally reacts with the diisocyanate or polyisocyanate, and more preferably between about 80% and 30% of the isocyanate groups that have been made react before the water reaction. Thus, in a preferred embodiment, the amount of water is sufficient to react with about 5% to about 35% of the isocyanate groups, most preferably between 10% and 20%. The preparation of the polyfluoro-urethane additive is exemplified by reacting, in the presence of a catalyst, a polyalkylene glycol terminated in alkyl, a fluoroalcohol or fluorol, and optionally an alcohol, l, or amine, with a diisocyanate or a diisocyanate extended in a suitable solvent such as a solution of met i lisobut i lcetona. Suitable catalysts are well known to those skilled in the art. For example, the catalyst is an organic metal used by dibutyltin dilaurate or tin octoate, or a tertiary amine, exemplified by trialkylamines, pyridine, ethylmorpholine, 1,4-diazabicyclo [2.2.2] -octane (DABCO, Aldrich Chemical Co., Milwaukee Wl) or 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, Aldrich Chemical Co., Milwaukee Wl). In addition, the reaction product is optionally reacted with water to give a polyurethane in methyl isobutyl ketone. The polyurethane in met ilisobutyl ketone is emulsified in water. In most cases, emulsification occurs easily with mixing. Emulsification is optionally facilitated by the use of homogenization equipment and the use of anionic (eg, alkylsulfonates) or nonionic surfactants (eg, alcohol ethoxylates or alkylphenol ethoxylates) chosen for compatibility with the dispersible coating composition in Water. The solvent of methyl isobutyl ketone is removed under reduced pressure to leave an aqueous dispersion. The dispersion is also added to an existing and completely mixed water dispersible coating composition. The modified results of the water dispersible coating composition is applied by standard means. Suitable solvents for the reaction are exemplified by ketones such as methylisobutyl ketone, methylamone, methyl ethyl ketone, esters such as ethyl acetate and aromatic solvents such as toluene or xylene. Water-modified fluorochemical carbamates are typically prepared by first charging the diisocyanate or polyisocyanate, the perfluoroalkyl compound, and a dry organic solvent such as methyl isobutyl ketone into a reaction vessel. The order of the addition of the reagent is not critical. The specific weight of the aliphatic diisocyanate or polyisocyanate, and the charge of the perfluoroalkyl compounds is based on their weight equivalency and on the working capacity of the reaction vessel and is adjusted so that all Zerewitinoff active hydrogens of the d reactant charged will react with some desired value between 40% and 100% of the total load of the NCO group. The weight of the dry solvent is typically 15% -30% of the total weight charge. The charge is stirred under nitrogen and heated to 40-70 ° C. A catalyst, typically dibutyltin dilaurate per se, or as a solution in methyl butyl ketone, is added in a charge-dependent amount, but is usually less, for example, 1 to 2 parts per 10,000 parts of the diisocyanate or polyisocyanate. After the resulting exothermic reaction, the mixture is stirred at a temperature between 65 and 105 ° C for 0-20 hours from the time of the catalytic addition, and then, after its temperature is adjusted between 55 and 90 ° C, it is treated with water per se or with wet methyl isobutyl ketone for 1 to 20 additional hours. The resulting product is stored and / or used as prepared or after dilution of the additional solvent, or converted by standard technology to an emulsion or dispersion. In some cases, the emulsion or dispersion is stabilized with surfactants; in others, a stable emulsion or dispersion can be prepared without the use of a surfactant. Emulsions of polyfluoro-urethane additives are formed by sequentially reacting the isocyanate, fluorinated, and non-fluorinated reagents, further extending the reaction product by reaction with water, and finally preparing an aqueous emulsion by adding water, optionally emulsions. auxiliaries, and eliminating the residual organic solvents. The polyurethane additives in the form of an aqueous emulsion can be easily incorporated into conventional water-dispersible coating compositions in concentrations sufficient to give a dry coating containing from about 100 to 20,000 μg / g of fluorine and preferably of about 500 to 2,000 μg / g of fluorine. For a typical latex paint containing from about 45% to 60% solids in the liquid paint, the polyfluorourethane additives of this invention are incorporated in the coating compositions in an amount sufficient to give a coating composition containing approximately 50 to 10,000 μg / g of fluorine and preferably about 250 to 1,000 μg / g of fluorine. For other coatings such as wood stains, masonry coatings, asphalt emulsions and similar compositions, the polyfluorourethane additives of this invention are incorporated in an amount sufficient to provide a coating composition containing from about 50 to about 10,000 μg / g of fluorine. The aggregate amount is adjusted taking into account the solids percent of the coating composition. The weight units of an aqueous emulsion of polyfluoroethane additives required to be added to each 100 weight units of the water dispersible coating composition, such that the resulting coating composition will dry a film containing fluorine F μg / g is provided by: 100FS / C (104f-F) where f is the percent of fluorine in the additives of poly fluorourethane, S is the percent of solids (non-volatile) in the original water dispersible coating composition, and C is the percent concentration of the polyf luorourethane additives in the aggregate emulsion. The water-dispersible coating composition containing the polyfluoro-urethane additives is stirred to provide a homogeneous mixture. The addition of the dispersion of the polyf luorourethane additives is made for a preformulated coating composition at the point of sale or use, but is preferably made at the time of manufacture of the water dispersible coating composition, when the processes of appropriate quality control will be available more easily. The application and drying properties of the water-dispersible coating compositions are not essentially affected by the addition of the polyfluorourethane additives. Alternatively, it is understood that the formulation of the refining composition can be modified when the polyfluorourethane additives are added. While the invention has been described with respect to certain specific embodiments, it will be appreciated that many modifications and changes may be made by those skilled in the art without departing from the invention. The present invention comprises aqueous emulsions of polyfluorourethane additives for water dispersible coating compositions which improve oil repellency, dirt resistance, and cleaning ability of the dry coating formed of such water dispersible coating compositions, when compared to control coatings without such additive. A dry coating can improve oil repellency when the advance and retreat of the hexadecane contact angles on the dry solution containing the compound or additive, measured according to Test Method 1, are greater than the contact angles of the hexadecane. hexadecane on the control coating without the compound or additive. A dry coating has better resistance to dirt when the mark produced by the bar in the process described later "Preparing the Dirty Sample" (Test Method 2 - Scouring Test Paint) before debugging is visually less than the mark corresponding to the control coating without the poly-fluorourethane additive. A dry coating has improved cleaning ability when the percentage of dirt removal from the dry coating containing the compound or additive, after debugging according to Test Method 2 and evaluation according to Test Method 3, is greater than the corresponding percentage of removal of dirt for the control coating without the compound or additive. The cleanliness test of the bar gives cleaning performance results that can be correlated with similar tests using other oily soils, including carbon black dispersible in a mineral oil and a source of tomato sauce.

PREPARATION OF THE SAMPLE The compound or additive is added to the weight percent indicated in the test data table of the water dispersible coating composition and mixed thoroughly with a paint stick. The paint is applied to a Mylar sheet (finished with a depression) at 0.15 mm (6 mil) wet thickness and 15 cm (6 inches) in width, or to a debug panel Model P121-10N. from Leneta Corporation, Mahwah NJ to 0.076 mm (3 mil) wet thickness, and allowed to dry for 7 days at room temperature and humidity (approximately 21 ° C (70 ° F) and 50% relative humidity). After drying, the water and the hexadecane contact angle measurements are made as in Test Method 1, the paint film sample is soiled and scrubbed as described in Test Method 2, and the capacity Cleaning is evaluated as described in Test Method 3.

TEST METHOD 1 CONTACT ANGLE MEASURE The contact angles are measured by the Sessile Drip Method which is fully described in A. W. Adamson, "the Physical Chemistry of Surfaces", fifth edition, Wiley & Sons, New York NY, 1990, Chapter II, incorporated herein by reference. Additional information on the need for equipment and procedure for measuring these contact angles is described more fully by RH Dettre and RE Johnson, Jr., in "Wettability," Edited by JC Berg, Mercel Dekker, New York NY, 1993, Chapter 1, which is incorporated herein by reference. A Ramé-Hart optical platform is used to hold the substrate in the horizontal position. The contact angle is measured with a telescope gionometer of the same manufacturer. A drop of this test liquid is placed on a surface and the tangent is precisely determined at the point of contact between the drop and the surface. An advance angle is determined to increase the size of the drop of the liquid and an angle of recoil is determined by the decrease in the size of the liquid drop. The data is typically presented as the advance and retreat of the contact angles. Hysteresis is the difference between the two angles. The relationship between water and organic liquid, contact angles and cleaning capacity and dirt retention is described in chapters XII and XIII of A. W. Adamson above. In general, the height, the contact angle, the dirtiest or the surface resistant to dirt and the ease of the surface, is to clean.

METHOD OF TEST 2 - PROOF OF PURIFICATION OF PAINTING Preparation of the Dirty Sample 2. 54 cm (one inch) are cut from each end of 10 by 43 cm (4 by 17 inches) of paint depression on a Leneta Scouring Test Panel, model number P121-10N (Available from Leneta Company, Mahwah NJ ), which was cured for 7 days under normal environmental conditions. Afterwards, increments of 5 cm (2 inches) and a blue bar mark (Crayola Co. Easton PA) applied in the area of 5 cm (2 inches) are marked using the following procedures to standardize the application. A wax pencil is flattened a little by rubbing on a piece of a piece of paper. The bar is placed in a 12-inch (30.5 cm) length of a 1.27 cm (1/2 inch) stainless steel rod, tilted at a 90 degree angle to provide an "L" shape with one end of 2.54 cm (one inch). A frame-lab connector is attached to the 2.54 cm (1 inch) section to hold the bar at a 45 ° angle to the surface. The inclination of the bar is held at the opposite end of the bar assembly, allowing the weight of the device to provide uniform force on the bar tip. The tip of the bar is rubbed back and forth 50 times to form a uniform mark on the paint. Typically this holder will deposit 100 g of force (0.98 N) on the surface. The articles are trimmed and tested on a debugging machine. The bar and connector are available from VWR Co. (South Plainfield NJ) as Catalog # 60079-533 and 60097-055 respectively.

Preparation of the Debugging Machine The composition of a 1% aqueous detergent solution of TIDE (Proctor and Gamble Co., Cincinnati OH) to be used for cleaning experiments. Using 0.45 kg (1 Ib) of a Gardner abrasive can (WA-1251, Paul N. Gardner Co., Pompano B FL), a skein of 22.9 cm (9 inches) of double gauze width (Grade 20B, Deroyal Textiles, Camden SC) is bent three times to form a 6.3 cm (2.5 in) wide cushion, this is firmly attached to the abrasive canister and 20 ml of the TIDE solution is applied. The canister is placed in the debugging machine (Gardner DV-10, Paul N. Gardner Co., Pompano Beach FL) and the example is. debugged by the number of debugging times indicated in the data table. A new piece of gauze is used for each test. The test article is engraved using transparent adhesive tape (for example, SCOTCH MAGIC TAPE from 3M Commercial Office Supply Division, St. Paul MN), to the middle of the debugging board so that approximately 1/2 of the marked surface will be cleaned by the machine. The board must be dry before it is recorded. After debugging, the item is removed, rinsed with water and air dried. The withdrawn amount is assessed visually or by using a reflectance meter as described in Test Method 3, as compared to the unpurified side.

METHOD OF TEST EVALUATION OF THE SAMPLES DECIDED DIRTY A value of -1 indicates that the mark is smeared and darkened. A value of 0 r.o indicates changes. The values from 1 to 10 indicate 10% to 100% respectively of the dirt that has been removed. The numerical evaluation shown in Table 1 is used: Table 1 Evaluation Criteria for Dirt Resistance and Cleaning Capacity # of Valuation Amount Withdrawn -1 0 0 0 1 10 2 20 3 30 4 40 5 50 6 60 7 70 8 80 9 90 10 95 + For a more quantitative evaluation of the purification panel, after the required number of cs, the panel is removed, rinsed under a water tap, and air dried. A cleaning capacity scale is created by measuring the reflectance, using an ae reflectance meter, of an unwashed dirt area, and assigning a cleaning capacity value of zero. The reflectance of an area without dirt is measured and a cleaning capacity value of 10 is assigned. The interval between these reflectance values is divided into ten equal intervals to create the scale of cleaning capacity values. The Munsell neutral value scale is used to assist in the assignment of cleaning capacity values if a reflectance meter is not available. If the reflectance is measured, a scale can be constructed as shown in the following for a painting that exhibits a maximum reflectance measured for the 80% dirt free area and the minimum reflectance measured for the dirty area of 20%.

Table 2 Scale of Cleaning Capacity Values It is wing of Capacity% Reflectance Cleaning 10 80 (Maximum 9 74 8 68 7 62 6 56 5 50 4 44 3 38 2 32 1 26 0 20 (Minimum) A dry coating is estimated to have an improved dirt resistance when the color intensity on the dry coating containing the polyfluorourethane additive, after fouling as in Test Method 2 and before debugging, and less than the intensity corresponding color on the control coating without the compound or the additive. The test is always run with a control (untreated paint) to compare the dirt resistance of the paint with and without the compound or polyfluorourethane additive. A dry coating is estimated to have an improved cleaning capacity when the Number of Values for the dry coating containing the polyfluorourethane additive, after debugging according to Test Method 2 and evaluation according to the Method of Test 3, is greater than the corresponding Number of Values for coating control without the polyfluorourethane additive. The test is always run with a control (untreated paint) to compare the cleaning capacity of the paint with and without the polyfluorourethane additive.

TEST METHOD 4 - SWELLING OF WOODEN SUBSTRATES The swelling of wooden substrates due to the application of the water-dispersible coating compositions is measured using the Swelling Meter instrument and the method described in ASTN-D-4446.

The polyurethane compounds of the present invention are useful as additives for water dispersible coating compositions to reduce swelling of wood substrates in applications of water dispersible coating compositions, and to provide dirt resistance, oil repellency and improved cleaning capacity to the dry coating. The coating compositions of the present invention containing such additives and the dry coatings of the present invention formed therein are useful for coating various substrates such as walls, furniture, woods, masonry coatings, cement, asphalt and other surfaces to which Paints, sealers, colors, finishes and emulsions are applied. The coating compositions are particularly useful on surfaces where dirt resistance and ease of cleaning are desired.

EXAMPLES Example 1 Preparation of the Polyfluorourethane Additive with MPEG-350 In a 1000 ml round-bottomed flask fitted with a mechanical stirrer, condenser and nitrogen inlet, and heated with a controlled heating blanket, place 256 g of N-163D (a 60% solution of methylisobutyl il-ketone from DESMODUR N). -100, from Bayer Corporation, Pittsburgh PA), 42 g of ZONYL BA Fluorotelomer Intermediate (from EI du Pont de Nemours and Company, Wilmington DE), and 235 g of MPEG-350 (from Union Carbide Company, Danbury CT). The contents were heated to 55 ° C. A solution of 20 g of methylisobutyl-ketone containing 0.040 g of dibutyltin dilaurate is added and the exothermic reaction is increased to the temperature of 90 ° C for a period of 20 minutes after the heating time is applied to maintain the container temperature at 90 ° C for additional 3 hours.

After maintaining 3 hours, the organic reaction mass is added for a period of half an hour to a different 2-liter shaker (150 rpm) containing 40 g of water and 100 g of methylisobutyl-ketone, and maintained at 75 ° C for 2 hours after the addition is complete. The agitator is disconnected and 600 g of water are added at 75 ° C for a period of 30 minutes. The mixture is stirred for 1 hour after a heated distillation, a condenser and a high vacuum were attached and a vacuum applied to remove the methyl isobutyl ketone / water azeotrope at a temperature of about 55 ° C and a pressure of 13 Kpa. The flask is allowed to cool to 50 ° C and then maintained at that temperature at 13 Kpa until the vessel material has an instantaneous flash point or flash point above 93 ° C (200 ° F). The distillation vessel contains 914 g of the solution having 44.5% solids. This solution is diluted with 33% solids with water and added to the water dispersible coating composition in an amount to produce the desired weight percent of the additive in the treated coating, as indicated in Table 4, typically 2. % and 5%. The coating composition is completely mixed by stirring. Ours of depression were prepared, soiled, purified and evaluated by Test Methods 2 and 3 with the results shown in Table 4. The contact angles were measured according to Test Method 1, the results are shown in the Table 3 Table 3 Contact Angle Measurements for Example 1 Contact Angle Hexadecane water Mués ra Advance Recoil Advance Recoil Reagent control without additive of polyfluoroure ano 71 Coating containing polyfluoro-urethane additive of Example 1 16 74 46 Table 4 Measurements of Cleaning Capacity and Dirt Repellency The depressions are prepared using commercially available coating compositions prepared with the 33% solids solution of the polyfluoro-urethane additive prepared as in Example 1. The commercial paints are designated by the letters A to V.

A B How do you 2% of 5% of How do you get 2% of 5% of Acquire Adi tívo Adit vo Acquire Adit vo Additive Purification Cycles 0 0 (depending on how dirty it is) 25 10 10 50 10 10 10 100 4 5 10 9 10 10 200 7 7 10 10 10 10 D How do you get 2% of 5% How do you get 2% of 5% of Adquire Adit i vo Adit ívo Ad uie re Additive Additive Purification cycles 0 (depending on how dirty it is) 0 0 0 0 0 7 9 7 10 50 9 10 9 10 10 100 10 10 10 10 10 200 LO 10 10 10 10 As 2 ': 5% ionium is 2% of 5 -i of Ad u: o re Adi tive Adi ti o Adqu i e re Adi i o Adi t ivo : those of Purified as it is dirty; 0 0 0 0 0 0 7 10 3 6 9 50 3 9 10 5 9 10 100 10 10 10 3 10 10 200 10 10 10 10 10 10 H How is 2% of 5% of How is 2% of 5% of Acquire Additive Additive Additive Additive Cleaning cycles 0 (depending on how dirty it is): 1 0 0 0 0 0 0 3 5 8 5 9 8 50 7 9 10 9 10 10 100 10 10 10 10 10 10 200 10 10 10 10 10 10 J How is 2% of 5% of How is 2% of 5% of Adqui e re Adi ti o or Adit ivo Acquire Adi t ive Adi ti ti o Purification cycles 0 (depending on how dirty it is) 0 0 0 0 0 5 7 2 9 50 9 8 5 9 10 100 10 10 9 10 10 200 10 10 10 10 10 K As 2 of 5 1 of As 2% of 54 of Additive Additive Adqu e e Adi i o Adi t ívo Purification cycles 0 (depending on how dirty it is: 0 0 0 0 2 9 1 9 50 4 10 5 10 100 10 9 10 200 10 10 10 10 M N As 2% of 5% of As 2% of 5% of Acquires Additive Additive Acquires Additive Additive Purification cycles 0 (depending on how dirty it is) 0 0 0 0 0 0 2 4 10 1 2 7 50 9 9 10 5 7 9 100 10 10 10 8 9 10 200 10 10 10 9 10 10 O As 2% of 5% of As 2% of 5% of Acquires Adi t ívo Adit i vo Acquires Adit vo Additive Purification cycles 0 (depending on how dirty it is) 0 0 0 0 0 2 9 9 8 9 50 7 10 10 9 9 9 100 9 10 10 10 10 10 200 10 10 10 10 10 10 How is 2% of 5% Purchase Adi tio Adi ti o Purification Cycles 0 (depending on gets dirty) 0 0 0 25 0 1 8 50 3 3 9 100 5 7 10 200 7 9 10 R As 21 of 5% of As is 2% of 5% of Acquires Ad; Additive Acquires Additive Additive Purification Cycles 0 (depending on how dirty it is)) 00 0 0 0 0 0 9 10 10 8 8 8 50 10 10 10 9 9 9 100 10 10 10 10 10 10 200 10 10 10 10 10 10 U Co o se 2% de 5% de Como se 2% de 5% de Adquie re Adi tivo Adi tivo Adquie re Adi t tivo Adi tivo Purification cycles 0 (depending on how dirty it is) 0 0 0 0 0 0 6 6 9 2 1 7 50 9 9 10 6 8 9 100 10 10 10 9 10 10 200 10 10 10 10 10 10 V How do I get 2% of 5 of Adquire re Adiivoative Adiivore Purification Cycles 0 (as it gets dirty ) 25 50 9 10 100 10 10 200 10 10 10 Example 2 Preparation of the Polyfluorourethane Additive with MPEG-750 In a 1000 ml round-bottomed flask fitted with a mechanical stirrer, condenser and nitrogen inlet, and heated with a controlled heating blanket, 65 g of A-147 (a 60% solution of methylisobutyl ketone) of DESMODUR is placed. N-100, from Bayer Corporation, Pittsburgh PA) and 200 g of methylisobutyl ilketone. The flask is heated to increase the temperature of the contents at 80 ° C, when 10 g of ZONYL BA Fluorotelomer Intermediate (from EI du Pont de Nemours and Company, Wilmington DE), 120 g of polyethylene glycol monomethether having a molecular weight average of 750, MPEG-750 available from Union Carbide, Danbury CT and 0.05 g of dibutyltin dilaurate are added. The contents were stirred for 2 hours at 80 ° C. Then 1 g of water is added and the heating is continued for an additional 2 hours. The organic solution is then added to 400 g of water and mixed in a Silverson mixer for 30 seconds. The resulting emulsion is distilled with solvent at approximately 50 ° C and pressure of 13 Kpa to leave 412 g of a clear fluid dispersion. Six percent by weight of this solution is added to a formulated white latex paint (Rohm &Haas, Philadelphia PA) to give 1000 μg / g of fluorine in the improved latex paint. A film of 5 thousand paint applied to an MYLAR film (polyester film, E. I. du Pont de Nemours and Company, Wilmington DE) and dried with air at ambient conditions for 24 hours. The dried film contains approximately 2,000 μg / g of fluorine.

Example 3 Preparation of the Polyfluorourethane Additive with MPEG-350 and Equal Proportions by Mol of an Alcohol Fluorochemical for polyethylene glycol monomethether In a 1000 ml round-bottomed flask fitted with a mechanical stirrer, condenser and nitrogen inlet, and heated with a heating blanket, 256 g of a 60% solution of methylisobutyl butyl ketone is placed in DESMODUR N- 100 (from Bayer Corporation, Pittsburgh PA), 180 g of ZONYL BA Fluorotelomer Intermediate (from EI du Pont de Nemours and Company, Wilmington DE), and 126 g of polyethylene glycol monomethether having an average molecular weight of 350, MPEG- 350 from Union Carbide, Danbury CT. The contents were heated to 55 ° C. A solution of 20 g of methylobutyl butyl ketone containing 0.040 g of dibutyltin dilaurate is added and the exothermic reaction is increased to the temperature of 90 ° C, which temperature is maintained for an additional 3 hours. After maintaining 3 hours, 8 g of water are added and the contents are stirred for an additional hour.

The contents are then added with stirring for a period of 10 minutes to a 2 liter flask containing 900 g of water and 100 g of methyl isobutyl ketone at 75 ° C. This flask is fitted with a heated distillation, a condenser and a vacuum extraction adapter and receiver. The mixture is stirred for 15 minutes and a vacuum is applied to remove the methylobutyl-ilketone / aceotrope water at a temperature of about 55 ° C and a pressure of 13 Kpa. The flask is allowed to cool to 50 ° C and then maintained at that temperature at 13 Kpa until the container material has an instantaneous flash point above 93 ° C (200 ° F). The distillation vessel contains 914 g of the solution having 44.5% solids. This solution is diluted to 33% solids with water, added to 1% by weight paints, and evaluated as previously described.

Example 4 Preparation of the Polyfluorourethane Additive with Perfluorooctyl Ethyl Thiol (Lodyne 924) and MPEG-350.

The preparation is carried out as for Example 3 except that the reagents were 130 g of a 60% solution of meth i li sobutyl ketone of DESMODUR N-100, (from Bayer Corporation, Pittsburgh, PA), 53 g (0.10 moles) ) of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadeca fluoro-1-decantiol, LODYNE 924 (from Ciba Corp. Ardsley NY), and 91 g of polyethylene glycol monomethether having an average molecular weight of 350, MPEG-350 from Union Carbide, Danbury, CT. After the flash point has been raised above 93 ° C (200 ° F), the distillation vessel contains 734 g of solution having 34.2% solids. The solution is diluted to 33% solids with water, added to 1% by weight paints, and evaluated as previously described.

Example 5 Preparation of the Polyfluorourethane Additive with N-ethyl-N- (2-hydroxyethyl) perfluorooctansulfonamide (FC-10) and MPEG-350.

The preparation is carried out as in Example 3 except that the reagents were 130 g of a solution of 60% methylisobutyl ilketone of DESMODUR N-100, (from Bayer Corporation, Pittsburgh, PA), 54 g (0.10 mole) of N-ethyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-N- (2-hydroxyethyl) -1- octansulfonamide, FC-10 (3M Corporation, Minneapolis M), and 91 g of polyethylene glycol monomethyl ether having an average molecular weight of 350, MPEG-350 (from Union Carbide, Danbury, CT). After the flash point can be raised above 93 ° C (200 ° F), the distillation vessel contains 568 g of solution having 37.3% solids. The solution is diluted to 33% solids with water, added to 1% by weight paints, and evaluated as previously described.

Example 6 Preparation of the Polyfluorourethane Additive with Perfluoroalkyl Ethyl Ethoxylate and MPEG-350 The preparation is carried out as in Example 3 except that the reagents were 130 g of a 60% solution of methyl isobutyl-ketone DESMODUR N-100, (from Bayer Corporation, Pittsburgh, PA), 75 g (0.10 moles) of ZONYL FSO-100, a fluorotelomer monoether with polyethylene glycol CAS No. 122525-99-9 (from EI du Pont de Nemours and Company, Wilmington DE), and 91 g MPEG-350 (from Union Carbide, Danbury, CT). After the flash point has been raised above 93 ° C (200 ° F), the distillation vessel contains 622 g of solution having 36.1% solids. The solution is diluted to 33% solids with water, added to 1% by weight paints, and evaluated as previously described.

Example 7 Evaluation of Perfluoroalkyl Polyurethanes as Latex Cleaning Capacity Agents The perfluoroalkyl polyurethanes of Examples 3-6 are evaluated as cleaning agents by adding 1 percent by weight of the material previously described in a commercial flat latex paint. The paint is stretched as previously described and the films are allowed to cure for 7 days at room temperature. The cleaning capacity of the films is evaluated as described in Test Method 2 and 3. The following results were obtained by a blue bar.

Table 4 Evaluation of Different Perfluoroalkyl Polyurethanes as Cleaning Capacity Agents Number of Purification Cycles 25 50 100 Cleaning Capacity Assessment Example 3 2 Example 4 4 9 Example 5 2 10 Example 6 2 7 9 None 2 3 9 Example 8 Evaluation of the Polyfluorourethane Additive as an Anti-swelling Agent for Wood A sample of 10 g of the material described in Example 3 is diluted to 200 g with water. A piece of wood is treated as described in Test Method 4, (ASTM D-4446-84) and air-dried for 7 days at ambient conditions. It is then placed inside a wooden swelling meter and is tested by the ASTM procedure. The treated wood swells 35% and 46% less than the untreated control.

Example 9 Evaluation of the Polyfluorourethane Additive as an Oil Repellent on Hard Surfaces The material described in Example 3 is diluted to 5% solids with water and applied with a paint brush to the surface indicated in the following. The oil and water contact angles were measured and summarized in the following Table.

Table 6 Oil and Water Repellency on Hard Surface Contact Angle Hectane Water Contact Angle Advancing Reverse Reverse Precedence Reversal Concrete Control Concrete Treatment 127 34 Brick Control * Brick Treaty 63 111 Terracotta Control + * Treated Terracotta b6 0 128 Slate Control 0 0 * Treated Slate 62 or 95 43 Granite Control 51 16 12 0 Granite Treated 42 0 80 56 Marble Control 52 0 12 0 Marble Treated 46 0 84 55 Wood Control * * Treated Wood 133 137 Limestone Stone Control Treated Limestone Liquid is absorbed within the surface Surface too rough for the measurement angles Example 10 Evaluation of the Polyfluorourethane Additive as an Oil Repellent for Asphalt The material described in Example 3 is diluted to 5% solids with water. A piece of asphalt is painted with this solution and left to dry overnight. Hexadecane drops and water are placed on the surface and are in a row against the untreated control.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers. Having described the invention as above, property is claimed as contained in the following:

Claims (9)

1. A polyfluorourethane compound characterized in that it is the product of the reaction of: (1) at least one diisocyanate, (2) at least one luorochemical compound f containing at least one Zerewitinoff hydrogen in an amount sufficient to react with % to 80% of the isocyanate groups in the diisocyanate, (3) at least one compound of the formula Rio- (2) k ~ YH, in one car. sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate, wherein Rio is a C? -C? 8 alkyl, an? -8? omega-omega-alkenyl radical, or omega-alkene what of C? -C? 8; R2 is -CnH2n- optionally crowned at the end with - [OCH2C (R4) H] p-, - [OCH? C (CH2C1) H] p- or -C (R5) (R6) (OCH2C- [CH2C1] H) P-, where R4, R5 and R6 they are the same or different, and they are hydrogen or an alkyl radical of C? -C6, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R7), wherein R7 is H or C? -C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate, the compound is useful as an additive for water dispersible coating compositions.

2. A polyfluorourethane compound characterized in that it is the product of the reaction of: (1) at least one polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule, (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 33% of the isocyanate groups in the polyisocyanate, (3) at least one compound of the formula R? 0- (R2) k- YH, in a sufficient amount to react with 5% to 80% of the isocyanate groups in the polyisocyanate and wherein Rio is a C? -C? 8 alkyl, an? -C? 8, or omega-alkenoyl ω-alkenyl radical of C? -C? 8; R2 is -CnH2n- optionally crowned therein. extreme by - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p- or -C (R5) (R6) (OCH2C- [CH2C1] H) P-, where R4, R5 and R6 are equal or different, and they are H or an alkyl radical of Ci-Cß, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R7), wherein R7 is H or d-C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the polyisocyanate, the compound is useful as an additive for water dispersible coating compositions.

3. An improved water dispersible composition characterized in that it comprises an emulsion, latex, or suspension of film-forming material dispersible in an aqueous medium, wherein the improvement comprises the incorporation into the aqueous medium of a polyfluorourethane compound which is the product of the reaction of: (1) at least one diisocyanate, or polyisocyanate or mixture of polyisocyanates containing at least three isocyanate groups per molecule (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula Rio- (R2) k-YH, in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and in which R 10 is a C 1 -C 8 alkyl, an ω-C ω-C ω-C omega-alkenyl radical ia; R2 is -CnH2n- optionally crowned at the end with; - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p- or -C (R5) (R6) (OCH2C- [CH2C1] H) P-, where R4, R5 and R6 are equal or different, and they are H or an alkyl radical of C? -C6, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R7), wherein R7 is H or C i -C e alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate.

4. The composition according to claim 3, characterized in that the film-forming material is selected from the group consisting of a polymer of latex or acrylate, acrylic vinyl-acrylic, vinyl or mixtures thereof.

5. The composition according to claim 3, characterized in that the luorochemical compound f is perfluoroalkyl in an amount sufficient to react with at least 40% of the isocyanate groups and wherein the compound of the formula Rio (R2) k * ~ YH it is polyethylene glycol methyl ether in an amount sufficient to react with at least 30% of the isocyanate groups.

6. A dry coating characterized in that it comprises the composition according to claim 3.

7. A method for improving the cleaning ability of a surface having deposited thereon a dry coating composition characterized in that it comprises the addition of the coating composition before drying a polyurethane compound which is the product of the reaction of: 1) at least one diisocyanate, (2) at least one luorochemical compound f containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula R? 0- (R2) -H, in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and wherein R10 is an alkyl of C? -C? 8, an omega-alkenyl radical of C? -C? 8, or omega-alkenoyl of C? -C? 8; R2 is -CnH n- optionally crowned at the end with - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p- O -C (R5) (R6) (OCH2C- [CH2C1] H) P-, wherein R4, R5 and Re are the same or different, and are H or an alkyl radical of d-C6, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R7), wherein R7 is H or C? -C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the isocyanate or polyisocyanate.

8. A method for improving the oil repellency of a surface having deposited therein a dry coating composition characterized in that it comprises adding to the coating composition before drying a polyurethane compound which is the product of the reaction of: 1) at least one polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule, (2) at least one luorochemical compound f containing at least one Zerewitinoff hydrogen in an amount sufficient to react with % to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula R? 0- (R2) k- YH, in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and wherein Rio is a C? -C? 8 alkyl, an? -C? 8 omega-alkenyl radical, or C? -C? 8 omega-alkenoyl radical; R2 is -CnH2n- optionally topped with - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p- or -C (R5) (R6) (OCH2C- [CH2C1] H) p -, wherein R4, R5 and R6 are the same or different, and are H or an alkyl radical of C? -C6, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R7), wherein R7 is H or C? -C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate.

9. A method for reducing swelling in wood in the application of a water dispersible coating composition characterized in that it comprises the addition to the coating composition before the application of a polyurethane compound which is the product of the reaction of: (1) at least one diisocyanate, or polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule, (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with % to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula Rio- (R2) k-YH, in an amount sufficient to react with 5% to 80% of the groups isocyanate in the diisocyanate or polyisocyanate and wherein Rio is a C? -C? 8 alkyl, an omega-alkenyl radical of CL-C18, or omega-alkenei of C? -C? 8; R? is -CnH2n- optionally crowned at the end with - [OCH2C (R4) H] p-, - [OCH2C (CH2C1) H] p- or -C (R5) (R6) (OCH2C- [CH1] H) P-, wherein R4, R5 and R6 are the same or different, and are H or an alkyl radical of C? -C6, n is from 0 to 12, p is from 1 to 50; Y is O, S or N (R), wherein R7 is H or C? -C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate.