MXPA06007129A - Compositions for aqueous delivery of fluorinated oligomeric silanes - Google Patents

Abstract

The invention relates to a dilutable, non-aqueous concentrate and an aqueous dilution used for aqueous delivery of fluorinated oligomeric silanes to a substrate, a method of treating a substrate with the aqueous dilution composition to render it oil and water repellent, and articles having coatings made from the aqueous dilution.

Description

COMPOSITIONS FOR AQUEOUS SUPPLY OF FLUORINATED OLIGOMERIC SILANOS Field of the Invention This invention relates to the aqueous supply of fluorinated oligomeric silanes to a substrate. More particularly, the present invention is a dilutable, non-aqueous concentrate which comprises at least one fluorinated oligomeric silane and at least one surfactant, which together with water or a mixture of aqueous solvent form an aqueous dilution which can be COATING AND CURE ON A SUBSTRATE BACKGROUND OF THE INVENTION Good water repellent and oil repellent coatings can be provided for certain substrates by applying fluorinated silanes in the molten state or dissolved in volatile organic solvents.

The fluorinated silanes applied are cured by heating with a catalyst to chemically fix the fluorinated silanes to the substrates. (See, for example, United States Patent No. 3,012,006 (Holbrook et al.)). However, the use of volatile organic solvents is generally hazardous to the environment, and can be dangerous due to the flammability of the solvents. Therefore, an alternative means for applying fluorinated silanes to substrates is developed, which is for use in Ref.: 173720 aqueous supply. (See, for example, U.S. Patent No. 5,274,159 (Pellerite et al.), U.S. Patent No. 5,702,509 (Pellerite et al.), And U.S. Pat. No. 5,550,184 (Halling)). A problem with the known compositions for the aqueous supply of fluorinated silanes to substrates is that they can not have long half-lives. Another problem is that they may require high shear mixing before they are coated on a substrate. The known compositions have high solids content, which results in thick coatings. Although the use of aqueous supply of fluorinated silanes to substrates is known in the art, it remains a desire to provide compositions for aqueous supply of fluorinated silanes that: 1) can be stored for relatively long periods of time; 2) do not require high shear mixing or other mechanical energy input; 3) have relatively low solids content, making them easier to lightly coat on glass and other substrates, and 4) at the same time, once applied to a substrate and cured, they can provide durable coatings. Such compositions have recently been described using fluorinated silanes and a fluorinated surfactant. See, for example, application WO 03/044075 and application WO 03/046056. Coating compositions containing fluorochemical oligomeric silanes have been described in U.S. Patent 5,739,369, U.S. Patent 5,527,931, U.S. Patent 222,157, U.S. Patent 225,187, and U.S. Patent 225,188. Summary of the Invention The present invention provides compositions for the aqueous delivery of fluorinated oligomeric silanes. One embodiment is a dilutable, non-aqueous concentrate and another embodiment is an aqueous dilution which uses the non-aqueous, dilutable concentrate and a dilution medium containing water or an aqueous solvent mixture. The compositions can be stored for long periods of time and are easy to prepare by simple mixing without the need for high shear emulsification. The coatings of the composition provide oil and water repellency and easy cleaning properties for hard or soft substrates. The present invention provides a non-aqueous, dilutable concentrate containing a homogeneous, non-aqueous mixture that includes: (a) at least one fluorinated oligomeric silane of the formula I AM £ 11Mh r-6 Where: A is hydrogen or a residue of an initiating species: Mf represents units derived from one or more fluorinated monomers; Mh represents units derived from one or more non-fluorinated monomers; Ma represents units derived from one or more non-fluorinated monomers having a silyl group; SiY3 where Y is a hydrolysable group; G is a residue of a transfer agent of the formula: wherein Y is a hydrolysable group and Q is an organic divalent linking group; n is an integer from 1 to 100; m is an integer from 0 to 100; and r is an integer from -0 to 100; and (b) at least one surfactant. The non-aqueous, dilutable concentrate must be diluted with water or a mixture of aqueous solvent before being coated on a substrate. Advantageously, the non-aqueous, dilutable concentrate has a relatively long half-life that is greater than about 1 day, preferably more than about 14 days, and more preferably more than about 6 months under appropriate storage conditions. The non-aqueous, dilutable concentrate can be transported and stored more economically than in diluted form. The concentrated, non-aqueous, dilutable can be diluted in the location where the coating is to be made, which advantageously allows greater flexibility in dilution choices and therefore the thickness of the coatings being applied. The non-aqueous concentrate, dilutable in water or an aqueous solvent mixture (to form the aqueous dilution) is dispersed simply by hand-stirring a non-aqueous, dilutable concentrate mixture and either water or a mixture of aqueous solvent. No additional mechanical processing is required, such as high shear mixing or ultrasonication. In another aspect, the present invention provides an aqueous diluted composition which contains: (a) a dilution medium which includes water or a mixture of aqueous solvent including water and at least one water miscible cosolvent; and (b) a. nonaqueous, dilutable concentrate containing a non-aqueous, homogeneous mixture that includes: (i) at least one fluorinated oligomeric silane as defined above; and (ii) at least one surfactant. The aqueous diluted composition can be coated on a substrate to provide a durable coating. Advantageously, the aqueous diluted composition of the present invention has a relatively low solids content, which makes it easier to thinly coat on glass or other siliceous substrates which may have, for example, optical properties which are sensitive to the thickness. The inventive aqueous dilution allows the elimination of or substantial reduction in the use of organic solvents in the process which may be flammable and / or hazardous to the environment. The aqueous diluted composition also has a half-life that is at least several hours under appropriate storage conditions. Other embodiments of the present invention include a method for treating a substrate, and an article which includes a substrate and a coating that is formed by coating and curing the aqueous diluted composition. DETAILED DESCRIPTION OF THE INVENTION Non-aqueous, dilutable concentrate The non-aqueous, dilutable concentrate of the present invention contains a homogeneous, non-aqueous mixture that includes at least one fluorinated oligomeric silane and at least one surfactant. The non-aqueous, dilutable concentrate may optionally also include at least one organic cosolvent, and / or at least one additive. A "homogeneous mixture" when referring to a non-aqueous concentrate dilutable, is defined as the non-aqueous concentrate dilutable which is stable, ie does not occur substantial precipitation or separation of substantial phases for at least the time needed to prepare a however, preferably, and for the purpose of being commercially practical, the dilutable concentrate is stable for at least about one day, and preferably up to about six months or more, under appropriate conditions Storage (closed container, without water, room temperature). The non-aqueous, dilutable concentrate may be clear or somewhat cloudy. By the term "non-aqueous" it is meant that water is not added as a component of the non-aqueous, dilutable concentrate. However, there may be adventitious water in the other components of the composition, but the total amount of water does not adversely affect the half-life or the stability of the dilute, non-aqueous concentrate (ie, preferably less than about 0.1% by weight of the concentrate). non-aqueous, dilutable). Fluorinated oligomeric silane The fluorinated oligomeric silane of the non-aqueous, dilutable concentrate has the formula A-MfnMhmMar-G wherein A represents hydrogen or the residue of an initiator species, for example, an organic compound, which has a radical and which is derived of the decomposition of a free radical initiator or that derived from a chain transfer agent; Mf represents units derived from one or more fluorinated monomers as described above; Mh represents units derived from one or more non-fluorinated monomers; Ma represents units having a silyl group represented by the formula: SiY3 where Y independently represents an alkyl group, an aryl group or a hydrolysable group as defined above; and G is a monovalent organic group which comprises the residue of a chain transfer agent, and having the formula: -S-Q-Y3 wherein Q is an organic divalent linking group as defined below; and Y independently represents a hydrolysable group. The total number of units represented by the sum of n, m and r is generally at least 2 and preferably at least 3 in order to reach the oligomeric compound. The value of n in the fluorochemical oligomer is between 1 and 100 and preferably between 1 and 20. The values of m and r are between 0 and 100 and preferably between 0 and 20. According to a preferred embodiment, the value of m is less than that of nyn + m + r is at least 2. The fluorochemical oligomers typically have an average molecular weight between 400 and 100000, preferably between 600 and 20,000, more preferably between 1000 and 10000. The fluorochemical oligomer preferably contains at least 5% in mol (based on the total moles of units Mf, Mh, Ma) of hydrolysable groups.

It will further be appreciated by one skilled in the art that the preparation of fluorochemical oligomers useful in the present invention results in a mixture of compounds and therefore, general formula I should be understood as to represent a mixture of compounds, wherein the indices n, m and r in formula I represent the molar quantities of the corresponding unit in such a mixture. Therefore, it will be clear that n, m and r can be fractional values. The Mfn units of the fluorochemical oligomer are fluorinated monomer derivatives, preferably fluorochemical acrylates and methacrylates. Examples of fluorinated monomers for the preparation of the fluorochemical oligomer include those which can be represented by the general formula: Rf-QE (II) Where Rf represents a partially or fully fluorinated aliphatic group which has at least 3 carbon atoms, Q represents an organic divalent linking group and E represents an ethylenically unsaturated group. The ethylenically unsaturated group can be fluorinated or non-fluorinated. The fluoroaliphatic group Rf, in the fluorochemical monomer can be a monovalent, fluorinated, stable, inert, preferably saturated, non-polar aliphatic radical. This can be straight chain, branched chain, or cyclic or combinations thereof. This may contain heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. Rf is preferably a fully fluorinated radical. The radical Rf has at least 2 and up to 18 carbon atoms, preferably 3 to 14, more preferably 2 to 8, especially 4. The terminal portion of the radical Rf is a perfluorinated portion, which preferably contains at least 5 carbon atoms. fluorine, for example CF3CF2-, CF3CF2CF2, and (CF3) 2CF. Preferred Rf radicals are fully or substantially fluorinated and are preferably those perfluorinated aliphatic radicals of the formula CnF2ll + 1- where n is 2 to 6, particularly 3 to 5. The compounds wherein the radical Rf is CFg- are generally more environmentally friendly that the compounds where the radical Rf consists of a group perfluorinated with carbon atoms. Surprisingly, in spite of the short C4 perfluorinated group, the fluorochemical oligomeric compounds prepared therewith are highly effective. The linking group Q in the above formula (II) links the polyether fluoroaliphatic or fluorinated group to be the polymerizable group E free radical, and is generally non-fluorinated organic linking groups. The linking group can be a chemical bond, but preferably contains from 1 to about 20 carbon atoms and can optionally contain oxygen, nitrogen, or sulfur-containing groups or a combination thereof. The linking group is preferably free of functional groups that substantially interfere with the oligomerization of free radicals (for example polymerizable olefinic double bonds, double bonds, thiols, and others of such functionality known to those in the art). Examples of suitable organic divalent linking groups include: * -COQ'-R1-Q "-CO-, * -COO-CH2-CH (OH) -R1-Q" -CO-, * LX-0 / -CONH- L2, -Rx-Q'-CO- * -COQ'-R1-, -R1-, * -COO / -R1-Q /, * -S0NRa-R1-0 -, * -S02NRa-R1, and * - S02NRa-Ra-Q "-C0 ~, Where Q" and Q "independently represent O or NRa, Ra is hydrogen or an alkyl group of 1 to 4 carbon atoms, R1 represents a cyclic, linear or branched alkylene group which may be interrupted by one or more heteroatoms such as O or N, L1 and L2 each independently represent a non-fluorinated organic divalent linking group which includes for example an alkylene group, a carbonyl group, an alkylene carbonamido group and / or an carboxyalkylene group and * indicates the position where the linking group is attached to the group Rf in the formula (II) .Preferred linking groups include -S02N (Rx) -OC (O) - and - (CH2) < 0C (0) -, where Ri is hydrogen or an alkyl group of C? ~ C and d is an integer from 1 to 20. The fluorochemical monomers monkeys Rf-Q-E as described above and methods for the preparation thereof are known and described, for example in the Patent of the United States of North America NO. 2,803,615. Examples of such compounds include general classes of acrylates, fluorochemical methacrylates, vinyl ethers, and allyl compounds containing fluorinated sulfonamido groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, acrylates or methacrylates derived from fluorochemical carboxylic acids, and acrylates or methacrylates from perfluoroalkyl as described in European Patent A-526 976. Perfluoropolyether acrylates or methacrylates are described in United States Patent 4,085,137. Preferred examples of fluorochemical monomers include: CF3 (CF2) 2CH2OC (O) CH = CH2, CF3 (CF2) 2CH2OC (O) C (CH3) = CH2, CF3 (CF2) 3CH2OCOC (CH3) = CH2 / CF3 (CF2) 3CH2OCOCH = CH2 / Ri! CF3 (C2) 3S02N (CH2) 2OCOCH = CH2 Rt CF3 (CF2) 3SO2N (CH2) 2? COC (CH3) = CH2 CF3 (CF2) 3S? 2NCH2CH2OCOC (CH3) = Cp2 I CH3 and CF3 (CF2) 3S02NCH2CH2OCOCH = CH2 I CH3 wherein Ri represents methyl, ethyl or n-butyl. The Mh units of the fluorochemical oligomer (when present) are generally derived from a non-fluorinated monomer, preferably a monomer consisting of a polymerizable group y. a portion of hydrocarbon. The monomers containing the hydrocarbon group are well known and generally commercially available. Examples of hydrocarbon-containing monomers include those according to the formula: Rh-QE (III) wherein Rh represents a hydrocarbon group, Q represents a chemical bond or a divalent linking group as defined above and E is an ethylenically unsaturated group as is defined above. The hydrocarbon group is preferably selected from the group consisting of a linear, branched or cyclic alkyl group, an aralkyl group, an alkylaryl group and an aryl group. Preferred hydrocarbon groups contain from 4 to 30 carbon atoms. Further non-fluorinated monomers include those wherein the hydrocarbon group in the formula (III) includes oxyalkylene groups or contains one or more reactive groups, such as hydroxy groups, amino groups, epoxy groups, halogens such as chlorine and bromine. Examples of non-fluorinated monomers from which the Mh units can be derived include general classes of ethylenic compounds capable of free radical polymerization, such as, for example, allyl esters such as allyl acetate and allyl heptanoate, alkylvinyl ethers or alkylaryl ethers, such as cetyl vinyl ether, dodecyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether; anhydrides and esters of unsaturated acids such as acrylic acid, methacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, for example vinyl acrylates and methacrylates, allyl, methyl, butyl, isobutyl, hexyl, heptyl , 2-ethylhexyl, cyclohexyl, lauryl, stearyl, isobornyl, or alkoxyethyl; alpha-beta unsaturated nitriles such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylates, allyl glycolate, acrylamide, methacrylamide, n-diisopropylacrylamide, diacetone acrylamide, N, N-diethylaminoethyl methacrylate, Nt- methacrylate butylamino ethyl, styrene and its derivatives such as vinyltoluene, alpha-methylstyrene, alpha-cyanomethylstyrene; lower olefinic hydrocarbons which contain halogen such as ethylene, propylene, isobutene, 3-chloro-lysobutene, butadiene, isoprene, chlorine and dichlorobutadiene and 2,5-dimethyl-l, 5-hexadiene and allyl or vinyl halides such as vinyl and vinylidene. Preferred non-fluorinated monomers include monomers containing hydrocarbon groups such as those selected from octadecyl methacrylate, lauryl methacrylate, butylacrylate, N-methylol acrylamide, isobutylmethacrylate, ethylhexylacrylate and ethylhexyl methacrylate; and vinyl chloride and vinylidene chloride. The fluorochemical oligomer useful in the invention generally also includes Ma units having a silyl group and hydrolyzable groups on the termination of the units derived from one or more fluorinated monomers as defined above. Examples of Ma units include those corresponding to the general formula: RH-Q-E-G-SiY3 (IV) Typical examples of such monomers include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, trimethoxysilylpropyl methacrylate and the like. The fluorochemical oligomer is conveniently prepared through free radical polymerization of a fluorinated monomer with optionally a non-fluorinated monomer and a monomer containing the silyl group in the presence of a chain transfer agent. A free radical initiator is generally used to initiate the polymerization or oligomerization reaction. Commonly known free radical initiators can be used and examples thereof include azo compounds, such as azobisisobutyronitrile (ABIN), azo-2-cyanovaleric acid and the like, hydroperoxides such as eumeno, t-butyl hydroperoxide and t-amyl, dialkyl peroxides such as di-t-butyl peroxide and dicumyl, peroxyesters such as t-butylperbenzoate and di-t-butylperoxyphthalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide. The oligomerization reaction can be carried out in any solvent suitable for organic free radical reactions. The reagents can be presented in the solvent in any suitable concentration, for example, from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture. Examples of suitable solvents include alicyclic and aliphatic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, glyme, diglyme, diisopropyl ether), esters (e.g. example, ethyl acetate, butyl acetate), alcohols (e.g., ethanol, isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g. , N-dimethylformamide, N, N-dimethylacetamide), halogenated solvents such as methylcycloroform, FRE0N ™ 113, trichlorethylene,, a, -trifluorotoluene, and the like, and mixtures thereof. The oligomerization reaction can be carried out at any suitable temperature to carry out an organic free radical reaction. The particular temperature and solvents for use can be easily selected by those skilled in the art based on considerations such as the solubility of reagents, the temperature required for the use of a particular initiator, desired molecular weight and the like. While it is impractical to list a particular temperature suitable for all initiators and all solvents, generally suitable temperatures are between about 30 ° C and about 200 ° C, preferably between 50 and 100 ° C. The fluorochemical oligomer is typically prepared in the presence of a chain transfer agent. Suitable chain transfer agents can include a hydroxy, amino, mercapto or halogen group. The chain transfer agent may include two or more such hydroxy, amino-, mercapto or halogen groups. Typical chain transfer agents useful in the preparation of the fluorochemical oligomer include those selected from 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol, 3-mercapto-1-propanol, 3-mercapto-1 , 2-propanediol, 2-mercapto-ethylamine, di (2-mercaptoethyl) sulfide, octyl mercaptan and dodecyl mercaptan. In a preferred embodiment, a chain transfer agent containing a silyl group having hydrolyzable groups is used in the oligomerization to produce the fluorochemical oligomer. Chain transfer agents including such silyl group include those groups according to formula V: HS-Q-SiY3 (V) wherein Q represents an organic divalent linking group such as for example an alkylene, arylene or aralkylene chain linear, branched or cyclic chain. An alkylene group of 1 to 20 carbon atoms is preferred, and Y is independently a hydrolysable group as defined above. A single chain transfer agent or a mixture of different chain transfer agents can be used. Preferred chain transfer agents are 2-mercaptoethanol, octyl mercaptan and 3-mercaptopropyltrimethoxysilane. A chain transfer agent is typically present in an amount sufficient to control the number of monomer units polymerized in the oligomer and to obtain the desired molecular weight of the oligomeric fluorochemical silane. The chain transfer agent is generally used in an amount of about 0.05 to about 0.5 equivalents, preferred and approximately 0.25 equivalents, per monomer equivalent including fluorinated and non-fluorinated monomers. The fluorochemical oligomer useful in the present invention contains hydrolysable groups. These hydrolysable groups can be introduced into the fluorochemical oligomer by oligomerization in the presence of a chain transfer agent having a silyl group containing hydrolyzable groups, for example a chain transfer agent according to Formula V above where Y represents a hydrolysable group. Alternatively, a functionalized chain transfer agent or functionalized comonomer can be used which can be reacted with a silyl group containing a reagent subsequent to oligomerization.

In this way, according to the first embodiment, a fluorochemical oligomer is prepared by oligomerizing a fluorinated monomer and optional non-fluorinated monomer with a monomer according to formula IV above wherein Y represents a hydrolysable group in the presence of a transfer agent chain which optionally may also contain a silyl group such as for example a chain transfer agent according to formula V above wherein Y represents a hydrolysable group. As a variation to the above method the oligomerization can be performed without the use of a silyl group containing monomer but with a chain transfer agent containing the silyl group. Surfactant A surfactant is defined as a "substance that, when present in a low concentration in a system, has the property of being adsorbed on the surfaces or interfaces of the system and of altering to a marked degree the surface or interfacial free energies of these surfaces. " (Milton J. Rosen, "Surfactants and Interfacial Phenomena," Second Ed., John Wiley &Sons, New York, NY, 1989, page 1). These surfactants have "a characteristic molecular structure consisting of a structural group that has very little attraction for a solvent, known as a lyophobic group, together with a group that has a strong attraction for a solvent, called the lyophilic group" (Milton J Rosen, "Surfactans and Interfacial Phenomena," Second Ed., John Wiley &Sons, New York, NY, 1989, pages 3-4). When the solvent is aqueous, the lyophobic group is typically a non-polar group such as alkyl or fluorinated alkyl, while the lyophilic group is a polar group. The term "fluorinated" (as in the term fluorinated surfactant) indicates that at least about 75 percent, preferably at least about 85 percent, more preferably at least about 95 percent, of the hydrogen atoms in the portion alkyl are replaced by fluorine atoms. Optionally, the remaining hydrogen atoms can be replaced by other halogen atoms, such as by chlorine atoms. The fluorinated surfactant acts to stabilize an emulsion (i.e., droplets of a liquid phase dispersed in another liquid phase), and may aid in the solubility or compatibility of the fluorinated silane and the organic co-solvent (if there is one or more organic co-solvents) of the concentrate. dilutable, not watery. The fluorinated surfactants useful in this invention are amphiphilic materials, which comprise one or more hydrophobic fluorochemical segments and one or more solubilizing and hydrophilic segments. Such materials are described in "Fluorinated Surfactants and Repellents," Second Edition, by E. Kissa, Surfactant Science Series, volume 97, Marcel Dekker, Inc .: New York, 2001, p. 1-21. The fluorinated surfactants have a fluorine content by weight of at least 10%. These fluorinated surfactants can be monomeric or polymeric, with molecular weights between about 300 and about 100,000 grams per mole, preferably between about 400 and about 20,000 grams per mole. Hydrophobic fluorochemical groups can be, for example, perfluoroalkyl which contains between about 3 and about 20 carbon atoms, or a mono- or divalent perfluoropolyether group with molecular weight between about 300 and about 10,000 grams per mole. Hydrophilic groups in the fluorinated surfactants may be of an anionic (such as carboxylate), cationic (such as quaternary ammonium), nonionic (such as oligo (oxyethylene)) or amphoteric (such as amine oxide) nature as long as they do not contain functionalities which cause instability in the concentrates of this invention, for example strongly acidic groups, strongly basic groups, or contamination by fluorine ions. Representative fluorinated surfactants include, but are not limited to, the following: C7F15C02-NH4 +, C8F17S02N (C2H5) (C2H40) 7CH3, CsF? 7 (C2H40) 10H, (C4F9S02) 2N-NH4 +, C4F9S02N (CH3) (C2H40) nCH3 (where navg ~ 7) and C3F70 (CF (CF3) CF20 ) r? CF (CF3) C02"NH4 + (where navg ~ 13) Examples of these and other fluorinated surfactants of the present invention are described, for example, in the Patent of the United States of North America No. 3,772,195 (Francen), 4,090,967 (Falk), 4,099,574 (Cooper et al.), 4,242,516 (Mueller), 4,359,096 (Berger), 4,383,929 (Bertocchio et al.), 4,472,286 (Falk), 4,536,298 (Kamei et al), 4,795,764 (Alm et al.), 4,983,769 (Bertocchio et al.) And ,085,786 (Alm et al.), Which are incorporated herein by reference. Many of these fluorinated surfactants are commercially available from Minnesota Mining and Manufacturing Company (St. Paul, Minnesota), which has the FLUORAD ™ brand, or commercially available from E.I.

DuPont de Nemours and Co. (Wilmington, Delaware), which has the ZONYL ™ brand. The polymeric fluorinated surfactants can also be used in the present invention. Examples of polymeric fluorinated surfactants that can be used in the present invention are found in U.S. Patent No. 3,787,351 (Olson), U.S. Patent No. 4,668,406 (Chang), and international application of the PCT WO 01/30873, which are incorporated herein by reference. Examples of polymeric fluorinated surfactants that may be used include fluorinated random copolymer surfactants. Examples of random copolymer fluorinated surfactants include the following structures: Wherein the molar ratio of a: b: c is about 30: about 1: about 32, and wherein the molecular weight of the surfactant is about 1,000 to about 4,000 grams per mol; n wherein the molar ratio of a ': b': c 'is about 3: about 3: about 1, and wherein the molecular weight of the surfactant is about 1,000 to about 40,000 grams per mole. The surfactant may also be a hydrocarbon or silicone surfactant. The hydrocarbon or silicone surfactant can be a co-surfactant with a fluorinated surfactant defined above. Typically a hydrocarbon surfactant includes nonionic surfactants, for example, alkylene diol polyethylene glycols, alkylphenol polyethylene glycols or mixtures thereof, such as Triton ™ X-305, Surfynol ™ 465 or Tween ™ 80; cationic surfactants such as Arquad ™ 2C-75, anionic surfactants such as Witcolate ™ 4085, amphoteric surfactants such as dicycloethyl ammonium chloride. Typically, a silicone surfactant includes, for example, alkylenoxy-containing silicone oligomers, such as Silwet ™ L-77 and Sylgard ™ 309. The surfactant is generally included in the dilutable, non-aqueous concentrate in an amount of up to about 50% by weight. weight of the dilutable, non-aqueous concentrate, preferably up to about 30% by weight, and more preferably up to about 15% by weight. Optional organic cosolvent A non-aqueous, dilutable concentrate of the present invention may also optionally include one or more organic cosolvents. An organic cosolvent is an organic liquid component that carries the surfactant and the compatible fluorinated silane (in case they are not compatible in the absence of the organic cosolvent), and decreases the viscosity of the non-aqueous, dilutable concentrate. Suitable organic cosolvents are organic solvents, or mixtures of organic solvents, including, but not limited to, aliphatic alcohols, such as methanol, ethanol, and isopropyl alcohol: ketones, such as acetone or methyl ethyl ketone; esters, such as ethyl acetate or ethyl formate; ethers, such as diisopropyl ether, 1,4-dioxane, and diethylene glycol dimethyl ether and amides, such as N-methylpyrrolidinone, and N, N-dimethylformamide. Fluorinated organic solvents, such as heptafluorobutanol, trifluoroethanol and hexafluoroisopropanol, or hydrofluoroethers, such as HFE-7100 (available from 3M Company) may be used alone or in combination with non-fluorinated organic cosolvents. Preferred organic cosolvents are aliphatic alcohols. Some examples of preferred aliphatic alcohols are ethanol, and isopropyl alcohol. Other examples include alkylene oxide-containing alcohols, such as DOWANOl ™ DPnP (available from Sigma-Aldrich, Milwaukee, Wl) and DOWANOL ™ DPM (available from Sigma-Aldrich), etc. t Preferably, the organic cosolvent is miscible in water. Also, preferably, the organic co-solvent has a boiling point that is below 200 ° C. The organic cosolvent can generally be included, if used, in the non-aqueous concentrate, dilutable in an amount of up to about 75% by weight of the non-aqueous, dilutable concentrate, and preferably up to about 50% by weight. Optional additives The non-aqueous, dilutable concentrate may also include one or more optional additives. Some examples of optional additives are catalysts to assist in the curing and / or cross-linking of the dilute, non-aqueous concentrate once it is diluted and coated on a substrate. A healing additive can be added when necessary to facilitate healing. Such a curing additive may take the form of an acid precursor, which releases an acid upon exposure to heat, ultraviolet light, visible light, electron beam radiation, or microwave irradiation. Acid precursors include, for example, sulfonium and iodonium salts, as well as allyl esters of alkane or fluoroalkanesulfonic acids, and are described in U.S. Patent No. 6,204,350 (Liu et al.) Incorporated herein. . Some additives, such as ammonium salts of acids such as perfluorocarboxylic acids, alkylsulfonic acids, arylsulfonic acids, perfluoroalkylsulfonic acids and perfluoroalkylsulfonimides can function as latent or thermally activated curing additives as well as function as surfactants. Therefore, the non-aqueous, dilutable concentrate may include one of these dual functional surfactants, and may not require a separate catalyst. Other possible optional additives include, but are not limited to, antimicrobial agents, UV absorbers, hydrocarbon silanes, alkoxysilanes, titanates, zirconates, and micro or nanoparticles of inorganic materials, such as silica or titania. An additive or optional additives may be included in the non-aqueous concentrate, dilutable in an amount of up to about 50% by weight of the non-aqueous, dilutable concentrate, more preferably up to about 5% by weight. The non-aqueous, dilutable concentrate can be prepared by combining the components in any order and in a manner that is known in the art. Preferably, for the embodiment comprising at least one fluorinated oligomeric silane, at least one surfactant and at least one organic cosolvent, the organic surfactant and cosolvent are first mixed and then the fluorinated oligomeric silane is added to the mixture. If the dilute, non-aqueous concentrate is not immediately homogeneous after mixing the ingredients, the concentrate may become homogeneous after "time has passed." In order to accelerate the homogeneity, however, the non-aqueous concentrate , dilutable can be heated For ease of manufacture, etc., the non-aqueous, dilutable concentrate is typically with a dilution medium (or the aqueous dilution composition is typically prepared) shortly before use.The presence of certain chemical functionalities such as strong acids (i.e., sulfonic, mineral, phosphoric, and perfluorinated acids) and species such as fluorine ion are preferably avoided in the non-aqueous, dilutable concentrate of this invention if they lead to instability of the corresponding aqueous dilution and / or the dilute concentrate, not aqueous by itself Aqueous dilution Another embodiment of the present invention is an aqueous dilution, which comprises e: the non-aqueous, dilutable concentrate described above; and, a dilution means comprising water or an aqueous solvent mixture comprising water and a miscible water cosolvent. The aqueous dilution may also include optional additives.

Dilution medium The dilution means of the aqueous dilution comprises water or a mixture of aqueous solvent. The aqueous solvent mixture comprises water and a water-miscible cosolvent. Examples of water miscible cosolvents include, but are not limited to an alcohol, e.g., ethane, isopropyl alcohol, DOWANOL ™ DPM; a ketone, for example, acetone, an ether, for example diethylene glycol dimethyl ether and others, such as N-methylpyrrolidinone. The amount of water-miscible cosolvent that is included in the aqueous dilution (if an aqueous solvent mixture is used) is dependent upon the coating technique that will be used to coat the aqueous dilution, as well as dependent on the performance characteristics that are desired in the resulting coated substrate. Optional additives The aqueous dilution may optionally also comprise at least one additive. Some exemplary additives are described above. The optional additive of the aqueous dilution may be additional to the additives in the non-aqueous, dilutable concentrate. As discussed above with respect to the dilutable, non-aqueous concentrates, additives which adversely affect the stability of the aqueous dilution are preferably avoided. These additives may include strongly acid species and fluorine ions. The pH of the aqueous dilution is in the range of about 2 to about 11, and more preferably and about 4 to about 8. The aqueous dilution can be prepared by first combining the components of the concentrate, non-aqueous, dilutable and then subsequently adding the concentrated, non-aqueous dilutable to the dilution medium. The aqueous dilution is preferably prepared, however, by adding the dilution medium to the non-aqueous, dilutable concentrate. The amount of the non-aqueous, dilutable concentrate that is typically in the aqueous dilution is from about 0.05% by weight to about 10% by weight of the aqueous dilution, preferably from about 0.1% by weight to about 5% by weight. The aqueous dilution can be a clear solution as well as a somewhat cloudy solution. An additive or optional additives may be added to the aqueous dilution after the non-aqueous, dilutable concentrate has been diluted. A preferred optional additive is a curing additive, such as those discussed above, which can be added to the aqueous dilution in an amount of up to about 3% by weight of the aqueous dilution.

The aqueous dilution is generally applied to a substrate (substrate described in detail below with respect to the method) in an amount sufficient to produce a coating that is repellent to water and oil. This coating can be extremely thin, for example, about 10 to about 20 nanometers in thickness, through practice a coating can be thicker, for example, up to about 50 to 100 nanometers in thickness. The aqueous dilution of the present invention is advantageously dispersed in a substrate to achieve uniform properties over the total surface of the treated substrate. In addition, aqueous dilutions minimize or eliminate the use of volatile organic compounds (VOCs), thereby reducing contamination and exposure to potentially dangerous vapors and other flammable solvents. Method The present invention also provides a method for treating a substrate, which comprises the steps of applying the aqueous dilution of the invention, as discussed above, to a substrate and curing the aqueous dilution to form a treated substrate. Suitable substrates which can be treated with the aqueous dilution of this invention include, but are not limited to, substrates having a hard surface preferably with functional groups, such as -OH groups occurring in "siliceous or metallic substrates, capable of reacting with the silane Preferably, such reactivity of the substrate surface is provided by functional groups having active hydrogen atoms, such as -OH.When such hydrogen atoms are not present, the substrate can first be treated in a plasma containing Oxygen or in a corona atmosphere to react it to the fluorinated silane Substrate treatment leads to the treated surfaces to be less retentive to earth and more quickly cleanable due to the oil and water repellent nature of the treated surfaces. are maintained despite extended exposure or repeated use and cleanings gone to the high degree of durability of the treated surface. Preferably, the substrate is cleaned before applying the aqueous dilution of the present invention to obtain optimum characteristics, particularly durability. That is, the surface of the substrate to be coated preferably is substantially free of organic contamination before coating. Cleaning techniques depend on the type of substrate and include, for example, a step of washing solvent with an organic solvent, such as acetone, or ethanol, or exposure to a reactive gas phase treatment such as air or UV plasma /ozone. Useful substrates include, but are not limited to, textiles, clothing, skin, paper, cardboard, carpets, ceramics, glazed ceramics, flat glass, hollow glass, metals (such as aluminum, iron, stainless steel, copper and the like), oxides metallic, natural and man-made stone, thermoplastic materials (such as poly (meth) acrylate, polycarbonate, vinyl, polystyrene, styrene copolymers such as styrene / acrylonitrile copolymers and polyesters such as polyethylene terephthalate), paints (such as those based on acrylic resins), powder coatings (such as polyurethane, epoxy powder coatings or hybrids) and wood. Preferred substrates include metals and siliceous substrates including ceramics, glass ceramics, glass, concrete, mortar, white cement, and natural and man-made stone. Particularly preferred substrates include glazed ceramics and glass. Various articles, which have at least one substrate, can be effectively treated with the inventive aqueous dilution to provide a repellent coating to water and oil therein. Examples include glassy ceramic mosaics, bathroom tubing and varnished toilets, glass shower panels, construction glasses, various parts of a vehicle (such as the mirror or windshield) and glazed or varnished ceramic pottery materials. Another particularly preferred substrate is a substrate which has an anti-reflective film (AR) thereon. Anti-reflective films (AR) prepared by vacuum diffusion of thin films of metal oxide into substrates made of glass or plastic are useful particularly in electronic equipment display devices. Such metal oxide films are relatively porous and consist of glomeruli of particles that form a relatively rough profile. AR films reduce brightness and reflection. When AR films are conductive, they also help reduce static discharge and electromagnetic emissions. Thus, a primary application for AR films is to provide contrast enhancement and antireflective properties to improve the readability of display devices, such as computer monitors. AR films are described in U.S. Patent No. 5,851,674 (Pellerite et al.), Which is incorporated herein by reference. Antireflective films made of diffused metal oxide are generally durable and uniform. Also, its optical properties are controllable, which makes them very desirable. They also have very high surface energies and refractive indexes. However, the high surface energy of a diffused metal oxide surface makes it prone to contamination by organic impurities (such as skin oils). The presence of surface contaminants results in a greater degradation of antireflective properties of the metal oxide coatings. Additionally, due to the high refractive indexes, surface contamination becomes noticeable to the end user. The method of the present invention allows a protective coating on an anti-reflective film that is relatively durable, and more resistant to contamination and easier to clean than the anti-reflective film itself. Preferably, the total coating thickness of the dry coating ("dried coating") of the aqueous dilution on an anti-reflective article is greater than a monolayer (which is typically greater than about 1.5 nanometers (nm) in thickness). That is, preferably, a coating from the aqueous dilution is at least about 2.0 nm in thickness for anti-sawing purposes in articles having an AR film, and more preferably, at least about 3.0 nm in thickness. The coating from the aqueous dilution is typically present in an amount that does not substantially change the antireflective characteristics of the anti-reflective article. Methods for applying aqueous dilution to a substrate include, but are not limited to, spray coating, spinning, submerging, flow and roller coating methods, etc. A preferred coating method for application of the aqueous dilution includes spraying application. The dispersion can be effected by passing the pressurized aqueous dilution through a jet, nozzle or orifice onto the surface of the substrate in the form of an atomized stream or mist. A substrate to be coated can typically be brought into contact with the aqueous dilution at room temperature (typical and about 20 ° C to about 25 ° C). Alternatively, the aqueous dilution can be applied to a substrate that is preheated at a temperature of, for example, between 60 ° C and 150 ° C. This is of particular interest for industrial production, where, for example, ceramic tiles can be treated immediately after the kiln is burned at the end of the production line. After application, the treated substrate can be dried and cured at room temperature or elevated for a sufficient time for drying or curing. The coating obtained on the substrate can be cured by UV or thermal radiation. For UV curing, curative additives (such as those optional additives described above) can be added. Thermal curing is performed at an elevated temperature of from about 40 to about 300 ° C, although high temperatures may not be required. The heat for curing can be supplied either through preheating of substrates having sufficient heat capacity to provide the heat for cure, or by heating the substrates coated with an external heat source subsequent to the coating. Article Another embodiment of the present invention is an article which comprises (a) a substrate (as described above); and, (b) a coating on the substrate obtained by applying the aqueous dilution (described above) on the substrate and curing the aqueous dilution. Examples The invention is further illustrated by the following Examples, but the particular materials and amounts thereof drawn up in these Examples, as well as other conditions and details, should not be constructed by unduly limiting this invention.

Glossary MeFBSEA, C4F9S02N (CH3) CH2CH20C (CH = CH2, can be prepared as described in the application WO 01/30873 Al, Example 2, part A and B FCS-1; C4F9S02N (CH3) (CH2CH20) 7.5CH3, can be prepared as described in the application WO 01/30873 A1, example 1 part A and B. FCS-2, can be prepared as described in the application WO 01/30873 Al, Example 16. C4F9S02N (CH3) H can be prepared as described in the application WO 01/30873 A1, Example 1, part A. Measurement of the contact angle The treated substrates are tested for their contact angles against water (W) and n-hexadecane (O) using an Olympus TGHM goniometer (Oly Purser Corp, Pompano Beach Fl) Contact angles are measured before (initial) and after abrasion (abrasion), unless otherwise indicated, the contact angles with water and hexadecane are measured at least 24 hours after application or after abrasion.The values are average values of 4 measurements and are reported in g The minimum measurable value for a contact angle is 20. A value < 20 means that the liquid disperses on the surface. Abrasion / debugging method Abrasion test is performed using an Erichsen cleaning machine (Available from DCI, Belgium), 3M ™ HIGH PERFORMANCE ™ Cloth (available from 3M Co., S. Paul, Minnesota) and CIF ™ cream cleaner (available from Lever, Faberge, France) using 40 cycles. Preparation 1: MeFBSEA / A-160 = 4/1 A 500 ml three-necked round bottom flask is charged, fixed with a condenser, stirrer and thermometer, with MeFBSEA (41.1 g, 0.1 mole), A-160 (4.9 g, 0.025 moles), ethyl acetate (46.0 g), and AIBN (0.1 g). The mixture is degassed three times using vacuum cleaner and filled with nitrogen. The mixture is reacted under nitrogen at 75 ° C for 8 hours. Additional AIBN (0.05 g) is added and the reaction is continued for another 3 hours at 75 ° C. Another aliquot of AIBN (0.05 g) is added and the reaction is continued in 82 ° C for 2 hours. A clear solution of the oligomeric fluorochemical silane MeFBSEA / A-160 = 4 / l is obtained. Preparation 2: MeFBSEA / ODMA / TMPMA / A-160- = 6 / l / l / l The preparation of MeFBSEA / ODMA / TMPMA / A-160 = 6/1/1/1 is carried out following the following procedure described for the Preparation 1 with the exception that the flask is charged with MeFBSEA (61.6 g, 0.15 mol), ODMA (8.5 g, 0.025 mol) TMPMA (6.2 g, 0.025 mol), A-160 (4.9 g, 0.025 mol) and AIBN (0.1 g). Preparation 3: (MeFBSEA) 4SCH2CH2OH and reaction product with OCN (CH2) 3Si (OCH2CH3) 3 The fluorochemical silane (MeFBSEA) 4SCH2CH2OH and the reaction product are prepared with OCN (CH) 3Si (OCH2CH3) following a two-step reaction . In a first step, a fluorochemical oligomer, (MeFBSEA) SCH2CH2OH, is made according to the following procedure: A 3-liter reaction flask equipped with 2 reflux condensers, a mechanical Teflon knife stirrer, a thermometer, is charged. a nitrogen inlet and vacuum outlet, with MeFBSEA (2.4 moles) and lime acetate (987 g). The reaction is heated at 40 ° C until all the material dissolves. Add HSCH2CH2OH (0.6 moles) and AIBN (0.15) and heat the solution to 80 ° C, while stirring at 160 rpm. The reaction is run under a nitrogen atmosphere at 80 ° C for 16 hours, after which more than 95% conversion is obtained. In a second step, the resulting fluorochemical oligomer is reacted with an equimolar amount of OCN (CH2) 3Si (OCH2CH3) 3 according to the following method: a 500 ml three-necked round bottom flask is charged, fixed with a condenser, stirrer and thermometer, with MeFBSEA / HSCH2CH2OH (0.02 mole of a 60% solution of fluorochemical oligomer) as prepared above, ethyl acetate (22 g), OCN (CH2) 3 Si (OCH2CH3) 3 (5 g) and 2 drops of stannous octate catalyst, under nitrogen atmosphere. The mixture is heated to 75 ° C under nitrogen and reacted for 16 hours. Residual isocyanate can not be detected by infrared analysis. A clear solution results. Preparation 4: MeFBSEA / TMPMA / A-160 = 4/1/1 Preparation of MeFBSEA / TMPMA / A-160 @ 4/1/1 is carried out following the procedure described for Preparation 1 with the exception that the flask is additionally charged with TMPMA (6.2 g, 0.025 mol). Preparation 5: C4F9S02N (CH3) (CH2) 3Si (0CH3) 3 The fluorochemical compound C4F9S02N (CH3) (CH2) 3Si (OCH3) 3, used in Comparative Example C-2 is made according to the following procedure: 3-neck 500 ml reaction flask, fixed with a condenser, stirrer, nitrogen inlet, and thermometer, with 0.1 mole of CF9S02N (CH3) H (0.1 mole) and 30 g of dry dimethylformamide (30 g) . NaOCH 3 (0.1 mol, 30% solution in methanol) is added and the reaction mixture is heated for 1 hour at 50 ° C under nitrogen. The methanol is removed under a vacuum cleaner while maintaining the temperature at 50 ° C. The reaction is cooled to 25 ° C, after which Cl (CH 2) 3 Si (OCH 3) 3 (0.1 mol) is added. The reaction mixture is heated under nitrogen at 90 ° C for 16 hours. The NaCl that forms during the reaction is filtered. The completion of the reaction is followed by GLC. A yellow-coffee solution results. The DMF is removed by vacuum distillation and the fluorochemical reaction product is distilled at 120-150 ° C (approximately 0.4 mm Hg), resulting in a slightly yellow liquid. Example 1 A 150 ml glass bottle is charged with Preparation 2 (60.0 g, containing approximately 50% fluorochemical solids) and FCS-2 (20.0 g, 50% solution of a fluorochemical oligomeric surfactant in ethyl acetate) . After 2 minutes of gentle agitation, a clear solution, containing 50% fluorochemical solids, results. From this mixture, 2 grams are diluted in 97 grams of DI water and 1 g of 37% HCl is added. This water-based dilution is then sprayed hot (temperature of approximately 120 ° C), in glass wall, white mosaics available from Villeroy & Boch, Germany. The excess coating is removed after approximately 10 minutes using a soft cloth. The contact angles are measured according to the previous procedure before and after the abrasion. The results are summarized in Table 1. Examples 2 to 8 and Comparative examples Cl and C2 Examples 2 to 8 and comparative Cl and C2, according to the procedure of Example 1, using the ingredients and amounts as listed in Table 1.

Table 1 The values for post-abrasion contact angles of Examples of the invention are significantly superior , to the values for the Comparative Examples. This indicates improved abrasion resistance of the coatings of the Examples. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (26)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A non-aqueous, dilutable concentrate characterized in that it comprises a mixture of: A-MfnMhmMar-G wherein: A is hydrogen or a residue of a species initiator; Mf represents units derived from one or more fluorinated monomers; Mh represents units derived from one or more non-fluorinated monomers; Ma represents units derived from one or more non-fluorinated monomers having a silyl group; SiY3 where Y is a hydrolysable group; and G is a residue of a transfer chain agent of the formula: -S-Q-Y3 in which Y is a hydrolysable group and Q is an organic divalent linking group; n is an integer from 1 to 100; m is an integer from 0 to 100; and r is an integer from 0 to 100; and (b) at least one surfactant.
2. 2. The concentrate according to claim 1, characterized in that the fluorinated monomer is of the formula: Rf-Q-E (II) wherein Rf is a perfluoroalkyl group of C2 to C8; Q is an organic divalent linking group and E is an ethylenically unsaturated group.
3. 3. The concentrate according to claim 1, characterized in that it comprises: (a) at least one fluorinated oligomeric silane of the formula Wherein Rf is a perfluoroalkyl group of C2 to C8; R is a hydrocarbon group of 4 to 30 carbon atoms which can be substituted by one or more reactive groups; R and R2 are independently hydrogen or a Cx-C4 alkyl group; Q is - (CH2) -, in which n 'is an integer from 1 to 20; 0 / is a linking group of the formula S02N (R_.) (CH2) d-0C (0) -; O 'is a linking group of the formula - (CH2) c_-0C (0) -, or a chemical bond n is an integer from 1 to 20; m and r are integers from 0 to 20; and d is an integer from 1 to 20.
4. 4. The concentrate according to claim 1, characterized in that it also comprises one or both of at least one organic cosolvent and at least one additive.
5. 5. The concentrate according to claim 4, characterized in that the cosolvent is an alcohol, a ketone, an ether, N-methylpyrrolidinone, N, N-dimethylformamide, or a mixture thereof.
6. 6. The concentrate according to claim 1, characterized in that at least one surfactant comprises a fluorocarbon, a hydrocarbon, a silicone surfactant or a mixture thereof. The concentrate according to claim 6, characterized in that at least one fluorocarbon surfactant comprises: C4F9S02N (CH3) (C2H40) nCH3 in which where navg is approximately 7. The concentrate according to claim 6, characterized in that the at least one fluorocarbon surfactant comprises C3F70 (CF (CF3) CF20) nCF (CF3) C02 ~ NH4 + wherein nag is approximately 13. The concentrate according to claim 6, characterized in that at least one Fluorocarbon surfactant is a polymeric surfactant. 10. The concentrate according to claim 6, characterized in that at least one fluorocarbon surfactant is a random copolymer surfactant. 11. The concentrate according to claim 10, characterized in that the random copolymer surfactant comprises wherein the molar ratio of a: b: c is about 30: about 1: about 32, and wherein the fluorinated random copolymer surfactant has a molecular weight of about 1,000 to about 4,000 grams per mole. 12. The concentrate according to claim 10, characterized in that the random copolymer surfactant comprises: wherein the molar ratio of a ': b': c "is about 3: about 3: about 1, and wherein the fluorinated random copolymer surfactant has a molecular weight of about 5,000 to about 40,000 grams per mole. concentrate according to claim 6, characterized in that the at least hydrocarbon surfactant is dicocomethylammonium chloride. 14. The concentrate according to claim 6, characterized in that the at least hydrocarbon surfactant comprises alkylene diol polyethylene glycols, alkyl phenol polyethylene glycols or a mixture thereof. 15. The concentrate according to claim 6, characterized in that the at least silicone surfactant comprises alkyleneoxy containing silicone oligomers. 16. The concentrate according to claim 2, characterized in that Rf is a C3-C5 perfluoroalkyl group. 17. The concentrate according to claim 2, characterized in that Rf is a perfluoroalkyl group of C4. 18. The concentrate according to claim 1, characterized in that Y is independently -Cl, OCH3, 0C2H5, or C3-C3 alkoxy interrupted by a quaternary oxygen atom. 19. The concentrate according to claim 18, characterized in that Y is -Cl, OCH3, 0C2H5. 20. An aqueous composition characterized in that it comprises: (a) a dilution medium which comprises water or an aqueous solvent mixture comprising water and at least one water miscible cosolvent; and (b) a non-aqueous, dilutable concentrate which comprises a homogeneous, non-aqueous mixture according to claim 1. 21. An aqueous composition characterized in that it comprises: (a) a dilution medium which comprises water or a mixture of aqueous solvent comprising water and at least one cosolvent miscible with water; and (b) a homogeneous mixture of nonaqueous concentrate, dilutable according to claim 3. 22. A method for treating a substrate characterized in that it comprises the steps of applying an aqueous composition according to claim 20 to the substrate, and curing the aqueous composition. 23. An article characterized in that it comprises: (a) a substrate; and (b) a coating on the substrate obtained in accordance with the method of claim 22. 24. The article according to claim 23, characterized in that the substrate comprises glass. 25. The article according to claim 23, characterized in that the substrate comprises ceramic. 26. The article according to claim 23, characterized in that the substrate comprises an anti-reflective film.