MXPA97009821A - Composition repellent to a - Google Patents

Abstract

A composition is described which is formed by the combination of water with an organic polymer, such as a polybutylene or an alkyd resin and an alkoxysilane of the formula RnSi (OR ') 4-n, where R is an alkyl radical of 1 to 10 atoms carbon, an alkenyl radical having from 2 to 8 carbon atoms, phenyl, chloropropyl or trifluoropropyl, n is 1 or 2, and R 'is an alkyl radical having from 1 to 6 carbon atoms. The composition is free of functional amine or quaternary ammonium silanes. It is conveniently emulsified and used to treat a cellulose or masonry surface and make it repellent to ag

Description

WATER-REPELLENT COMPOSITION This application is related to US Patent No. 5,421,866, filed June 6, 1995, entitled "Water Repellent Compositions" and is commonly assigned to the present owner. This invention is directed to water repellent compositions containorganosilicon compounds and organic polymers such as polybutylene or an alkyd resin. We have unexpectedly discovered an improvement in the water repellent compositions of the aforementioned patent. In it, water repellents require, as essential edients, (i) an alkoxysilane, (ii) a silane couplagent, (iii) polybutylene, and (iv) water. The silane couplagent is a functional amine or quaternary ammonium silane. The silanes (i) and (ii) are used in a molar ratio of 0. 5: 1 to 3: 1. The silanes are introduced as a cold mixture, but, preferably, they are first reacted with a limited amount of water, ie, less than the stoichiometric amount, to form a partial hydrolyzate containalcohol, ie, ROH, which is formed as a byproduct of the hydrolysis reaction. Accordy, when the alkoxysilane (i) and the silane couplagent (ii) are mixed, in the presence of water, a reaction product is formed.

REF: 26365 To our surprise, however, there is the fact that when the silane (ii) containthe amino or quaternary ammonium functional groups is removed, significant improvements in the effectiveness of the water repellent are achieved (water repellent effectiveness -WRE ), water repellency (water repellency - WR), water absorption (WA) and pearl formation capacity. Accordy, while the repellent compositions accordto our invention are similar to those of the Patent North American 5,421,866, our water-repellent compositions are "free of functional amine or quaternary ammonium silanes," which are essential in it. Our invention relates to a water-repellent composition that is free of functional amine or quaternary ammonium silanes. This composition contains from 0.1 to 70 percent, by weight, of an organic polymer, such as polybutylene or an alkyd resin; from 0.1 to 70 percent, by weight, of an alkoxysilane RnSi (OR ') 4 -? -; where the balance of the composition is water (one hundred percent, by weight). Preferably, the combined amount of the organic polymer and the alkoxysilane make up a total of at least 3.0 percent, by weight, of our composition. The composition includes as optional components from 0 to 70, preferably from 3 to 70 percent, by weight, of an organic wax; from 0 to 70, preferably from 3 to 70 percent, by weight, of a polysiloxane; from 0 to 20, preferably from 0.1 to 2 percent, by weight of a pearlizagent; from 0 to 2, preferably from 0.1 to 2 percent, by weight, of a catalyst; a solvent in a certain amount to provide our composition with a volatile organic compound (VOC) content of less than 600 grams per liter; from 0 to 10, preferably from 0.1 to 10 percent, by weight, of a surfactant; and from 0 to 1, preferably from 0.1 to 1 percent, by weight, of a condom; an antifoamagent; a fungicide and a UV absorb/ UV stabilizsubstance. An organic polymer suitable for our invention is. a polybutylene polymer or oligomer, havan average molecular weight number (Mn) of from 200 to 2,300, preferably less than 1,500; and more preferably, less than 100. These polymers and oligomers are known in the art and many are commercially available in a variety of molecular weights and combinations of terminal groups. We have found that polybutylenes of relatively low molecular weight, i.e., Mn < 1,000, which have terminal groups, which are bound by hydrogen bondto hydroxyl groups, generally found in cellulose or masonry substrates, provide particularly superior water repellent compositions, in our invention. Accordingly, the preferred polybutylene polymers have at least one terminal group that contains a functional group such as epoxide, halide, alkoxyphenylene, hydroxyl, carboxyl, chlorosilyl, isocyanate, amino or amido. A highly preferred terminal group is the epoxide group. The other organic polymer suitable for our invention is an alkyd resin, including alkyd resins classified as oil-based, such as alkyd, long oil resins (ie, containing more than 55 percent, by weight, oil). fatty acid); alkyd oil resins, medias (i.e., containing 35 to 55 percent, by weight, of fatty acid oil); and alkyd, oil, short resins (ie, containing less than 35 percent, by weight, of the fatty acid oil, generally defined by their phthalic content, and alkyd resins of the oil type such as acid alkyd resins fatty acid oil (tall oil fatty acid - TOFA), alkyd resins of soybean oil (SOYA), alkyd resins of linseed oil, alkyd resins of vegetable oil, alkyd resins of fish oil, alkyd resins of coconut oil; and alkyd resins from castor oil.Alternative modified alkyd resins can also be used, such as alkyds modified with turpentine resin, alkyd resins modified with phenolic compounds, resins modified with rosin-phenolic compounds, modified alkyd resins with hydrocarbon and alkyd resins modified with styrene The alkyd resins can be alkyd resins solvent base, alkyd resins that can be dispersed in water, alkyd resins modified with monomer, soluble in water or air-dried alkyd resins. Representative alkyd resins are sold under the names of Arolon ™, Aroplaz ™, Beckosol ™ and Kelsol, by Reichhold Chemicals, I nc. , Durham, North Carolina. The most preferred alkyd resins of our invention are alkyd oil resins, averages (ie, soya oil alkyd resins (SOYA) and liquid resin oil (TOFA) alkyd resins), due to their external durability and stability. Also included here are silicone-modified alkyd resins, representative examples of which are described more fully in US Patent Nos. 3, 015, 637 and 3, 284, 384. These patents also contain more detail on alkyd resins in general Alkyd resins are still described in greater detail, for the interested reader, in the Encyclopedia of Poly mer Science and Engineering, Volume 1, Second Edition, pp. 644-679, John Wiley & Sons, (1985), and the Kirk-Oth mer Encyclopedia of Chemical Technology, Volume 2, Fourth Edition, pages 53-85, John Wiley &Sons, (1992). Accordingly, the term "alkyd resin" refers here to the products of the reaction of polyhydric alcohols and polybasic acids, i.e., polyesters, but polyesters containing monobasic acids such as long chain fatty acids. The alkoxysilane which is used herein is a simple alkoxysilane or a mixture of alkoxysilanes. It has the formula RnSi (OR ') 4-n. R is an alkyl radical of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; an alkenyl radical having from 2 to 8 carbon atoms; phenyl; chloropropyl or trifluoropropyl; n is 1 or 2; and R 'is an alkyl radical having from 1 to 6 carbon atoms. However, it is preferred that R is a methyl or isobutyl radical and that R 'is a methyl or ethyl radical. Some suitable alkoxysilanes are methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, etiltributoxisilano, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane (IBTES), butyltriethoxysilane, hexyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dietildimetoxisilano, diisobutyldimethoxysilane, phenyltrimethoxysilane, and dihexildimetoxisilano dibutildietoxisilano. Among the optional ingredients that are used according to our invention is an organic wax. The organic wax is preferably carnauba wax (Brazilian wax) or a mixture of petroleum and synthetic waxes. More particularly, organic wax is a mixture that includes both paraffin and polyethylene waxes. Polyethylene waxes can be high or low density polyethylene waxes, or mixtures of high density and low density polyethylene waxes. An exemplary organic wax and an organic wax that has been found especially suitable, according to our invention, is JONWAX® 125, a product and brand of SC Johnson &; Sons Inc., Racine, Wisconsin. JONWAX® 125 is sold as an aqueous emulsion of polyethylene and paraffin waxes, with a solids content of thirty-five percent. Other waxes of the paraffin and polyethylene mixture type can also be used. Another optional ingredient that is used according to our invention is a polysiloxane. A suitable polysiloxane is a polydimethylsiloxane with silanol termination, of structure HOMe2SiO (Me2SiO) xSiMe2ΔH, where Me is methyl and x typically ranges from 10 to 1,000. In general, these silanol fluids have a viscosity ranging from 15 to 20,000 centistokes (mm / 8), measured at 25 ° C. The terminal silanols make these fluids susceptible to condensation under both slightly acidic and slightly basic conditions. When the end groups are exposed to moisture, a rapid crosslinking reaction is carried out. Examples of these silane fluids are polydimethylsiloxanes with hydroxyl endings, having viscosities of 55 to 90 mm 2 / s, measured at 25 ° C, and having a hydroxyl content of 1 to 2.5 weight percent; polydimethylsiloxanes having hydroxyl endings and having viscosities of 1,800 to 2,200 mm2 / s, measured at 25 ° C; polydimethylsiloxanes with hydroxyl endings having viscosities of 3,500 to 4,500 mm2 / s, measured at 25 ° C; and polydimethylsiloxanes having viscosities of 11,000 to 14,000 mm 2 / s, measured at 25 ° C, where 85 to 95 percent of the end groups are silanol and from 5 to 15 percent of the terminal groups are trimethylsiloxyl. Another suitable polysiloxane is a silicone resin. More preferred are the solutions, in solvent, of the organosiloxane resinous copolymers, with hydroxyl functional groups, consisting essentially of CH3SIO3 / 2 units, (CH3) 2Si? 22 units, C6H5SÍO32 units and (C6H5) 2Si? 22 units, in a molar ratio of 25: 19: 37: 19 and having a hydroxyl content of 0.5 percent, by weight, up to 3.0 percent by weight. A specific silicone resin that is useful is a xylene / toluene solution, 1: 1, containing 50 percent, by weight, solids of a resinous organosiloxane copolymer with hydroxyl functional groups, with CH3SÍO3 / 2 units, units (CH3) 2Si? 22, units C6H5SÍO32 and units (C6H5) 2Si? 2/2, in a molar ratio of 25: 19: 37: 19 and having a hydroxyl content of 0.5 percent, by weight.

Another suitable silicone resin, which is useful, is a toluene solution containing 60 weight percent solids of a resinous organosiloxane copolymer, with hydroxyl functional groups, with CH 3 SiO 3/2 units, (CH 3) 2 Si units. ? 22, units and units (C? H5) 2 Si? 22, in a molar ratio of 25: 19: 37: 19 and having a hydroxyl content of 3.0 percent, by weight. A third specific silicone resin, which is suitable, is a xylene solution containing 50 weight percent solids of a resinous organosiloxane copolymer, with hydroxyl functional groups, with CH 3 SiO 3/2 units, (CH 3) 2 Si units? 22, units C6H5SÍO3 / 2 and units (CßH5) 2Si? 2/2, in a molar ratio of 25: 19: 37: 19. Examples of other silicone resins that are useful include the organosilicon resinous copolymers, which include SÍO4 / 2 units and one or more units of R3SÍO1 / 2, units R2SÍO2 / 2 and units RSiO.3 / 2, in such a molar ratio that the average molecular weight number of the resinous copolymer is from 1,200 to 10,000 dalton. R is an alkyl radical with 1 to 3 carbon atoms; an aryl radical such as phenyl, tolyl and xylyl; an alkenyl radical such as vinyl and allyl; or a trifluoropropyl radical. Following are three (3) specific resinous copolymers that can be used: I. A resinous copolymer soluble in an organic solvent (i.e., preferably benzene) with triorganosiloxyl units (R3SIO1 / 2) and Sio4 / 2 units with a molar ratio of 0.7 moles of triorganosiloxyl units per mole of SIO4 / 2 units. R has the meaning mentioned above. This resin has an average molecular weight number of 5,000 dalton, based on gel permeation chromatography analysis, using silicate resin standards. The triorganosiloxyl units are trimethylsiloxyl units and dimethylvinylsiloxyl units and the resin includes from 1.4 to 2.2 weight percent vinyl radicals attached to the silicon. II. A resinous copolymer siloxane which is prepared: (i) by forming a homogeneous, acidic mixture of a silanol containing resinous copolymer siloxane with units R3SIO1 / 2 and units SIO4 / 2; an organohydrogen polysiloxane, with the formula RmHnSiO (4m-n) / 2 where m and n are positive integers, with a sum less than four, preferably 1.9 to 2.1; and an organic solvent, and (ii) heating the mixture to remove substantially all of the organic solvent. R has the meaning defined above. R may also be an arylalkyl radical such as beta-phenylethyl and beta-phenylpropyl; or a cycloaliphatic radical such as cyclopentyl, cyclohexyl and cyclohexenyl. III. A resinous siloxane copolymer including R3SIO1 / 2 units and Si04 / 2 units in a molar ratio such that the average molecular weight number is from 1,200 to 10,000 daltons. Preferably, the molar ratio is 0.7: 1.0 and the average molecular weight number is 5,000. R is as defined above. The resin contains 2.5 weight percent OH groups bonded with silicon. The resin may also contain units R2SÍO2 / 2 and units RSi? 32. These silicone resins are described in detail in numerous patents, including U.S. Patent Nos. 2,504,388; 2,676,182; 2,706,190; 3,079,281; 4,310,678; and 4,322,518. Another suitable polysiloxane is a silsesquioxane resin, non-polar, in solid chips, containing 72.5 mole percent of C6H5SIO3 / 2 units; 27.5 mol percent of C3H7SIO3 / 2 units; and 5 weight percent OH groups. This type of resinous composition can be represented as (PhSi? 3/2) x (PrSi? 3/2) and OH in which Ph is phenyl, Pr is propyl and the ratio of x: y is 7: 3. Another suitable polysiloxane is an aqueous emulsion of silicone resin, which is prepared (A) by hydrolyzing at least one organochlorosilane in the presence of an organic solvent to form a hydrolyzate solution of the silicone resin, whereby the hydrolyzate of the resin of silicone has a hydrolysable residual chloride content of 15 to 100 parts per million, by weight; (B) exting the hydrolyzate solution to reduce the organic solvent content thereof; and (C) emulsifying the solution resulting from step (B), in water, with the aid of at least one anionic surfactant to form a uniform emulsion; with the proviso that the reduction in solvent content, according to step (B), provides an emulsion that forms a continuous film when applied to a subse and dried thereon. The silicone hydrolyzate includes at least two units such as the units MeSi? 3/2, the units MeSi? 2/2, units PhMeSi? 2/2, units PI1SÍO3.2, units PI12SÍO2 / 2 and units PrSiOs / 2; where Me is methyl, Ph is phenyl and Pr is propyl, in which the silicone has a hydroxyl content of 0.5 to 6.0 weight percent. This aqueous emulsion of the silicone resin is described more fully in U.S. Patent No. 5,300,327. Another optional ingredient that is used in our invention is a pearling agent. Representative examples are stearates such as aluminum stearate and magnesium stearate; Borate salts such as sodium borate and hydrophobic silica. These materials help in the spillage of water films from a surface forming droplets. Another optional ingredient is a catalyst. Representative examples of the catalysts are metal titanates such as dibutyltin dilaurate (DBTDL) and dibutyltin diacetate (DBTDA); acids, such as acetic acid; and bases, including amines such as triethanolamine (TEA), morpholine and diethylamine. These catalysts are capable of converting alkoxysilanes to resinous products by hydrolysis and condensation. Another optional ingredient of our invention is a solvent. Representative examples of solvents are organic solvents such as isopropanol and mineral spirits; glycol ethers such as diethylene glycol butyl ether and propylene glycol methyl ether sold under the emark Dowanol® by Dow Chemical Company, Midland, Michigan; and polyglycols such as ethylene glycol and propylene glycol. Another optional ingredient used in our invention is a surfactant. More preferred is a combination of nonionic surfactants with a low and high HLB value. As used herein "HLB" means value of the hydrophilic-lipophilic balance. The nonionic surfactant with low HLB has an HLB value less than 10.5, preferably less than 6.0. Representative emulsifiers in this category are: (a) Brij ™ 52 which is a polyoxyethylene cetyl ether and a product of ICI Americas Inc., Wilmington, Delaware, which has an HLB value of 4.9; (b) Brij ™ 72 which is a polyoxyethylene stearyl ether and a product of ICI Americas Inc., Wilmington Delaware, which has an HLB value of 4.9; (c) Arlacel ™ 60 which is sorbitan stearate and a product of ICI Americas Inc., Wilmington Delaware, which has an HLB value of 4.7; (d) Aldo® MS which is glycerol monostearate and a product of Lonza Inc., Fairlawn, New Jersey, which has an HLB value of 3.9; (e) Aldo® PGHMS which is propylene glycol monostearate and a Lonza Inc. product, Fairlawn, New Jersey, which has an HLB value of 3.0; (f) Mapeg® EGMS, which is ethylene glycol monostearate and product of PPG / Mazer, Gurnee, Illinois, which has an HLB value of 2.9; (g) Hodag ™ DGS, which is diethylene glycol monostearate and a product of Hodag ™ Chemical Corp., Skokie Illinois, which has an HLB value of 4.7; (h) Ethox ™ SAM-2, which is a polyoxyethylene stearyl amine and a product of Ethox Chemicals I.nc, Greenville, South Carolina, having an HLB value of 4.9; e (i) Macol® SA-2, which is a polyoxyethylene stearyl ester and a product of PPG / Mazer, Gurnee, Illinois, which has an HLB value of 4.9. Fatty alcohols, such as lauryl alcohol, myristyl alcohol and cetyl alcohol, are considered non-ionic surfactants, with an HLB value of one and are included as a non-ionic surfactant for purposes of our invention. The nonionic surfactant with high HLB has an HLB value greater than 15.0, and preferably greater than 17.0. Representative emulsifiers in this category are: (i) Brij ™ 700, which is a polyoxyethylene stearyl ether and a product of ICI Americas Inc., Wilmington, Delaware, which has an HLB value of 18.8; (ii) Mapeg® S-40K, which is a polyoxyethylene monostearate and a product of PPG / Mazer, Gurnee, Illinois, which has an HLB value of 17.2; (iii) Macol® SA-40, which is esteareth-40 and a product of PPG / Mazer, Gurnee, Illinois, which has an HLB value of 17.4; (iv) Triton® X-405, which is octylphenoxy polyethoxy ethanol and a product of Union Carbide Chem. & Plastics Co., Industrial Chemicals Div., Danbury, Connecticut, which has an HLB value of 17.9; (v) Macol® SA-20, which is steareth-20 and a product of PPG / Mazer, Gurnee, Illinois, which has an HLB value of 15.4; and (vi) Tergitol® 15-S-20, which is a secondary alcohol ethoxylate, C11-C15, and a product of Union Carbide Chem. & Plastics Co., Industrial Chemicals Div., Danbury, Connecticut, which has an HLB value of 16.3. The above surfactants are merely stated for the purpose of identifying representative emulsifiers that can be used according to our invention. Other equivalent nonionic emulsifiers can also be substituted. Accordingly, it would be appropriate to use, for example, (i) other alcohol ethoxylates, in addition to Brij ™ 52, Brij ™ 72, and Brij ™ 700; (ii) other alkylphenol ethoxylates, in addition to Triton® X-405; (iii) other glycerol esters of the fatty acids, in addition to Aldo® MS; and (iv) other glycol esters of the fatty acids, in addition to Aldo® PGHMS and Hodag ™ DGS. Accordingly, non-ionic surfactants, such as fluorocarbon-based surfactants, sold as Fluorad ™, are included herein by 3M Company, St. Paul, Minnesota; block copolymers of ethylene oxide and propylene oxide, sold under the trademark Pluronic®, by BASF Corporation, Pasippany, New Jersey; fatty acid esters, sold as Span ™, by ICI Surfactants, Wilmington, Delaware. Certain polymeric anionic emulsifiers can be used in combination with these nonionic surfactants, such as hydrophobically modified, crosslinked, polyacrylic acid polymers, sold as Pemulen®, by BF Goodrich, Brecksville, Ohio; and the hydrophobically modified, crosslinked polyacrylic acid copolymers sold as Carbopol®, by BF Goodrich, Brecksville, Ohio. In addition, synthetic water-soluble resins, such as polyvinyl alcohols (C2H40) X, can be used. If desired, an anionic surfactant can be formed in situ by including in the mixture a base, such as sodium hydroxide, triethanolamine or morpholine; and a fatty acid, such as stearic acid, oleic acid or a fatty acid of liquid resin. Another optional ingredient of our invention is a condom to reduce and / or eliminate microbial activity in water-based emulsions. Representative examples are 5-chloro-2-methyl-4-isothiazolin-3-one, sold under the tradename Kathon ™ LX, by Rohm and Haas Co., Philadelphia, Pennsylvania; and l- (3-chloroalyl) -3,5,7-triaza-l-azonia-adamantane chloride, sold under the tradename Dowicil® 75, by Dow Chemical Company, Midland, Michigan. Another optional ingredient that can be used in our invention is an antispamper. Suitable defoamers are silicone defoamers, such as polydimethylsiloxane with a silica-based bead-forming agent, sold by Dow Corning Corporation, Midland, Michigan; and organic defoamers such as hydrocarbon oils, sold under the Advantage® trademark, by Hercules Incorporated, Wilmington, Delaware. Another optional ingredient in our invention, when the composition is intended to be used as an outer coating, is a fungicide, including materials classified as algaecides, antimicrobials, bactericides, disinfectants or fungicides; which are organic or inorganic materials that reduce biological activity in a substrate. Representative examples of some suitable fungicides include proprietary fungicides sold under the trademark Troysan® Polyphase® P-20T, by the Troy Chemical Company, East Hanover, New Jersey; diiodomethyl-p-tolylsulfone, sold under the trademark Amical®, by Angus Chemical Co., Buffalo Grove, Illinois; tribasic copper sulfate; and the stabilized chlorine dioxide. Another optional ingredient of our invention, where the composition is intended to be used as an outer coating, is a UV absorber / UV light stabilizer. Suitable UV absorbers / UV light stabilizers are substituted benzotriazole and hindered amines sold under the trademark Tinuvin®, by Ciba Geigy Corporation, Hawthorne, New York. The water repellent compositions for the treatment of surfaces, according to our invention, are manufactured by simple mixing of various ingredients. Where a composition in the form of an emulsion is desired, it is manufactured by (i) making an emulsion of various ingredients; (ii) making several emulsions, where each one contains one or more of the ingredients and then the various emulsions are combined; and (iii) following the procedure for (i) or (ii) and then adding some of the ingredients directly into the water. These blends and emulsions are manufactured using any suitable source of shear stress, such as a high-speed stirrer, homogenizer, sonicator, microfluidizer, Turello ™ mixer with can change, Ross ™ mixer or an Eppenbach colloid mill ™. The process for making the mixtures and mixtures includes the direct addition of oil to the water, or the indirect addition of water to the oil. Preferably, the particle size of the active ingredient (s), in the discontinuous or internal phase, is between 0.2 micrometers (μm) and 500 micrometers (μm).

These water repellent compositions can be formulated as a concentrated emulsion having a high solids content, for later dilution and direct application to a substrate; or they can be formulated as ready-to-use emulsions, with a low solids content, for their direct application to the substrate. The actual amount employed of the water repellent composition will vary depending on the nature of the substrate being treated, but, in general, it must be sufficient to provide the substrate with a coating containing from 3 to 40 percent, in weight, of the solids in the composition repels the water that is being applied. Suitable substrates for treatment with water repellent compositions, according to our invention, include n cellulose surfaces, such as wood, cloth, fiber, paper and cardboard; masonry surfaces such as porous inorganic substrates, including concrete, mortar, brick, stone, plaster, stucco, terracotta, adobe, plaster, limestone, marble, porcelain and tile; and concrete structures for construction. The method of application of our water-repellent composition is preferably by means of a topical treatment, or by means of topical coating of the substrate. However, the use of these water repellent compositions may also include their incorporation directly into the substrate during their manufacture, i. and. , as an additive in the paper mix, or as an ingredient in a concrete mix before it solidifies. When applied topically, for best results, it is preferred that the substrate be treated when it is dry, but the substrates may be treated when wet or damp. Then there are several examples to illustrate our invention in more detail. In the examples, as well as in the Tables that accompany them, all the percentages are based on weight, unless otherwise indicated.

Example I - Preparation of the sample. Aqueous emulsions of the water repellent compositions were prepared by mixing the various components at the indicated active levels, which are shown below. In preparing these emulsions, the polybutylene component and the non-water dispersible silicone were mixed until they were completely combined, using a standard laboratory mixer. Air or electrically driven mixers were used, depending on the viscosity of each mix. The surfactant (s) was (are) incorporated in the oil phase or in the aqueous phase, depending on the nature of the surfactant (s). In some cases, one surfactant was incorporated into the aqueous phase and another surfactant was incorporated into the acene phase. The oil phase and the aqueous phase were combined with vigorous stirring until an oil-in-water emulsion was obtained, achieving the desired particle size, i.e., generally from 0.2 micrometers (μm) to 500 micrometers (μm). The remaining water was slowly incorporated into the emulsion to achieve the desired active levels, i.e., generally from 3 to 70 percent, by weight. In some embodiments, the emulsion was then mixed with a wax emulsion and any other silicones dispersible in water. The resulting mixture was diluted to the final, active, desired level, ie, a concentrated emulsion having a high solids content, for further dilution and application to a substrate, or an emulsion ready for use, with a low solids content. , for direct application to the substrate. While it is apparent that many different types and combinations of surfactants can be used to prepare these emulsions, it was found that the nonionic surfactants Triton® X-45 and Triton® X-705 are particularly effective. The polybutylene (PIB) used in the examples, and in the accompanying Tables, was (i) a polybutylene with vinyl terminations, having an average molecular weight number of 1,340, which is a product sold with the trade name Indopol® H-300, by Amoco Chemical Company, Chicago, Illinois; (ii) a polybutylene with vinyl endings, having an average molecular weight number of 2,160, which is a product sold as Indopol® H-1500, by Amoco Chemical Company, Chicago, Illinois; and (iii) an epoxidized polybutylene having an estimated average molecular weight number of 1,000, which is a product sold as Vikopol® 64, by Elf Atochem North America Philadelphia, Pennsylvania. The optional wax ingredient, used in these examples, and referred to in the accompanying Tables, was a 35% solids emulsion of a wax consisting of 50% polyethylene and 50% paraffin. These wax emulsions are commercially available from SC Johnson & Sons Inc., Racine, Wisconsin, as JONWAX® 125; and of Michelman Inc., Cincinnati, Ohio.

Example II - Wood. An aqueous, water repellent composition for the treatment of wood, representative of our invention, was prepared according to the procedure of Example I. The composition contained, on a weight basis, the following active ingredients, where the balance of the 100% composition is water: Quantity (%) Ingredient 2.10 PIB Indopol® H-300 0.90 Isobutyltriethoxysilane 4.00 Wax - Emulsion wax, Michelman Inc. . 00 Surfactant The surfactant was a mixture containing (i) a non-ionic fatty acid surfactant, sold as Actinol® FA-3, by Arizona Chemical Company, Panama City, Florida; (ii) triethanolamine; and (iii) Triton® X-705, a trademark of Union Carbide Chem. & Plastics Co., Industrial Chemicals Div., Danbury, Connecticut, for octylphenoxy polyethoxyethanol, a non-ionic surfactant. This composition did not contain functional amine or quaternary ammonium silane.

Example III - Wood. Another water-repellent aqueous composition for the treatment of wood, representative of our invention, was prepared according to the procedure of Example I. The composition contained, on a weight basis, the following active ingredients, where the balance at 100%, in the composition, is water: Quantity (%) Ingredient 1.50 PIB Indopol® H-300 0.75 Isobutyltriethoxysilane 0.75 Silicone resin - units Mß2Si? 22 and PhMeSi02 / 2 4.00 Wax - Emulsion wax, Michelman Inc. . 00 Surfactant.

The surfactant mixture that was used in Example II was used in this Example. This composition also did not contain a functional amine or quaternary ammonium silane.

Eje mplo IV - Comparison - Wood. An aqueous, water repellent composition was prepared for the treatment of the wood, NOT representative of our invention, according to the procedure of Example I. The composition contains, on a weight basis, the following active ingredients, where the balance of the composition at 100% is water: Quantity (%) Ingredient 2.51 PIB Indopol® H-300 1.24 Isobutyltriethoxysilane 1.25 A mixture of water, methyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane This composition DOES contain a functional amine or quaternary ammonium silane, i. and. , N- (2-aminoethyl) -3-aminopropyl trimethoxysilane. It is representative of the water repellent compositions taught by US Pat. No. 5, 421, 866, on which our invention is an improvement.

Eiemp lo V - Comparison - Wood. Another water-repellent aqueous composition for the treatment of wood was prepared, NOT representative of our invention, according to the procedure, according to the procedure in Example I. The composition contained, on a weight basis, the following active ingredients, where the balance of the composition at 100% is water. Amount (%) Ingredient 2.50 PIB Indopol® H-300 2.50 A mixture of water, methyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane . 00 Surfactant - Tergitol ™ TMN-6 This composition S? contained a functional amine or quaternary ammonium silane, i.e., N- (2-aminoethyl) -3-aminopropyl trimethoxysilane. It is also representative of the water repellent compositions taught by Patent 5,421,866, on which our invention is an improvement. The water-repellent compositions, prepared according to Examples II-V, were used for the treatment of wood and evaluated in their ability to repel water, according to three primary, standard, industry test methods.

The three methods used were (i) the Swelling Meter Test Method, in accordance with Federal Specification TT-W-572B and ASTM D4446; (ii) the Gravimetric Test Method, in accordance with ASTM D5401; and (iii) the Test Method of the Pearl formation.

The Swelling Meter Test Method - Fed. Spec. TT-W-572B or ASTM D4446. This test evaluates the protection provided to wood by various treatments, by measuring both the water uptake and the dimensional stability of samples of treated wood versus untreated. The wood samples were wafers of 6.4 x 38.1 x 254 cm (0.25 x 1.5 x 10 inches) of cross section, cut from the pine swamp pine tree (Pinus echinata), of straight granulate, without knots, tangentially sawed, clean, of average density , dried in the oven. All wood wafers were conditioned at 50 ± 5% relative humidity and at 70 ± 5 ° F (21 ± 3 ° C) until a constant weight was obtained (± 0.5 g in 24 hours) and a constant moisture content (12.5%). The moisture content was determined by the method ASTM D4442. The wood was dried in an oven at 217 ± 5 ° F (103 ± 2 ° C) and the moisture content was calculated by the formula: (original dough - dough dried in the oven)% MC = X 100 (dough dried in the oven) The wafers were removed from the conditioning room and treated immediately by soaking 3 minutes in water-based formulations, 30 seconds in solvent-based formulations. The treated wafers were then placed on a raised screen or frame at a 45 ° angle and allowed to air dry under ambient conditions overnight. An untreated wafer, taken from consecutive pieces of the same table, was used as a control for each treated wafer. Groups of treated and untreated pairs were then placed in a chamber and conditioned at 65 ± 5% relative humidity and at a temperature of 70 ± 5 ° F (21 ± 3 ° C), until a constant weight was reached (7). days). The wafers were then placed in a swelling measuring test apparatus, which was then immersed in deionized water, maintained at a temperature of 75 ± 5 ° F (24 ± 3 ° C) for 30 minutes. The change in the dimensions of the wafer treated with water was measured by the gauge of the swelling meter during soaking and was used to calculate the% Water Repellency (WR - Water Repellency). After removing it from the calibrator, the wood was weighed and determined the% Water Exclusion (WE - Water Exclusion), from the degree of gain in weight. The water repellency% (% WR) was calculated by comparing the swelling of the treated wafer with that of the untreated wafer with the formula: (swelling of the control - swelling of the treated wafer)% WR = - X 100 (swelling of the wafer) control) The percent water exclusion (% WE) was calculated by comparing the weight gain of the treated wafer with the untreated wafer, using the formula: (control H2O uptake - H2O uptake of the treated wafer)% WE = X100 (control weight gain) The Gravimetric Test Method in accordance with ASTM D5401. The test method was used to evaluate the effectiveness of clear, water repellent coatings on wood. The substrates were tables of the ponderosa pine tree (Pinus ponderosa) of 1.5 x 10.2 xl5.2 cm (2 x 4 x 6 inches) of straight granulate, without knots, tangentially sawn, dried in the oven, conditioned at a relative humidity of 50 ± 5% and a temperature of 70 ± 5 ° F (21 ± 3 ° C) until a constant weight (± 1 g in 24 hours) and humidity (12.5%) were reached. The moisture content was determined by means of the method ASTM D4442, in the same way described above. After reaching these conditions, the boards were removed from the conditioning room and treated immediately by soaking 3 minutes in water-based formulations or 30 seconds in solvent-based formulations. The treated boards were placed in a raised frame and left to cure in the laboratory at ambient conditions throughout the night. Three control tables were left untreated for each day of the test and were kept in the room at 50% humidity. The tables were then balanced in the room at 50% humidity until the change in weight, of two successive measurements of 24 hours, was less than 0.5 g (6-7 days). The treated and untreated boards were weighed, each, and then left floating in distilled / deionized water, maintained at a temperature of 75 ± 5 ° F (24 ± 3 ° C) for 30 minutes, 15 minutes per side, turning them around The boards were removed. The excess water was cleaned and each was reweighed. The percentage of Water Repellent Effectiveness (% WRE-Water Repellent Effectiveness) was calculated by comparing the weight gain of the treated tables with the average weight gain of the untreated controls using the formula: (control H2O uptake - H2O uptake of the treated wafer)% WRE = X 100 (control H2O uptake) The Pearl Formation Test Method. The pearl formation test was used to evaluate the pearl formation ability of several samples on the wood. Pearl formation for each composition was evaluated using the gravimetric tables described above before evaluation. Approximately 6 to 8 drops of water were dropped on the board using an eye dropper and then the boards were sprayed with water. Pearl formation was evaluated on a scale of 0 to 5, where 5 is an exceptional pearl formation with tight spherical beads, 3 is a moderate pearl formation with pearls plus irregularly shaped beads and 0 there is no pearl formation. Table I shows the results on the wood for the water repellent compositions of Examples II to V in the evaluations according to (i) the Swelling Meter Test Method, (ii) the Gravimetric Test Method, and ( iii) the Pearl Formation Test Method.

TABLE I Example% WRE% WE% WR Gravimetric Formation Bead Meter Meter Inflation Inflation 0 to 5 II 86 77 67 4 + III 88 78 70 4 + IV 6 1 6 1 3 + V 72 1 4 3. 4 The water-repellent compositions according to our invention, in Examples II and III, were much more effective in all the evaluated categories, as seen in Table I, in comparison with the water-repellent compositions which are NOT in accordance with our invention, shown in Examples IV and V. In particular note that the values for% Water Exclusion (WE) and% Water Repellency (WR) varied up to 10 to 20 times, or more.

Example VI - Stoneware (Sandstone) A water-repellent aqueous composition for the stoneware treatment representative of our invention was prepared according to the procedure of Example I. The composition contained, on a weight basis, the following active ingredients, where the balance of the composition at 100% is water: Quantity (%) Ingredient 1.00 PIB Indopol® H-300 1.00 PIB Indopol® H-1500 1.00 Isobutyltriethoxysilane 4.00 Wax - Emulsion Wax, Michelman Inc. 5.00 Surfactant The surfactant was the same mixture used in Examples II and III, and contained (i) Actinol® FA-3; (ii) Triethanolamine; and (iii) Triton® X-705. This composition did not contain functional amine or quaternary ammonium silane.

Example VII - Comparison - Stoneware An aqueous water repellent composition was prepared for stoneware treatment, NOT representative of our invention, according to the procedure of Example I. This composition contained on a weight basis, the same active ingredients used in the invention. Example V, ie, Indopol® H-300 PIB; Methyltrimethoxysilane; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Tergitol® TMN-6 and water. The composition YES contained a functional amine or quaternary ammonium silane, i.e., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. It is representative of the water repellent compositions taught by US Pat. No. ,421,866, on which our invention is an improvement.

Example VIII - Mortar An aqueous water repellent composition for the mortar treatment representative of our invention was prepared according to the procedure of Example I. The composition contained, on a weight basis, the same active ingredients used in the Example VI, ie, Indopol® H-300 GDP; Indopol® H-1500 GDP; Isobutyltriethoxysilane; Wax Emulsion, Michelman Inc .; and the surfactant was the same mixture used in Examples II, III and VI, and contained (i) Actinol® FA-3; (ii) Triethanolamine; and (iii) Triton® X-705.

This composition did not contain a functional amine or quaternary ammonium silane.

Example IX - Mortar Another aqueous water repellent composition was prepared for the mortar treatment, representative of our invention, according to the procedure of Example I. The composition contained, on a weight basis, the following active ingredients, where the balance of the composition at 100% is water: Quantity (%) Ingredient 28.00 PIB Indopol® H-300 10.00 Isobutyltriethoxysilane 40.00 Silicone resin - units Me2Si? 2/2 and PhMeSi02 / 2 5.00 Surfactant The surfactant was the same mixture used in the Examples II, III, VI and VIII, and contained (i) Actinol® FA-3; (ii) triethanolamine; and (iii) Triton® X-705. This composition also did not contain a functional amine or quaternary ammonium silane.

Example X - Comparison - Mortar A water-repellent aqueous composition for mortar treatment, NOT representative of our invention, was prepared according to the procedure of Example I. This composition contained, on a weight basis, the same active ingredients used in Examples V and VII, ie, PIB Indopol® H-300; Methyltrimethoxysilane; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; Tergitol® TMN-6 and water. This composition YES contained a functional amine or quaternary ammonium silane, i.e., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. It is representative of the repellent compositions taught by US Pat. No. 5,421,866, on which our invention is an improvement. The water-repellent compositions prepared according to Examples Vi and VII were used to treat stoneware and the water-repellent compositions, prepared according to Examples VIII to X, were used to treat mortar and evaluated for water absorption (WA ), water exclusion (WE) and pearl formation, according to industry standard, primary test methods. The methods used were (i) Federal Specification SS-W-110C, a test procedure for masonry, which covers stoneware and mortar; and (ii) the Pearl Formation Test Method, mentioned above. Test Procedure - Masonry - Federal Specification SS-W-110C. This specification covers clear penetrating solutions that provide water repellency to exterior materials for masonry, such as stoneware and mortar. The water absorption (WA) characteristics of a substrate are evaluated by soaking each block in 6.4 mm (1/4 inch) of water for three days. The results are reported as percent of water absorption (% WA) based on the dry weight of the cube, and as a percent of water exclusion (% WE), based on the difference in water uptake between treated cubes and not treated. Substrates were treated in duplicate for each of the emulsions prepared in Examples VI to X. The stoneware cubes were cut from Briar Hill stoneware to the dimensions of 2.5 x 2.5 x 10.2 cm (1 x 1 x 4 inches). The mortar cubes were manufactured with Type I cement cured for 28 days and cut into 2 inch cubes. The surface of each substrate was brushed with a wire brush and the excess powder was blown with air. The cubes were dried in an oven at 80 ° C ± 5 ° C, until they reached a constant weight, i.e., with a variation of less than 0.2 grams in a period of more than four hours. After the cubes had reached a constant weight, they were allowed to cool to room temperature. The weight of each earthenware and mortar cube was determined up to 0.1 g and recorded. The untreated control cubes were placed in 6.4 mm (1/4 inch) of water for 24 hours. Then the cubes were removed from the water and the excess water was removed with a damp cloth. Wet weights were determined and the amount of water absorbed was calculated as one percent dry weight. The cubes were returned to the oven until they reached a constant weight. Once the untreated cubes had reached a constant weight, they were allowed to cool to room temperature, weighed and treated immediately with the test composition for 30 seconds. The amount of coverage was determined by the difference of dry weight to wet weight, i.e., 151 / grams of treatment = 6.0132 m2 / m3 (151 / grams of treatment x 4.07 = ft2 / gal). The treated cubes were placed in a rack in the laboratory and rotated every minute for the first hour. The cubes were allowed to cure at room temperature for 48 hours. After 48 hours, the weight of each cube was determined and the cubes were submerged in 6.4 mm (1/4 inch) of water for 72 hours. The appearance of each cube was noted, as well as the ability of the substrate to make the water form pearls, before the cubes were placed in the water. The cubes were removed after 72 hours and the excess water was removed with a cloth. The cubes were weighed and the amount of water absorbed was calculated based on the dry weight of the cube. The calculations were made using the following formulas:% WE = (C2 - Cl) - (S2 - SI) < C2 - Cl) x 100% WA = (S2 - SI) Sl x 100 where Cl is the uncoated substrate before immersion; C2 is the uncoated substrate after immersion; If it is the substrate treated before the immersion; and S2 is the substrate treated after immersion. Table II shows the stoneware results for the water repellent compositions of Examples VI and VII, in the evaluations according to (i) Federal Specification SS-W-110C, Masonry Testing Procedure; and (ii) the Pearl Formation Test Method.

Table II Example% WA% WE Formation of SS-W-110C SS-W-110C Pearls 0 to 5 v 0 ~ 6 92 VII 8.8 -20 The water-repellent compositions, according to our invention, in Example VI, were again much more effective in all the evaluated categories, as seen in Table II, in comparison with water-repellent compositions that are NOT according to this invention, shown in Example VII. In particular, note that the values for the% Water Absorption (WA) and% Water Exclusion (WE), varied significantly and that the formation of pearls was much better.

Table III shows the results on the mortar for the repellent compositions of Examples VIII to X, in evaluations in accordance with (i) Federal Specification SS-W-110C, Test Procedure for Masonry; and (ii) the Pearl Formation Test Method.

Table III Example% WA% WE Formation of ss -W-110C SS -W-110C Pearls 0 to 5 VIII 1.6 80 1 + IX 0.4 95 1 X 7.9 11 2 The water-repellent compositions of our invention, in Examples VIII and IX, were again much more effective, as seen in Table III, compared to the water-repellent compositions which are NOT according to our invention, shown in Example X. In particular, note that the values for the% Water Exclusion (WE) varied significantly. The following Examples further illustrate our invention, wherein the organic polymer used in preparing the water repellent composition was an alkyd resin, rather than polybutylene, which was used in Examples II to X.

Example XI - Wood A water-repellent aqueous composition for the treatment of wood, representative of our invention, was prepared by the procedure of Example I. The composition contained on a weight basis, the following active ingredients, the balance being composition, 100%, water; Quantity (%) Ingredient 2.00 Alkyd Resin Modified with medium soybean oil 1.00 Isobutyltriethoxysilane 4.00 Wax - Wax Emulsion, Michelman Inc. 5.00 Surfactant The surfactant was the same mixture used in Examples II, III, VI, VIII and IX, which contained (i) Actinol® FA-3; (ii) triethanolamine; and (iii) Triton® X-705. This composition did not contain a functional amine or quaternary ammonium silane.

Example XII - Comparison - Wood An aqueous composition, water repellent, was prepared for the treatment of wood, NOT representative of our invention, according to the procedure of Example I. The composition contained, on a weight basis, the following ingredients assets, where the balance of the composition at 100% is water: Amount (%) Ingredient 2.00 Alkyd resin modified with medium soybean oil 1.00 Isobutyltriethoxysilane 4.00 Wax - Wax Emulsion, Michelman Inc. 0.20 N- (2-aminoethyl) -3-aminopropyltrimethoxysilane . 00 Surfactant The surfactant was the same mixture as the one used in the Examples II, III, VI, VIII, IX and XI, and contained (i) Actinol® FA-3; (ii) triethanolamine; and (iii) Triton® X-705. This composition did contain a functional amine or quaternary ammonium silane, i.e., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. The following table shows the results on wood for the repellent compositions of Examples XI and XII, in the evaluations according to (i) the Meter Test Method of Swelling, (ii) the Gravimetric Test Method, and (iii) the Pearl Formation Test Method, all mentioned above. TABLE IV Example% WRE% WE% WR Gravimetric Formation Bead Meter Meter Inflation Swelling 0 to 5 XI 89 59 32 3+ XII 89 64 49 4 The water repellent compositions of our invention in Example XI, were equivalent in comparison with the water repellent compositions that are NOT according to our invention, shown in Example XII. It is noted that, in relation to this date, the best known method for the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or substances to which it refers. Having described the invention as above, the content of the following is claimed as property.

Claims (9)

REVINDICAT IONS

1. A composition, characterized in that it comprises a mixture formed by the combination of water; an organic polymer selected from the group consisting of polybutylene and an alkyd resin; and an alkoxysilane of the formula R n S i (OR ') 4 -, wherein R is an alkyl radical of 1 to 10 carbon atoms, an alkenyl radical having 2 to 8 carbon atoms, phenyl, chloropropyl or trifluorop ropyl; n is 1 or 2; and R 'is an alkyl radical having from 1 to 6 carbon atoms; where the composition is free, functional amine silanes or quaternary ammonium.

2. The composition, according to claim 1, characterized in that the alkoxysilane is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, pyrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diisobutyldimethoxysilane, phenyltrimethoxysilane, dibutyldiethoxysilane and dihexyldimethoxysilane.

3. The composition, according to claim 1, characterized in that the organic polymer is a polybutylene polymer or oligomer having a number average molecular weight of 200 to 2, 300 and containing at least one terminal group selected from the group consisting of of epoxide, halide, alkoxyphenylene, hydroxyl, carboxyl, chlorosilyl, isocyanate, amino and amido.

4. The composition, according to claim 1, characterized in that the organic polymer is an alkyd resin, selected from the group consisting of long oil alkyd resins, containing more than 55 percent by weight of fatty acid oil. , alkyd resins of medium oil, containing from 35 to 55 percent, by weight, of fatty acid oil, the short oil alkyd resins, containing less than 35 percent, by weight, of fatty acid oil, resins alkyds of liquid resin fatty acid, alkyd soy oil resins, alkyd alkali resins of flax oil, vegetable oil alkyd resins, fish oil alkyd resins, coconut oil alkyd resins, castor oil alkyd resins, alkyd resins modified with turpentine resin, alkyd resins modified with phenolic compounds, alkyds resins modified with rosin-phenolic compounds icos, alkyd resins modified with styrene and alkyd resins modified with silicone.

5. The composition according to claim 1, characterized in that it also comprises at least one additional component selected from the group consisting of an organic wax, a polysiloxane, a pearlizing agent, a catalyst, a solvent in an amount such as provide the composition with a content of volatile organic compounds of less than 600 grams per liter, a surfactant, a preservative, a defoamer, a fungicide and a UV absorber / UV stabilizer compound.

6. The composition, according to claim 5, characterized in that the additional component is a polysiloxane which is a silicone resin or a polydimethylsiloxane with silanol endings.

7. The composition, according to claim 5, characterized in that the additional component is at least two surfactants, where one surfactant has a hydrophilic-lipophilic balance value less than 10.5 and the other surfactant has a hydrophilic-lipophilic balance value greater than 15.

8. The composition, according to claim 7, characterized in that the composition is emulsified.

9. A method for rendering a cellulose or masonry surface water repellent, wherein the method is characterized in that it comprises applying to the surface the composition according to claim 1.