MX2008007252A - Epoxy silane oligomer and coating composition containing same - Google Patents

Abstract

A process for producing an epoxy silane oligomer including a reaction glycidoxy silane and/or cycloaliphatic epoxy silane having 2 or 3 alkoxy groups and, optionally, a copolymerizable silane other than glycidoxy and cycloaliphatic epoxy silane, with less than 1.5 equivalents of water in the presence of a catalyst, wherein said water is continuously fed during the reaction.

Description

OLIGOMERO EPOXI SILA O AND COMPOSITION OF COATING CONTAINING THE SAME CROSS REFERENCE WITH RELATED APPLICATIONS This application is a partial continuation of the co-pending US Patent Application Serial No. 11 / 100,840, filed on April 7, 2005, the total contents of which are incorporated for reference herein.

BACKGROUND OF THE INVENTION There is extensive literature describing the use of monomeric epoxy functional silanes. Such silanes are used either alone or in combination with appropriate polymers. However, one of the main difficulties in the use of monomeric epoxysilanes in water is their sensitivity to hydrolysis and condensation, which is difficult to control. Furthermore, the stability of the epoxy functionalities, when the monomeric epoxysilanes are used in water, is difficult to control because of the tendency of the epoxy functionalities to exhibit ring opening. The use of pre-hydrolyzed and pre-condensed silanes is a response to such questions. A pre-hydrolyzed and condensed silane can be an oligomeric structure that has specific characteristics such as controlled molecular weight, usually good film formation and dispersion properties since the silane terminations are already partially or fully condensed, and curing rates are faster. This aspect of the oligomers makes them attractive for the coatings industry, since it broadens the field of applications and also helps to obtain faster properties of application or formulation. However, high molecular weight oligomers can also condense into larger siloxane networks, which result in the formation of structures that are difficult to make soluble in water. For example, U.S. Patent No. 6,391,999 discloses multi-functional epoxysiloxane oligomers for use in a solvent-free or solvent-based system. These multifunctional epoxy siloxane oligomers have high molecular weights and a negligible amount of residual silane functional groups. In this way, it is very difficult to prepare the water-soluble oligomers. Another disadvantage of the use of monomeric epoxysilanes is that they release a large amount of volatile organic compounds (VOCs) expressed as the alcohol content introduced by the alkoxy functionalities. A general trend in the industry is to decrease or eliminate the release of VOCs or hazardous air pollutants (HAPS). It is desirable to reduce the methanol content of any structure that could be involved in applications of coatings, adhesives and sealants. It is also desirable to prepare water-based coatings, which are chemical resistant as well as corrosion resistant, based on metal powders such as aluminum, zinc, bronze and other metallic or organic pigments. As metallic pigments are sensitive to water, there is also a need to have superior protection of such metal powders in water against a well-known mechanism called hydrogen evolution. It is also desirable to design water-based coatings having superior adhesion properties, mechanical or chemical resistances with outstanding wear behaviors and which can be applied on a variety of substrates such as metal or plastic substrates, cellulose or natural substrates, concrete and any other material Generally used in the coatings and adhesives and sealants industries. Therefore, there is a need to produce a water soluble epoxy silane oligomer that is useful in a waterborne system. There is also a need for an epoxysilane oligomer structure having epoxy functional groups for use in waterborne systems for corrosion protection, zinc-rich primers, primer sheets, pigment dispersions. metallic or other coating applications.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, there is provided a process for producing an epoxysilane oligomer comprising reacting glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups and, optionally, a copolymerizable silane other than glycidoxysilane and epoxysilane. cycloaliphatic, with less than 1.5 equivalents of water in the presence of a catalyst, where water is supplied continuously during the reaction. In addition, according to the present invention, a coating composition is provided which contains epoxy silane oligomer made by the aforementioned process. Still further, according to the present invention, there is provided a waterborne composition which comprises at least one epoxy silane oligomer, wherein the epoxysilane oligomer is produced by the reaction of glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups and, optionally, a copolymerizable silane other than glycidoxysilane and cycloaliphatic epoxysilane, with less than 1.5 equivalents of water in the presence of a catalyst, wherein the water is continuously supplied during the reaction, and one or more optional ingredients selected from the group consisting of a surfactant, pH adjusting agent, co-solvent, monomeric silane, binder, crosslinker and pigment paste dispersion. A process for producing a waterborne coating composition according to the present invention is also provided, which comprises pre-solubilizing at least one epoxysilane oligomer in an aqueous solution under acidic conditions with one or more optional ingredients selected from the group consists of pH adjusting agent, co-solvent, surfactant and monomeric silane, wherein the epoxysilane oligomer is produced by reacting glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups and, optionally, a copolymerizable silane different from glycidoxysilane and cycloaliphatic epoxysilane, with less than 1.5 equivalents of water in the presence of a catalyst, wherein water is continuously supplied during the reaction, and dispersing a particulate metal in the aqueous solution. Unlike the epoxysilane oligomers described in US Patent No. 6,391,999 which are not readily soluble in water, the epoxysilane oligomers made by the process of the invention exhibit good water solubility making them particularly useful as components of waterborne coatings. Y transported by water. Some other features, aspects and advantages of the present invention will become more apparent with reference to the following description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart describing a process for forming paint according to the prior art. Figure 2 is a flow chart describing a process for forming paint according to an embodiment of the present invention. Figure 3 is a flow chart describing a process for forming paint according to another embodiment of the present invention. Figure 4 is a flow chart describing a process for forming paint still according to another embodiment of the present invention. Figure 5 is a flow chart describing a process for forming paint still according to another embodiment of the present invention. Figure 6 is a flow chart describing a process for forming a metal paste according to another embodiment of the present invention. Figure 7 is a flow chart describing a process for forming a protective coating according to another embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Oligomer of epoxysilane synthesized with glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups, optionally, with a copolymerizable silane other than glycidoxysilane and cycloaliphatic epoxysilane, with less than 1.5 equivalents of water in the presence of a catalyst, where water is supplied continuously during the reaction. According to an embodiment of the present invention, an epoxysilane oligomer is synthesized using hydrolysis and controlled condensation of an epoxysilane monomer with continuous introduction of water and a strong cation exchange resin as a catalyst. The epoxysilane monomer can be either a glycidaxy or cycloaliphatic epoxysilane having 2 or 3 alkoxy functional groups. According to another embodiment of the present invention, the epoxysilane monomers can be based on glycidoxyhexysilanes or cycloaliphatic epoxysilanes in combination with other monomeric silanes which can provide specific organofunctional characteristics such as vinyl, methacryl, alkyl, polyalkyleneoxide and others, with the proviso that interact with epoxy functionalities. According to another embodiment of the present invention, the epoxysilane monomer is combined with a polyalkylenoxide functional silane, the latter improving the solubility in water and the stability of the oligomer of the two silanes. Other monomeric silanes, as referenced in US Patent Nos. 3,337,496, 3,341,469 and 5,073,195 which are incorporated herein by reference, may be added to improve the solubility and stability of the epoxysilane oligomers. According to another embodiment of the present invention, the glycidoxysilane can be one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane and the like. According to another embodiment of the present invention, the cycloaliphatic epoxysilane can be one or more of beta- (3,4-expoxycyclohexyl) -ethyltrimethoxysilane, beta- (3,4-expoxycyclohexyl) -ethyl-methymethoxysilane, beta- (3,4- expoxycyclohexyl) -ethyl-methyldiethoxysilane, beta- (3,4-epoxycyclohexyl) -ethyltriethoxysilane and the like. The catalyst can be an ion exchange resin such as Purolite® CT-175 or CT 275 available from Plurolite, Amberlite® IRA 400, 402, 904, 910 or 966 available from Rohm & Haas, Lewatit® M-500, M-504, M-600, M-500-A, M-500 or K-2641, available from Bayer, Dowex® SBR, SBR-P, SAR, MSA-I or MSA 2 , available from Dow or DIAON® SA10, SA12, SA 20A, PA-302, PA-312, PA-412 or PA-308, available from Mitsubishi. The catalyst may also be an alkylammonium salt such as hexadecyltrimethylammonium chloride, tetra-n-butylammonium chloride or benzyltrimethylammonium chloride or bromide or the hydroxide form of these alkylammonium salts, either alone or in combination with the halide salts. Also useful as catalysts are the reaction products of organofunctional quaternary ammonium silanes and supports such as ceramics (including glass), silica gel, precipitated or smoked silica, alumina, aluminosilicate, etc. According to another embodiment of the present invention, the molar ratio of water to the silane monomer (s) is from about 0.1 to about 1.5. In accordance with yet another embodiment of the present invention, the molar ratio of water to the silane monomer (s) is from about 0.4 to about 1.0. In accordance with yet another embodiment of the present invention, the molar ratio of water to the silane monomer (s) is less than about 0.5. According to another embodiment of the present invention, the epoxysilane oligomer (ESO) is synthesized in the presence of a chemically stable solvent, without alcohol, for example, an aliphatic hydrocarbon, a paraffin such as naphtha or mineral spirits, an aromatic hydrocarbon such as toluene, xylene or higher boiling homologue thereof; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, amyl ketone, an ester such as ethyl, n-propyl, n-butyl or amyl acetate and the like. In another embodiment of the present invention, alcohol is removed as a by-product continuously during the reaction. In accordance with still another embodiment of the present invention, there is provided a coating composition carried by water which comprises a particulate metal; a surfactant; an epoxysilane oligomer produced according to the invention; and one or more optional ingredients selected from the group consisting of pH adjusting agent, co-solvent and epoxysilane monomer. According to another embodiment of the present invention, the water-borne coating composition includes the particulate metal in an amount of about 0.1 to about 80 weight percent, the surfactant in an amount of about 0.05 to about 10 weight percent. , the epoxysilane oligomer in an amount of about 0.1 to about 30 weight percent, water in an amount of about 5 to about 99 weight percent, optional pH adjusting agent, where present, in an amount sufficient to provide a pH of about 4 to about 6, optional co-solvent , in the cases in which it occurs, in an amount of from about 0.1 to about 60 weight percent, and optional silane monomer, where present, in an amount of up to about 10 weight percent. For the purpose of assisting the dispersion of ESO, which is done in accordance with the process of the present invention in a water transported system, a pH adjusting agent is added during the dispersion of the ESOs in a water transported system. The pH can be adjusted between 4 and 6. The pH adjusting agent can be boric acid. According to another embodiment of the present invention, the pH adjusting agent is orthophosphoric acid, acetic acid or citric acid or any other acids that could not have detrimental effects for protection against corrosion, for example, carboxylic acids. According to another embodiment of the present invention, co-solvents are added during the dispersion of ESO in a water transported system. The co-solvent can be dipropylene glycol methyl ether (for example, Dowanol® DPM) available from Dow Chemical) or other glycol ethers as well as alcohols. According to another embodiment of the present invention, a combination of the pH adjusting agent and co-solvent is added during the dispersion of the ESO in the formulation of a water-borne system. According to another embodiment of the present invention, a surfactant is added during the dispersion of ESO in a water transported system. The surfactant can be either an alkyl-phenol-ethoxylate surfactant (APEO) or a surfactant without APEO. According to another embodiment of the present invention, the surfactant is a cationic, anionic or non-ionic surfactant, or a polyethersiloxane-based surfactant or any combination thereof. In accordance with yet another embodiment of the present invention, a surfactant having a hydrophilic-lipophilic (HLB) balance of 13 is used. According to another embodiment of the present invention, the surfactant can be a package of several surfactants with different values of HLB ranging from about 5 to about 15 or a package of nonionic surfactant including a siloxane surfactant. According to another embodiment of the present invention, the surfactant can be selected from the group consisting of alkyl phenol-ethoxylate surfactant, cationic surfactant, surfactant anionic, nonionic surfactant, a polyethersiloxane based surfactant and any combination thereof. Specific examples of the surfactants include ethoxylated alcohols, ethoxylated sorbitan esters, ethoxylated fatty acids, ethoxylated fatty esters, fatty esters, alkyl sulfosuccinates, dialkylsulfosuccinates, alkyl ether sulphates, alkyl phosphate esters, sugar lipids, alkyl glucosides, amine ethoxylates, alkyl phenol ether sulphates, ethoxylates of amides and any combination thereof. According to another embodiment of the present invention, ESOs are used in waterborne zinc-rich primers or protective coating systems, dispersions of metal pigment pastes, a combination of metal paste dispersion with latex or dispersions carried by water for primers, coatings or inks, waterborne protective coatings, waterborne primers, dispersions of metallic pigments and their use in ink or printing coatings, latex crosslinkers and waterborne dispersions including but not limited to anionic and cationic dispersions , acrylic-styrene-acrylic, polyurethane and epoxy dispersions, vinyl resins, adhesion promoters for the same systems described above, additive systems or binders for dispersion of metal fillers and pigments, dispersion of pigments for inorganic fillers such as calcium carbonate, kaolin, clay, etc., waterborne protective coatings using zinc and other metallic pigments as protective pigment, waterborne decorative paints for metal , plastics and other substrates. According to another embodiment of the present invention, there is provided a waterborne coating composition which includes water in an amount of about 5 to about 99 weight percent of the solvent content, a particulate metal, a surfactant and an aqueous medium. including an epoxysilane oligomer and water, wherein the epoxysilane oligomer is produced by reacting either a glycidoxy or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups with less than 1.5 equivalents of water in the presence of a catalyst resin, wherein the Water is supplied continuously during the reaction, and separating the catalyst resin from the epoxysilane oligomer. The waterborne coating may also include an epoxysilane monomer and / or an additional epoxysilane oligomer. The additional epoxysilane monomer can be gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- glycidoxypropylmethyldimethoxysilane and a gamma-glycidoxypropylmethyldiethoxysilane. The additional epoxysilane oligomer may be the same as the epoxysilane oligomer used in the dispersion phase, or an ESO formed from a starting epoxysilane monomer or different water to silane ratio. In addition to an epoxysilane oligomer produced in accordance with the present invention and a monomeric epoxysilane, the waterborne coating composition may include an epoxysilane monomer and / or a monomeric non-epoxy based silane such as a vinylsilane, an alkylsilane or an alkylene silane. . Typical monomeric silanes not based on epoxy can be vinyltrimethoxysilane (for example, Silquest® A-171 available from GE Silicones), vinyltriethoxysilane (for example, Silquest® A-151 available from GE Silicones), vinylmethyldimethoxysilane (for example, Silquest® A -2171 available from GE Silicones), vinyltriisopropoxy silane (e.g., CoatOSil® 1706 available from GE Silicones), n-octyltriethoxysilane (e.g., Silquest® A-137 available from GE Silicones), propyltriethoxysilane (e.g., Silquest® A-138 available from GE Silicones), propyltrimethoxysilane, methyltrimethoxysilane (for example, Silquest® A-1630 available from GE Silicones), methyltriethoxysilane (for example, Silquest® A-162 available from GE Silicones), polyalkylene oxide trimethoxysilane (by example, Silquest® A-1230 available from GE Silicones), 3-methacryloxypropyltrimethoxysilane (e.g., Silquest® A-174 available from GE Silicones), 3-methacryloxypropyltriethoxysilane (e.g., Silquest® Y-9936 available from GE Silicones) or 3 -metacriloxypropyltriisopropoxysilane (for example, CoatOSil® 1757 available from GE Silicones). The aqueous medium of the waterborne coating may include a pH agent. The pH adjusting agent can be, but is not limited to, boric acid, orthophosphoric acid, acetic acid, glycolic acid, malic acid, citric acid or other carboxylic acids. In addition, according to one embodiment of the present invention, the pH adjusting agent is present in an amount ranging from about 0.5 to about 4.0 weight percent of the aqueous medium. The aqueous medium of the waterborne coating may include a co-solvent. The co-solvent can be dipropylene glycol methyl ether. Other solvents may include one or combinations of glycol ether solvents or the like. According to another embodiment, the co-solvent is ethylene glycol monomethyl ether (EGME), ethylene glycol monoethyl ether (EGEE), ethylene glycol monopropyl ether (EGPE), ethylene glycol monobutyl ether (EGBE), ethylene glycol monomethyl ether acetate (EGMEA), monohexyl ether ethylene glycol (EGHE), ethylene glycol mono-2-ethylhexyl ether (EGEEHE), ethylene glycol monophenyl ether (EGPhE), diethylene glycol monomethyl ether (diEGME), diethylene glycol monoethyl ether (diEGEE), diethylene glycol monopropyl ether (diEGPE), diethylene glycol monobutyl ether (diEGBE) , butylcarbitol, dipropylene glycol dimethyl ether (diEGME), butyl glycol, butyl diglycol or esters based on esters. According to another embodiment, the solvent-based esters include ethylene glycol monobutyl ether acetate (EGEEA), diethylene glycol monoethylether acetate (diEGEEA), diethylene glycol monobutyl ether acetate (diEGBEA), n-propyl acetate, n-butyl acetate , isobutyl acetate, methoxypropyl acetate, butyl cellosolve actetate, butylcarbitol acetate, propylene glycol n-butyl ether acetate, t-Butyl acetate or a solvent based on alcohols. According to still another embodiment, the solvent based on alcohols can be n-butanol, n-propanol, isopropanol or ethanol. According to another embodiment of the present invention, the co-solvent is present in an amount ranging from about 0.1 to about 60 weight percent of the aqueous medium. According to another embodiment of the present invention, the aqueous medium includes an epoxysilane monomer. The epoxysilane monomer can be gamma- glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane or gamma-glycidoxypropylmethyldiethoxysilane. The aqueous medium of the waterborne coating may include a surfactant. The surfactant can be an alkyl-phenol-ethoxylate surfactant, a cationic surfactant, anionic surfactant, a non-ionic surfactant or a polyethersiloxane-based surfactant or any combination thereof. According to one embodiment of the present invention, the surfactant has a hydrophilic-lipophilic balance (HLB) ranging from about 5 to about 13. According to another embodiment of the present invention, the aqueous medium includes two or more surfactants, wherein each of the surfactants independently has a HLB value ranging from about 5 to about 15. In addition, the surfactant can be present in an amount ranging from about 3 to about 6 weight percent of the aqueous medium. In accordance with yet another embodiment of the present invention, the aqueous medium of the waterborne coating includes a surfactant and a pH adjusting agent. The particulate metal of the coating composition, in general, can be any pigment metallic such as aluminum, manganese, cadmium, nickel, stainless steel, tin, magnesium, zinc, alloys thereof or finely divided ferroalloys. According to another embodiment of the present invention, the particulate metal is zinc powder or zinc foil or aluminum powder or aluminum foil in the form of a powder or paste dispersion. The particulate metal can be a mixture of any of the foregoing, as well as understand alloys and intermetallic mixtures thereof. The foil can be combined with dusty metal powder, but typically only with minor amounts of powder. The metal powders typically have a particle size such that all of the particles pass a 100 mesh and a major amount passes 325 mesh ("mesh" as used herein is Standard U.S. Strainer Series). The powders are generally spherical instead of the characteristic sheets of the foil. According to another embodiment of the present invention, the metal particle is a combination of aluminum and zinc. Where the metal particle is the combination of zinc with aluminum, the aluminum can be present in a much smaller amount, for example, from only about 2 to about 5 percent by weight, of the particulate metal, and still provide a coating of appearance sparkly. Usually aluminum will contribute at least about 10 weight percent of the particulate metal. In this way, frequently, the weight ratio of aluminum to zinc in such combination is at least about 1: 9. On the other hand, by economy, aluminum will favorably contribute with no more than about 50 weight percent of zinc and total aluminum, so that the ratio of aluminum to zinc weight may reach 1: 1. The particulate metal content of the coating composition will not exceed more than about 35 weight percent of the weight of the total composition to maintain a better coating appearance, but will usually contribute at least about 10 weight percent to achieve consistent way a desirable glossy coating appearance. In a favorable manner, where aluminum is present, and especially where it is present without another particulate metal, the aluminum will provide from about 1.5 to about 35 weight percent of the weight of the total composition. Typically, when particulate zinc is present in the composition, it will provide from about 10 to about 35 weight percent of the weight of the total composition. The metal can contribute a smaller amount of liquid, for example, dipropylene glycol or mineral spirits. The particulate metals that contribute with liquid are used usually as pastes, and these pastes can be used directly with other ingredients of the composition. However, it should be understood that the particulate metals can also be used in dry form in the coating composition. According to another embodiment of the present invention, the metal particle can be a corrosion protection filler or pigment such as anticorrosive pigments containing chromates (for example, zinc chromates and zinc and potassium chromates), pigments containing phosphates (for example, zinc phosphates, aluminum triphosphates, calcium and magnesium phosphates, barium phosphates, aluminum and zinc phosphates, molybdates, tungstates, zirconates and vanadates), organic metal inhibitors such as zinc salts of 5-nitrophthalic acid or conductive pigments such as iron phosphide. For the purpose of assisting the dispersion of the particulate metal, a dispersing agent, i.e., surfactant, which serves as a "wetting agent" or "humidifier", may be added as such terms are used herein. Wetting agents or mixture of suitable wetting agents include nonionic agents such as polyethyoxy non-ionic adducts of alkylphenol, for example. Also, anionic wetting agents can be used and, very favorably, these are anionic foam moistening agents controlled These wetting agents or mixture of wetting agents may include anionic agents such as organic phosphate esters, as well as the diester sulfosuccinates as represented by sodium bistridecyl sulfosuccinate. The amount of such a wetting agent typically occurs in an amount of about 0.01 to about 3 weight percent of the total coating composition. It is contemplated that the composition may contain a pH modifier, which is capable of adjusting the pH of the final composition. Usually, the composition, without pH modifier, will be at a pH within the range of about 6 to about 7.5. It will be understood that, as the coating composition is produced, particularly in one or more phases where the composition has some, but less than all the ingredients, the pH in a particular phase may be below 6. However, when the complete coating composition is produced, and especially after it is allowed to stand, whose rest will be discussed herein in the following, then the composition will achieve the requisite pH. In cases where a modifier is used, the pH modifier is generally selected from the alkali metals oxides and hydroxides, with lithium and sodium as the preferred alkali metals for enhanced integrity of coating; or it selects from the oxides and hydroxides usually from the metals belonging to Groups IIA and IIB in the Periodic Table, which compounds are soluble in aqueous solution, such as strontium, calcium, barium, magnesium, zinc and cadmium compounds. The pH modifier can also be another compound, for example, a carbonate or nitrate, of the foregoing metals. According to another embodiment of the present invention, the coating composition may contain what is usually referred to herein as a "boric acid component" or "boron-containing compound". For the "component" or for the "compound", as the terms are used herein, it is convenient to use orthoboric acid, commercially available as "boric acid", although it is also possible to use various products obtained by heating and dehydrating orthoboric acid, such as metaboric acid, tetraboric acid and boron oxide. The coating composition may also contain a thickener. It has previously been considered that the thickener was an important ingredient, as discussed in US Patent No. 5,868,819. However, it has now been found that usable coating compositions can be produced which do not contain a thickener and, however, desirable characteristics of the coating composition can be achieved as stability in storage. For the present invention, the thickener in this manner is an optional substituent. The thickener, when present, may contribute an amount of between about 0.01 to about 2.0 weight percent of the weight of the total composition. This thickener can be a water-soluble cellulose ether, including the thickeners "Cellosize" (trademark). Suitable thickeners include the hydroxyethylcellulose ethers, methylcellulose, methylhydroxypropylcellulose, ethylhydroxyethylcellulose, methyl ethylcellulose or mixtures of these substances. Although the cellulose ether needs to be soluble in water to increase the thickening of the coating composition, it does not need to be soluble in the organic liquid. When thickener is present, less than about 0.02 weight percent of the thickener will be insufficient to impart a favorable thickness of the composition, while more than about 2 weight percent of thickener in the composition may lead to high viscosities, which provide compositions with which it is difficult to work. In accordance with one embodiment of the present invention, to thicken without a harmful high viscosity, the total composition will contain from about 0.1 to about 1.2 weight percent of thickener. It will be understood that, although the use of a cellulosic thickener is contemplated and, in this way, the thickener can to be referred to herein as a cellulosic thickener, a little to all the thickener may be another thickener ingredient. Such different thickening agents include xanthan gum, associative thickeners, such as urethane associative thickeners and non-urethane non-ionic associative thickeners, which are typically opaque, high boiling point liquids, e.g., that boil above 100 ° C. . Other suitable thickeners include modified clays such as highly beneficiated hectorite clay and organically modified and activated smectite clay. When thickener is used, it is usually the last ingredient added to the formulation. The coating composition may still contain additional ingredients, in addition to those already listed above. These other ingredients may include phosphates. It should be understood that phosphorus-containing substituents may be present, even in a slightly soluble or insoluble form, for example, as a pigment such as ferrophos. Additional ingredients will often be substances that may include inorganic salts, often used in the metal coating technique to impart some corrosion resistance or corrosion resistance enhancement. Materials include calcium nitrate, dibasic ammonium phosphate, calcium sulfonate, 1-nitropropane carbonate and lithium (also useful as a pH modifier) or the like and, if used, these are very commonly employed in the coating composition in a total combined amount of from about 0.1 to about 2 weight percent. More than about 2 weight percent of such additional ingredient can be used where it is presented for a combination of uses, such as lithium carbonate used as a corrosion inhibitor and also as a pH adjusting agent. Very usually the coating composition is free of these even more additional ingredients. In another embodiment of the present invention, the formulation may include, when necessary, a surfactant to reduce foam or assist in deoxygenation. The antifoaming and deoxygenating agent can include material based on mineral oil, silicone-based material, a polyethersiloxane or any combination thereof. The concentration of the surfactants can be adjusted to the range of about 0.01% to about 5% active material. The surfactants can be used as a pure material or as a dispersion in water or any other suitable solvent to disperse them in the final water transported composition. The coating composition may also contain surface effect agents to modify a surface of the coating composition such as increased resistance to damage, reduced coefficient of friction, flattening effects, improved resistance to abrasion. Examples may include silicone polyether copolymers such as, for example, Silwet® L-7608 and other variants available from GE Silicones. Typical crosslinkers can also be used in the coating composition of the present invention. For example, the crosslinker may be isocyanates, epoxy curing agents, amino agents, aminoamido agents, epoxyamino adducts, carbodiimides, melamine anhydrides, polycarboxylic anhydrides, carboxylic acid resins, aziridines, titanates, organofunctional titanates, organofunctional silanes, etc. The additives discussed in the above may be added at any stage of the use of an ESO produced according to the present invention or at any of the different stages of the production of a composition transported by water produced according to the present invention. The coating formulation may also contain corrosion inhibitors. Examples of inhibitors may include chromate, nitrite and nitrate, phosphate, tungstate and molybdate, or the organic inhibitors include sodium benzoate or ethanolamine. According to another embodiment of the present invention, the formulations discussed herein using an ESO of the present invention may be free of chromium. In accordance with another embodiment of the present invention, it may be desirable to prepare a formulation containing chromium using an ESO of the present invention. Such anti-corrosion pigments containing chromium for example are zinc chromates such as zinc and potassium chromates and zinc tetrahydroxychromates. Other anti-corrosive pigments may include molybdates, tungstates, zirconates, vanadates, zinc phosphates, chromium phosphates, aluminum triphosphates, barium phosphates and aluminum and zinc phosphates. Such anticorrosive pigments can also be combined with an organic corrosion inhibitor such as zinc salt, for example, 5-nitrophthalic acid. Alternatively, a waterborne composition of the present invention is provided, which comprises a dispersion of a particulate metal in an aqueous solution that includes at least one epoxysilane oligomer, as described herein, with one or more optional ingredients selected from the group consisting of a surfactant, pH adjusting agent, co-solvent, monomeric silane, binder and any other ingredients typically used in coatings, for example, thickeners, crosslinkers, etc. The binder can be an inorganic and organic binder. The inorganic binder can be a silicate, ethyl silicate, silica nanoparticle solution or silicone resin. The organic binder may be vinyl resins, polyvinyl chlorides, vinyl chloride copolymers, vinylacetate copolymers, vinylacetate copolymers, acrylic copolymers, styrene-butadiene copolymers, acrylate, acrylate copolymer, polyacrylate, styrene-acrylate copolymers, resins phenolic, melamine resins, epoxy resins, polyurethane resins, alkyd resins, polyvinyl butyral resins, polyamides, polyamidoamine resins, polyvinyl ethers, polybutadienes, polyester resins, organosilicon resin, organopolysiloxane resin and any combinations thereof . Natural binders such as cellulose derivatives such as nitrocellulose resins, carboxymethyl cellulose, cellulose esters of organic acids, cellulose ethers such as hydroxymethyl or ethyl cellulose, modified natural rubbers, natural gums or solution forms of polymers and copolymers. The organic binders can also be a stabilized nonionic resin, an anionic stabilized emulsion or a cationic stabilized emulsion. The coating composition can be formulated in a variety of methods. For example, as an alternative to directly using ESO, according to the present invention in the above, ESO can be used as a binding agent in concentrated form or as a more diluted premix of ESO, such as ESO mixed with a diluent. The diluent can be selected from the substituents that provide the liquid medium of the coating composition, such as water, or water plus boric acid component, or water plus low boiling organic liquid including acetone. Additionally, it is contemplated that the ESO binding agent may be initially mixed together with any of the other necessary ingredients of the composition. Therefore, the ESO in liquid form, such as in a diluent, can be mixed with other ingredients of the coating composition which are in solid or liquid form. However, it will almost always be presented in any composition before a particulate metal is added to that composition. In addition, the ESOs, according to the present invention discussed in the foregoing, can be incorporated into many different formulations having many different uses such as those described in U.S. Patent Nos. 6,270,884 and 6,656,607, which are incorporated herein by reference in its entirety For example, in accordance with an exemplary embodiment of the present invention, there is provided a waterborne composition which comprises at least one prepared epoxysilane oligomer. according to the present invention described hereinbefore, with one or more optional ingredients selected from the group consisting of a surfactant, pH adjusting agent, co-solvent, monomeric silane, binder, crosslinker and pigment paste dispersion. . The epoxysilane oligomer, in a first embodiment, may be in the range of about 0.05 to about 40 weight percent of the composition, in a second embodiment in the range of about 0.1 to about 20 weight percent of the composition, in a third embodiment in the range of about 0.1 to about 10 weight percent of the composition, in a fourth embodiment in the range of about 0.5 to about 10 weight percent of the composition. The package concepts, as well as formulation considerations for how the coating composition is prepared, can be taken into consideration when the ingredients of the composition are put together. Thus, it is contemplated that less of all the ingredients of the coating composition may be present in other premixes of the composition. Such may include, for example, a wetting agent, or a wetting agent plus a boric acid component, or an aqueous medium plus a boric acid component. Such premixes can be constituted with liquid which may or may not include the aqueous medium, and may or may not include an organic liquid. Even considering storage stability, the composition may be a formulation of a package of all the ingredients of the coating composition or a two-pack formulation. It will be understood that the final coating composition, as well as the separate pre-combined packages, can be prepared in concentrated form. In cases where particulate aluminum will be used in the coating composition, and especially where both particulate zinc and particulate aluminum will be used, a variant of the above package considerations may be used. According to another embodiment of the present invention, it is desirable to use a combination of zinc and aluminum and start with a mixture, capable of packing, of about 0.1 to 15 percent wetting agent, about 0.1 to 5 percent acid component boric acid, approximately 0.5 to 35 percent silane binding agent and a balance of aqueous medium to provide 100 weight percent of the weight of the total mixture. In this mixture, then particulate metal can be dispersed, usually as a lamella, for example, zinc lamellae. Additional aqueous medium can be added, whereby the resulting metal-containing dispersion can contain about 25 to about 45 weight percent of the particulate metal and as much as about 40 to about 60 weight percent aqueous medium, both based on the total weight of the resulting metal-containing dispersion. Typically, a precursor blend in an additional package is then prepared separately to introduce the particulate aluminum into the final coating composition. This particulate aluminum will generally be aluminum foil, but it should be understood that other foil-like metals, e.g., zinc foil, may be present with aluminum. Even when made as a formulation of a package, the final coating composition has a highly desirable storage stability. This confirms the binding capacity of the ESOs, according to the present invention, to protect the particulate metal from the deleterious reaction with other ingredients of the composition during extensive storage. Such extensive shelf stability was unexpected, due to recognized problems of reaction of particulate metal in water-reducible systems, for example, evolution of hydrogen gas from aqueous compositions containing particulate zinc. However, even after storage as a single package, the compositions of the present invention may be unpacked, prepared for coating application. as by dynamic agitation, then easily applied readily. The resulting coatings can have the desirable corrosion resistance, and often the other coating characteristics, of coatings applied from freshly prepared compositions. In cases where a bath of the coating composition has been prepared, it has been found desirable to let this combination stand. Resting can help provide better coating performance. Usually, the rest of the combination will be for at least 1 hour, and favorably for at least about 2 hours to about 7 days or more. Rest for less than 1 hour may be insufficient to develop desirable bathing characteristics, while rest for more than 7 days may be uneconomical. The final coating composition, either freshly prepared or after storage, can be applied by various techniques, such as immersion techniques, including bath-draining and bath-spin procedures. In cases where the parts are compatible therewith, the coating can be applied by curtain coating, brush coating or roller coating and includes combinations of the foregoing. It is also contemplated to use a technique of sprinkling as well as combinations, for example, sprinkling and spinning and sprinkling and brush techniques. Coated articles that are at an elevated temperature can be coated, often without extensive cooling, by a process such as dip-spin, dip-drain or spray coating. The protected substrate can be any substrate, for example, a ceramic substrate or the like, but very particularly is a metal substrate such as a zinc or iron substrate, for example, steel, an important consideration being that any such substrate supports the conditions of heat curing for the coating. By a "zinc" substrate is meant a substrate of zinc or zinc alloy, or a metal such as steel coated with zinc or zinc alloy, as well as a substrate containing zinc in intermetallic mixture. Also, the iron of the substrate may be in the form of an alloy or intermetallic mixture. Especially where such are metal substrates, which are very usually ferrous substrates, these can be pretreated, for example, by treatment with chromate or phosphate, before the application of the inner coating. In this way, the substrate can be pretreated to have, for example, a coating of iron phosphate in an amount of about 538.2 (50) to about 1076.4 mg / m2 (100 mg / ft2) or a phosphate coating of zinc in an amount of about 2152.8 (200) to about 21528 mg / m2 (2,000 mg / ft2). For substrates containing an applied coating composition, subsequent curing of the composition on the substrate will usually be curing in a hot air oven, although other curing methods may be used, for example, infrared light cooking and induction curing. The coating composition will be cured by heat at an elevated temperature, for example, in the order of approximately 232.22 ° C (450 ° F), but usually higher, than the air temperature of the furnace. Curing will typically provide a substrate temperature, usually as a peak metal temperature, of at least about 232.22 ° C (450 ° F), the furnace air temperatures may be higher, such as in the order of 343.33 ° C (650 ° F), but for economy, the temperature of the substrate needs not to exceed approximately 232.22 ° C (450 ° F). Curing, such as in a hot air convection oven, may be continued for several minutes. Although the cure times may be less than 5 minutes, more typically they are in the order of about 10 to about 40 minutes. It should be understood that curing times and temperatures may be carried out in cases where more than one coating is applied or in cases where a coating will be used. superior heat-cured subsequently applied. In this way, the shorter time and lower temperature curing can be employed when one or more additional coatings or an upper coat that proceeds through a high temperature bake in a longer curing time will be applied. Also, where more than one coating is applied or a heat curable topcoat will be applied, the first coating, or interior coating, may need to be dried only, as discussed above. Then, curing may proceed after the application of a second coating, or a topcoat cured by heat. The resulting weight of the coating on the metal substrate can vary to a considerable degree, but will always be present in an amount that provides more than 5382 mg / m2 (500 mg / ft2) of coating. A smaller amount will not lead to an intensified corrosion resistance in a desirable manner. Favorably, a coating of more than about 10764 mg / m2 (1,000 mg / ft2) of coated substrate will be presented for better corrosion resistance, while more typically it will present between about 21528 to 53820 mg / m2 (2,000 to 5,000 mg). / ft2) of coating. In this coating, it will generally be about 4305.6 mg / m2 (400 mg / ft2) to about 48438 mg / m2 (4,500 mg / ft2) of metal particulate Prior to use, a topcoat, for example, with silica substance, may be applied to the coated substrate. The term "silica substance", as used herein for the topcoat, is intended to include both silicates and colloidal silicas. Colloidal silicas include those based on solvents as well as aqueous systems, with colloidal silicas based on water being very favorable for economy. As is typical, such colloidal silicas may include additional ingredients, for example, thickeners such as, for example, up to about 5 weight percent of a water soluble cellulose ether discussed in the foregoing. Also, a minor amount, for example, 20 to 40 percent by weight, and usually a lesser amount, of the colloidal silicas can be replaced by colloidal alumina. In general, the use of colloidal silicas will make possible heavier upper layers of silica substance on the substrates materials with lower layer. It is contemplated to use colloidal silicas containing up to 50 weight percent solids, but, typically, much more concentrated silicas will be diluted, for example, in cases where spray application of the top coat will be used. When the top coat silica substance is silicate, it may be organic or inorganic. The Useful organic silicates include alkyl silicates, for example, ethyl, propyl, butyl and polyethyl silicates, as well as alkoxy silicates such as ethylene glycol monoethylsilicate. Very generally, by economics, the organic silicate is ethyl silicate. Advantageously, inorganic silicates are used for better economy and corrosion resistance performance. These are typically used as aqueous solutions, but solvent-based dispersions can also be used. When used herein in reference to silicates, the term "solution" means that it includes true solutions and hydrosols. The preferred inorganic silicates are the aqueous silicates which are the water-soluble silicates, including sodium, potassium, lithium and sodium / lithium combinations, as well as other related combinations. Other ingredients may be present in the topcoat composition of silica substance, for example, wetting agents and colorants, and the composition may contain chromium substituents if desired, but may be chromium-free as defined above, to provide a coating completely without chrome. Substances that may additionally be present may include thickeners and dispersants as well as pH adjusting agents, but all such ingredients will typically not add more than about 5. percent by weight, and usually less, of the topcoat composition so that enhanced stability of the coupled coating composition is allowed with increased integrity of the coating. The top coating of silica substance can be applied by any of the various techniques described above for use with the coating composition, such as immersion techniques including bath-draining and bath-spin procedures. By any coating process, the top layer should be present in an amount above about 538.2 mg / m2 (50 mg / ft2) of coated substrate. By economics, the weights of the upper layer for the cured top coat will not exceed approximately 21528 mg / m2 (2,000 mg / ft2) of coated substrate. This range is for the top cured coating of silica substance. Preferably, for better coating efficiency and economy of the upper layer of silica substance, the top layer is an inorganic silicate that provides from about 2152.8 (200) to about 8611.2 mg / m2 (800 mg / ft2) of topcoat of cured silicate. For curing the upper layer of silica substance, it is typical to select the curing conditions according to the particular silica substance used. For the colloidal silicas, air drying may be sufficient; but, for efficiency, curing at elevated temperature is preferred for all silica substances. Curing at elevated temperature can be preceded by drying, such as air drying. Regardless of the above drying, a lower curing temperature, for example, in the order of about 65.55 ° C (150 ° F) to about 148.88 ° C (300 ° F), will be useful for colloidal silicas and organic silicates. For inorganic silicates, curing typically takes place at a temperature in the range of about 148.88 ° C (300 ° F) to about 260 ° C (500 ° F). In general, curing temperatures in the order of about 65.55 ° C (150 ° F) to about 426.66 ° C (800 ° F) or more, as peak temperatures for metal, may be useful. At higher temperatures, curing times can be as fast as about 10 minutes, although longer curing times, up to about 20 minutes, are more usual. Also, to the articles a topcoat with the top layer of silica substance may be applied while the articles are at elevated temperature, from the curing of the water-reducible coating composition. The said could be done as by spray coating or bath-draining, that is, an immersion of the article at elevated temperature in the top layer composition, which can provide an extinction of the article. With the removal of the top coating composition, the article can be drained. On the one hand all the curing of the top layer can be achieved by the operation. Prior to use, an additional topcoat with any other suitable topcoat, i.e., a paint or primer, including electrocoat primers and solderable primers, may also be applied to the substrate coated with the coating of the water reducible coating composition. as the zinc-rich primers that can typically be applied prior to electric resistance welding. For example, it has already been shown in US Patent No. 3,671,331 that a top primer coating containing an electrically conductive particulate pigment, such as zinc, is highly usable for a metal substrate that is first coated with another coating composition. Other topcoat paints may contain pigment in a binder or may be non-pigmented, for example, generally cellulose lacquers, resin varnishes, and oleoresin varnishes such as, for example, stick oil varnish. Paints can be reduced in solvents or can be reduced in water, for example, resins soluble in latex or water, including modified or soluble alkyds, or paints can have reactive solvents such as in polyesters or polyurethanes. Additional suitable paints that can be used include oils, including phenolic resin paints, reduced alkyds in solvents, epoxies, acrylics, vinyl, including polyvinyl butyral, and wax-like coatings such as linseed-paraffin oil paints. Of special interest, the substrate coated with the coating of the water-reducible coating composition can form a particularly suitable substrate for the deposition of paint by electrocoating. The electrodeposition of film-forming materials is well known and may include electrocoating simply from a film-forming material in a bath or such a bath, which may contain one or more pigments, metal particles, drying oils, dyes, thinners and similar and the bath can be an ostensible dispersion or solution and the like. Some of the well-known resinous materials useful as film-forming materials include polyester resins, alkyd resins, acrylate resins, hydrocarbon resins and epoxy resins, and such materials can be reacted with other organic monomers and / or polymers including hydrocarbons such as ethylene glycol, monohydric alcohols, ethers and ketones.

For this, it has also been taught, for example in U.S. Patent No. 4,555,445, that suitable topcoat compositions can be pigmented dispersions or emulsions. These may include dispersions of copolymers in liquid medium as well as emulsions and aqueous dispersions of suitable waxes. An overcoat may be applied to the articles in these compositions, articles which are at an elevated temperature, such as after curing the applied coating reducible in water, by methods including a bath-drainage or a spray coating operation. By such an extinguishing coating operation, all top coating curing can be achieved without additional heating. The extinguished coating with solutions, emulsions and polymer dispersions, and with hot baths, has also been discussed in US Patent No. 5,283,280. Before coating, in most cases it is advisable to remove foreign matter from the surface of the substrate, such as when cleaning and degreasing completely. Degreasing can be achieved with known agents, for example, with agents containing sodium metasilicate, caustic soda, carbon tetrachloride, trichlorethylene and the like. Commercial alkaline cleaning compositions, which combine washing and treatments moderate abrasives can be used to clean, for example, an aqueous solution of trisodium phosphate-sodium hydroxide cleaning. In addition to cleaning, the substrate can be subjected to more etched cleaning, or more shot-blasting. In addition, the organic and inorganic binders can be cured with one or some external crosslinkers such as isocyanates, epoxy curing agents, amino or aminoamido agents, epoxyamino adducts, carbodiimides, polycarboxylic anhydrides and carboxylic acid resins of melamine anhydrides, aziridines, titanates , organofunctional titanates, organofunctional silanes such as epoxysilanes, aminosilanes, isocyanatosilanes, methacrylsilanes, vinylsilanes. The following examples are illustrative of the present invention and the results obtained by the test procedures. It should be understood that the examples are not intended and should not be construed as limiting the scope of the invention. A person skilled in the applicable arts will appreciate, from these examples, that this invention can be represented in many different forms, other than as specifically described.

EXAMPLE 1: SYNTHESIS PROCEDURES FOR THE PREPARATION OF EXAMPLES 1-9 OF EPOXISILANE OLIGOMER ESO Example 1 was prepared using the procedure detailed in US Pat. No. 6,391,999. Examples 2 through 9 of ESO were prepared using the following procedures. A reactor was pre-charged with an epoxysilane and solvent. Then, a cation exchange resin was introduced, and the total charge was preheated to reflux. Then, water was introduced slowly, drop by drop, using a separate funnel at the reflux temperature. The introduction times were varied from 1 to 2 hours. Different reaction times were applied at atmospheric pressure, for example, from 25 minutes to 2.5 hours. The distillation was performed immediately after the reaction time to remove the solvent using vacuum from atmospheric pressure to -2,039 kgf / cm2 (-0.2 bar). More particularly, a 2-liter reactor with a heating jacket was equipped with mechanical stirring, an introduction funnel and a water condenser for solvent reflux. The reactor was then charged with a silane of the type and amount listed in Table 1, a solvent of the type and amount listed in Table 1 and a catalyst resin of the type and amount as listed in Table 1.

The mixture was then heated to reflux, at a temperature ranging from about 70 to about 73 ° C. The separation-introduction funnel was charged with distilled water of the amount listed in Table 1. Water was then introduced dropwise while stirring with the mechanical stirrer for different times (See Table 1). After complete introduction of water, the reaction was left for different times after the reaction (See Table 1). Next, the condenser was configured as a distillation condenser and equipped with a round flask collector. The solvents were removed either at atmospheric pressure or under vacuum for appropriate times so that all the solvents would evaporate at the reactor temperature and final vacuum of -2,039 kgf / cm2 (-0.2 bar). The reactor was allowed to cool to room temperature before the product was extracted and filtered through filter paper, followed by a sintered glass filter of number 3. The descriptions and quantities of each example are listed in Table 1.

Table 1 Example 1 of ESO shows that a product using isopropanol as co-solvent, and having a high water to silane ratio, has a high visco. In fact, the product of Example 1 of ESO has the behavior of the silicone oil. Which results in difficulties with the filtration of the ion exchange resin, lack of dispersibility or water solubility and / or poor compatibility with organic polymers.

Examples 2 to 9 of ESO had viscosities ranging from 86 to 23 mPa.s, which were much lower than the viscosity of Example 1 of ESO, which had a viscosity of 680 mPa. s. Example 7 of ESO is the only product for which there was no apparent reaction and the pure monomer was recovered (95% monomer content for the recovered material and almost identical epoxy content). This can be explained by the lower hydrolysis rate of the ethoxy groups of gamma-glycidoxypropyltriethoxysilane, in comparison with the methoxy groups of gamma-glycidoxypropyltrimethyloxysilane of Examples 2 to 6 and 8 of ESO. The epoxy contents measured in all products, except for Example 7 of ESO, indicate that the epoxy rings are still closed and significant oligomerization occurred for most of the products. The mass balances also indicate that the methanol has been released during the reactions, except for Example 7 of ESO. The monomeric content of the free epoxysilane monomer, left in the oligomers, indicates an incomplete reaction. The higher water to silane ratios gave higher condensation rates and lower residual monomer, as seen in Examples 2, 3, 4 and 5 of ESO. The optimization of the water to silane ratio, as well as the conditions of Cured, even when they are not finished, help reduce the monomer content left in the oligomer. A low monomer content helps to maximize the conversion rate and in this way to comply with the Toronto definition of a polymer, and increases the overall performance of ESO. According to the Toronto definition: a "polymer" means a substance consisting of molecules characterized by the sequence of one or more types of monomer units and comprising a simple weighted majority of molecules containing at least three monomer units. which are covalently bound to at least one other monomer unit or another reactant, and consists of less than one. simple weighted majority of molecules of the same molecular weight. Such molecules must be distributed over a range of molecular weights wherein the differences in molecular weight are mainly attributable to differences in the number of monomer units. In the context of this definition, a "monomer unit" means the reacted form of a monomer in a polymer. Shorter introduction times, combined with longer times after the reaction, increased the conversion rates of Examples 3 and 4 of ESO to 12.5 and 16% of free monomer, respectively, and Examples 5 and 6 of ESO to 22 and 15% monomer content free, respectively. The use of an ethanol solvent leads to a higher conversion rate (eg, Example 8 of ESO, which has a free monomer content below 7.5%). However, ethanol solvents also lead to higher viscosity products, again indicating that the choice of the alcohol solvent is critical to maintaining low viscosity products. In addition, the analysis of Example 8 of ESO shows that some degree of trans-esterification took place, as illustrated by the GC analysis, as shown in Table 2 in the following.

Table 2 The resulting epoxy weight% of Example 8 of ESO with correction for individual monomers yields 22.9% of the significantly lower value than examples 2 to 6 of ESO, based on gamma-glycidoxypropyltrimethoxysilane in acetone. This also indicates that trans-esterification took place in this example.

Example 9 of ESO is a representative example of a co-oligomer of epoxysilane between gamma-glycidoxypropyltrimethoxysilane (for example, Silquest® A-187 available from GE Silicones) and trimethoxysilane of alkylene oxide (for example, Silquest® A-1230 available of GE Silicones). The weight% of epoxy given for this material indicates that a portion of the epoxy content has been replaced by an ethylene oxide chain, thereby reducing the weight% of epoxy. The weight loss observed during the reaction indicates that methanol has been released during the process. The synthesis was carried out without any solvent and the distillate analysis recovered during the distillation phase was analyzed as pure methanol.

EXAMPLE 2: PARAMETERS FOR WATER SOLUBILIZATION OF AN EPOXISILAN OLIGOMER The following examples demonstrate the very satisfactory and superior results obtained when the ESOs, according to the present invention, become water-soluble by varying the parameters for solubilization in water in order to use such oligomers in formulations transported by water. Water. The parameters included pH and the influence of solvents and coalescents, as well as the influence of the surfactants.

Test procedure: In a metal beaker, equipped with magnetic stirrer, the different ESO prepared according to the procedure, were mixed with the appropriate solvent or surfactant, or mixture or both (according to Tables 3 to 6), this in order to obtain a homogeneous phase. Then, appropriate amounts of water or boric acid solution (according to Tables 3 to 6) are added under stirring. The mixture is stirred with the magnetic stirrer until it is finished, a clear solution is obtained. The time for the completion of such a transparent solution and the final pH of the solutions were reported. With respect to Example 1 of ESO, or the reference ESO, it has been observed that, except at high coalescence concentration of Dowanol® DPM, ESO Example 1 is not soluble in water. The dimethyl ether level of dipropylene glycol Dowanol® DPM or the like required to render ESO Example 1 soluble in water could result in a very high VOC content, well above the acceptable ranges for waterborne coatings (above 45 ° C). % of VOC). As such, Example 1 of ESO could be very difficult to solubilize and could be more difficult to use in a formulation, transported by water (See Table 3 in the following for test results).

Table 3 With respect to ESO Example 2, the water solubility of the ESO Example 2 data showed that rapid solubilization can be achieved with a lower content of solvent and acid conditions. In particular, Test 20 is observed as a good balance in the contents of boric acid and Dowanol® DPM. This faster solubilization rate was expected as part of the original design of the oligomer using a water to silane ratio of 0.48, leaving some alkoxy groups available for further hydrolysis and also because of the lower molecular weight illustrated by a lower viscosity of ESO .

Table 4 With respect to Example 3 of ESO, the water solubility of Example 3 of ESO was prepared with a water to silane ratio of 0.96, which had a higher water to silane ratio compared to Example 2 of ESO having a ratio water to silane of 0.48 tested in the above. The results, listed in Table 5 in the following, show that Example 3 of ESO is more difficult to solubilize than the Example 2 of ESO. However, with appropriate dispersion times, solubilization could still be achieved after 18 hours. In addition, the higher water to silane ratio leads to higher condensation rates that make ESO more hydrophobic and less prone to hydrolysis and solubilization.

Table 5 EXAMPLE 3: INFLUENCE OF THE HUMANTABILITY OF ESO STRUCTURES The following examples demonstrate the effects of surfactants on ESOs, according to the present invention. The introduction of specific surfactants used in the dispersion of metal powders was used to improve the wettability of the ESOs. More particularly, APEO surfactants (alkylphenol ethoxylate) having an HLB of 13.3 and 8.9 were used in this test (for example, Berol® 09 and 26 and Berol® 48 available from AKZO Noble Surface Chemistry, respectively). In addition, a surfactant without APEO was also compared with Berol® 09. The following test was used to prepare the examples in the following. First, a pre-combination of surfactant, Dowanol® DPM and Example 2 of THAT. Next, the pre-combination was added in a solution containing water and boric acid. The mixture was then stirred with a magnetic stirrer until a complete solution was obtained. The results are presented in Table 6 in the following.

Table 6 The results show that adding an appropriate surfactant can reduce the dissolution time or reduce the need for co-solvent and / or acid. An APEO surfactant with an HLB of 13.3 (for example, Berol® 09) better reduces the dissolution time than the combination of APEO surfactants with an HLB of 13.3 and 9.0.

EXAMPLES 4-17 The following examples relate to coating formulations that include the use of ESOs, according to the present invention, compared to coating formulations that include an epoxysilane monomer. In these examples, most of the work was done using Examples 2, 3, 5 and 6 of ESO. The different procedures used to produce the coatings in Examples 4-17 are described in Figures 1-5. Preparation, application and painting test of Examples 4-17: All formulations were mixed and dispersed using a Cowles blade disperser with a blade speed of 10 m / min. The dispersion of metallic powder requires a high torque and was carried out in batches of 250ml in order to optimize the quality of the dispersion. The stability of the formulations was graded from the resistance to hydrogen evolution of the formulations after the appropriate storage times. All products were stored in hermetically sealed PE containers. The generation of foam at the top of the formulations, which in most cases leads to "slow expansion" of the containers, was given as a clear sign of hydrogen generation. The viscosity was adjusted to 20-30 DIN in cup number 4 either with water when it was very high, or HEC (solution Natrosol® available from Hercules) when it was very low.

Preparation of test panels: Two types of metal test panels were used. Panels of Cold Rolled Steel (CRS) and electrogalvanizados (EG). The CRS panels were prepared by cleaning the surfaces of the panel with acetone and then ethanol. Next, the surfaces were brushed with an abrasive cleaner / detergent. Then, the panels were rinsed under tap water and dried with an air dryer before applying the paint. The EG panels were prepared by cleaning the surfaces with acetone and then ethanol. Next, the panels were immersed in a 1% solution of HN03 for 2 minutes. The panels were then rinsed under tap water and dried with an air dryer before applying paint. All test panels were used immediately after cleaning.

Paint application and baking conditions: The paint application was made using a spray gun in a spray booth. The viscosity of the paint was adjusted to approximately 20 DIN in cup number 4 by proper dilution with water. An application layer was deposited on a test panel with an objective deposition of 20-25gr./m2 of dry paint. The curing of the paints was performed by air drying at 70 ° C for 20 minutes in an oven, followed by baking in an oven at 300 ° C for 30 min.

Test Procedures: The following tests were performed in Examples 4-17: Adhesion test, Cohesion-Spray Test of Metallic Fillers, Neutral Salts Spray test and Hot Salt Soak test. The Adhesion test was done directly on the panels cured in accordance with ISO 2409-1972. The Cohesion-Spray Test of Metal Fillers is the evaluation of the cohesion of the metallic powders to join the surface of the coatings once applied and completely cured. This test reflects the cohesion of the film and the union of particles in the film layer. The cohesive-spray test is carried out by visual evaluation of the amount of metal powder removed by a tape adhesive applied to the surface coating according to ISO 2409-1972. After the adhesion test, a visual evaluation was made of the amount of metallic powder removed by the tape adhesive applied to the surface coating. High resistance to spray is observed: Excellent Medium spray resistance is observed: Medium Low spray resistance is observed: Poor The Neutral Salt Spray test, or salt spray test, is an accelerated corrosion test. The purpose of this accelerated corrosion test is to duplicate, in the laboratory, the corrosion performance of a product in the field. The salt spray test has been used extensively in this application for this purpose. The accelerated corrosion test was carried out in accordance with ISO 7253-1984 with the general conditions of the tests mentioned below as follows: - NaCl solution at 50 +/- 5g / l -pH of solution between 6.5 and 7.2 - Temperature of Cabinet 35 ° C +/- 2 ° C - Spray rate for a period of 24 hours; 1 to 2 ml / h for an area of 80 m2. -Plates oriented towards the top in 20 ° +/- 5o -Red oxide is noticed by visual inspection. The corrosion performance was graded according to the number of hours that the salt solution described above was sprayed on the surface of a panel until 5% of the surface was covered with red oxide. The performance from each of the different coatings was then cited as the relative hours for a 5% coverage of red oxide related to the amount of coating deposited on the test panel, according to the following equation: NSS - 5% Red Oxide (hours / g) = 5% Red Oxide (hours) / Deposit of coatings (g) The corrosion resistance of the protected panels is often cited as hours of protection against corrosion by deposit. The Hot Salt Soak Test (HSS) is also an accelerated corrosion test that was used for comparison purposes. This test includes immersion of a coating applied on a galvanized test panel in a 3% NaCl solution for 5 days at 55 ° C, which can be compared to a 1000-hour Neutral Sales Spray testing program when applied in some steel or CRS coated protected. In the HSS test, the test panels are first scratched with two parallel strokes (deep in the base metal) of approximately 10 cm in length. After immersion in a Hot Soak bath for a predetermined period of time, the panels were washed with tap water and observed for the appearance of red oxide as well as the average drag of the trace. In addition, the NaCl solution was renewed every 2 days in the tests. The performance was rated similar to that of the Neutral Sales Spray test described above. For example, the time in hours for 5% and the ratio of hours for the coverage of 5% red oxide to appear by the weight of the coating deposit, according to the following equation: HSS - 5% Red Oxide (hours / g) = 5% Red Oxide (hours) / Deposit of coatings (g) EXAMPLE 4: USING A MONOMERIC EPOXISILAN OF GAMMA-GLICIDOXIPROPYLTRIMETOXISILANE AND THE PROCEDURE DESCRIBED IN FIGURE 1 In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were placed in the beaker: 18.92% by weight demineralized water, 0.58% by weight of boric acid and 9.0% by weight of Silquest® A-187 (available from GE Silicones). The solution was mixed for 3 hours. Then, the following ingredients were added while stirring: 33.0% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26) and 4.8% by weight of Dowanol® DPM, 2.0% by weight of additional Silquest® A-187. The components were then mixed for ten minutes Next, the following metal fillers were added under agitation: 28.0 wt% zinc GTT foil followed by 3.0 wt% Chromal VII aluminum powder. So0.4% by weight of Aerosol®® OT75 (available from Cyte'c) was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final products were then stored for appropriate times (eg, 2 days, 7 days and three months) before the subsequent addition of 2.9% by weight of additional Silquest® A-187. The protective coating was then applied to the two test panels (one EG and one CRS test panel as described above). A thin and uniform layer of paint was deposited on the test panels using a spray gun. The coating was adjusted to approximately 20 to 25 g / m2 of cured deposit. This adjustment was calculated after baking the plates. The test plates were baked according to the curing cycle mentioned in the above. The cured panels were then tested according to the different procedures described in the above. The results for Example 4 are discussed in the following.

The product was stable with storage and no hydrogen evolution was observed, which indicates a good protection of the metal particles by the coupling of silanes.

Example 4: On a CRS test panel after 2 days of rest Example 4: On a CRS test panel after 7 days of rest Example 4: On a CRS test panel after 3 months of rest Example 4: On an EG test panel after 7 days of rest The corrosion resistance achieved with the monomeric silane (for example, Silquest® A-187 available from GE Silicones), using the procedures described above, provided 200 hours of protection in a CRS test panel and 480 hours in a control panel. EG test for 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation had a limited impact on the performance of the coating, but the performance was not achieved before several days. This parameter is critical in the design of protective coatings since it is related to the induction times in the vessel before the final performance can be reached.

EXAMPLE 5: USING MONOMERIC GLICIDOXYPROTRYTYLLOGYLISILAN AND THE PROCEDURE DESCRIBED IN FIGURE 1 In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were placed in the beaker: 28.92% by weight of demineralized water, 0.58% by weight of boric acid, 3.0% by weight of Dowanol® DPM and 3.0% by weight of glycidoxypropyltriethyloxysilane (for example, Silquest ® A-1871 available from GE Silicones). The solution was mixed for 3 hours.

Then, the following ingredients were added while stirring: 23.0% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26), 1.8% by weight of Dowanol® DPM and 2.0% by weight of additional Silquest® A-1871, available from GE Silicones. The components were mixed for ten minutes. Then, metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol®® OT 75 was added to the final dispersion. During the introduction, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final products were then stored for 7 days before the subsequent addition was made as a double package of 2.9% by weight of additional Silquest® A-1871. The modified product with subsequent addition of Silquest A-1871 was also kept in storage for three months for reexamination. The protective coatings were then applied to two test panels (one EG and one CRS test panel as described above). A thin layer and Paint uniform was deposited on the test panels using a spray gun. The coating was adjusted to 20 to 25 g / m2. This adjustment was calculated after the baking of the test plates. The test plates were baked according to the curing cycle described in the above. The cured test panels were then tested according to the different procedures described in the above. The results for Example 5 are indicated as follows: The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 5: On a CRS test panel after 7 days of rest Example 5: On a CRS test panel after 3 months of rest Example 5: On an EG test panel after 7 days of rest The corrosion resistance achieved with monomeric silane, for example, Silquest® A-1871 available from GE Silicones, provided about 200 hours of protection in a CRS test panel and 480 hours in an EG test panel for 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation had an impact on the coating performance. The yield of the coating after two days was significantly lower than after resting for 7 days and 3 months.

EXAMPLE 6: USING EXAMPLE 2 OF THAT COMBINED WITH GLICIDOXITRIETOXISILANE AND THE PROCEDURE DESCRIBED IN FIGURE 2. In this case, ESO Example 2 was pre-solubilized in water using the formulation described in the above with respect to Table 4 and it was combined with a trietoxiepoxysilane as a two-pack system. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were placed in the beaker: 30.92% by weight demineralized water, 0.58% by weight boric acid, 4.8% by weight Dowanol® DPM and 4.25% by weight of Example 2 of that. The solution was mixed for 18 hours until a clear solution was obtained. Then, the following ingredients were added while stirring: 21.75% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09) and 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final product was then stored for 7 days before the subsequent addition was added as a double pack of 2.9 wt% of glycidoxypropyltriethoxysilane. The product was kept for three months and was tested without any further addition of glycidoxypropyltriethoxysilane (eg, Silquest® A-1871 available from GE Silicones) prior to application. The protective coating formed in the above was then applied to the two test panels (an EG test panel and a CRS test panel as described above). A thin and uniform layer was deposited on the test panels. The coating was then adjusted to around 20 to 25 g / m2 based on a calculation made after the baking of the test plates. The substrates were then baked according to the curing cycle described in the above. The cured test panels were then tested according to the different procedures described in the above. The results for Example 6 are discussed in the following. The product was stable with storage and no hydrogen evolution was observed, which indicates a good protection of the metal particles by the coupling of silanes.

Example 6: On a CRS test panel after 7 days of rest Example 6: On an EG test panel after 7 days of rest The corrosion resistance achieved by a combination of ESO Example 2 with the subsequent addition of glycidoxypropyltriethoxysilane (e.g., Silquest® A-1871) provided about 160 hours of protection in a CRS test panel and 500 hours in a test panel EG for 20 g / m2 of coating deposited on the test panels before more than 5% of the surface of the test panel could be covered by red oxide. This example shows that an Epoxysilane Oligomer used in the dispersion phase of zinc and aluminum powders, and combined with an ethoxy-based epoxysilane as a two-pack system, provided very good stability and protection against corrosion.

EXAMPLE 7: USING EXAMPLE 2 OF THAT AND THE PROCEDURE DESCRIBED IN FIGURE 3. In this case, Example 2 of ESO was pre-solubilized in water using the formulation described above with respect to Table 4 and combined with a glycidoxypropyltriethoxysilane (e.g., Silquest® A-1871 ) during the dispersion phase. No further addition of silane was made after dispersion. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were placed in the beaker: 33.07% by weight of demineralized water, 0.58% by weight of boric acid, 3.3% by weight of Dowanol® DPM and 4.15% by weight of Example 2 of ESO. The solution was mixed for 18 hours until a clear solution was obtained. Then, the following ingredients were added while stirring: 19.6% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26) and 3.0% by weight additional glycidoxypropyltriethoxysilane (for example, Silquest® A-1871). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol®® OT 75 was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours . The final product was then stored for 7 days and three months before application and testing. The conditions of application and testing were the same as those described for Example 4. The results for Example 7 are described in the following. The product was stable with storage and no evolution of hydrogen was observed, which consequently indicates a good protection of the metallic particles by the coupling of silanes.

Example 7: On a CRS test panel after 7 days of rest Example 7: On a CRS test panel after 3 months of rest Example 7: On an EG test panel after 7 days of rest The corrosion resistance achieved by a combination of ESO Example 2, with the addition of Silquest® A-1871 in the dispersion phase, provided about 200 hours of protection in a CRS test panel and 550 hours in a test panel EG for 20 grams / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation did not affect the performance of the coating. This example shows that an Oligomer of Epoxysilane, according to the present invention, combined with an ethoxy-based epoxysilane used in the zinc and aluminum dispersion phase, provides very good stability and protection against corrosion. The system in this case is a real system of a package with excellent durability and exceeds the coatings described in Examples 4 and 5.

EXAMPLE 8: USING EXAMPLE 5 OF THAT AND THE PROCEDURE DESCRIBED IN FIGURE 3. In this example, ESO Example 2 was pre-solubilized in water using the formulation described above with respect to Table 4 and was also used in the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were placed in the beaker: 18.96% by weight of demineralized water, 0.59% by weight of boric acid, 3.3% by weight of Dowanol® DPM and 4.15% by weight of Example 5 of ESO. The solution was mixed for 18 hours until a clear solution was obtained. Then, the following ingredients were added while stirring: 34.2% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5% by weight of APEO surfactant (HLB 9-Berol® 26) and 2.5% in additional weight of Example 5 of ESO was added just before the dispersion. The components were mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol®® OT 75 was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final product was then stored for 7 days and three months before application and testing. The conditions of application and testing are the same as those described in the above for Example 4. The results for Example 5 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, which consequently indicates a good protection of the metallic particles by the coupling of silanes.

Example 8: On a CRS test panel after 7 days of rest Example 8: On a CRS test panel after 3 months of rest In Example 8 described above, the corrosion resistance was achieved by Example 2 of ESO as a water soluble binder and in the dispersion phase, which provided about 130 hours of protection in a CRS test panel after of 7 days of rest, increasing to 196 hours after 3 months of rest, of 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation improved the coating performance. This example illustrates that the use of a pure Epoxysilane Oligomer, according to the present invention, provides an improved waterborne protective coating.

EXAMPLE 9: USING EPOXISILANE OLIGOMER EXAMPLE 5 COMBINED WITH A VINOLETOXISILANE AND THE PROCEDURE DESCRIBED IN FIGURE 3. In this example, ESO Example 5 was pre-solubilized in water using the formulation described above with respect to Table 4 and was combined with a vinyltriethoxysilane (for example, Silquest® A-151 available from GE Silicones) during the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added: 18.96% by weight of demineralized water, 0.59% by weight of boric acid, 3.3% by weight of Dowanol® DPM and 4.15% by weight. weight of Example 5 of ESO. The solution was mixed for 18 hours until the clear solution was obtained. Then, the following ingredients were added while stirring: 34.8% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26) and 1.9% by weight of additional vinyltriethoxysilane. The components were mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. The final product was then stored for 2 and 7 days before application and testing. The conditions of application and testing are the same as those described in the above in Example 4. The results for Example 9 are described in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 9: On a CRS test panel after 2 days of rest Example 9: On a CRS test panel after 7 days of rest The corrosion resistance achieved by a combination of Example 5 of ESO with vinyltriethoxysilane (for example, Silquest® A-151 available from GE Silicones) in the dispersion phase, which provided approximately 180 hours of protection in a CRS test panel after of 2 days of rest, increasing to 200 hours after 7 days of rest, to 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation did not affect the performance of the coating. This example shows that an Epoxysilane Oligomer, according to the present invention, combined with a vinylethoxysilane used in the zinc and aluminum dispersion phase, provides very good stability and protection against corrosion. The system is a real system of a package with excellent durability. In addition, this system overcomes the coatings described in the above in Examples 4 and 5.

EXAMPLE 10: USING EXAMPLE 5 OF THAT COMBINED WITH A Cycloaliphatic EPOXISILAN TRIETOXY AND THE PROCEDURES DESCRIBED IN FIGURE 3.

In this example, Example 5 of ESO was pre-solubilized in water using the formulation described with respect to Table 4 and combined with a cycloaliphatic epoxytriethoxysilane (Coatosil® 1770 available from GE Silicones) during the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added in the beaker: 18.96% by weight of demineralized water, 0.59% by weight of boric acid, 3.3% by weight of Dowanol® DPM and 4.15% by weight of Example 5 of ESO described hereinbefore. The solution was mixed for 18 hours until a clear solution was obtained. Then, the following ingredients were added while stirring: 33.8% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5 % by weight of APEO surfactant (HLB 9-Berol® 26) and 2.9% by weight of cycloaliphatic epoxytriethoxysilane (Coatosil® 1770 available from GE Silicones). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. The final product was then stored for 2 days and 7 days before application and testing. The conditions of application and testing were the same as those described in the above in Example 4. The results for Example 10 are described in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 10: On a CRS test panel after 2 days of rest Example 10: On a CRS test panel after 7 days of rest The corrosion resistance achieved by the combination of ESO Example 5 described herein, with the addition of a cycloaliphatic tri-ethoxysilane (for example, Coatosil® 1770 available from GE Silicones) in the dispersion phase, provided approximately 200 hours of protection on a CRS test panel after 2 or 7 days of rest for 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The rest of the formulation did not affect the performance of the coating. This example shows that an Epoxysilane Oligomer, according to the present invention, combined with a cycloaliphatic triethoxysilane (Coatosil® 1770 available from GE Silicones) used in the zinc and aluminum dispersion phase, provides very good stability and protection against corrosion. The system in this case is a real system of a package with excellent durability. In addition, this system overcomes the coatings described in Examples 4 and 5 in the above.

EXAMPLE 11: USING EXAMPLE 5 OF THAT, DESCRIBED HEREIN ABOVE, COMBINED WITH A PROPYLTRIETOXISILANE AND THE PROCEDURE DESCRIBED IN FIGURE 3. In this example, ESO Example 5 was pre-solubilized in water using the described formulation in the above with respect to Table 4 and combined with a non-organoreactive triethoxysilane (e.g., Silquest ® A-138 available from GE Silicones) during the dispersion phase.

In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added in the beaker: 18.96% by weight of demineralized water, 0.59% by weight of boric acid, 3.3% by weight of Dowanol® DPM. and 4.15% by weight of Example 5 of ESO. The solution was then for 18 hours until a clear solution was obtained. So, the following ingredients were added while stirring: 34.7% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5% by weight of APEO surfactant (HLB 9-Berol® 26) and an additional 2.0% by weight of propyltriethoxysilane (for example, Silquest® A-138 available from GE Silicones). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol®® OT 75 was added to the final dispersion. The final product was then stored for 2 days and 7 days before application and testing. The conditions of application and testing were the same as those described in the above in Example 4. The results for Example 11 are discussed in the following. The Product was stable with storage and not Hydrogen evolution was observed, which indicates a good protection of the metal particles by the coupling of silanes.

Example 11: On a CRS test panel after 2 days of rest Example 11: On a CRS test panel after 7 days of rest The corrosion resistance achieved by a combination of Example 5 of ESO with the combined addition of propyltriethoxysilane (eg, Silquest® A-138 available from GE Silicones) in the dispersion phase, provided approximately 120 hours of protection in a test panel CRS after 2 or 7 days of rest for 20 g / m2 of coating deposited on the surface of the test panel before more than 5% of the surface of the test panel was covered by red oxide. Even though the yields are slightly lower compared to Example 7, it is interesting to note that a non-reactive silane can be used in the dispersion phase together with an ESO, according to the present invention, to provide a stable composition rich in zinc, transported by water, having an improved resistance to corrosion.

EXAMPLE 12: USING EXAMPLE 3 OF THAT AND THE PROCEDURE DESCRIBED IN FIGURE 4. In this example, Example 3 of ESO was pre-solubilized in water with the formulation described above with respect to Table 4 using a combination of boric acid, Dowanol® DPM and surfactant. The pre-solubilized ESO was then used only in a dispersion including metal powders. This example represents a simpler processing process, since no further addition is required in the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added in the beaker: 33.62% by weight of demineralized water, 0.58% by weight of boric acid, 4.8% by weight of Dowanol® DPM. , 1.5% by weight of APEO surfactant HLB 13 (Berol® 09) and 6.6% by weight of Example 3 of ESO. The solution was mixed for 18 hours or until a clear solution was obtained. Then, the following ingredients were then added while stirring: 19.6% by weight of water demineralized, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250) and 1.5% by weight of APEO surfactant (HLB 9-Berol® 26). The components were mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final product was then stored for 2 days, 7 days and three months before application and testing. The conditions of application and testing were the same as those described in Example 4. The results for Example 12 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 12: On a CRS test panel after 2 days of Rest Example 12: In a CRS after 7 days of Rest The corrosion resistance achieved by the use of ESO Example 3 as the sole component in a one-stage process provided approximately 230 hours of protection in a CRS test panel after 2 days of rest and increasing to more than 300 hours after 7 days. rest days for 20 g / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The yields achieved with this specific ESO significantly exceeded a conventional system based on pure monomeric silanes, such as Examples 4 and 5. This system is a real system of a package with excellent durability. The manufacturing process is simpler than Example 4 and, thus, could impact the cost of processing for protective coatings carried by water.

EXAMPLE 13: USING EXAMPLE 2 OF THAT AND THE PROCEDURE DESCRIBED IN FIGURE 4 In this example, ESO Example 2 was pre-solubilized in water using the formulation described above with respect to Table 4 in an acid combination boricum, Dowanol® DPM and a surfactant. This ESO was solubilized faster and was used alone in a dispersion of metal powders. This example represents a simpler and shorter processing process, since no further addition was required in the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added in the beaker: 33.62% by weight of demineralized water, 0.58% by weight of boric acid, 4.8% by weight of Dowanol® DPM , 1.5% by weight of APEO surfactant HLB 13 (Berol® 09) and 6.6% by weight of Example 2 of ESO. The solution was mixed for 2 hours or until a clear solution was obtained. Then, the following ingredients were added while stirring: 19.6% by weight of demineralized water, 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250) and 1.5% by weight of APEO surfactant (HLB 9-Berol® 26). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of Zinc Lamella GTT followed by 3.0% by weight of Chromal VII Aluminum Powder. Finally, 0.4% by weight of Aerosol®® OT 75 was added to the final dispersion. During the introduction, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final product was then stored for 2 or 7 days and three months before application and testing. The conditions of application and testing are the same as those described above for Example 4. The results for Example 13 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 13: On a CRS test panel after 2 days of rest Example 13: On a CRS test panel after 7 days of rest The corrosion resistance achieved by ESO Example 2, as a single component in a one-step process, was approximately 240 hours of protection in a CRS test panel after 2 days of rest and more than 190 hours after • 7 days of rest for 20 grams / m2 of coating deposited on the test panel before more than 5% of the surface of the test panel was covered by red oxide. The manufacturing process is simpler than Example 4 and, thus, could impact the cost of processing for protective coatings carried by water.

EXAMPLE 14: USING EXAMPLE 6 OF THAT COMBINED WITH A MONOMERIC EPOXISILANE AND THE PROCEDURE DESCRIBED IN FIGURE 4. In this example, Example 6 of ESO was pre-solubilized in water together with a glycidoxytriethoxysilane (Silquest® A-1871) using the formulation described in the above with respect to Table 4 and in a combination of boric acid and Dowanol® DPM. The ESO solubilized together with the monomeric silane was used directly for the dispersion of the metal powders. This example represents a further process simple processing, since no further addition was required in the dispersion phase. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added to the beaker: 22.68% by weight demineralized water, 0.77% by weight boric acid, 3.85% by weight Dowanol® DPM , 4.8% by weight of Example 6 of ESO and 2.9% by weight of glycidoxytriethoxysilane (Silquest® A-1871). The solution was mixed 4 hours until a clear solution was obtained. Then, the following ingredients were added while stirring: 30.4% by weight of demineralized water, 0.2% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09) and 1.5% by weight of APEO surfactant (HLB 9-Berol® 26). The components were mixed in the course of ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 1 hour. The final product was then stored for 2 or 7 days and three months before the application and test. The conditions of application and testing were the same as those described above for Example 4. The results for Example 14 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 14: On a CRS test panel after 2 days of rest Example 14: In CRS after 7 days of rest The corrosion resistance achieved by a combination of Example 6 of ESO with glycidoxytriethoxysilane (eg, Silquest® A-1871) used in a one-step process was approximately 190 hours of protection on a CRS test panel after 2 or 7 days of rest for 20 grams / m2 of coating deposited in the test panel before more than 5% of the surface was covered by red oxide. The yields achieved with this specific combination of ESO and epoxysilane monomers were with respect to the total processing time, which was only 5 hours in total. The product was a one-pack system with good performance.

EXAMPLE 15: USING EXAMPLE 6 OF THAT ONLY AND DIRECTLY SOLUBILIZED AND DISPERSED IN WATER AND METALLIC POWDERS AND THE PROCEDURE DESCRIBED IN FIGURE 5. In this example, Example 6 of ESO was not pre-solubilized in water prior to dispersion of pigments Instead, ESO was added directly into the formulation using all the components and mixed to obtain a homogeneous mixture. The homogeneous mixture was not in a soluble phase until all metal powders were added and dispersed for about 6 hours. This procedure, as described in Figure 5, is a one-step process. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added in the beaker: 52.49% by weight of demineralized water, 0.51% by weight of boric acid, 5.4% by weight of Dowanol® DPM. , 7.7% by weight of the Example 6 of ESO, 0.2% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09) and 1.5% by weight of APEO surfactant (HLB 9-Berol® 26). The components were mixed for ten minutes.

Next, the following metal fillers were added under agitation: 28.0% by weight of Zinc Lamella GTT followed by 3.0% by weight of Chromal Aluminum Powder VII. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction of the components and ingredients, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 6 hours. The final product was then stored for 2 or 7 days and three months before the application and test. The application and test conditions applied in this example were the same as those described in the above in Example 4. The results for Example 15 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 15: On a CRS test panel after 2 days of rest Example 15: On a CRS test panel after 7 days of rest The corrosion resistance achieved by Example 6 of ESO, used in a direct dispersion process, provided approximately 180 hours of protection on a CRS test panel after 2 or 7 days of rest for 20 grams / m2 of coating deposited on the Test panel before more than 5% of the surface of the test panel was covered by red rust. The performance achieved with this specific ESO was that the total processing time was only 6 hours. This product is a one-pack system with good performance.

EXAMPLE 16: USING EXAMPLE 6 OF THOSE ONLY WHICH IT SOLUBILIZED AND DISPERSED DIRECTLY IN WATER AND METALLIC POWDERS AND USING THE PROCEDURE DESCRIBED IN FIGURE 5. In a metal beaker equipped with Cowles mechanical stirring and blade, the following components were placed in the beaker: 52.49% by weight of demineralized water, 0.51% by weight of boric acid, 5.4% by weight of Dowanol® DPM, 0.2% by weight of Hydroxyethylcellulose (Natrosol® HHR 250), 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5% by weight of APEO surfactant (HLB 9-Berol® 26) and 7.9% by weight of Silquest® A-187. The components were mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction of the ingredients, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 6 hours. The product was stored for stability inspection and showed a strong hydrogen evolution after less than one hour. The monomeric silane (for example, Silquest® A-187) can not be used in a direct dispersion process with metal powders such as ESOs according to the present invention, for example, Example 6 of ESO. This example illustrates a major difference between a regular monomeric silane and the inventive Epoxysilane Oligomers of the current invention description.

EXAMPLE 17: USING EXAMPLE 9 OF ESO AND THE PROCEDURE DESCRIBED IN FIGURE 4. In this example, Example 9 of ESO was pre-solubilized in water with the formulation described in the following using a combination of boric acid, Dowanol® DPM and surfactant. The pre-solubilized ESO was then used only in a dispersion including metal powders. This example represents a simpler processing process, since no further addition is required in the dispersion phase. This example illustrates the application of co-oligomers of an epoxyalkylene oxide silane, according to one embodiment of the present invention, in zinc-rich protective coatings carried by water. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following components were added to the beaker: 32.00 wt% demineralized water, 0.77 wt% boric acid, 5.25 wt% Dowanol® DPM and 7.0% by weight of Example 9 of ESO. The solution was mixed for 18 hours or until a clear solution was obtained. Then, the following ingredients were added while stirring: 23.7% by weight of demineralized water, 1. 5% by weight of APEO surfactant HLB 13 (Berol® 09), 0.4% by weight of Hydroxyethylcellulose (Natrosol® HHR 250) and 1.5% by weight of APEO surfactant (HLB 9-Berol® 26). The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol®® OT 75, available from Cytec Industries, Inc., was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The final product was then stored for 7 days before application and testing. The final pH of the formulation was stabilized at 6.9 and the viscosity was at 35 seconds with DIN cup number 4. The conditions of application and testing were the same as those described in Example 4. The results for Example 17 are discussed in the next. The product was stable with storage and no evolution of hydrogen was observed, which indicates a good protection of the metallic particles by the coupling of silanes.

Example 17: In a CRS after 7 days of Rest The corrosion resistance achieved by the use of ESO Example 9 as the sole component in a one-stage process provided approximately 270 hours of protection in a CRS test panel after 7 days of rest for 20 g / m2 of coating deposited on the Test panel before more than 5% of the surface of the test panel was covered by red rust. The performance achieved with this specific ESO significantly exceeded a conventional system based on pure monomeric silanes, such as Examples 4 and 5. This system is a real system of a package with excellent durability. The manufacturing process is simpler than Example 4 and could thus significantly reduce the cost associated with making a protective coating transported by water. It is also observed that it has been possible to increase up to the concentration of ESO in the hydrolysis phase of the process. The co-solvent content in Dowanol® DPM was also lower compared to other examples, for example Examples 2 to 12. This indicates that the co-oligomer of an epoxysilane and an alkylene oxide can increase the rate of solubilization as well as reduce the amount of coalescent necessary to make the ESO soluble in water. The corrosion yields are not affected by the contribution of alkylene oxide in the ESO as prepared in Example 9.

EXAMPLE 18: USING AN EPOXISILAN OLIGOMER SOLUTION OF DYNASILAN® HS 2926 AND THE PROCEDURE DESCRIBED IN FIGURE 4 An Epoxysilane Oligomer pre-solubilized in accordance with the present description of the invention does not perform in a similar manner to the Epoxysilane Oligomer made in water as it currently exists in commercial form with a product called Dynasilan® HS 2926 (Available from Degussa Huís). In this example, a comparison was made between the Dynasilan® HS 2926 material in the same formulation as described above in Examples 12 and 13. The product was used in equal siloxane loading, assuming that the dry content given for the product was 40% non-volatile as indicated. In this case, the HS 2926 was already solubilized in water and was used directly for the dispersion of the metal powders.

In a metal beaker equipped with mechanical agitation and a Cowles blade, the following ingredients were added while stirring: 16.6% by weight of Dynasilan® HS 2926, 43.62% by weight of demineralized water, 0.58% by weight of boric acid, 1.5% by weight of APEO surfactant (HLB 13-Berol® 09), 1.5% by weight of APEO surfactant (HLB 9-Berol® 26) and 4.8% by weight of Dowanol DPM. The components were then mixed for ten minutes. Next, the following metal fillers were added under agitation: 28.0% by weight of GTT zinc foil followed by 3.0% by weight of Chromal VII aluminum powder. Finally, 0.4% by weight of Aerosol® OT 75 was added to the final dispersion. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The product was stored and followed with respect to stability. After a couple of hours, a strong evolution of hydrogen occurred, and the product generated a significant amount of foam. Indicating in this way a poor stability of the product compared to the formulations in Examples 12 and 13. This example illustrates that the structure of the ESOs in accordance with the present invention provided stable products with varying solutions of water compared to an already hydrolyzed epoxysilane oligomer (eg, Dynasilan® HS 2926).

DISPERSIONS OF PIGMENTS TRANSPORTED BY WATER AND ITS USES EXAMPLE 19: DISPERSION OF PREPARED ALUMINUM PASTE USING THE PROCEDURE DESCRIBED IN FIGURE 6 The process used in this example was similar to the process used in Example 12 described above, except that the aluminum powder was used alone at a higher concentration high (36.1% instead of 28% Zinc along with 3% Aluminum). The ratio of silane to pigment was adjusted to 1 of ESO to 9 of aluminum. The purpose here is to prepare aluminum concentrates that can be further extended with additional binders to formulate coatings containing aluminum. In a metal beaker equipped with mechanical stirring and Cowles blade, the following ingredients were added while stirring: 56.23% by weight of demineralized water, 0.47% by weight of boric acid, 0.94% by weight of APEO surfactant (HLB 13 -Berol® 09), 0.94% by weight of APEO surfactant (HLB 9-Berol® 26), 2.7% by weight of Dowanol® DPM and 3.41% by weight of Example 6 of ESO. The components were dispersed for 18 hours until the clear solution was obtained. Then, 35.3% by weight of Chromal VII Aluminum Powder was added. During the introduction of the ingredients, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The product obtained was stored for 2 months and was followed with respect to stability. During this period of rest, no evolution of hydrogen was observed. Sedimentation was observed, but it was easily re-suspended with moderate agitation.

EXAMPLE 20: ZINC DUST PIGMENT PASTE The same procedure, see Figure 6, was applied in this example as in Example 18 for aluminum, except that in this example Zinc Powder was used instead of Aluminum Powder. Due to the higher density of the zinc powder, the zinc content was increased to 56% by weight. The purpose here is to prepare zinc concentrates that can be further extended with additional binders to formulate coatings containing aluminum. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following ingredients were added while stirring: 33.1% by weight of demineralized water, 0.60% by weight of boric acid, 1.3% by weight of APEO surfactant (HLB 13-Berol® 09), 1.3% by weight of APEO surfactant (HLB) 9-Berol® 26), 3.4% by weight of Dowanol® DPM and 4.30% by weight of Example 6 of ESO. The components were dispersed for 18 hours until the clear solution was obtained. Next, 56% by weight of GTT Zinc Lamella was added while stirring and dispersing. During the introduction of the components, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 4 hours. The product obtained was stored for 2 months and was followed with respect to stability. During this period of rest, no evolution of hydrogen was observed. Sedimentation was observed, but it was easily re-suspended with moderate agitation.

EXAMPLE 21: PROTECTIVE COATING WHEN MIXING PASTE OF PIGMENTS USING THE PROCEDURE DESCRIBED IN FIGURE 7 In this example the content of zinc and aluminum, used in Example 5 above and following, was introduced using prepared aluminum and zinc pastes respectively according to Examples 19 and 20. The two pastes are simply mixed with ESO solution as described in the previous examples. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following ingredients were added while stirring: 23.87% by weight of demineralized water, 0.74% by weight of boric acid, 4.1% by weight of Dowanol® DPM and 5.29 % by weight of Example 6 of ESO. The components were mixed for 18 hours until a clear solution was obtained. Next, 50% by weight of Zinc paste (Example 20) and 8.5% by weight of aluminum paste (Example 19) followed by 0.4% by weight of Aerosol® OT 75, 0.15% by weight of Natrosol® 250 HRR in 6.95% by weight of demineralized water were added while stirring and mixing for 30 minutes. The conditions of application and testing were the same as those discussed in the above in Example 4. The results for Example 21 are discussed in the following. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by the coupling of silanes.

Example 21: On a CRS test panel after 2 days of rest Example 21: On a CRS test panel after 7 days of rest The corrosion resistance achieved by the formulation of this example provided approximately 170 hours of protection on a CRS test panel after 2 or 7 days of rest for 20 grams / m2 of coating deposited on the test panel before more than 5 hours. % of the surface of the test panel will be covered by red oxide. The product is still a one-pack system with good performance. It was observed, according to Examples 19 and 20, that they can be used as a simple combination or mixed with additional systems of ESO-based binders, prepared according to the present invention. It was also observed that the zinc and aluminum pastes, prepared in Examples 19 and 20 according to exemplary embodiments of the present invention, can be combined with a silane monomer or other solutions of epoxysilane oligomers as tested in Example 18.

EXAMPLE 22: METALLIC INKS OR COATING WHEN MIXING PIGMENT PASTES In Examples 19 and 20, it was shown that the pigment pastes described therein can be used in a simple combination with a conventional styrene-acrylic resin as is typically employed in the industry. of printing inks and coatings. In the present example, a styrene-acrylic latex was selected and simply mixed with an aluminum paste according to the following procedure. In a metal beaker equipped with mechanical stirring and a Cowles blade, the following ingredients were added while stirring: 60% by weight of a styrene-acrylic latex (e.g., Worleecryl® 8410 available from Worlee Gmbh) and 60% by weight of aluminum paste produced according to Example 19 discussed in the above. The components were mixed for 10 minutes. This example (with reference to "ESO-based ESO" in the following Table 8 in the following) illustrates that it is possible to prepare aluminum-based coatings or inks by simply mixing a pre-dispersed aluminum with a solubilized ESO, in accordance with the present invention. .

In order to compare the performance and stability of such preparation, a dispersion of the same aluminum powder was made directly in a styrene-acrylic latex selected according to the following procedure: In a metal beaker equipped with mechanical stirring and stirring Cowles, the following ingredients were added while stirring: 84.0% by weight of Worleecryl® 8410 (styrene-acrylic resin available from Worlee Gmbh), 1.0% by weight of APEO surfactant (HLB 13-Berol® 09), 1.0% by weight of APEO surfactant (HLB 9-Berol® 26). The components were mixed for 10 minutes. Next, 14.0% by weight of Chromal VII aluminum powder was added. During the introduction of the aluminum, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 30 minutes. This example (with reference to "Direct Dispersion Process" in Table 8 in the following) illustrates the typical preparation used to make a coating or ink based on aluminum in styrene-acrylic latex.

Table 8 The formulation prepared according to the direct dispersion mode was not stable at all. The direct dispersion product experienced strong degassing and foaming during the first hours of storage. Meanwhile, ESO's dispersed paste-based product was very stable for more than 2 months. The simple combination of the ESO aluminum paste, according to the present invention, was stable and could be applied using a standard hand-held paper applicator. The coating made has very good print quality as well as brightness. A similar behavior was achieved by the use of the dispersed zinc paste in ESO. Such a combination of zinc paste with anionic resins could give the possibility of preparing coatings rich in zinc based on latex or dispersions or primers.

EXAMPLE 23 In another aspect of the use of current ESOs, demonstrated in the following example that it is possible to use an ESO as an external crosslinker for latex transported by water. It is known in the prior art that Epoxysilane monomers can be used as crosslinkers in latex and water dispersions based on anionic or cationic. In the following examples, a typical wood coating formulation was used as a model system to show what influence current ESOs have on such formulations, as well as to compare the use of current ESOs for conventional epoxysilane monomers. The formulation was prepared according to Table 9 in the following using the following procedure. In a metal beaker equipped with mechanical stirring and Cowles blade, the following ingredients were added while stirring: 69.52% by weight of SCX® 8225 acrylic latex (available from SC Johnson Polymer), 1.185% by weight of Wetlink 78 (formulation 2 in Table 9) or 1185% by weight of Example 5 of Epoxysilane Oligomer ESO (formulation 3 in Table 9). The formulation was stirred for 30 minutes. Then, 0.2% by weight of a wetting agent (eg, Coatosil® 1211 available from GE Silicones), 9.0% by weight of Coalescent (eg, Proglyde® DPnB available from Dow Chemical), 4.3% was added to the formulation. by weight of matte wax (for example, Aquamat® 128 available from Byk Wax), 2.5% by weight of PE wax (Ultralub® D819 available from Keim-Additec Surface) and a necessary amount of water to make 100% by weight. The components were then mixed for 30 minutes. As an unmodified standard, the same formulation was applied without any silane (formulation 1 is listed in Table 9). Typical epoxysilanes used as an external crosslinker for anionic latexes were used for comparison with gamma-glycidoxypropylmethyldiethoxysilane (Wetlink® 78 available from GE Silicones).

Table 9 In a first set of tests applied to the modified polymers, mixtures of acrylic latex with water and the corresponding epoxysilane monomer or oligomer were applied in Teflon cells after the appropriate curing at room temperature for 15 days. The formed films were then peeled off from the Teflon cells and weighed accurately before immersion in water. The absorption of water and remaining polymer was measured after further drying. The gel content was also measured in the same samples. The results are given in Table 10 in the following.

Table 10 The results show that an ESO, in accordance with the present invention, significantly enhances the water resistance of the anionic latexes, at a level at least comparable to the epoxysilane monomers.

In a second set of tests, total coatings of Formulations 1-3 were applied on glass substrates in order to allow the measurement of hardness. 200 microns of the coatings were applied to the glass substrates and dried to increase the period of time during which the Koenig Hardness was followed. Table 11 in the following shows the hardness evolution of the films.

Table 11 The results show that an ESO, for example, the Example 5 of ESO intensifies significantly the hardness of the wood coating. In fact, the results were even better than with the use of a conventional epoxysilane monomer. Finally, Total Formulations 1-3 were applied on wood panels (oak plywood) using a spray gun. A deposit of 150 g / m2 was applied and also dried for 15 days at room temperature. The resistance to staining was then tested according to the conditions listed in Table 12 in the following. The results are illustrated in Table 13 in the following.

Table 12 Table 13 * = the surface of the coating is not physically damaged but the staining of the wood is visible ** = the surface of the coating is physically damaged and a strong stain is visible Here again, the results show that the Example 5 of ESO significantly enhances the chemical resistance and stain resistance of a wood coating. Very particularly the effect is quite obvious in resistance to staining against ammonia solution for which wood staining is significantly reduced. This example test exhibits the possibility of using ESO as external crosslinkers in acrylic latex or also as an anti-staining agent for wood coatings.

EXAMPLES 24-26: SOLUBILIZING EXAMPLE 6 OF THAT IN WATER UNDER ACID CONDITIONS, DISPERSING METALLIC POWDERS THEREOF AND TESTING THE SAME Example 24: Preparation of ESO Example 6 of Pre-solubilization in Water This example describes the pre-solubilization of the Example 6 of ESO in water to be used later for the dispersion of a metal powder therein. Example 24 was prepared by the following method. The following ingredients were added under continuous stirring in a glass of metal precipitate equipped with mechanical stirring and a Cowles blade: 10.0 weight percent of Example 6 of ESO, 5.0 weight percent of Dowanol DPM, 30.0 weight percent of a 45/1 solution of boric acid in demineralized water and 5.0 percent by weight of demineralized water. The solution was mixed for 7 days until a clear solution was obtained.

Example 25: Preparation of a Metal Dispersion Example 25 illustrates the dispersion of metal powders in the solution of Example 24. In this example, zinc and aluminum alloy in paste, available from Eckaart, was used instead of zinc alloy flakes and regular aluminum and zinc flakes mixed together. Example 25 was prepared by the following method: under continuous agitation, 2.2 weight percent of free APEO surfactant (HLB 13-Berol® 48), 1.9 weight percent of free APEO surfactant (HLB 9-Lauroxal 3) and 0.5 weight percent Y-15702 (siloxane antifoam available from GE Silicones) were added to the solution obtained in Example 24 and mixed for ten minutes. Then, under continuous agitation, 35.0 weight percent zinc and aluminum alloy paste (STAPA ZnAl 7 paste available from Eckaart Germany) and 5.0 weight percent zinc flake powder (Zinc flake GTT) available from Eckaart Germany) were added to the mix. During the introduction, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 1 hour at 900 rpm. After dispersion, 0.4 percent by weight of Aerosol® OT 75 was added to the dispersion and stirred for 10 minutes at 500 rpm. Finally, 5.5 weight percent of a 2% HEC solution in water was added to the dispersion and mixed for 10 minutes at 500 rpm. The final dispersion had a viscosity of 32 seconds DIN in cup number 4 and pH of 6.9. The resulting dispersion was then stored for appropriate times (eg, 2 days, 7 days and three months) before the subsequent addition of 2.9 weight percent of additional Silquest® A-187. The product was stable with storage and no evolution of hydrogen was observed, indicating good protection of the metal particles by a silane of the present invention.

Example 26: Application of a thin cover of the Example 25 in a CRS Text Panel Example 26 describes the application of Example 25 in a CRS test panel and the test results thereof. A thin uniform layer of Example 25 was deposited on a test panel using a spray gun. He coating was adjusted to approximately 20 to 25 g / m2 of cured deposit. This adjustment was calculated after baking the plate. The test plate was baked according to the curing cycle mentioned in the above. The cured panel was then tested according to the different procedures described in the above. The results for Example 26 are discussed in the following.

Example 26: Results of Example 25 in a CRS test panel after 1 day of rest The corrosion resistance achieved by a combination of ESO Example 6 with addition of co-solvent and solubilization under acidic conditions was approximately 650 hours of protection in a CRS test panel after 1 day of rest for 30 grams / m2 of deposited coating in the test panel before more than 5% of the scratch was covered by red oxide. In addition, during the test, it was observed that white rust did not appear until after 552 hours of exposure to salt spray, and the red oxide did not appear on the surface of the panel until after 650 hours of exposure and the scratch was covered by 5 hours. % oxide red after 650 hours of exposure. These results illustrate the dramatic impact that the choice of filler and formulation can have on the corrosion resistance of a waterborne protective coating. In this area, the zinc and aluminum alloy tends to offer much better protection against corrosion.

EXAMPLE 27-29: SOLUBILIZING EXAMPLE 6 OF THAT IN WATER UNDER ACID CONDITIONS, DISPERSING METALLIC POWDERS THERE AND PROVING THE SAME Example 27: Solubilization of Example 6 of ESO This example describes the pre-solubilization of Example 6 of ESO in low water Acid conditions followed by neutralization. The pre-solubilized ESO will then be used for the direct dispersion of metallic powders therein. In this example, pulp of zinc and aluminum alloys available from Eckaart was used.

Example 27 was prepared by the following method.

The following ingredients were added under continuous stirring in a metal beaker equipped with mechanical stirring and a Cowles blade: 10.2 weight percent of Example 6 of ESO, 5.1 weight percent of dipropylene glycol and 10.0 weight percent of a solution 45/1 boric acid in demineralized water. The resulting mixture was then mixed for 2 hours until a clear solution was obtained. The pH was then adjusted to about 6.5 with 3.4 weight percent of a 1/1 solution of caustic soda in demineralized water. The solution was stored under neutral conditions for 18 hours before use.

Example 28: Metallic Powder Dispersion in the Solution of Example 27 Example 28 illustrates the dispersion of metal powder in the solution obtained in Example 27. Example 28 was prepared by the following method: under continuous stirring, 2.2 weight percent of free APEO surfactant (HLB 13-Berol® 48), 1.9 percent by weight of free APEO surfactant (HLB 9-Lauroxal 3) and 0.5 percent by weight of siloxane antifoam (Y-15702 available from GE Silicones) they were added to the solution obtained in Example 27 and mixed for 10 minutes. Then, under continuous agitation, 39.0 weight percent of a 90% zinc aluminum alloy paste in mineral spirits (STAPA 4 ZnAl 7 slurry available from Eckaart Germany) followed by 5.0 weight percent of a Slipper Powder. of 90% zinc in dipropylene glycol paste (STAPA DG GTT available from Eckaart Germany) were added to the mixture. During the introduction of the metal powders, the speed of the agitator was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 1 hour at 900 rpm. 0.4 percent by weight of Aerosol® OT 75 was then added to the dispersion and mixed for 10 minutes at 500 rpm. Finally, 12.3 weight percent water and 5.0 weight percent of a 2% HEC solution in water were added to the dispersion and stirred for 10 minutes at 500 rpm. The final dispersion had a viscosity of 29 seconds DIN in cup number 4 and pH of 6.8. After 20 days, a very slight release of hydrogen was observed.

Example 29: Application and Test of the Dispersion of Example 28 The application and test conditions used in this example are the same as those described in the above in Example 4. The results for Example 29 are discussed in the following.

Example 29: Results after 1 day of rest The corrosion resistance achieved by a combination of ESO Example 6 with addition of co-solvent and solubilization under acidic conditions before neutralization to near-neutral conditions was approximately 720 hours of protection in a CRS test panel after 1 day of rest for 30 grams / m2 of coating deposited on the test panel. During the test, it was observed that white oxide did not appear in the scratch before 384 hours of exposure to salt spray, red oxide did not appear on the surface of the panel before 720 hours of exposure and the scratch was covered by 5% of the red oxide only after 552 hours of exposure. This example illustrates the. solubilization of an ESO of the present in acidic conditions and neutralizing the solution before the dispersion of the metallic fillers, stabilizing consequently the metallic fillers with greater sensitivity to the pH conditions.

EXAMPLES 30-32: PREPARATION OF A WATER TRANSPORTED PRIMER SHEET USING EXAMPLE 6 OF THAT, APPLICATION AND TEST OF SAME Example 30: Pre-Solubilization Of Example 6 Of That Example 30 illustrates the pre-solubilization of Example 6 of ESO in water in combination with a solution of boric acid and di-propylene glycol. The pre-solubilized ESO will then use in the direct dispersion of zinc powder. Example 30 was prepared by the following method. The following ingredients were added under continuous stirring in a metal beaker equipped with mechanical stirring and a Cowles blade: 3.3 weight percent of Example 6 of ESO and 1.65 weight percent of dipropylene glycol. 1.65 weight percent of a 0.1% solution of orthophosphoric acid solution in water was then added to the resulting mixture and mixed until a clear solution was obtained. Under continuous agitation, 4.4 weight percent of a solution of 45 g / 1 of boric acid in demineralized water was added to the clear solution and mixed for 16 hours until a clear solution was obtained. After an acid solution of ESO, the pH of the clear solution was adjusted to about 6.0 with 2.2 weight percent of a solution of 1 g / 1 of caustic soda in water.

Example 31: Metallic Powder Dispersion in the Solution of Example 30 Example 31 illustrates the dispersion of metal powder in the solution obtained in Example 30. Example 31 was prepared by the following method: under continuous stirring, 0.48 weight percent of free APEO surfactant (HLB 13-Berol® 48), 0.44 weight percent of free APEO surfactant (HLB 9-Lauroxal 3) and 0.22 weight percent siloxane antifoam (Y-15702 available from GE Silicones) were added to the solution obtained in Example 30 and mixed for about 10 minutes. After mixing, the following metal filler was added under continuous agitation: 80.8 weight percent zinc powder (DP 16 zinc dust particles available from Umicore). During the introduction of the metallic filler, the agitator speed was progressively increased in order to maintain an appropriate torque of dispersion. The dispersion was maintained for 1 hour at 1000 rpm. 7.0 weight percent of an epoxy dispersion (New Gen DP 6870 available from Hexxion) was then added to the dispersion and stirred for 10 minutes at 500 rpm. Finally, 0.06 weight percent of Aerosil® R 972 (available from Degussa Huís) was added to the dispersion and stirred for 10 minutes at 500 rpm. The final dispersion had a viscosity of 90 seconds DIN in cup number 4 and pH of 6.9. This dispersion will then be used as part A of an epoxy dispersion of two packs of a water-borne primer. The dispersion was maintained at room temperature for more than 4 months without any signs of hydrogen degassing or issues of heavy sedimentation.

Example 32: Preparation of a water-borne primer plate of 2 A-t-B packs. Example 32 describes the preparation of a 2-pack water-borne primer using the dispersion of Example 31 (designated as Part A). Example 32 was prepared by the following method. Parts A and B, described and in the amounts listed in Table 14, were mixed in a metal beaker under moderate agitation for 20 minutes at 500 rpm. The mixture was then adjusted to 18 seconds DIN in cup number 4 with demineralized water. There was a significant increase in the viscosity of the primer plate carried by water after 24 hours. The characteristics of the water-borne primer plate of Example 32 are described in the following in Table 15.

Table 14 Table 15: Characteristics of the Water Transported Primer Plate of Example 32 EXAMPLES 33-37: APPLICATION OF THE PLATE OF WATER TRANSPORTABLE PRIMER OF EXAMPLE 32 IN CRS PANELS Examples 33-37 illustrate the application of the waterborne primer plate of Example 32 in CRS panels and the curing of the panels under different curing conditions. Examples 33-35 were prepared by spraying a uniform layer, having a thickness of about 17 to about 20 microns, of the waterborne primer plate of Example 32 into CRS panels and curing the panels at room temperature for 24 hours. Examples 36-37 were prepared by spraying a uniform layer, having a thickness from about 25 to about 27, of the water-carried primer plate of Example 32 into CRS panels and curing the panels when air-drying at 70 ° C. in an oven for 5 minutes and then remove the panels from the oven and finish the curing at room temperature for 24 hours. The physical characteristics and curing conditions of Examples 33-37 are detailed in Table 16 in the following. Once cured, the panels of Examples 33-37 were tested for the following characteristics: Dry to touch, time to leave no marks on contact; No stickiness, time to leave no marks during dry-driving, time for the coating to resist scratching and rubbing; Adhesion, adhesion test by bucking; Impact resistance, reverse impact - falling ball 2kg-100cm; Water resistance (drained), time for water resistance drained; Water resistance (immersion), time to resist immersion in water for 24 hours; MEK rub resistance; Resistance to scrubbing after 24 hours of storage at room temperature; Test of resistance to the spraying of salts; Propagation of trailing corrosion; and appearance of red oxide in the striped. The results of the preceding test of Examples 33-37 are illustrated in Table 17 and discussed in the following.

Table 16: Physical Characteristics and Curing Conditions of Examples 33-37 The results show that the water-borne primer plate described above dries quickly and provides good metal adhesion. The results also show that the water-borne primer plate described above is a fast-drying coating with good metal adhesion. The water resistance reached good levels after very short drying times at room temperature. The chemical resistance was also very good. The adhesion and mechanical resistance tests show that the water-borne primer showed fast and easy mechanical handling without degradation of the coatings. The results also show that the primer sheet transported by water using an epoxy silane oligomer as a dispersing and stabilizing agent for a zinc powder provided excellent corrosion protection against trailing oxide propagation. The shelf stability of part A of the water-borne primer was excellent and exceeded 4 months.

EXAMPLES 38-47 Examples 38-41: Application of Water Transported Primer on CRS Panels Examples 38-41 describe the application of the waterborne priming sheet of Example 32 on CRS panels. Examples 38-39 and 40-41 were prepared according to the methods described in the above in Examples 33-34 and 36-37, respectively. The physical characteristics of the coatings are described in Table 17 in the following.

Table 17: Physical Characteristics and Curing Conditions of Examples 38-41 Examples 42-47: Application of solvent-borne base layer Examples 42-45 were prepared by spraying a solvent-borne base layer on the primer-coated panels of Examples 38-41, respectively. Examples 46-47 were prepared, as a control, by spraying the solvent-borne base layer directly onto a CRS panel without primer. The solvent-borne base layer is a product commercially available from Sigma Kalon. Examples 42-45 were prepared by spraying a uniform layer, having a thickness of about 73 to about 95 microns dry, of solvent-borne coating on the primer-coated panels of Examples 38-41, respectively. Examples 46-47 were prepared by spraying a uniform layer, having a thickness from about 81 to about 116, of coating carried by solvent on CRS panels without any primer. Each of examples 42-47 was cured for 7 days under ambient conditions. The physical characteristics and curing conditions of Examples 42-47 are detailed in Table 19 in the following. After curing, the tests described in the above in Examples 33-37 were performed in each of the panels of Examples 42-47, which are illustrated in Table 20 in the following.

Table 19: Physical Characteristics and Curing Conditions of Examples 42-47 Table 20: Test Results of Examples 42-47 The durability deposited by a solvent-borne coating on the top of a waterborne primer plate of the present invention significantly extended the corrosion resistance of the CRS panels. In addition, the VOC content was around 80 g / 1 without loss in drying or curing efficiency. While exemplary embodiments have been shown and described, it will be understood by those skilled in the art that various modifications and substitutions may be made to them without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation.

Claims (37)

CLAIMS 1. A process for producing a waterborne coating composition which comprises: (i) pre-solubilizing at least one epoxysilane oligomer in an aqueous solution under acidic conditions with one or more optional ingredients selected from the group consisting of pH adjusting agent, co-solvent, surfactant and monomeric silane, wherein the epoxysilane oligomer is produced by reacting glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups and, optionally, a copolymerizable silane other than glycidoxysilane and cycloaliphatic epoxysilane, with less than

1. 5 equivalents of water in the presence of a catalyst, wherein the water is supplied continuously during the reaction; and (ii) dispersing a particulate metal in the aqueous solution.

2. The process of Claim 1, wherein the reaction of the silane is carried out in the presence of an alcohol-free solvent.

3. The process of Claim 1, wherein the glycidoxysilane is at least one member selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and gamma-glycidoxypropyl methyldiethoxysilane; the cycloaliphatic expoxysilane is at minus one member selected from the group consisting of beta- (3,4-expoxycyclohexyl) -ethyltrimethoxysilane and beta- (3,4-epoxycyclohexyl) -ethyltriethoxysilane; and different glycidoxy and cycloaliphatic epoxy silane optional copolymerizable silane is at least one member selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltriisopropoxysilane, octyltriethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, polialquilenoxidetrimetoxisilaño, metacriltrimetoxisilano, metacriltrietoxisilano and metacriltriisopropoxisilano.

4. The process of Claim 1, wherein the reaction includes reacting from about 0.4 to about 1.0 equivalents of water.

5. The process of Claim 1, wherein the reaction includes reacting less than about 0.5 equivalents of water.

The process of Claim 2, wherein the non-alcohol solvent is at least one member selected from the group consisting of acetone, toluene, aliphatic hydrocarbon, paraffin, aromatic hydrocarbon, ketone and ester.

The process of Claim 1, which further comprises continuously removing by-product alcohol produced during the reaction.

8. The process of Claim 1, wherein the catalyst is at least one member selected from the group consisting of ion exchange resin, titanate, Lewis acid, zirconate, alkylammonium salt, quaternary ammonium functional silane reacted with at least one one of ceramic, silica gel, precipitated or smoked silica, alumina or aluminosilicate.

9. The process of Claim 1, which further comprises neutralizing the aqueous solution of step (i) to a pH of less than about 7.0 after pre-solubilization of at least one epoxy silane oligomer.

The process of Claim 1, wherein the metal particle is selected from the group consisting of aluminum, manganese, cadmium, nickel, tin, magnesium, zinc, alloys thereof, ferroalloys and any combination thereof.

The composition of Claim 1, wherein the particulate metal is selected from the group consisting of zinc powder, zinc foil, aluminum powder, aluminum foil, zinc and aluminum alloy powder, zinc alloy flakes. and aluminum and any combination thereof.

12. The process of Claim 1, wherein the co-solvent is at least one member of the group consisting of of dipropylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, butylcarbitol, dipropylene glycol dimethyl ether, butyl glycol, butyl diglycol, ethylene glycol monobutyl ether acetate, of diethylene glycol monoethyl ether, diethylene glycol monobutyl ether acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methoxypropyl acetate, butyl cellosolve actetate, butylcarbitol acetate, propylene glycol n-butyl ether acetate, t-acetate -Butyl, n-butanol, n-propanol, isopropanol and ethanol.

The process of Claim 1, wherein the surfactant is selected from the group consisting of alkyl phenol ethoxylate surfactant, cationic surfactant, anionic surfactant, nonionic surfactant, a polyethersiloxane based surfactant and any combination thereof.

The process of Claim 1, wherein the pH adjusting agent is at least one member selected from the group consisting of boric acid, acid orthophosphoric, acetic acid, ascorbic acid and citric acid.

The process of Claim 1, wherein the monomeric silane is at least one member selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-metacriloxipropiltriisopropoxisilano, octyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, polialquilenoxidotrimetoxisilaño, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-metacriloxipropiltriisopropoxisilano.

16. A waterborne composition comprising: (i) at least one epoxysilane oligomer, wherein the epoxysilane oligomer is produced by the reaction of glycidoxysilane and / or cycloaliphatic epoxysilane having 2 or 3 alkoxy groups and, optionally, , a copolymerizable silane different from glycidoxysilane and cycloaliphatic epoxysilane, with less than 1.5 equivalents of water in the presence of a catalyst, wherein water is supplied continuously during the reaction; and, (ii) one or more optional ingredients selected from the group consisting of a surfactant, pH adjusting agent, co-solvent, monomeric silane, binder, crosslinker and pigment paste dispersion.

17. The water-borne composition of Claim 16, wherein at least one epoxysilane oligomer is pre-solubilized in an aqueous solution.

The composition of Claim 16, wherein the optional pH adjusting agent is at least one member selected from the group consisting of boric acid, orthophosphoric acid, acetic acid, ascorbic acid and citric acid; the optional co-solvent is at least one member of the group consisting of dipropylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monohexyl ether, mono-2- ethylene glycol ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, butylcarbitol, dimethyl ether dipropylene glycol, butyl glycol, butyl diglycol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methoxypropyl acetate, butyl cellosolve actetate, butylcarbitol, propylene glycol n-butyl ether acetate, t-Butyl acetate, n-butanol, n-propanol, isopropanol and ethanol; and monomer optional silane is at least one methacryloxypropyltriethoxysilane gamma member selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, isilano, vinyltriethoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane viniltrimeto, , gamma-methacryloxypropyltriisopropoxysilane, octyltriethanesilane, propyltrimethoxysilane, propyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, polyalkylenoxydrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-methacryloxypropyltriisopropoxysilane.

19. The composition of Claim 16, in wherein the surfactant is at least one member selected from the group consisting of alkyl phenol ethoxylate surfactant, cationic surfactant, anionic surfactant, nonionic surfactant, a polyethersiloxane based surfactant and any combination thereof.

20. The composition of Claim 16, wherein the surfactant has a hydrophilic-lipophilic balance value of from about 5 to about 15.

The composition of Claim 16, wherein the binder is selected from the group consisting of organic or inorganic binders.

22. The composition of Claim 21, wherein the inorganic binder is selected from the group consisting of silicates, ethylsilicates, solutions of silica nanoparticles and silicone resins.

The composition of Claim 21, wherein the organic binder is selected from the group consisting of stabilized nonionic resins, stabilized anionic emulsions and cationic stabilized emulsions.

The composition of Claim 23, wherein the organic binder is selected from the group consisting of vinyl resins, polyvinyl chlorides, vinyl chloride copolymers, vinylacetate copolymers, vinylacetate copolymers, copolymers acrylics, styrene-butadiene copolymers, acrylate, acrylate copolymer, polyacrylate, styrene-acrylate copolymers, phenolic resins, melamine resins, epoxy resins, polyurethane resins, alkyd resins, polyvinyl butyral resins, polyamides, polyamidoamine resins , polyvinyl ethers, polybutadienes, polyester resins, organosilicone resins, organopolysiloxane resins, nitrocellulose resins, carboxymethylcellulose, cellulose esters of organic acids, cellulose ethers, modified natural rubbers, natural gums, a solution of polymers and copolymers and any combination of them.

The composition of claim 16, wherein the crosslinker is selected from the group consisting of isocyanates, epoxy curing agents, amino agents, aminoamido agents, epoxyamino adducts, carbodiimides, melamine anhydrides, polycarboxylic anhydrides, carboxylic acid resins , aziridines, titanates, organofunctional titanates and organofunctional silanes.

26. The composition of Claim 25, wherein the organofunctional silane is selected from the group consisting of epoxysilanes, aminosilanes, isocyanatosilanes, methacrylsilanes, and vinylsilanes.

27. The composition of Claim 16, wherein the pigment paste dispersion is selected from group consisting of dispersions of organic pigments and dispersions of inorganic pigments.

The composition of Claim 16, wherein at least one epoxysilane oligomer is present in the range of about 0.05 to about 40 weight percent of the composition.

29. The cured composition of Claim 16.

30. An adhesive, sealant or coating composition which comprises the waterborne composition of Claim 16.

31. The composition of Claim 17, wherein the aqueous solution comprises a metal particulate dispersed in it.

32. The composition of Claim 31, wherein the particulate metal is selected from the group consisting of aluminum, manganese, cadmium, nickel, tin, magnesium, zinc, alloys thereof, ferroalloys and any combination thereof.

The composition of Claim 31, wherein the particulate metal is selected from the group consisting of zinc powder, zinc foil, aluminum powder, aluminum foil, zinc and aluminum alloy powder, zinc alloy flakes. and aluminum and any combination thereof.

34. The composition of Claim 31, in where the particulate metal is in the form of a powder or paste dispersion.

35. The composition of Claim 31, wherein the particulate metal is selected from the group consisting of zinc chromate, zinc and potassium chromate, zinc phosphates, aluminum triphosphates, calcium and magnesium phosphates, barium phosphates, phosphates. aluminum and zinc, molybdates, tungstates, zirconates, vanadates, zinc salts of 5-nitrophthalic acid and iron phosphide.

36. A coating composition which comprises the composition of Claim 31.

37. The cured product of Claim 36.