Single package ambient curing polymers

Abstract: The present invention relates to the preparation of aqueous based polymers bearing reactive functional groups. More particularly, this invention relates to waterborne or water dispersed polymers that are equivalent in performance in applications formerly dominated by solvent based polymers. Polymers of the present invention have many uses including adhesives, saturant applications, solutions or dispersions in water or water-cosolvent mixtures, and are most useful as coatings and sealants for wood, glass, metal, concrete and binders for mortars and non-wovens. More specifically, surface coatings produced from polymers of the present invention exhibit improved properties such as, for example, durability, toughness, solvent resistance, dirt pickup resistance, print and block resistance and mar resistance.

Description: This invention relates to waterborne or water dispersed polymers that are equivalent in performance in applications formerly dominated by solvent based polymers. Polymers of the present invention have many uses including adhesives, saturant applications, solutions or dispersions in water or water-cosolvent mixtures, and are most useful as coatings and sealants for wood, glass, metal, concrete and binders for mortars and non-wovens. More specifically, surface coatings produced from polymers of the present invention exhibit improved properties such as, for example, durability, toughness, solvent resistance, dirt pickup resistance, print and block resistance and mar resistance. In applications where the development of a high degree of durability and toughness under ambient conditions are important, polymers dispersed in organic solvent have traditionally been employed or used. Additionally, solvent-based polymers allow the formulator to produce coatings with all the necessary formulation ingredients in a single package. However, more recently, solvent-based coatings have come under extreme pressure because of health, safety and environmental concerns. In an attempt to address these concerns, formulators are demanding from raw material suppliers polymers which give equivalent performance with decreasing levels of volatile organic solvents. In response to health, safety and environmental concerns, formulators have increased their use of aqueous-based polymers. However, aqueous-based polymers, when cured under ambient conditions, have inherent shortcomings with respect to durability and to toughness when compared to solvent-based polymers. Consequently, waterborne coatings have not found wide acceptance in applications where strength and durability are important. Another shortcoming of aqueous-based polymers is the need for multiple package systems for equivalent performance of solvent-based systems. Multiple package systems require the end-user to mix at least two components prior to the coating application. However, there are instances where the use of multiple package systems are impractical and inconvenient. It is well known that incorporation of silane functionality into a polymer can yield compositions which can self-crosslink at about 25° C. Crosslinking occurs due to the facile hydrolysis of alkoxysilane groups to silanols and their subsequent condensation to form Si-O-Si linkages in the presence of water (See e.g., Feasibility of Using Alkoxy Silane Functional Monomers for the Development of Crosslinking Emulsions , T.R. Bourne, B.G. Bufkin, G.C. Wildman and J.R. Grave in the Journal of Coatings Technology, Vol. 54, No. 684, Jan. 1982). However, because of the ease of hydrolysis and subsequent condensation of the silane functionality, it is difficult to produce stable and useful silicone-modified waterborne polymers in a single package. This is particularly problematic for applications where high levels of crosslinking and therefore high levels of silane modification are required. European Patent Application EP 0 442 653 A2 discloses a process for the production of a polymer having desired functional group(s). The functional group(s) can be adhesion promoters, silicones, olefinically unsaturated groups, etc. The desired groups(s) are incorporated into the composition by producing a precursor polymer having -NH- and/or -NH2-bound functionality which is further reacted with a molecule which contains at least one enolic carbonyl capable of forming an enamine with the -NH- or -NH2- functionality, and at least one of the desirable groups. Acetoacetoxy ethyl methacrylate is an example of a species which contains both the enolic carbonyl and a desirable, in this case, an olefinic unsaturation, group. The -NH-and/or -NH2- functional precursor is produced, for example, from the reaction of a carboxylic acid functional polymer and an aziridine-containing species. European Patent Application EP 0 483 583 A2 discloses a use for an aminosilane as a hardener for a non-aqueous acetoacetate and/or acetoacetamide functional polymer. Cure of this composition results from the hydrolysis and subsequent condensation of the alkoxy silane groups from the presence of water liberated during enamine formation from atmospheric moisture. This is a two package system in that the silane and acetoacetate functional polymer must be mixed or blended just prior to use. US Serial No. 091,489 (Rohm and Haas) discloses the functionalization of a polymer with various desirable groups such as adhesion promoters, steric stabilizers, etc., by reacting an enolic carbonyl containing precursor polymer with a species which contains at least one of the desired functional groups and at least one amine capable of forming an enamine with the enolic carbonyl. However, US Serial No. 091,489 does not disclose the use of amino functional silanes. The present invention aims to produce a single package ambient-curing polymer. The present invention provides a process for a process for the preparation of a waterborne or water dispersed, self-crosslinking, ambient-curing, film-forming polymer, the process comprising reacting an aqueous-based polymer having acetoacetate functional groups, formed by polymerising a monomer mixture comprising an acetoacetate-functional monomer and a vinyl monomer, with an amino-functional silance, the level of amino-functional silane to react with the polymer being from 0.1 to 1 moles of amine moiety to one mole of acetoacetoxy group. The process of the present invention allows the production of a waterborne or water dispersed polymer which cures at ambient temperature and which can be formulated into a single package. The polymer forms a coating having the durability and toughness produced by solvent-based polymer systems. The coatings also exhibit improved properties such as solvent resistance, dirt pickup resistance, print and block resistance, mar resistance, adhesion and tensile properties, such as impact resistance, and tensile strength. The inventors have found that many of the problems associated with developing a single package, self-crosslinking waterborne polymer are avoided by the post-reaction of an acetoacetoxy functional polymer with an amine functional silane. Polymers The preferred polymers for use in this invention are vinyl polymers with pendant acetoacetate groups, alternately known as beta-ketoesters. The term "pendant" is used in the specification to mean "attached to the polymer backbone and available for further reaction." Pendant should not be read in the strict sense which would exclude the attachment of such groups at the termini of a polymer chain. Thus, polymer having acetoacetate functionality introduced on the chain end by an acetoacetate functional mercaptan, as taught in U.S. Patent 4,960,924, would be useful in this invention. Generally, the pendant acetoacetate groups are attached to the polymer backbone via an organic divalent radical R 1 which in turn is attached to the acetoacetate moiety or by a trivalent organic radical R 2 bearing two acetoacetate groups. The acetoacetate functional polymers can be prepared by means known in the art. A preferred method is polymerization through incorporation, which includes an acetoacetate functional monomer. A preferred monomer is acetoacetoxyethyl methacrylate which is conveniently referred to throughout this specification as AAEM, shown below. Examples of other monomers useful for introduction of acetoacetate functionality are acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate, 2,3-di(acetoacetoxy)propyl methacrylate, and the like. In general, any polymerizable hydroxy functional monomer can be converted to the corresponding acetoacetate by reaction with diketene or other suitable acetoacetylating agent (See e.g. Comparison of Methods for the Preparation of Acetoacetylated Coating Resins , Witzeman, J. S.; Dell Nottingham, W.; Del Rector, F. J. Coatings Technology; Vol. 62, 1990, 101. (and references contained therein)). The vinyl polymers of this invention are most often copolymers of the acetoacetate functional monomer and other monomers. Examples of useful comonomers are simple olefins such as ethylene, alkyl acrylates and methacrylates where the alkyl group has 1 to 20 carbon atoms (more preferably 1 to 8 carbon atoms), vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, styrene, isobornyl methacrylate, acrylamide, hydroxyethyl acrylate and methacrylate, hydroxypropyl methacrylate and acrylate, N-vinyl pyrolidinone, butadiene, isoprene, vinyl halides such as vinyl chloride and vinylidene chloride, alkyl maleates, alkyl fumarates, fumaric acid, maleic acid, itaconic acid, and the like. It is also possible, and sometimes desirable, to include low levels of divinyl or polyvinyl monomers such as glycol polyacrylates, allyl methacrylate, divinyl benzene, and the like, to introduce a controlled amount of gel in the latex particle. It is important, however, to be sure that when this is done, the quality of the film formation is not seriously impaired. Additionally, one may wish to include chain transfer agents to control molecular weight of the polymer. The acetoacetate functional polymer may contain from about 0.5 percent to 100 percent of the acetoacetate functional monomer by weight. In any application, the amount of acetoacetate functional monomer required will vary from case to case depending upon the desired degree of post functionalization necessary for the particular end-use application. Generally, however, the acetoacetate monomer concentration will be between 1 percent and 40 percent. Conventional coatings will usually contain from about 0.5 percent to 20 percent acetoacetate monomer by weight. Polymers having a molecular weight of from 1,000 to over one million can be used. The lower molecular weight polymers should contain a sufficiently high level of acetoacetate to maximize the degree of post functionalization. For example, a copolymer of AAEM having a molecular weight under 10,000 would typically contain 30 percent or more of AAEM. Generally, the vinyl polymer is prepared as a dispersion or emulsion polymer in water by a suitable free radical initiated polymerization technique, using a free radical initiator and appropriate heating. Since a film-forming polymer is sometimes desired, useful emulsion polymers will generally have glass transition temperatures under 60 degrees Centigrade, since these polymers with coalescent will form good quality films at ambient temperatures. If soluble polymers are used in the film-formation process, polymers of higher glass transition temperature are readily used since they are film-forming. In certain aspects of the invention, polymerization in an aqueous medium and, in particular, aqueous emulsion polymerization, is used to prepare the polymer. Conventional dispersants can be used (e.g. anionic and/or nonionic emulsifiers such as alkali or ammonium alkyl sulfates, alkyl sulfonic acids, and fatty acids, oxyethylated alkyl phenyls, and the like). The amount of dispersant used is usually 0.1 percent to 6 percent by weight based on the weight of total monomer. Either thermal or redox initiation processes may be used. Conventional free radical initiators may be used (hydrogen peroxide, organic hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, ammonium and/or alkali persulfates, organic peroxides such as t-butyl perpivalate, t-butyl perbenzoate, benzoyl peroxide, di(n-propyl) peroxydicarbonate, acetyl cyclo-hexylsulfonyl peroxide, and the like); typically 0.05 percent to 3.0 percent by weight based on the weight of total monomer. Redox systems using the same initiators coupled with a suitable reductant (for example: reducing sugars such as isoascorbic acid, sodium bisulfite, sodium thiosulfate, hydroxyl amine, hydrazine, sodium hydrosulfite) can be used at similar levels, oftentimes in conjunction with a metal catalyst such as salts of transition metals, examples of which are iron sulfate, copper sulfate, vanadium sulfate, and the like. Additionally, non-oxidizing thermal initiators such as 2,2'-Azo-bis-isobutyronitrile, 4,4'-Azo-bis(4-cyanopentanoic acid), 2,2'-Azo-bis(2-amidinopropane) dihydrochloride, and the like. Frequently, a low level of chain transfer agent such as a mercaptan (for example: n -octyl mercaptan, n -dodecyl mercaptan, butyl or methyl mercaptopropionate, mercaptopropionic acid at 0.05 percent to 6 percent by weight based on total weight of monomer) is employed to control molecular weight. The invention may also be practiced using a solvent-soluble or water-soluble polymer. When this is desired, the polymer may be prepared directly in water if the monomer mix is water-soluble or, as is most often the case, the polymerization solvent is a water miscible solvent such as isopropanol, butyl cellosolve, propylene glycol, and the like. In this case, water may be included in the polymerization mixture or post added after the polymerization is complete. In some cases, the polymer is prepared in a conventional organic solvent such as xylene, butyl acetate, methyl ethyl ketone, methyl tertiary butyl ether, and the like. When organic solvent is employed with or without water, it is convenient to use organic soluble-free radical initiators such as azo-bis-isobutyronitrile, t-butyl-peroctoate, or benzoyl peroxide and whatever heat is convenient to assure smooth copolymerization. Another route to preparation of a water-soluble polymer for this invention is to prepare a vinyl dispersion polymer having enough acrylic or methacrylic acid or other polymerizable acid monomer (usually greater than 10 percent) so that the emulsion polymer can be solubilized by addition of ammonia or other base. Water-soluble polymers of this type are advantageously used as blends with conventional dispersion polymers, preferably those which also have pendant acetoacetate functionality. The blend of alkali-soluble resin and latex polymer has a particularly advantageous property combination of gloss and rheology and is useful in coatings and printing ink applications. In another embodiment of this invention, an aqueous dispersion contains copolymer particles made up of at least two mutually incompatible copolymers. These mutually incompatible copolymers may be present in the following morphological configurations, for example, core/shell, core/shell particles with shell phases incompletely encapsulating the core, core/shell particles with a multiplicity of cores, interpenetrating network particles, and the like. In all of these cases, the majority of the surface area of the particle will be occupied by at least one outer phase and the interior of the particle will be occupied by at least one inner phase. The mutual incompatibility of the two polymer compositions may be determined in various ways known in the art. The use of scanning electron microscopy using staining techniques to emphasize the difference between the appearance of the phases, for example, is such a technique. The emulsion polymerization techniques used to prepare such dispersions are well known in the art. It is sometimes advantageous to introduce some crosslinking or gel structure by the sequential polymerization process in the core via low levels of a crosslinking monomer such as allyl methacrylate, diallylphthalate, diallyl maleate, butylene glycol dimethacrylate, divinyl benzene, triallyl isocyanurate, ethylene glycol diacrylate, and the like. The lightly crosslinked core does not adversely affect film formation and does in some cases result in better coatings, particularly when the pendant acetoacetate is concentrated in the shell. As indicated above, a major use for this technology is for functionalizing vinyl polymers dispersed or dissolved in aqueous solvents. Unfortunately, vinyl polymers containing pendant acetoacetate are prone to hydrolysis in water, particularly on heat aging. The hydrolysis occurs at nearly any pH and yields acetoacetic acid, which in turn decomposes to acetone and carbon dioxide. In an earlier application, U.S. Serial No. 632,302, the solution to this problem was provided by treating the aqueous acetoacetate polymer after preparation with one molar equivalent of ammonia or a primary amine such as ethanolamine, methyl amine, or isopropyl amine. As described in that application, typically, the polymer is neutralized to a basic pH with one of the aforementioned amines, preferably to a pH greater than 9. Under these conditions, the enamine is formed. The reaction to form the enamine is generally rapid with the rate of formation increasing with temperature. In general, enamine formation is complete within 8 hours. An alternative approach is to raise the pH to about 9, allow the system to equilibrate, and readjust the pH to about 9 to replace the amine consumed by enamine formation. The enamine is stable to hydrolysis at pH's typically greater than 7. Another approach to preparation of vinyl polymers containing equivalent pendant enamine functionally is to use preformed enamine monomers derived from the appropriate amine and the acetoacetate monomer. In this case, the pH must be kept on the alkaline side during polymerization to avoid hydrolysis of the enamine back to the acetoacetate. Amino Functional Silanes Aminosilane-modified polymers of this invention are prepared by adding an effective amount of an aminosilane to a polymer having acetoacetate functionality introduced on the polymer chain by an acetoacetate functional monomer such as, for example, acetoacetoxy ethyl methacrylate. The quantity of aminosilane that is added to the polymer is a function of the acetoacetate functionality content of the polymer. As mentioned above, the level of acetoacetoxy functional monomer is generally from about 1 weight percent to about 40 weight percent, based on the weight of the polymer. The level of aminosilane to modify the polymer is from about 0.10 to about 1.0 moles of amine moiety to one mole of acetoacetoxy group. If insufficient aminosilane is used in relation to the acetoacetate functional vinyl polymer, properties, such as, for example, solvent resistance, dirt pickup resistance, print and block resistance, and mar resistance of the dried coating may be compromised. Whereas, on the other hand, if the ratio of the moles of aminosilane to the moles of acetoacetate functionality is much greater than 1 of the vinyl polymer, coating properties such as film formation may become imparted do to excessive precrosslinking of the silicone groups. This may also lead to increased water sensitivity as well as discoloration of some substrates such as, for example, wooden substrates. Preferably, the amino-functional silane comprises from 0.1 to 20 percent preferably from 0.5 percent to 20 percent by weight of amino-functional silane, based on the total weight of the acetoacetate-functional polymer. Aminosilanes of various molecular weights and structures may be used to modify the acetoacetate function polymer in practicing the invention. The general structure of the aminosilanes useful for the invention is R 1 - Si (R 2 ) 3-n (OR 3 )n, where n is the greater or equal to 1 but less than or equal to 3, R 1 is an alkyl or phenyl group or combinations thereof and contains at least one amine group capable of forming an enamine with the acetoacetoxy group, R 3 is alkyl, phenyl or hydrogen atom or combinations thereof, and R 2 is a hydrogen atom phenyl or alkyl group or combinations thereof. The group R 2 may also be oligomers of silane, which may or may not contain OR 3 groups and may or may not include amine functionality capable of undergoing enamine formation with acetoacetoxy groups. Preferably, however, the aminosilanes have an average molecular weight, as may be determined by gel permeation chromatography, of from about 140 to about 500, most preferably from about 150 to about 250. Practical considerations such as solubility, hydrolysis rate, compatibility with the acetoacetate precursor polymer, polymer stability, and the like, are the only limitations placed upon the structure and molecular weight of the aminosilane. Although for convenience purposes, it is most preferred that the molecular weight not exceed a maximum of about 190 to about 250, that n is equal to 1 or 2, that R 2 is a methyloxy or ethyloxy group and that R 1 is an alkyl group of 3 to 6 carbon atoms and contains no more than one amine group capable of forming an enamine with the acetoacetoxy group. Amino silanes found to be effective modifiers of acetoacetate functional vinyl polymer polymers may be selected from the group consisting of trimethoxysilylpropyldiethylenetriamine, N-methylaminopropyltrimethoxysilane aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020), aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric aminoalkylsilicone, aminoethylaminoethylaminopropyl-trimethoxysilane, N-methylaminopropyltrimethoxysilane, methylamino-propyltrimethoxysilane, aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, oligomeric aminoalkylsilane and the like, which are available from Dow Corning, Midland, Michigan, Union Carbide Specialty Chemicals Division, Danbury Connecticut and Huls of America, Piscataway, New, Jersey, Wacker Silicones Corporation of Adrian Michigan. In the practice of the invention, aminosilane-modified coatings are prepared by adding a specific quantity of aminosilane to acetoacetate functional vinyl polymer. The quantity of silane added should be in specific proportion, for reasons stated earlier, to the acetoacetate content of the polymer. The amino-functional silane is added after the polymerization of the acetoacetate functional vinyl emulsion polymer. In general, the aminosilane can be added directly to the acetoacetate functional precursor polymer. However, for optimum performance and processing of the final silicone-modified polymer, an auxiliary surfactant may be required. This is particularly true, for example, in some cases where the precursor polymer is produced by emulsion polymerization. In this case, the surfactant can provide, for example, enhanced stability, as well as enhanced desirable properties such as mar resistance when used in conjunction with aminosilane. The auxiliary surfactant can be added preferably before or after the addition of the aminosilane, or as part of the preparation of the precursor, as in the case, for example, of emulsion polymerization. Surfactants may be characterized by their "Hydrophilic-Lipophilic Balance" (HLB) value. Surfactants with HLB values of less than 10 are considered to possess more lipophilic character, while surfactants with HLB values greater than 10 are considered to possess more hydrophilic character. In the context of the preferred surfactants, non-ionic surfactants with HLB values with more hydrophilic character, HLB > (greater than) 10 are desirable. More preferably, the HLB value should be greater than 15. Surfactant levels of up to 10 percent of the weight of the precursor can be used. The more preferable level of surfactant is between 3 percent and 6 percent of the weight of the precursor. The only limitations on the surfactant level are, for example, poor water resistance, instability, and the like. Examples of surfactants which may be used in the practice of the present invention are selected from the group consisting of non-ionics, such as octylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, polypropyloxyethoxy alcohols, and the like, and ionics, such as sodium lauryl sulfate, sodium stearate, and the like. Additives The acetoacetate functional vinyl polymer-modified with aminosilanes of this invention may be formulated for the chosen end use. Additives such as thickeners, dispersants, pigment, extenders, fillers, anti-freeze agents, plasticizers, adhesion promoters, coalescents, wetting agents, defoamers, colorants, non-aldehyde based biocides, soaps and slip agents may be incorporated. TEST METHODS Evaluating the Performance of Clear Coatings Based on Silicon-Modified Lattices Mar Resistance This test is based on striking the coating at a shallow angle with a hard object; in the examples provided, the object was the fingernail of the individual performing the test. This test gives an indication of how the coating will resist marring, which leads to gloss reduction of the coating. After the coating is applied to the substrate and allowed to cure, the coated substrate is placed on a solid surface such as a table top and struck with the operator's fingernail. The operator's fingernail is kept parallel to the coated surface and the impact angle is greater than 45° from the normal of the surface, to increase the likelihood of marking the coating. When comparing coatings, it is important that the same operator perform the test. This test is designed to distinguish relative differences. We used the following rating system: Rating Appearance 1 Excellent No perceptible marks 3 Good Marks which appear as thin scratches 5 Poor Marks which are wide Black Heel Mark and Scuff Resistance The method for determining black heel and scuff resistance is described in Chemical Specialty Manufacturers Association Bulletin No. 9-73 , except commercially available rubber shoe heels were used in place of the recommended 2" rubber cubes and the substrates were wood (maple) panels rather than vinyl tile. We determined the percentage of the coated substrate area which was covered by black heel and scuff marks; this is conveniently performed with transparent graph paper. Black heel marks are an actual deposition of rubber onto or into the coating. Black heel marks can be temporary and may be removed with dry cheesecloth, for example, or with cheesecloth and an appropriate solvent such as odorless mineral spirits. A scuff mark, on the other hand, results from a physical displacement of the coating and appears as an area of reduced gloss. Scuff and black heel marks can occur simultaneously at the point where the heel impacts the substrate; i.e., upon removal of a black heel mark, a scuff may be present. Floor Wear Test Coatings were applied to wood panels, and cured at 25_ centigrade for a specific time prior to their placement in a heavily traveled corridor. The corridor used experienced foot traffic as well as wheeled traffic from maintenance carts, sample trays etc. The gloss at 60 and 20 degrees as well as scuffing and scratching before and after a sufficient exposure time were measured. Black Mark Removal with a Dry Cloth After the test panels were exposed to rubber heels as described above, the coatings were tested for ease of rubber mark removal with a dry cloth. Cheesecloth was rubbed over the black rubber marks with moderate pressure after which removal was rated as "complete" meaning all black rubber marks were removed; "partial" meaning less than all of the black rubber marks were removed; and "none" meaning all of the black rubber marks were present after wiping. The following examples are provided to illustrate some embodiments of the invention. They should not be read as limiting the scope of the invention which is more fully described in the specification and claims. Unless otherwise indicated, percentages are by weight based on the total solids. EXAMPLES Example I Example I shows the enhancement of coating performance aminosilane modification brings to the AAEM containing latex. We also show the effect of aminosilane level and aminosilane type on coating performance. Preparation of Precursor Latex The details for the preparation of the precursor lattices I-A and I-B are described below. Both Precursors are identical in their preparation except the monomer acetoacetoxy ethyl methacrylate (AAEM) was omitted from I-B. Table I-A shows the composition of the precursors as well as some characteristics. To a glass vessel add 121.3g deionized water (DIW) and 6.1g of ALIPAL CO436. To this 4.8g of sodium lauryl sulphate followed by 326.3g butyl acrylate (BA), 386.8g methyl methacrylate (MMA), 7.25 allyl methacrylate (ALMA) and 3.65g methacrylic acid was added and then stirred to emulsify. This is monomer emulsion 1 (ME-1). To another glass vessel 260g DIW and 14.2g of ALIPAL CO436 was added. To this 380.9g BA, 515g MMA, 167.8g AAEM and 27.5g of MAA was added and then stirred to emulsify. This is monomer emulsion 2 (ME-2). To a polymerization vessel 1282.3g DIW was charged under dry nitrogen followed by 18.6g of ALIPAL CO436. This mixture was stirred and then heated to 85_ C. Next, 100g of ME-1 was added. Two minutes later, 3.6g of sodium persulphate (SP) in DIW was added. After ten minutes, 7.2 g of sodium carbonate in DIW was added. Five minutes later, ME-1 was cofed with 0.90g of SP in DIW over 90 minutes. After the addition of ME-1 was complete, the ME-1 vessel was rinsed with 40g of DIW. The polymerization vessel was held at 85°C for an additional 15 minutes. Next, the cofed of ME-2 was started with 0.90g SP in DIW. This cofeed was carried over a 90 minute period. Following the addition of ME-2, the ME-2 vessel was rinsed with 40g DIW. The polymerization vessel was held for 30 minutes at 85°C. After the 30 minute hold at 85°C, the vessel was cooled to 55°C and the monomers were "chased" by, in the order, 5g of 0.15% FeSO4, 5g of 1% versene and 0.5g of 70% t-BHP all in DIW. After one minute, 0.30g of isoascorbic acid in DIW was added. After an additional 30 minute hold at 55°C, 62.5g of 28% aqueous ammonia was added. The resulting polymer was cooled to room temperature before modification with the aminosilane. Precursors I-A and I-B are identical in their preparation, two-stage process, and composition except AAEM was omitted from I-B. Preparation of Silicon-Modified Latex Into a mixing vessel, precursor I-A, whose preparation is described above, was charged. With stirring, TRITON X405 (70%) was added to the stirring precursor over the course of about 5 minutes. Approximately 10 minutes after the X405 addition, the aminosilane was added drop-wise over the course of about 5 minutes. The mixture was allowed to stir for about one hour after the addition of the aminosilane was complete. The amounts of materials used are shown in Table I-2. The silane-modified latex was allowed to stand for about 16 hours before it was formulated into a sealer. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Table I-3 gives the sealer formulation used to evaluate compositions I-1 through I-9. A general formulation is shown as well as a specific example based on composition I4. To a mixing vessel, all materials except the latex were added. With stirring, the silane-modified latex was added and stirred for at least an additional hour and allowed to stand for at least 16 hours before use. Testing of Sealers Based on Compositions I-1 to I-9 To maple wood panels, 3 coats of sealers based on compositions I-1 to I-9 were applied with about one to two hours between coats. After the final coat, the sealed panels were allowed to cure at 25°C for 72 hours before testing. The test results are displayed in Table I-4. Characteristics of AAEM Containing Precursors AAEM Precursor Solids (wt%) Meq. AAEM/gram-solid IA 46.0 0.42 IB 46.1 0.00 Composition of Precursor IA: 1st Stage 40% of 45 BA/53.5 MMA/1 ALMA/0.5 MAA 2nd Stage 60% of 35 BA/47.5 MMA/2.5 MAA/15 AAEM Composition of Precursor IB: Same as IA except AAEM was omitted. Formulations of Silicone Modified Lattices (Quantities in parts by weight) Composition I1 I2 I3 I4 I5 I6 I7 I8 I9 (In order of addition) Material Precursor IA 100 100 100 100 100 100 100 Precursor IB 100 100 Triton X405 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 A0700 0.0 1.5 2.9 4.3 5.8 4.3 0.0 A0800 3.5 1.2 Meq. Silane/ Meq. AAEM 0.00 0.33 0.66 1.00 1.33 0.33 1.00 1.00 0.00 Aqueous Wood Sealer Formulations for Latex Compositions I1 to I9 General Formulation (25% Solids, Order of addition shown) Material Amount (parts by weight) Silane modified Latex 25 pph (solids) DE 35 % on latex solids FC-120 1.2 pph SWS-211 0.02 pph Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealer Based on Composition I-4 Material Amount (parts by weight) Latex Composition I4 53.87 DE 8.14 FC-120 1.2 SWS-211 0.02 Water 40.60 Properties of Aqueous Wood Sealers Based on Composition 1 to 9 Latex Composition Mar Resistance % Black Heel marks Black Heel Mark Removal(dry cloth) I1 5 2.3 none I2 2 1.5 partial I3 1 1.1 complete I4 1 1.6 complete I5 1 1.5 complete I6 4 1.5 none I7 4 2.0 partial I8 5 2.6 none I9 5 2.9 none EXAMPLE II Example II shows the enhancement of coating performance aminosilane modification brings to the precursor AAEM containing latex. We also show the effect of aminosilane level and aminosilane type on coating performance. Preparation of Precursor Latex A monomer emulsion (ME) was prepared by adding 475g DIW, 20g of sodium lauryl sulphate (SLS), 600g ethyl acrylate, 335g MMA, 15g MAA and 50g AAEM followed by stirring. To a polymerization vessel, under nitrogen, 800g DIW and 25g SLS was added. After the temperature was increased to 85°C, 4.2g of ammonium persulfate (ASP) in DIW was added. After the addition of the APS, add ME along with a feed of 2.1 APS in DIW at approximately 12.5g/minute and 0.88cc/minute respectively was initiated. After the addition of the ME was completed, the emulsion jar was rinsed with 30g of DIW. The vessel was cooled to 56°C over a 1 hour period after which 1g of t-BHP in DIW and 0.5g isoascorbic acid in DIW was added. The vessel was cooled to room temperature and filtered before modification with aminosilanes. Table II displays some characteristics of precursor IIA. Preparation of Silicon-Modified Latex The procedure for the preparation of a silicone-modified latex based on precursor II-A was the same as described in Example I, except the materials and proportions used are shown in Table II-2. The silane-modified latex was allowed to stand for 4 days before it is formulated into a sealer. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Table II-3 gives the sealer formulation used to evaluate compositions II-1 through II-4. A general formulation is shown as well as a specific example based on composition II-4. To a mixing vessel, all materials except the latex were added. With stirring, the silane-modified latex was added. The mixture was stirred for at least an additional hour and allowed to stand for at least 16 hours before use. Testing of Sealers Based on Compositions II-1 to II-4 To maple wood panels, 3 coats of sealers based on compositions II-1 to II-4 were applied with about one to two hours between coats. After the final coat, the sealed panels were allowed to cure at 25° for 72 hours before testing. The test results are displayed in Table II-4. Characteristics of AAEM Containing Precursor IIA Solids (wt%) Meq. AAEM/gram-solid 40.1 0.23 Composition of precursor IIA: 60 EA/33.5 MMA/1.5 MAA/5 AAEM Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Composition (In order of addition) II1 II2 II3 II4 Material Precursor IIA 100 100 100 100 Triton X405 2.9 2.9 2.9 2.9 A0700 0.0 0.7 2.1 A0699 1.9 Meq. Silane/ Meq. AAEM 0.00 0.33 1.00 1.00 Aqueous Wood Sealer Formulations for Latex Compositions II-1 to II-4 General Formulation (25% Solids, Order of Addition Shown) Material Amount (parts by weight) Silane-Modified Latex 25 pph (solids) DE 35 % on latex solids FC-120 1.2 pph SWS-211 0.02 pph Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealer Based on Composition II-4 Material Amount (parts by weight) Latex Composition II-4 64.18 DE 9.98 FC-170C 0.20 SWS-211 0.02 Water 25.63 Properties of Aqueous Wood Sealers Based on Composition II-1 to II-4 Latex Composition Black Heel (Relative ) % Scuffing II1 3 3.3 II2 2 1.6 II3 2 0.0 II4 1 0.0 EXAMPLE III Example III shows that coating performance is effected by the structure of the aminosilane. Preparation of Precursor Latex Precursor latex, IA, described above in Example I, was used. Preparation of Silicone-Modified Latex The procedure for the preparation of a silicone-modified latex based on precursor IA was the same as described above in Example I, except the materials and proportions used are shown in Table III-1 and a common preblend of precursor/ Triton 405(70%) was used. The silane-modified lattices were allowed to stand for 1 day before they were formulated into sealers. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Table III-2 gives the sealer formulation used to evaluate compositions III-1 through III-4. A general formulation is shown as well as a specific example based on composition III-1. Coating preparation is described in Example I. Testing of Sealers Based on Compositions II-1 to II-4 To maple wood panels, 4 coats of sealers based on compositions III-1 to III-5 were applied with about one to two hours between coats. After the final coat, the sealed panels were allowed to cure at 25°C for 4 days before testing. The test results are displayed in Table III-3. Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Preblend = 100 Precursor latex IA 3.3 Triton X405 (70%) Composition (In order of addition) III1 III2 III3 III4 III5 Material Preblend 103.3 103.3 103.3 103.3 Precursor IA 100 Triton X405 3.3 A0700 3.4 A0699 3.2 A0800 2.8 A0742 2.9 Meq. Silane/ Meq. AAEM 0.00 0.80 0.80 0.80 0.80 Aqueous Wood Sealer Formulations for Latex Compositions III-1 to III-5 General Formulation (25% Solids, Order of Addition Shown) Material Amount (parts by weight) Silane-modified Latex 25 pph (solids) DE 35 % on latex solids FC-120 1.2 pph SWS-211 0.02 pph Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealer Based on Composition III-2 Material Amount (parts by weight) Latex Composition III-2 54.19 DE 8.14 FC-120 1.2 SWS-211 0.02 Water 36.30 Properties of Aqueous Wood Sealers Based on Composition III-1 to III-5 Latex Composition % Black Heel Marks Mar % Scuffing Resistance III-1 3.8 2.2 5 (Poor) III-2 2.2 0.0 1 (Exc.) III-3 1.0 0.0 1 (Exc.) III-4 1.7 1.0 4 (Fair) III-5 1.2 0.0 1 (Exc.) EXAMPLE IV Example IV shows that silicone modification improves the performance of a coating based on a room temperature film-forming precursor latex. Preparation of Precursor Latex IV The preparation and characteristics of the precursor latex, IVA, is described above in Example I, except the ratio of BA/MMA in ME-I (Monomer Emulsion I) was changed from 35/47.5 to 69.8/12.7, giving a softer, lower glass transition temperature, first stage. The solids of precursor IVA was 45.3. Preparation of Silicone-Modified Latex The procedure for the preparation of a silicone-modified latex based on precursor IVA was the same as described above in Example I, except the materials and proportions used are shown in Table IV-1. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Table IV-2 gives the sealer formulation used to evaluate composition IV-1. The procedure is the same as previous examples. Note no cosolvent (DE) was used as both composition IV1 and precursor IVA form films below room temperature. Testing of Sealers based on Compositions IV-1 and Precursor IV To maple wood panels, 4 coats of sealers based on compositions IV1 and precursor IVA were applied with about one to two hours between coats. After the final coat, the sealed panels were allowed to cure at 25°C for 3 days before testing. The test results are displayed in Table IV-3. Preparation of Silicone-Modified Latex IV1 (Quantities in parts by weight) (In order of addition) Material Precursor IVA 100.0 Triton X405 3.2 A0700 4.3 Meq. Silane/Meq. AAEM 1.00 Aqueous Wood Sealer formulations for Composition IV1 (25% Solids, Order of Addition Shown) Material Amount (parts by weight) Water 45.65 39.85 FC-120 0.93 0.93 SWS-211 0.02 0.02 Composition IV1 50.00 Precursor IVA 50.00 Properties of Aqueous Wood Sealers Based on Composition IV1 Latex Composition % Black Heel Marks Mar % Scuffing Resistance IV1 2.0 0 1 (exc) Precursor IV 3.5 2.2 5 (poor) EXAMPLE V Floor Wear Test In this example, composition III-5 was prepared and formulated as described in Example III. The control (precursor not modified with aminosilane) was composition III-1 of Example III, except X405 was omitted and formulated into a sealer according to Example III. Five coats of each coating were applied to maple panels and cured at 25°C for one week prior to placement on the floor of the exposure area. Table V-1 shows the effects of 26 days of wear. Comparison of Silane-Modified and Unmodified Precursor I-1 in a Wear Test Latex Composition % Gloss Retained at 20° % Gloss Retained at 60° Appearance Precursor I-1 (unmodified) 62 72 Highly scuffed and scratched III-5 91 82 Few minor scuffs and scratches Footnotes: 1. Gloss retained = (final gloss/initial gloss) x 100 EXAMPLE VI In Example VI, we show neutralization with potassium hydroxide rather than ammonia. Preparation of Precursor Lattices The preparation and characteristics of precursor lattices VI-A and VI-B are described above in Example I, except neither latex was neutralized with NH 3 and VI-B was prepared by a homogeneous process where all monomers were introduced from a single monomer emulsion. The solids of precursor VI-A and VI-B were 47.6% and 47.8% respectively. Preparation of Silicon-Modified Latex The procedure for the preparation of silicone-modified lattices based on precursors VI-A and VI-B is described in Example I, except the materials and proportions used are shown in Table VI-1. Also, the pH of the precursor lattices was increased to about 7.5 with aqueous potassium hydroxide before the addition of the other materials. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Table VI-2 gives the sealer formulation used to evaluate compositions VI-1 to VI-5. The procedure was the same as previous examples. Testing of Sealers Based on Compositions IV-1 and Precursor IV To maple wood panels, 4 coats of sealers based on compositions IV1 and precursor IV were applied with about one to two hours between coats. After the final coat, the sealed panels were allowed to cure at 25°C for 3 days before testing. The test results are displayed in Table VI-3. Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Composition (In order of addition) VI1 VI2 VI3 VI4 VI5 Material Precursor VI-A 100 100 Precursor VI-B 100 100 100 KOH (2.1N) 1.70 1.70 1.50 1.50 1.50 Water 5.08 11.36 5.52 11.20 11.72 Triton X405 3.40 3.4 3.4 A0700 3.6 A0742 3.06 3.1 Meq. Silane/ Meq. AAEM 0.00 0.80 0.00 0.80 0.80 General Formulation (25% Solids, Order of Addition Shown) Material Amount (parts by weight) Silane-modified Latex 25 pph (solids) DE 35 % on latex solids FC-120 1.2 pph SWS-211 0.02 pph Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealer Based on Composition VI-2 Material Amount (parts by weight) Latex Composition VI-1 35.00 DE 3.80 FC-120 0.94 SWS-211 0.02 Water 22.70 Properties of Aqueous Wood Sealers Based on Composition IV1 Latex Composition % Black Heel % Scuffing Mar VI1 2.4 2.5 5 (poor) VI2 1.6 < 0.1% 1 (exc) VI3 1.6 1.7 5 (poor) VI4 1.3 < 0.1% 1 (exc) VI5 1.5 0.0 1 (exc) EXAMPLE VII Effect of Neutralization and Process Example VII shows the silicon-modified latex can be prepared by adding a preblend of aminosilane and surfactant to the precursor rather than added individually. This gives an improved mode for preparation since the addition of diluted materials are less likely to "shock" the latex and cause latex flocculate. We also show neutralization by potassium hydroxide can be eliminated. Preparation of Precursor Lattices The latex, precursor VIIA, described in Example I, was prepared without NH 3 neutralization. The solids level was 46.5%. Preparation of Silicon-Modified Latex The silicon-modified lattices were prepared as described in Example VI, except a preblend of the aminosilane, surfactant and water was used in two of the compositions (see Table VII-1). Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Aqueous sealers, based on precursors VII1 to VII4, were prepared as described in Example VI, except adjustments were made for precursor solids. The sealers were applied to wood panels and cured as described in the previous examples. The test results are displayed in Table VI-3. Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Composition (In order of addition) VII1 VII2 VII3 VII4 Material Precursor VII-A 100.00 100.00 100.00 100.00 KOH (2.1N) 0.70 0.60 0.60 Premix 8.1 8.4 Water 1.76 Triton X405 3.20 A0742 2.97 Meq. Silane/Meq. AAEM 0.00 0.80 0.83 0.80 Properties of Aqueous Wood Sealers Based on Composition IV1 Latex Composition Flocculate (Sedimentation) % Black Heel Mar VII1 None 1.4 5 (poor) VII2 None 1.0 1 (exc) VII3 None 0.90 1 (exc) VII4 Slight 1.0 1 (exc) Example VIII Example VIII shows the importance of the surfactant for optimum sealer performance. Preparation of Precursor Latex To a polymerization vessel, 812.5g of DIW was heated to 85°C, after which 20.4 g of SIPONATE DS-4 was added under a nitrogen atmosphere. In a separate vessel, a monomer emulsion (ME) was prepared by mixing 12g of DS-4, 150g DIW, 110g BA, 355 MMA and 10g MAA. To the polymerization vessel, 31g of the ME and 10g of DIW followed by 1.5g ammonium persulphate (APS) in water and 1.5g of sodium carbonate in water was added. To the ME vessel, 25g of ALMA was added. The ME was then added to the polymerization vessel over a 90 minute period along with a cofeed of 1.5g APS in 150g of DIW at a rate of 0.84g/min. After the addition of ME was complete, the APSDIW feed was terminated. The polymerization vessel was then held for an additional 30 minutes at 85°C. A second ME was prepared as above but used 12g DS-4, 150g DIW, 212.5 ethyl hexyl acrylate, 67.5 styrene, 125g acrylonitrile, 75g AAEM and 20 g MAA. This ME was added to the polymerization vessel over a 90 minute period along with the resumption of the APS/DIW cofeed. After the addition of the ME was complete, the emulsion vessel was rinsed with 25g DIW. The polymerization vessel was held for an additional 30 minutes at 85°C, after which it was cooled to 60°C and chased in a similar manner as described in Example I. Preparation of Silicon-Modified Latex Precursor VIII-A, described in Example I, was prepared without NH 3 neutralization at a solids level of 45.9%. The preparation of Precursor VIIIB is described in Attachment VIII and has the following characteristics. Composition: 1st Stage: 50% of 22 BA/71 MMA/5 ALMA/2 MAA 2nd Stage: 50% of 42.5 EHA/13.5 STY/25 AN/15 AAEM Solids: 39.7% Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Aqueous sealers, based on precursors VIII1 to VIII6, were prepared according to Table VIII-2. The sealers were applied to wood panels and cured as described in the previous examples. The test results are displayed in Table VIII-3. Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Composition (In order of addition) VIII1 VIII2 VIII3 VIII4 VIII5 VIII6 Material Precursor VIIIA 100.00 100.00 100.00 Precursor VIIIB 100.00 100.00 100.00 Premix 5.67 6.82 7.96 3.44 2.45 0.0 Characteristics X405 Level 0.0 2.5% 5.0% 5.0% 0.0 0.0 Meq. Silane/ Meq. AAEM 0.80 0.80 0.80 0.80 0.80 0.0 Aqueous Sealer Formulations for Compositions VIII (30% Solids) Material (in order of addition) Water 23.09 24.09 25.04 15.88 13.50 11.89 DE 7.05 6.89 6.73 6.73 7.05 7.50 FC120 (1%) 1.50 1.50 1.50 1.50 1.50 1.50 KP-140 1.41 1.38 1.35 1.35 1.41 1.50 EG 2.00 2.00 2.00 2.00 2.00 2.00 Defoamer 0.02 0.02 0.02 0.04 0.04 0.04 Charge the above into mixing vessel. With stirring add the following: VIII1 64.91 VIII2 64.10 VIII3 63.34 VIII4 72.50 VIII5 74.50 VIII6 75.57 Performance of Aqueous Sealers Based on Compositions VIII Latex Composition Mar Resistance % Black Heel Marks VIII-1 5 (poor) 0.8 VIII-2 3 (good) 1.1 VIII-3 1 (exc) 1.2 VIII-4 1 (exc) 0.9 VIII-5 5 (poor) 0.5 VIII-6 5 (poor) 1.2 EXAMPLE IX Example IX shows that the surfactant does not have to be present for optimum performance of the silicone-modified latex. Preparation of Silicon-Modified Latex The precursor described in Example VI was used to prepare silicon-modified latex compositions IX-1 to IX-4 (see Table IX). Composition IX3 was prepared by post-addition of X405 to a portion of IX1, which was 24 hours old. Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Aqueous sealers, based on precursors IX1 to IX4, were prepared according to Table VIII-2. The sealers were applied to wood panels and cured as described in the previous examples. Properties of Aqueous Sealers Based on Compositions IX Testing of the sealers was the same as in Examples I through VIII with the exceptions that the Snell capsule used was smaller, the heels in the capsule were larger and the time of exposure of the panels was 10 minutes rather than 5 minutes. This gave testing conditions more rigorous than in the previous examples. The results are shown in Table IX-3. Formulations of Silicone Modified-Lattices (Quantities in parts by weight) Composition (In order of addition) IX1 IX2 IX3 IX4 Material Precursor 100.00 100.00 100.00 100.00 Premix 5.67 7.96 5.67 X405 (70%) 3.35 Characteristics X405 Level 0.0 5.0% 5.0% 0.0 Meq. Silane/Meq. AAEM 0.80 0.80 0.80 0.0 Aqueous Sealer Formulations for Compositions IX (30% Solids) Material (in order of addition) Water 20.84 22.77 22.17 19.94 DE 7.05 6.73 6.73 7.50 FC120 (1%) 1.50 1.50 1.50 1.50 KP-140 1.40 1.40 1.40 1.40 EG 2.00 2.00 2.00 2.00 Defoamer 0.20 0.20 0.20 0.20 Charge the above into mixing vessel. With stirring add the following: IX-1 64.91 IX-2 63.30 IX-3 63.91 IX-4 65.36 After 30 min. of stirring add the following: Acrysol RM-1020 2.1 2.1 2.1 2.1 Performance of Aqueous Sealers Based on Compositions IX Latex Composition Mar Resistance % Black Heel Marks % Scuff Marks IX-1 3-4 (fair) 1.4 1.2 IX-2 2 (very good) 1.1 0.9 IX-3 1 (exc) 1.0 0.7 IX-4 5 (poor) 2.8 1.8 EXAMPLE X Example X shows the hydrophilic/lipophilic balance (HBL) of the surfactant can effect the performance of the silicon-modified latex. Preparation of Silicon-Modified Latex The precursor described in Example VI was used to prepare silicon-modified latex compositions X-1 to X-3. The milliequivalents of surfactant to precursor solids was held constant at 0.25. As described above in Example IX, a premix of surfactant, aminosilane and water was added to the precursor with stirring (see Table X-1). Preparation of Aqueous Wood Sealers Based on Silane-Modified Lattices Aqueous sealers, based on precursors IX1 to IX4, were prepared according to Table X-2. The sealers were applied to wood panels and cured as described in the previous examples. Properties of Aqueous Sealers Based on Compositions IX Testing of the sealers was the same as in Examples I through VIII with the exceptions that the Snell capsule used was smaller, the heels in the capsule were larger. The time in the Snell capsule was 5 minutes. This gave testing conditions more rigorous than in the previous examples. The results are shown in Table X-3. Formulations of Silicone-Modified Lattices (Quantities in parts by weight) Composition (In order of addition) X1 X2 X3 Material Precursor 108.93 108.93 108.93 Premix 10.38 8.70 6.94 Characteristics Surfactant X705 X405 X100 Surfactant HBL 13.5 17.9 18.7 Meq. Silane/ Meq. AAEM 0.80 0.80 0.80 Note in all premixes wt. water/wt. silane = 0.93. Aqueous Sealer Formulations for Compositions X (30% Solids) Material (in order of addition) Water 23.89 22.72 21.63 DE 6.63 6.73 6.83 FC120 (1%) 1.50 1.50 1.50 KP-140 1.40 1.40 1.40 EG 2.00 2.00 2.00 Defoamer 0.15 0.15 0.15 Charge the above into mixing vessel. With stirring add the following. IX-1 62.33 IX-2 63.30 IX-3 64.39 After 30 min. of stirring add the following: Acrysol RM-1020 2.1 2.1 2.1 Performance of Aqueous Sealers Based on Compositions X Latex Composition Mar Resistance 1 % Black Heel Marks Comments X-1 1 (exc) 0.80 Hazy film X-2 1 (exc) 1.2 X-3 4 (fair) 1.4 EXAMPLE XI Floor Wear Test In Example XI, the aminosilane-modified composition X-2 of Example X is compared to a commercially available solvent dispersed, oil-modified urethane (OMU). The coating formulation for composition X-2 is given in Table X2. To maple panels, 3 coats of the commercially available OMU, (Hillyard Chemical Company, St. Joseph, MO), was applied. To another maple panel, 2 coats of a clear waterborne primer was applied, followed by 2 coats of the coating based on composition X-2. Both panels were cured for 72 hours at 25°C before placement in the floor test area. Table XI-I compares the gloss at 20° and 60° as a function of exposure time. The aminosilane-modified polymer exhibits gloss retention superior to the single pack solvent dispersed OMU. 60°/20° gloss: Initial After 11 day exposure After one month Exposure Comp X-2 63/27 66/27 64/24 OMU 73/29 63/16 67/15

Claims: A process for the preparation of a waterborne or water dispersed, self-crosslinking, ambient-curing, trim-forming polymer, the process comprising reacting an aqueous-based polymer having acetoacetate functional groups, formed by polymerising a monomer mixture comprising an acetoacetate-functional monomer and a vinyl monomer, with an amino-functional silane, the level of amino-functional silane to react with the polymer being from 0.1 to 1 moles of amine moiety to one mole of acetoacetoxy group. The process of claim 1, wherein the acetoacetate-functional monomer is selected from the group consisting of acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate and 2,3-di(acetoacetoxy)propyl )propyl methacrylate. The process of claim 2, wherein the acetoacetate-functional monomer comprises from 0.5 percent to 100 percent by weight, preferably from 0.5 percent to 20 percent, based on the total weight of the polymer. The process of Claims 1, or 3, wherein the amino-functional silane is selected from the group consisting of trimethoxysilylpropyldiethylenetriamine, N-methylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020), aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric aminoalkylsilicone, aminoethylaminoethylaminopropyl-trimethoxysilane, N-methylaminopropyltrimethoxysilane, methylamino-propyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, and oligomeric aminoalkylsilane. The process of Claim 4, wherein the amino-functional silane comprises from 0.1 percent by weight to 20 percent by weight of amino-functional silane, based on the total weight of the acetoacetate-functional polymer. The process of any one of claims 1-5, wherein the amino-functional silane has a weight average molecular weight of from 140 to 500, preferably from 150 to 250, as determined by gel permeation chromatography. The process of any one of claim 1-6, wherein the acetoacetoxy-functional polymer is reacted with the aminosilane in the presence of a surfactant selected from the group consisting of octylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, polypropyloxyethoxy alcohols, sodium lauryl sulfate, and sodium stearate; wherein preferably the level of the surfactant is from 0.5 weight percent to 20 weight percent, preferably from 3 weight percent to 6 weight percent, based on the weight of the acetoacetoxy-functional polymer; wherein preferably the surfactant's hydrophiliclipophilic balance is greater than or equal to 8, preferably greater than or equal to 15; and wherein preferably the surfactant is non-ionic A coating composition, preferably a sealer composition, comprising the product of any one of process claims 1-7. A process for improving the mar resistance and scuff resistance of a wooden substrate, the process comprising applying the aminosilane-modified acetoacetate functional polymer produced by any one of Claims 1-7 to the wooden substrate.

Inventors: ROSANO WILLIAM JOSEPH, SCHINDLER FREDERICK JAMES, ROSANO, WILLIAM JOSEPH, SCHINDLER, FREDERICK JAMES
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1995
Main classification: C08F8
IPC codes: C08F210, C08F220, C08F8, C08K5