MXPA95000788A - Polymers that cure the environment, from a solopaqu - Google Patents

Abstract

The present invention relates to a process comprising: 1) mixing: a) at least one aqueous-functional acetoacetate polymer, and b) at least one amino functional silane, and 2) applying the aqueous base mixture to a substratum.

Description

POLYMERS THAT CURE ALAMBIENTE. OF A SINGLE PACKAGE FIELD OF THE INVENTION The present invention relates to the preparation of water-based polymers, which carry reactive functional groups. More particularly, this invention relates to polymers that carry water or are dispersed in water, which are equivalent in performance in applications previously dominated by solvent-based polymers. The polymers of the present invention have many uses, including that of adhesives, saturation applications, solutions or dispersions in water or mixtures of water and a cosolvent, and are more useful as coatings and sealants for wood, glass, metal, concrete and agglutinate for mortars and non-woven products. More specifically, the surface coatings produced from the polymers of the present invention exhibit improved properties such as, for example, durability, firmness, solvent resistance, dirt pick-up resistance, printing resistance and block formation and resistance to deterioration. . BACKGROUND OF THE INVENTION In applications where the development of a high degree of durability and firmness is important, with environmental conditions, the polymers dispersed in organic solvents have been used or traditionally used. In addition, 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, due to health, safety and environmental concerns. In an attempt to remedy these concerns, formulators have required the dispensers of polymeric raw materials that give an equivalent performance with decreasing levels of volatile organic solvents. In response to health, safety and environmental concerns, formulators have increased the use of water-based polymers. However, water-based polymers, when cured under ambient conditions, have inherent disadvantages with respect to durability and firmness, when compared to solvent-based polymers. Consequently, waterborne coatings have not found wide acceptance in applications where strength and durability are important. Another drawback of water-based polymers is the need for multi-pack systems for equivalent performance of solvent-based systems. Multi-pack systems require the end user to mix at least two components before applying the coating.

However, there are cases where the use of multi-package systems is not practical or convenient. We have found as novel and unanticipated a polymer that carries water or dispersed in water, that cures at room temperature and can be formulated in a single-package coating, and has the durability and firmness of solvent-based polymer systems. This is achieved by the subsequent reaction of a functional acetoacetoxy polymer with an amine functional silane. RELATED PREVIOUS TECHNIQUE It is well known that the incorporation of the silane functionality into a polymer can deliver self-interlocking compositions at about 25 centigrade. The entanglement occurs due to the easy hydrolysis of the alkoxysilane groups to the silanols and their subsequent condensation to form Si-O-Si bonds, in the presence of water (see, for example Viability of Using Functional Monomers of Alkoxy-Silane for the Development of Interlacing Emulsions, TR Bourne, BG Bufkin, GC ildman and JR Grave in Journal of Coatings Technology, Vol. 54, No. 684, January 1982). However, due to the ease of hydrolysis and the subsequent condensation of the silane functionality, the production of polymers carrying water is difficult., modified with silicone, stable and useful, in a single package. This is particularly problematic for applications where high levels of entanglement are required and, therefore, high levels of silane modification. We have found that many of the problems associated with the development of a self-enclosing, water-carrying polymer from a single package are avoided by the subsequent reaction of a functional acetoacetoxy polymer with an amine functional silane. Therefore, while it is generally known to modify the properties of polymers by the incorporation of functional groups, no prior art discloses the preparation of polymers containing acetoacetate functional groups, and the post-polymerization reaction of the acetoacetate group with a silane functional of amine. European Patent Application EP 0 442 653 A2 describes a process for the production of a polymer having the desired functional group (s). These functional groups can be adhesion promoters, silicones, olefinically unsaturated groups and the like. They are incorporated into the composition by producing a precursor polymer having the linking functionality of -NH- and / or -NH2, which is further reacted with a molecule containing at least one enol carbonyl, capable of forming an enamine with the functionality -NH- or -NH2-, and at least one of the desirable groups. Acetoacetoxy ethyl methacrylate is an example of species containing both an enol carbonyl group and a desirable group, in this case a group of olefinic unsaturation. The precursor of -NH- and / or -NH2 is produced, for example, from the reaction of a functional carboxylic acid polymer and a species containing aziridine. European Patent Application EP 0 483 583 A2 describes the use of an aminosilane, as a hardening element, or a functional polymer of acetoacetate and / or acetoacetamide. The curing of this composition results from the hydrolysis and subsequent condensation of the alkoxysilane groups, from the presence of the liberated water, during the formation of the enamine, from the atmospheric humidity. This is a two pack system, in which the silane and the functional acetoacetate polymer must be mixed or combined before use. U.S. Patent Application, Serial No. 091,489 (Rohm and Haas) describes the functionalization of a polymer with various desirable groups, such as adhesion promoters, steric stabilizers, etc., by the reaction of a precursor polymer. containing enolyl carbonyl, with species containing at least one of the desired functional groups and at least one amine, capable of forming an enamine with the enol carbonyl. However, Application No. 091,489 does not disclose the use of functional amino silanes. SUMMARY OF THE INVENTION The present invention provides a process for the polymerization of polymers containing acetoacetate functional groups and then, following polymerization, the subsequent reaction of the functional polymer of acetoacetate with an amino functional silane, to produce self-polymer. interlacing, that heal the environment, that make movies. DETAILED DESCRIPTION The present invention provides self-crosslinking polymers, which cure the environment, of aqueous base, which form films, which contain functional acetoacetate groups which are subsequently reacted with an amino functional silane. The coatings, produced from the polymers of the present invention, exhibit improved properties, such as solvent resistance, dirt pick-up resistance, printing resistance and block formation, deterioration resistance, adhesion and tensile properties, such as the impact resistance and the tensile strength.

Polymers Preferred polymers for use in this invention are vinyl polymers with pendant acetoacetate groups, alternatively known as beta-ketoesters. The term "slope" is used in this specification to mean "attached to the polymer backbone and available for further reaction". Slope should not be read in the strict sense, which would exclude the union of such groups at the terminals of the polymer chain. Thus, the polymer having an acetoacetate functionality introduced at the end of the chain by an acetoacetate functional mercaptan, as taught in U.S. Patent No. 4,960,924, would be useful in this invention. In general, the pendant acetoacetate groups are attached to the polymer backbone via a divalent organic radical R1, which, in turn, is bound to the acetoacetate part or by a trivalent organic radical R2, which It has two groups of acetoacetate.

O O O O II II II II -Ri Q C CH2 C CH3 R2 (O C CH2C CH3) 2 Functional acetoacetate 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 by this specification, as AAEM, shown below.

O 0 0 ?? ?? ti CH2 = C - CO CH2 CH20 C CH2 C CH3 CH3 Examples of other monomers useful for the introduction of acetoacetate functionality are acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate, 2,3-di (acetoacetoxy) propyl methacrylate. , and similar. In general, any polymerizable hydroxy functional monomer can be converted to the corresponding acetoacetate by reaction with the diketene or other suitable acetoacetylating agent (see, for example, Comparison of Methods for the Preparation of Acetoacetylated Coating Resins). Witzeman, JS, Dell Nottingham, W. Del Rector, FJ Coatings Technology, Vol 62, 1990 (and references therein)). The vinyl polymers of this invention are very often copolymers of the functional monomer of acetoacetate and other monomers. Examples of useful comonomers are simple olefins, such as ethylene, alkyl acrylates and methacrylates, where the alkyl group has from 1 to 20 carbon atoms (more preferably from 1 to 8 carbon atoms), vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, styrene, iso-bornyl methacrylate, acrylamide, hydroxyethyl acrylate and methacrylate, methacrylate and hydroxypropyl acrylate, N-vinyl pyrrolidinone, butadiene, isoprene, vinyl halides, such as chloride of vinyl and vinylidene chloride, alkyl maleates, alkyl fumarates, fumaric acid, maleic acid, itaconic acid and the like. It is also possible, and sometimes convenient, to include low levels of divinyl or polyvinyl monomers, such as the glycol polyacrylates, allyl methacrylate, divinyl-benzene, and the like, to introduce a controlled amount of gel into the latex particle. However, it is important to be sure, when this is done, the quality of the film formation does not seriously damage it. In addition, one may wish to include chain transfer agents to control the molecular weight of the polymer. The functional acetoacetate polymer may contain from about 0.5 to 100 weight percent of the acetoacetate functional monomer. In any application, the amount of the functional acetoacetate monomer required will vary from case to case, depending on the desired degree of subsequent functionalization necessary for the particular end-use application. However, in general, the concentration of the acetoacetate monomer will be between 1 and 40 percent. Conventional coatings will usually contain from 0.5 to 20 weight percent of the acetoacetate monomer. Polymers that have a molecular weight of 1, 000 to more than one million, can be used. Polymers of lower molecular weight must contain a sufficiently high level of acetoacetate to maximize the degree of subsequent functionalization. For example, an AAEM copolymer having a molecular weight of less than 10,000 will typically contain 30 percent or more of AAEM. In general, the vinyl polymer is prepared as a dispersion or emulsion polymer in water, by a polymerization technique initiated by a suitable free radical, which employs a free radical initiator and the appropriate heating. Since the film-forming polymer is sometimes desired, useful emulsion polymers will generally have a glass transition temperature of less than 60 ° C, since these polymers with a coalescent will form good quality films at ambient temperatures. If the soluble polymers are used in the film-forming process, the polymers of a higher glass transition temperature are easily used, since they are film formers.

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 (for example anionic and / or nonionic emulsifiers, such as alkali or ammonium alkyl sulfates, alkylsulphonic acids and fatty acids, oxyethylated alkyl phenols, and the like). The amount of the dispersant used is generally from 0.1 to 6 weight percent, based on the weight of the total monomer. Initiation or thermal or redox procedures may be used. Conventional free radical initiators (hydrogen peroxide, organic hydroperoxides, such as t-butyl hydroperoxide, eumenohydroperoxide, t-amyl hydroperoxide, ammonium and / or alkali persulfates, organic peroxides, such as the t-butyl pivalate, t-butyl perbenzoate, benzoyl peroxide, di (n-propyl) peroxydicarbonate, acetyl-cyclohexylsulfonyl peroxide, and the like); typically from 0.05 to 3.0 weight percent, based on the weight of the total monomer. Redox systems, which use the same initiators coupled with a suitable reducing agent (for example: reducing sugars, such as iso-ascorbic acid, sodium bisulfite, sodium thiosulfate, hydroxyl amine, hydrazine, sodium hydrosulfite) can be use at similar levels, often in conjunction with a metal catalyst, such as transition metal salts, 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-amidino) dihydrochloride -propane) and the like. Frequently, a low level of the chain transfer agent, such as a mercaptan (for example n-octyl-mercaptan, n-dodecyl-mercaptan, butyl mercaptopropionate or methyl, mercapto-propionic acid 0.05 to 6 percent in weight, based on the total weight of the monomer) is used to control the molecular weight. The invention can also be practiced using a solvent soluble or water soluble polymer. When this is convenient, the polymer can be prepared directly in water, when the monomer mixture is soluble in water or, as is more often the case, the polymerization solvent is a water-miscible solvent, such as iso-propanol , butyl-Cellosolve propylene glycol, and the like. In this case, the water may be included in the polymerization mixture or 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 an organic solvent is used, with or without water, it is conventional to use organic, free-radical, soluble inhibitors, such as azo-bis-isobutyronitrile, t-butyl peroctoate or benzoyl peroxide, and heat is always convenient for ensure a uniform copolymerization. Another route to the preparation of a water-soluble polymer for this invention is to prepare a vinyl dispersion polymer having sufficient acrylic or methacrylic acid or other polymerizable acid monomer (usually greater than 10 percent) so that the emulsion polymer can be solubilized by the addition of ammonia or another base. Water-soluble polymers of this type are advantageously used as mixtures with conventional dispersion polymers, preferably those which also have acetoacetate pendant functionality. The mixture of the alkali-soluble resin and the latex polymer has a combination of gloss and rheology advantageous properties and is useful in coatings of printing ink applications. In another embodiment of this invention, an aqueous dispersion contains copolymer particles composed of at least two mutually incompatible copolymers. These mutually incompatible copolymers can be present in the following morphological configurations, for example core / cover, core / shell particles with shell phases that incompletely encapsulate the core, core / shell particles with a multiplicity of cores, particles of interpenetrating networks, and the like. In all these cases, the majority of the surface area of the particle will be occupied by at least one external phase and the interior of the particle will be occupied by at least one internal sewer. The mutual incompatibility of the two polymer compositions can be determined in various ways known in the art. The use of electron scanning microscopy, with the use of dyeing techniques to highlight the difference between the appearance of the phases, for example, is one of the techniques. The emulsion polymerization techniques used to prepare these dispersions are well known in the art. It is sometimes advantageous to introduce some interlacing or gel structure, by the sequence polymerization process, in the core, via low levels of an entanglement monomer, such as allyl methacrylate, diallyl phthalate, diallyl maleate, butylene glycol di-methacrylate, divinyl benzene, triallyl isocyanurate, ethylene glycol diacrylate, and the like. The slightly entangled core does not adversely affect the formation of the film and, in some cases, results in better coatings, in particular, when the acetoacetate is concentrated on the cover.

As indicated above, one main use of this technology is to make vinyl polymers dispersed or dissolved in aqueous solvents functional. Unfortunately, vinyl polymers containing the pendant acetoacetate are prone to hydrolysis in water, particularly in heat aging. Hydrolysis occurs at approximately any pH and supplies the acetoacetic acid: CH3 C CH3 + C02 t 0 0 0 O • 1 II H20 II II -Ri Q C CH2 C CH2 - > -R1 OH + CH3 CCH2 COH which in turn is broken down into acetone and carbon dioxide. In a previous application, Serial No. of E. U. A. 632,302, the solution to this problem was provided by treating the aqueous polymer of acetoacetate, after preparation with a 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 at a basic pH with one of the amines mentioned above, preferably at a pH greater than 9. Under these conditions, the enamine is formed. The reaction to form enamine is generally rapid, with the rate of formation increasing with temperature. In general, the formation of the enamine is complete within 8 hours. An alternative proposal is to raise the pH to about 9, allow the system to equilibrate and readjust the pH by about 9 to replace the amine consumed by the formation of the enamine. The enamine is stable to hydrolysis at pH typically greater than 7. Another proposal for the preparation of vinyl polymers containing the equivalent pendant enamine functionality, is to use the previously formed enamine monomers, derivatives of the appropriate amine, and the monomer of acetoacetate. In this case, the pH must be maintained on the alkaline side during the polymerization, to avoid the hydrolysis of the enamine back to the acetoacetate.

Functional Amino Silanes The aminosilane modified polymers of this invention are prepared by adding an effective amount of an aminosilane to a polymer having the functionality of acetoacetate introduced into the polymer chain by an acetoacetate functional monomer, such as, for example, Acetoacetoxy-ethyl methacrylate. The amount of the aminosilane that is added to the polymer is a function of the content of the acetoacetate functionality of the polymer. As mentioned above, the functional monomer level of acetoacetoxy is generally about 1 to 40 weight percent, based on the weight of the polymer. The level of aminosilane for modifying the polymer is from about 0.10 to 1.0 moles of the amine moiety to one mole of the acetoacetoxy group. If insufficient aminosilane is used in relation to the functional vinyl polymer of acetoacetate, the properties, such as, for example, solvent resistance, dirt pick-up resistance, printing resistance and block formation and deterioration resistance of the dry coating , they can be compromised. Meanwhile, on the other hand, if the ratio of the moles of the aminosilane to the moles of the acetoacetate functionality is much greater than 1 in the vinyl polymer, the properties of the coating, such as the formation of the film can reach to be damaged, due to the excessive pre-entanglement of the silicone groups. This can also produce an increased sensitivity to water as well as discoloration of some substrates, such as, for example, wood substrates.

Aminosilanes of various molecular weights and structures can be used to modify the polymer with acetoacetate function in the practice of the invention. The general structure of the aminosilanes useful in the invention is: Rl - Si (R2) 3-n (° R3) n * where n is greater than or equal to 1, but less than or equal to 3, 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, R3 is alkyl, phenyl or a hydrogen atom, or combinations thereof, and R2 is a hydrogen atom, or a phenyl or alkyl group, or combinations thereof. The group R can also be silane oligomers, which may or may not contain 0R3 groups and may or may not include the amine functionality, capable of undergoing the formation of the enamine with the acetoacetoxy groups. Preferably, however, the aminosilanes will have an average molecular weight, as determined by gel permeation chromatography, of from about 140 to 500, more preferably from about 150 to 250. Practical considerations, such as solubility, regime of hydrolysis, compatibility with the acetoacetate precursor polymer, stability of the polymer and the like, are the only limitations placed on the structure and molecular weight of the aminosilane.

Although for convenience purposes it is more preferred that the molecular weight does not exceed a maximum of about 190 to 250, that n is equal to 1 or 2, that R is a methyloxy or ethyloxy group and that R ^ is an alkyl group with 3 to 6 carbon atoms and containing not more than one amine group, capable of forming an enamine with the acetoacetoxy group. Aminosilanes found modifiers are effective polymers functional vinyl acetoacetate, can be selected from the group consisting of: trimethoxysilylpropyldiethylene, N-methylaminopropyltrimethoxysilane, aminoetilaminopropilmetildimetoxisilano, aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020), aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric aminoalkylsilicone, aminoetilaminoetilaminopropil -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 Huís of America, Piscataway , New Jersey, Wacker Silicones Corporation of Adrian Michigan. In the practice of the invention, the aminosilane modified coatings are prepared by adding a specific amount of aminosilane to the functional vinyl polymer of acetoacetate. The amount of silane added must be in specific proportion, for the reasons mentioned above, to the acetoacetate content of the polymer. The functional amino silane is preferably added after the polymerization of the functional vinyl emulsion polymer of acetoacetate. In general, aminosilane can be added directly to the functional precursor polymer of acetoacetate. However, for the optimum performance and the process of the final polymer modified with silicone, an auxiliary surfactant may be required. This is particularly true, for example, in some cases where the precursor polymer is produced by the emulsion polymerization. In this case, the surfactant can provide, for example, increased stability, as well as increased desirable properties, such as resistance to spoilage, when used in conjunction with the aminosilane.

The auxiliary surfactant may be added preferably before or after the addition of the aminosilane, or as part of the preparation of the precursor, as in the case of, for example, emulsion polymerization. Surfactants can be characterized by their "Hydrophilic-Lipophilic Balance" ("HLB") value. Surfactants with HLB values less than 10 are considered to have a more lipophilic character, while surfactants with HLB values greater than 10 are considered to have a more hydrophilic character. In the context of preferred surfactants, non-ionic surfactants with HLB values with a more hydrophilic character, HLB > (greater than) 10, are desirable. More preferably, the HLB value should be greater than 15. Levels of surfactants up to 10 weight percent of the precursor can be used. The most preferable level of the surfactant is between 3 and 6 percent of the weight of the precursor. The only limitations of the surfactant level are, for example, poor water resistance, instability, and the like. Examples of surfactants that can be used in the practice of the present invention are selected from the group consisting of nonionic substances, such as octylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, polypropyloxyethoxy alcohols, and the like, and ionic substances, such as lauryl sulfate. sodium, sodium stearate, and the like.

Additives The acetoacetate functionalized vinyl polymer, modified with aminosilanes of this invention, can be formulated for a selected end use. Additives may be incorporated, such as thickeners, dispersants, pigments, diluents, fillers, anti-freeze agents, plasticizers, adhesion promoters, coalescents, wetting agents, defoamers, colorants, non-aldehyde based biocides, soaps and agents Sliding.

METHODS OF TEST EVALUATION OF THE PERFORMANCE OF CLEAR COATINGS. BASED ON LATEX MODIFIED WITH SILICONE Resistance to Deterioration This "test is based on the impact of the coating, at a shallow angle, with a hard object, in the examples provided, the object was the fingernail of a person performing the test. it gives an indication of how the coating will resist deterioration, which leads to a reduction in the brightness thereof.

After the coating is applied to the substrate and allowed to cure, the coated substrate is placed on a solid surface, such as on the top of a table, and tapped with the fingernail of an operator's finger. This fingernail remains parallel to the coated surface and the impact angle is greater than 45 degrees from normal to 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. The following classification system is used: Classification Appearance 1 - Excellent No noticeable marks 2 - Good Marks appear as thin scrapes 3 - Insufficient Marks such as wide scrapes Resistance to Black Heel and Scratch Marks The method to determine the resistance to black heel and scratch marks is described in Chemical Specialty Manuf acturers Association Bulletin No. 9-73, except that rubber shoe heels were used, commercially available, instead of the 5 cm rubber buckets. recommended, and substrates were wood panels (maple) instead of vinyl slabs. The percentage of the area of the coated substrate was determined, which was covered by the black marks of heels and scratches; This is conveniently done with transparent graph paper. Black heel marks are a real reservoir of rubber on or inside the coating. The black heel marks can be temporary and can be removed with a dry thin cloth, for example, or with a thin cloth and a suitable solvent, such as odorless mineral spirits. A scratch mark, on the other hand, results from a physical displacement of the coating and appears as an area of reduced brightness. The marks of scratches or heels can occur simultaneously at the point where the heel hits the substrate, that is, when removing a black heel mark or a scratch may be present.

Floor Wear Test Coatings were applied to wood panels and cured at 252C for a specific time, before being placed in a dense traffic corridor. The used corridor experienced pedestrian traffic as well as traffic from maintenance carts, sample trays, etc. The brightness was measured at 60 and 20 degrees, as well as scratches and scrapes before and after a sufficient time of exposure.

Removal of Black Heel Marks with a Dry Fabric After exposing the test panels to the rubber heels, as described above, the coatings were tested in the ease of removing the rubber marks with a dry cloth. A thin cloth was rubbed over the black rubber marks with moderate pressure, after which the "complete" cone removal was classified, which means that all the black rubber marks were removed; "partial", which means that all the black rubber marks were not removed; and "none", which means that all black rubber marks were present after rubbing. 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 described more fully in the specification and the claims. Unless stated otherwise, the percentages are by weight, based on total solids.

EXAMPLES Example I Example I shows the performance improvement of the coating that the aminosilane modification produces to the latex containing AAEM. The effect of the aminosilane level and the aminosilane type on the performance of the coating is also shown.

Preparation of the Precursor Latex The details for the preparation of the precursor latex, I-A and I-B are described below. Both precursors are identical in their preparation, except that the acetoacetoxy-ethyl methacrylate monomer (AAEM) was omitted from I-B. Table I-A shows the composition of the precursors as well as some characteristics. To a glass vessel were added 121.3 g of deionized water (DI) and 6.1 g of ALIPAL CO 436. To this, 4.8 g of sodium lauryl sulfate was added followed by 326.3 g of butyl acrylate (BA), 386.8 g of methyl methacrylate (MMA), 7.25 g of allyl methacrylate (ALMA) and 3.65 g of methacrylic acid, and then stirred to form an emulsion. This is the Emulsion of Monomers 1 (EM-1). To another glass container, 260 g of DI water and 14.2 g of ALIPAL C0436 were added. To this, 380.9 g of BA, 515 g of MMA, 167.8 g of AAEM and 27.5 g of MAA were added, and then stirred to form an emulsion. This is the Emulsion of Monomers 2 (EM-2). To a polymerization vessel, 1282.3 g of DI water were charged under dry nitrogen, followed by 18.6 g of ALIPAL C0436. This mixture was stirred and then heated to 85 ° C. Next, 100 g of EM-1 was added. Two minutes later, 3.6 g of sodium persulfate (SP) in DI water was added. After ten minutes, 7.2 g of sodium carbonate in DI water was added. Five minutes later, the EM-1 was fed in conjunction with 0.90 g of SP in DI water in 90 minutes. After completing the addition of EM-1, the EM-1 vessel was rinsed with 40 g of DI water. The polymerization vessel was maintained at 85 ° C for an additional 15 minutes. The joint loading of EM-2 with 0.90 g of SP in DI water was then started. This overall load was made in a period of 90 minutes. Following the addition of EM-2, the EM-2 vessel was rinsed with 40 g of DI water. The polymerization vessel was maintained for 30 minutes at 852C. After holding for 30 minutes at 85 ° C, the vessel was cooled to 55 ° C and the monomers were "hunted" for, in this order, 5 g of 0.15% FeS04, 5 g of 1% versen and 0.5 g of t-BHP 70% in DI water. After one minute, 0.30 g of isoascorbic acid in DI water was added. After maintaining 30 seconds at 55 seconds, 62.5 g of 28% aqueous ammonia were added. The resulting polymer was cooled to room temperature, before modification with the aminosilane. The precursors I-A and I-B are identical in their preparation, a two-step process, and composition, except that the AAEM of the I-B was omitted.

Preparation of the Silicone Modified Latex The precursor I-A, whose preparation was described above, was charged into a mixing vessel. With shaking, TRITON X405 (70%) was added to the precursor by shaking for a period of about 5 minutes. Approximately 10 minutes after the addition of X-405, the aminosilane was added dropwise in the course of about 5 minutes. The mixture was allowed to stir for about one hour, after completing the addition of the amiosilane. The quantities of the materials used are shown in Table 1-2. The silane-modified latex was allowed to stand for about 16 hours, before being formulated in a sealer.

Preparation of Aqueous Wood Sealers Based on Latex Modified with silane. Table 1-3 gives the sealant formulation used to evaluate compositions 1-1 through 1-9. A general formulation is also shown as a specific example based on composition 1-4. To a mixing vessel, all the materials except the latex were added. With stirring, the modified silane latex was added and stirred for at least one more hour and allowed to stand for at least 16 hours before use.

Sealers Test Based on compositions 1-1 to 1-9 Maple wood panels were applied 3 coatings of sealers based on compositions I-1 to 1-9, with approximately one to two hours between coatings . After the final coating, the sealed panels were allowed to cure for 72 hours, before testing. The test results are illustrated in Table I-4.

TABLE 1-1 Characteristics of Precursors Containing AAEM Precursor of AAEM Solids.% By weight) Meq. AAEM / qra of solids 46.0 0.42 Ib 46.1 0.00 Composition of Precursor IA: Stage 40% of 45BA / 53.5 MMA / 1 ALMA / 0.5 MAA 2nd Stage 60% of 35BA / 47.5 MMA / 2.5 MAA / 15 AAEM.

Composition of the IB Precursor: The same as IA, except that the AAEM was omitted TABLE 1-2 Latex Formulations Modified with Silicone (Quantities in parts by weight Composition II 12 13 14 15 16 17 18 19 (In order of addition) Precursor Material IA 100 100 100 100 100 100 100 Precursor IB 100 100 Triton X4051 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 A07002 0.0 1.5 2.9 4.3 5.8 4.3 0.0 Meq. Silane / Q QQ Q 33 Q g6 1 QQ 33 Q 33 1 QQ 1 QQ 1 QQ Meq .. AAEM Footnotes: 1 70% Concentration 2 Aminoethyl-aminopropyltrimethoxysilane 3 Aminopropyltrimethoxysilane.

TABLE 1-3 Formulations of Aqueous Wood Sealers for Compositions II to 19 General Formulation (25% Solids, order of addition shown) Material Quantity (parts by weight) Silane-modified latex 25 ppc1 (solid) DE2 35% latex solids FC-1203 1.2 ppc SWS-2114 0.02 ppc Water Dilute to 25% solids Specific Example of the Wooden Water Sealer. Based on Composition 1-4 Material Quantity (parts by weight) Latex Composition 14 53.87 DE 8.14 FC-120 1.2 SWS-211 0.02 Water 40.60 Footnotes: 1. ppc = parts per hundred parts of sealant 2. Diethylene glycol monoethyl ether 3. Fluorad 120, 1 moistening aid % active in water / dipropylene glycol methyl ether: 47/1 4. Silicone defoamer, by Wacker.

TABLE 1-4 Properties of Aqueous Wood Sealants. Based on the compositions l a 9 Resistance Composition Brands Latex Removal to Black Deterioration of Black Heel Marks (%) Heel (dry cloth) II 5 2.3 none 12 2 1.5 partial 13 1 1.1 complete 14 1 1.6 complete 15 1 1.5 complete 16 4 1.5 none 17 4 2.0 partial 18 5 2.6 none 19 5 2.9 none EXAMPLE II Example II shows the performance improvement of the coating that the modification of aminosilane produces the latex containing the precursor of AAEM. It also shows the effect of the aminosilane level and the aminosilane type in coating performance.

Preparation of the Precursor Latex An emulsion of monomers (EM) was prepared by adding 475 g of DI water, 20 g of sodium lauryl sulfate (SLS), 600 g of ethyl acrylate, 335 g of MMA, 15 g of MAA and 50 g. g of AAEM, followed by agitation. To a polymerization vessel, under nitrogen, 800 g of DI water and 25 g of SLS were added. After the temperature increased to 852C, 4.2 g of ammonium per-sulfate (APS) in DI water was added. After the addition of the APS, the addition of EM was started together with a loading of 2.1 g of APS in DI water, at approximately 12.5 g / minute and 0.88 cc / minute, respectively. After completing the addition of the MS, the emulsion pot was rinsed with 30 g of DI water. The vessel was cooled to 56SC over a period of 1 hour, after which 1 g of t-BHP in DI water and 0.5 g of isoascorbic acid in DI water were added. The vessel was cooled to room temperature and filtered before modification with the aminosilanes. Table II exhibits some characteristics of the IIA precursor.

Preparation of the Silicone Modified Latex The process for the preparation of the silane modified latex based on the precursor II-A was the same as described in Example I, except that the materials and the proportions used are as shown in the Table. II-2. The silane-modified latex was allowed to stand for 4 days before its formulation in a sealer.

Preparation of Aqueous Wood Sealers. Based on Latex Modified with Silane Table II-3 gives the sealant 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 reaction vessel, all materials, except latex, were added. With stirring, the modified silane latex was added. The mixture was stirred for at least one more hour and allowed to stand for at least 16 hours before use.

Test of Sealers Based on Compositions Il-1 to II-4 To maple wood panels, 3 coatings of sealers based on compositions II-1 to II-4 were applied, with approximately one to two hours between coatings. After the final coating, the sealed panels were cured at 25SC for 72 hours, before testing. The results of the test are shown in Table II-4. TABLE II-l characteristics of the IIA Precursor that contains AAEM Solids (% by weight) Meq. AAEM / grams of solids 40.1 0.23 Composition of the precursor IIA: 60 EA / 33.5 MMA / 1.5 MAA / 5 AAEM TABLE II-2 Latex Formulations Modified with Silicone (Quantities in parts by weight) Composition III 112 113 114 (in order of addition) Material Precursor IIA 100 100 100 100 Triton X405i 2.9 2.9 2.9 2.9 A07002 0.0 0.7 2.1 A06993 1-9 Meq. Silane / 0.00 0.33 1.00 1.00 Meq. AAEM Footnotes: 70% concentration 2 Aminoethyl-aminopropyl-trimethoxysilane 3 Aminoethyl-aminopropyl-methyl-di-ethoxysilane TABLE II-3 Aqueous Formulations of Wood Sealants for Latex Compositions I-1 to II-4 General Formulation (25% Solids, Addition Order Shown) Material Quantity (parts by weight Latex Modified with Silane 25 ppc1 (solids) DE2 35% latex solids FC-1203 1.2 ppc SWS-2114 0.02 ppc Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealer in Composition II-4 Material Quantity (parts by weight) Latex Composition II-4 64.18 FROM 9.98 FC-170C 0.20 SWS-211 0.02 Water 25.63 Footnotes: 1. ppc = parts per hundred parts of sealant 2. Diethylene glycol mono-ethyl ether 3. 3M Fluorad 170, auxiliary humectant 4. Defoamer silicone, Wacker.

TABLE II-4 Properties of Aqueous Sealants for Wood, Based on Compositions Il-l a II-4 Composition of Black Marks of% Scratches Latex Heels (Relative1) III 3 3.3 112 2 1.6 113 2 0.0 114 1 0.0 Footnote: 1 1 = better with a coverage of around 2.5%. The increase in number implies a decrease in performance.

EXAMPLE III Example III shows that the performance of the coating is carried out by the structure of the aminosilane.

Preparation of the Precursor Latex The precursor latex IA, described above in Example I, was used.

Preparation of Silicone Modified Latex The process for the preparation of a silicone modified latex based on precursor IA was the same as described above in Example I, except that the materials and proportions used are shown in Table III-1 and the common premix precursor / Triton 405 (70%) was used. The latexes modified with silane were allowed to stand for 1 day before being formulated in sealants.

Preparation of Aqueous Wood Sealers. Based on Latex Modified with Silane Table III-2 gives the sealant 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. The coating preparation was described in Example I.

Sealer Test Based on compositions II-1 to II-4 To maple wood panels, 4 sealant coatings were applied based on compositions III-1 to III-5, with approximately one to two hours between coatings. After the final coating, the sealed panels were cured at 25 ° C for 4 days, before the test. The results of the test are shown in Table III-3.

TABLE III-l Latex Formulations Modified With Silicone (Quantities in parts by weight) Previous mixture = 100 Precursor Latex IA 3.3 Triton X405 (70%) Composition III1 III2 III3 III4 III5 (in order of addition) Material Previous mixture 103.3 103.3 103.3 103.3 Precursor IA 100 Triton X4051 3.3 A07002 3.4 A06993 3.2 A08004 2.8 A07425 2.9 Meq. Silano / O.OC 0.80 0.80 0.80 0.80 Meq. AAEM Footnotes: 1. 70% concentration 2. Aminoethyl-aminopropyl-trimethoxysilane 3. Aminoethyl-aminopropyl-methyl-dimethoxysilane 4. Aminopropyl-trimethoxysilane 5. Aminopropyl-methyl-diethoxysilane TABLE III-2 Aqueous Wood Sealer Formulations for Latex Compositions III-1 to III-5 General Formulation (25% solids Addition Order Shown) Material Quantity (parts by weight) Silane modified latex 25 ppc1 (solids) DE2 35% latex solids FC-1203 1.2 ppc SWS-2114 0.02 ppc Water Dilute to 25% Solids Specific example of Aqueous Wood Sealant. Based on Composition III-2 Material Quantity (parts by weight) Latex Composition III-2 54.19 DE 8.14 FC-120 1.2 SWS-211 0.02 Water 36.30 Footnotes: 1. ppc = parts per hundred parts of sealer 2. Diethylene glycol mono-ethyl ether 3. Fluorad 120, active 1% wetting aid in water / dipropylene glycol methyl ether: 47/1 4. Silicone defoamer, from Wacker.

TABLE III-3 Properties of Aqueous Wood Sealants. Based on Compositions III-1 to III-5 Composition% of Brands% of Scratches Resistance to Latex Black Deterioration Heels III-l 3.8 2.2 5 (poor) III-2 2.2 0.0 1 (Excellent) III-3 1.0 0.0 1 (Excellent) III-4 1.7 1.0 4 (Regular) III-5 1.2 0.0 1 (Excellent) EXAMPLE IV Example IV shows that the silicone modification improves the performance of a coating based on a precursor latex that forms a film at room temperature.

Preparation of the Precursor Latex IV The preparation and characteristics of the precursor latex, IVA, were described above in Example I, except that the ratio of BA / MMA in the EM-I (Emulsion of Monomers I) was changed from 35 / 47.5 to 69.8. /12.7, providing a softer first stage, with a lower glass transition temperature. The solids of the IVA precursor were 45.3%.

Preparation of the Silicone Modified Latex The process for the preparation of the silicone modified latex, based on the IVA precursor, was the same as described above in Example I, except that the materials and the proportions used are shown in FIG.

Table IV-1.

Preparation of Aqueous Wood Senators. Based on Latex Modified with Silane Table IV-2 gives the latex formulation used to evaluate composition IV-1. The procedure is the same as in the previous examples. Note that no cosolvent (DE) was used since both the IV1 composition and the IVA precursor form films below room temperature.

Sealer Test Based on Compositions IV-1? Precursor IV To maple wood panels, 4 sealant coatings based on the IV1 compositions and the IVA precursor were applied, with approximately one to two hours between the coatings. After the final coating, the sealed panels were cured at 25ac for 3 days before testing. The test results are shown in Table IV-3.

TABLE IV-1 Preparation of Latex IV! Modified with Silicone (Quantities in parts by weight) (in order of addition) Material Precursor VAT 100.0 Triton X4051 3.2 A07002 4.3 Meq. Silano /. __ Meq. AAEM Footnotes: 1. 70% concentration 2. Aminoethyl-aminopropyltrimethoxysilane.

TABLE IV-2 Aqueous Formulations of Wood Sealers for Composition IV! (25% solids, Addition Order Shown) Material Quantity (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 VAT 50.00 TABLE IV-3 Properties of Aqueous Wood Sealers Based on Composition IV! Composition of% of Brands% of Scratches Resistance to Latex Black Deterioration Heels IV1 2.0 1 (excellent) 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-l of Example III, except that X405 was omitted and formulated in a sealer according to Example III. Five coatings of each of them were applied to maple panels and cured at 252C for one week, before laying on the floor of the exposed area. Table V-1 shows the effects of 26 days of wear.

TABLE V-1 Comparison of Precursor 1-1 Modified with Silane and Unmodified, in the Wear Test Composition% Shine% Shine Latex Appearance Retained at 2Qa Retained at eos Precursor I 62 72 Highly (no scraping and modifying) scratched III-5 91 82 A few minor scratches and scrapes Footnote: 1. Retained brightness = (final brightness / initial brightness) x 100.

EXAMPLE VI In this example, neutralization with potassium hydroxide is shown instead of ammonia. Preparation of the Precursor Latex The preparation and characteristics of the precursor latexes VI-A and VI-B were described above in Example I, except that the latex was not neutralized with NH3 and VI-B was prepared by a homogeneous process, where all the monomers were introduced from a single monomer emulsion. The solids of precursors VI-A and VI-B were 47.6 and 47.8%, respectively.

Preparation of Silicone Modified Latex The process for the preparation of silicone modified latexes, based on precursors VI-A and VI-B are described in Example I, except that the materials and the proportions used are shown in FIG. Table VI-1. Likewise, the pH of the precursor latexes was increased to about 7.5 as aqueous potassium hydroxide, before the addition of the other materials.

Preparation of Aqueous Wood Sealers. Based on Latex Modified with Silane Table VI-2 gives the sealant formulation used to evaluate compositions VI-1 to VI-5. The procedure was the same as in the previous examples.

Test of Sealers Based on Compositions Vl-1 and Precursor IV To maple wood panels, 4 sealant coatings were applied based on the compositions IV1 and the precursor IV, with approximately one to two hours between coatings. After the final coating, the sealed panels were cured at 25SC for 3 days, before the test. The results of the test are shown in Table VI-3.

TABLE VI-1 Latex Formulations Modified with Silicone (Quantities in parts by weight) Composition Vil VI2 VI3 VI4 VI5 (in order of addition) Precursor Material VI-A 100 100 Precursor VI-B 100 100 100 KOH (2.1 N) 1.70 1.70 1.50 1.50 1.50 Water 5.08 11.36 5.52 11.20 11.72 Triton X4051 3.40 3.40 3.40 A07002 3.6 A0742 3.06 3.1 Meq. Silane / 0.00 0.80 0.00 0.80 0.80 Meq. AAEM Footnotes: 1. 70% concentration 2. Aminoethyl-aminopropyl-trimethoxysilane 3. Aminoethyl-aminopropyl-methyl-dimethoxysilane TABLE Vf-2 General Formulation (25% Solids Addition Order Shown) Material Quantity (parts by weight) Silane modified latex 25 ppc1 (solids) DE2 35% latex solids FC-1203 1.2 ppc SWS-2114 0.02 ppc Water Dilute to 25% Solids Specific Example of Aqueous Wood Sealers Based on Composition VI-2 Material Quantity (parts by weight) Latex Composition VI-1 35.00 OF 3.80 FC-120 0.94 SWS-211 0.02 Water 22.70 Footnotes: 1. ppc = parts per hundred parts of the sealant 2. Diethylene glycol mono-ethyl ether 3. Fluorad 120, auxiliary of wetting to 1% active in water / dipropylene glycol methyl ether: 47/1 4. Silicone defoamer, by Wacker.

TABLE VI-3 Properties of Aqueous Wood Sealers Based on Composition IV! Composition% of Brands% of Scratches Deterioration of Black Latex Heels Vil 2.4 2.5 5 (poor) VI2 1.6 < 0.1% 1 (excellent) VI3 1.6 1.7 5 (poor) VI4 1.3 < 0.1% 1 (excellent) VI5 1.5 0.0 1 (excellent) EXAMPLE VII Effect of Neutralization and Process Example VII shows that the silicone-modified latex can be prepared by adding a premix of aminosilane and a surfactant to the precursor, rather than being added individually. This gives an improved mode for the preparation, since the addition of diluted materials will less likely "impact" the latex to cause flocculation thereof. It is also shown that neutralization with potassium hydroxide can be eliminated.

Preparation of the Precursor Latexes The latex, precursor VIIA, described in Example I, was prepared without neutralization with NH3 # The solids level was 46.5%.

Preparation of Silicone Modified Latex Silicone modified latexes were prepared as described in Example VI, except that a premix of aminosilane, surfactant and water was used in two of the compositions (see Table VII-1).

Preparation of Aqueous Wood Sealers Based on Latex Modified with silane Aqueous sealers, based on the HIV to VII4 precursors, were prepared as described in Example VI, except that adjustments were made for the precursor solids. The sealants were applied to wood panels and cured as described in the previous examples. The results of the test are shown in Table VI-3.

TABLE VII-1 Latex Formulations Modified with Silicone (Quantities in parts by weight) Composition HIV VII2 VII3 VII4 (in order of addition) Precursor Material VII-A 100.00 100.00 100.00 100.00 KOH (2.1N) 0.70 0.60 0.60 Premix1 8.1 8.4 Water 1.76 Triton X4052 3.20 A07523 2.97 Meq. Silane / 0.00 0.80 0.83 0.80 Meq. AAEM Footnotes: 1 Premix = 36.9 A0742 / 41.2 X405 / 21.8 water. After the preparation, the premix was added immediately to the precursor, as shown. 2 70% concentration 3 Aminoethyl-aminopropyl-methyl-dimethoxysilane TABLE VII-2 Properties of Aqueous Sealants. Based on Composition IV! Composition Flocculated% of Marks Latex Deterioration (sedimentation) Black Heels HIV None 1.4 5 (poor) VII2 None 1.0 1 (excellent) VII3 None 0.90 1 (excellent) VII4 Mild 1.0 1 (excellent) EXAMPLE VIII Example VIII shows the importance of the surfactant for the optimum performance of the sealant.

Preparation of the Precursor Latex To a polymerization vessel, 812.5 g of DI water was added, which was heated to 852C, after which 20.4 g of SIPONATE DS-4 was added, under a nitrogen atmosphere. In a separate vessel, an emulsion of monomers (EM) was prepared by mixing 12 g of DS-4, 150 g of DI water, 110 g of BA, 355 MMA and 10 g of MAA. To the polymerization vessel, 31 g of MS and 10 g of DI water were added, followed by 1.5 g of ammonium persulfate (APS) in water and 1.5 g of sodium carbonate in water. To the MS container, 225 g of ALMA were added. The MS was then added to the polymerization vessel in a period of 90 minutes, together with a combined load of 1.5 g of APS in 150 g of DI water at a rate of 0.84 g / minute. After completing the MS addition, the charge of APS / DI water was terminated. The polymerization vessel was then held for an additional 30 minutes at 85SC. A second MS was prepared as above, but using 12 g of S-4, 150 g of DI water, 212.5 g of ethylhexyl acrylate, 67.5 g of styrene, 125 g of acrylonitrile, 75 g of AAEM and 20 g of MAA. This MS was added to the polymerization vessel in a period of 90 minutes together with the resumption of the joint charge of APS / DI water. After the addition of the MS was complete, the emulsion vessel was rinsed with 25 g of DI water. The polymerization vessel was maintained for an additional 30 minutes at 85 ° C, after which it was cooled to 60 ° C and "hunted" in a manner similar to that described in Example I.

Preparation of the silicone modified latex The precursor VIII-A, described in Example I, was prepared without neutralization with NH3 at a solids level of 45.9%. The preparation of Precursor VIIIB was described in Annex VIII and has the following characteristics: Composition: 12 Stage: 50% of 22BA / 71MMA / 5 ALMA / 2 MAA 22 Stage: 50% of 42.5 EHA / 13.5 STY / 25AN / 15 AAEM Solids: 39.7%.

Preparation of Aqueous Wood Sealers Based on Latex Modified with silane Aqueous sealers, based on precursors VIIH to VIII6, were prepared according to Table VIII-2.

The sealants were applied to wood panels and cured as described in the previous examples. The test results are shown in Table VIII-3 TABLE VIII-1 Latex Formulations Modified with silicone (Quantities in parts by weight) Composition VIII1 VIII2 VIII3 VIII4 VIII5 VIII6 (in order of addition) Precursor Material VIIIA 100.0 100.0 100.0 Precursor VIIIB 100.0 100.0 100. O1 Premix2 5.67 6.82 7.96 3.44 2.45 0.0 Characteristics X4053 level 0.0 2.5% 5.0% 5.0% 0.0 0.0 Meq. Silane / 0.80 0.80 0.80 0.80 0.80 0.0 Meq. AAEM Notes dß pjé: 1 Neutralized with NH3 (aqueous) at pH = 7.5 2 The premixes were prepared as follows: Composition 1: 3.56 water + 3.95 A0742 Composition 2: 3.92 water + 2.41 X405 (70%) + 4.32 A0742 Composition 3 : 4.38 water + 8.23 X405 (70%) + 7.39 A0742 Composition 4: 1.27 water + 2.38 X405 (70%) + 2.14 A0742 Composition 5: 1.98 water + 2.14 A0742 3 Percent in solids of the precursor.

TABLE VIII-2 Aqueous Formulations of Sealants 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 EG2 2.00 2.00 2.00 2.00 2.00 2.00 Defoaming 3 0.02 0.02 0.02 0.04 0.04 0.04 Load the above into a mixing container. With agitation, add the following: VIIH 64.91 VIII2 64.10 VIII3 63.34 VIII4 72.50 VIII5 74.50 VIII6 75.57 Foot notes: 1. Tributoxy-ethyl-phosphate 2. Ethylene glycol 3. Silicone defoamer TABLE VIII-3 Performance of Aqueous Sealers Based on Compositions VIII Composition Resistance to Latex Black Marks Deterioration of Heels VIII-1 5 (poor) 0.8 VIII-2 3 (good) 1.1 VIII-3 1 (excellent) 1.2 VIII-4 1 (excellent) 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 the optimal performance of the silicone-modified latex.

Preparation of the Silicone Modified Latex The precursor, described in Example VI, was used to prepare the latex compositions, modified with silicone, IX-1 through IX-4 (see Table IX). The 1X3 composition was prepared by the subsequent addition of the X405 to a portion of the 1X1, which was 24 hours ready.

Preparation of Aqueous Wood Sealants, Based on Latex Modified with Silane Aqueous sealers, based on the 1X1 to 1X4 precursors, were prepared according to Table VI11-2. The sealants were applied to wood panels and cured as described in the previous examples.

Properties of Aqueous Sealants. Based on the Compositions IX The test of the sealants was the same as in Examples I to VIII, with the exceptions that the Snell capsule used was smaller, the heels in the capsule were larger and the exposure time of the panels was 10. minutes instead of 5 minutes. This gives more rigorous test conditions than in the previous examples. The results are shown in Table IX-3.

TABLE IX-1 Latex Formulations Modified with Silicone (Quantities in parts by weight) Composition 1X1 1X2 1X3 * 1X4a (in order of addition) Precursor 100.00 100.00 100.00 100.00 Pre-mix3 5.67 7.96 5.67 X405 (70%) 3.35 Characteristics X4054 level 0.0 5.0% 5.0% 0.0 Meq. Silane / 0.80 0.80 0.80 0.0 Meq. AAEM Foot notes: 1. Prepared by mixing the X405 (70%) in the 1X1 composition of 24 hours in a ratio of 100 parts of the Composition 1X1 to 3.1 parts of X405 (70%) 2. Neutralized with NH3 (aqueous) to a pH of 8.1 3. Premixes were prepared as follows: Composition a: 3.56 water + 3.85 A0742 Composition 2: 4.38 water + 8.23 X405 (70%) + 7.39 A0742 Composition 3: 3.56 water + 3.85 A0742 4. Percent in solids of the precursor.

TABLE IX-2 Aqueous Formulations of Sealants 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-1401 1.40 1.40 1.40 1.40 EG2 2.00 2.00 2.00 2.00 Defoaming3.

Load the above into a mixing container. With stirring, add the following: IX-1 64.91 IX-2 63.30 IX-3 63.91 IX-4 65.36 After 30 minutes of agitation, add the following: Acrysol RM-10204 2.1 2.1 2.1 2.1 Footnotes: 1. Tributoxy-ethyl-phosphate 2. Ethylene-glycol 3. Foamaster 111 4. Rheology modifier.

TABLE IX-3 Performance of Aqueous Sealers Based on Co-Positions IX Composition of Resistance to% of Trademarks% of Trademarks of Latex Deterioration1 Black Scratches Heels IX-l 3-4 (regular) 1.4 1.2 IX-2 2 (very good) 1.1 0.9 IX-3 1 (excellent) 1.0 0.7 IX-4 5 (poor) 2.8 1.8 Footnote: 1. After curing for 3 weeks at 252c.

EXAMPLE X Example X shows that the hydrophilic / lipophilic balance (HBL) of the surfactant can affect the performance of the silicone-modified latex.

Preparation of the silicone-modified latex The precursor described in Example VI was used to prepare the latex compositions modified with silicone, X-1 to X-3. The milliequivalents of the surfactant to the precursor solids remained constant at 0.25. As described above in Example IX, a premix of the surfactant, aminosilane and water were added to the precursor, with stirring (see Table X-1).

Preparation of Aqueous Wood Sealers Based on Latex Modified with silane Aqueous sealers, based on precursors 1X1 to 1X4, were prepared according to Table X-2. The sealants were applied to wood panels and cured as described in the previous examples.

Properties of Aqueous Sealants Based on Compositions IX The sealant test was the same as in Examples I to 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 gives more rigorous test conditions than in the previous examples. The results are shown in Table X-3.

TABLE X-l Latex Formulations Modified with Silicone (Quantities in parts by weight) Composition Xl X2 X3 (in order of addition) Material Precursor 108.93 108.93 108.93 Premix1 10.38 8.70 6.94 Characteristics Surfactant X705 X705 X100 HLB tensile agent 13.5 17.9 18.7 active Meq. Silane / 0.80 0.80 0.80 Meq. AAEM Footnotes: 1. Premixes were prepared as follows: Composition 1: 2.38 water + 11.94 Triton X705 (70%) + 6.43 A0742 Composition 2: 3.82 water + 7.15 Triton X405 (70%) + 6.43 A0742 Composition 3: 5.96 water + 1.49 Triton X100 (100%) + 6.43 A0742 Note: In all premixtures the water weight / silane weight ratio is equal to 0.93.

TABLE X-2 Aqueous Formulations of Sealants for Compositions X (30% Solids) Material (in order of addition) Water 23.89 22. 72 21. 63 OF 6.63 6.73 6 .83 FC120 (1%) 1.50 1.50 1.50 KP-1401 1.40 1. 40 1.40 EG2 2.00 2. 00 2. 00 Defoamer3"0.15 0. 15 0. 15 Load the above into a mixing vessel With agitation, add the following IX-1 62.33 IX-2 63.30 IX-3 64.39 After 30 minutes of agitation, add the following: Acrysol RM-10204 2.1 2.1 2.1 Footnotes: 1. Tributoxy-ethyl-phosphate 2. Ethylene glycol 3. Foamaster 111 4. Rheology modifier TABLE X-3 Performance of Aqueous Sealers Based on Compositions X Composition of Resistance to% of Marks Comments Latex Deterioration1 Black of Heels x-l 1 (excellent) 0.80 Film marred X-2 1 (excellent) 1.2 X-3 4 (regular) 1.4 EXAMPLE XI Floor Wear Test In Example XI, the modified aminosilane composition X-2 of Example X was compared to a commercially available, dispersed solvent, oil modified urethane (OMU). The coating formulation for composition X-2 is given in Table X2. To maple panels, 3 commercially available OMU coatings were applied (Hillyard Chemical Company, St. Joseph, MO). To another maple panel, 2 coatings of a clear sizing carrying water were applied, followed by 2 coatings of the coating based on composition X-2. Both panels were cured for 72 hours at 252C, before being placed in the floor test area.

Table XI-I compares the brightness at 20 and 602, co or a function of the exposure time. The aminosilane modified polymer exhibited a superior gloss retention to that of the OMU dispersed in solvent, from a single package.

TABLE XI-I Brightness 6Qg / 2Qg Initial After 11 After a day of exposure month exposure Comp. X-2 63/27 66/27 64/24 OMU 73/29 63/16 67/15

Claims (15)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the content of the following is claimed as property: CLAIMS 1. A procedure for the subsequent reaction of polymers having acetoacetate functional groups, the which comprises polymerizing a monomer mixture, containing an acetoacetate functional monomer and a vinyl monomer, and then, following the polymerization, reacting the product of the acetoacetate functional polymer with an amino functional silane.
2. 2. The process according to 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 methacrylate methacrylate. 2,3-di (acetoacetoxy) propyl.
3. 3. The method according to claim 1, wherein the functional acetoacetate monomer comprises about 0.5 to 100 weight percent, preferably 0.5 to 20 weight percent, based on the total weight of the polymer.
4. 4. The process according to claim 1, wherein the amino functional silane is selected from the group consisting of: trimethoxysilylpropyl diethylenetriamine, N-methylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020), aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric aminoalkylsilicone, aminoethylaminoethylaminopropyl- trimethoxysilane, N-methylaminopropyltrimethoxysilane, methylamino-propyltrimethoxysilane, aminopropyl ethyldiethoxysilane, to inopropyltriethoxysilane 4. aminobutyltriethoxysilane and oligomeric aminoalkylsilane.
5. The method according to claim 1, wherein the amino functional silane comprises about 0.1 to 20 weight percent of the functional amino silane, based on the total weight of the functional polymer of acetoacetate.
6. 6. The process according to claim 1, wherein the amino functional silane has a weight average molecular weight of about 140 to 500, preferably about 150 to 250, as determined by gel permeation chromatography.
7. 7. The process according to claim 1, wherein the amino functional silane is aminopropylmethyl diethoxysilane.
8. 8. A coating composition using the subsequently reacted aminosilane-modified acetoacetate functional polymer according to claim 1.
9. 9. A sealant composition using the subsequently reacted aminosilane-modified acetoacetate functional polymer according to claim 1.
10. A process for improving the deterioration resistance and scratch resistance of a wood substrate, which comprises applying to the wood substrate the functional polymer of acetoacetate, modified with aminosilane, according to claim 1.
11. 11. The process, according to Claim 10, in which the subsequent reaction of the functional polymer of acetoacetoxy and the aminosilane is conducted in the presence of a surfactant, selected from the group consisting of octylphenoxypolyethoxyethanols, nonylphenoxy polyethoxy ethanols, polypropyloxyethoxy alcohols, sodium lauryl sulfate and sodium stearate.
12. 12. The method according to claim 11, wherein the level of the surfactant is from about 0.5 to 20 weight percent, preferably from about 3 to 6 weight percent, based on the weight of the functional acetoacetoxy polymer.
13. The method according to claim 12, wherein the hydrophilic-lipophilic balance of the surfactants is greater than or equal to 8, preferably greater than or equal to 15.
14. The process according to claim 12, wherein the Tensoactive agent is not ionic.
15. 15. The process according to claim 14, wherein the surfactant is octylphenoxypolyethoxy ethanol.