MXPA01005189A - Coating compositions and coatings formed therefrom - Google Patents

Abstract

Coating compositions contain a polymer and a silane, the polymer having at least one reactive group and at least one hydrazide group. The silane can be selected from the group consisting of silanes and polysilanes. Optionally, the coating composition includes a pigment. Coatings made from such compositions are also described. Methods of preparing a coating by applying the coating composition to a substrate and curing to form a film are also described herein.

Description

COATING COMPOSITIONS AND COATINGS FORMED FROM THEMSELVES DESCRIPTIVE MEMORY This description relates to novel coating compositions prepared from a reactive polymer, a hydrazide compound and a silane compound. The coating compositions, which may be free of formaldehyde and free of isocyanate, are cured to provide an interpenetrating network (IPN) coating with excellent properties. The paintings can be considered within two general categories, mainly, water-based paints and solvent-based paints. The category of paint suitable for a given application depends on the conditions that the painting experiences. Conventional water based paints have generally been considered inferior to solvent based paints in terms of weather resistance, solvent resistance and adhesion. However, recently, the use of solvent-based paints has become unfavorable, in terms of the environment, with emphasis on achieving acceptable results with paints with a relatively lower volatile organic content ("VOC"). Specifically, efforts have been made to provide paints or coatings that are free of isocyanate and free of formaldehyde having acceptable physical characteristics.

It is therefore an object of the present invention to provide a coating composition which is free of isocyanate and free of formaldehyde, exhibiting good adhesion, durability, chemical resistance, water resistance and resistance to printing. This desired combination of properties has now been achieved by the coating compositions described herein. The novel coating compositions disclosed herein include a polymer and a silane. The polymer has at least one reactive functional group and a hydrazide group. The silane can be selected from the group consisting of silanes and polysilanes. Optionally, the coating composition includes a pigment. Coatings made from said compositions are also described. Also described herein are methods for preparing a coating by applying the coating composition to a substrate and curing it to form a film. Preferred coating compositions in accordance with this disclosure are free of formaldehyde and isocilanate free, can be cured with air or at elevated temperature and provide coatings that exhibit improved adhesion to the substrate, improved printing and blocking resistance and improved solvent and water resistance . The novel coating compositions in accordance with this disclosure include, (a) a polymer having at least one group In addition to functional reactive UMite, the polymer also has a hydrazide group attached thereto; and (b) a silane. Polymers useful for forming the coating compositions include, for example, acrylic polymers, modified acrylic polymers, polyepoxides, polyesters, polycarbonates, polyurethanes, polyamides, polyimides, polysioxanes, polycarbamates and mixtures thereof. The molecular weight of the polymer is not critical. The polymer will generally have a molecular weight of 2,000 to 2,000,000 and preferably 100,000 to 1,000,000. The polymer includes reactive functional groups. The functional groups may provide a binding site for the hydrazide-containing compound and may also provide a site for interlacing by the silane compound as described in detail below. Suitable reactive functional groups include, for example, carboxyl, hydroxyl, epoxy, aminoalkylamino, multi-functional amine, amido and keto groups or combinations thereof. The degree of substitution of the reactive functional groups is not critical, but can preferably be adjusted to provide a coating with the desired characteristics. For example, in this way, where carboxyl groups are present in the polymer, acid numbers of less than about 20 should provide adequate interlacing to form a coating. However, if a coating that can withstand 200 rubs with MEK is desired, an acid number should be used on the scale of about 40 to I SAID? ** Íí mé ^^ ^^^^^^^^^^^ l ^ ^ approximately 80. The polymer can self-entangle or heal with U.V. It is within the field of view of the person skilled in the art to prepare suitable polymers containing reactive functional groups. Suitable polymers are commercially available from a variety of suppliers. Where acrylic polymers are used, said polymers can be prepared from monomers such as acrylic acid and methacrylic acid, alkyl and cycloalkyl acrylates and methacrylates having 1 to 18, preferably 4 to 13, carbon atoms in the alkyl or cycloalkyl portion , Or mixtures of said monomers. Examples of these include methylacrylate, methyl methacrylate, ethylacrylate, ethyl methacrylate, butylacrylate, n-butylacrylate, n-butyl methacrylate, 2-ethylhexylacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate. The reactive functionality in the acrylic polymer can is incorporated by reacting functional monomers with carboxyl, hydroxyl, epoxy, amino, and alkylamino functional groups. The carboxyl-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-acryloxymethoxy-O-phthalic acid, 2-acryloxy-1-methylethoxy-0-hexafyrnephthalic acid. The Hydroxy functional monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, and metal alcohol. Functional epoxy monomers include glycidyl methacrylate. Examples of acrylates and MUMETHYL Alkylamino methacrylates include aminomethyl, aminopropyl, aminobutyl and aminohexylacrylates and methacrylates, dimethylaminoethylacrylate, and dimethylaminoethyl methacrylate. Other suitable monomers include N- • alkoxymethylacrylamide, and N- (butoxymethyl) acrylamide. Other ethylenically unsaturated monomers such as vinyl, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene may also be included to provide the desired physical characteristics. Particularly useful polymers are carboxylated styrene acrylate polymers. Modified acrylics can also be used as the acrylic polymer. Examples of these include acrylics modified with polyester or acrylics modified with polyurethane, which are also known in the art. An example of a polyester-modified acrylic is an acrylic polymer modified with d-caprolactone. Said polyester modified acrylic is described in the patent of E.U.A. No. 4,546,046 to Etxell et al.

Acrylics modified with polyurethane are well known in the art. An example is set forth in the patent of E.U.A. No. 4,584,354, the disclosure of which is incorporated herein by reference. Polyesters having hydroxyl groups, acid groups, or amino groups as reactive functional groups can also be used as the polymer in the compositions herein. Such polyesters are well known in the art, and can be prepared by polyesterification of organic polycarboxylic acids (for example, phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid) or their anhydrides, m Émt_ ^ ^^^^ with organic polyols containing primary or secondary hydroxyl groups. The polyurethanes useful as the polymer in the compositions herein can be prepared by reacting polyisocyanate and polyol with an equivalent OH: NCO ratio greater than 1: 1, to obtain polyurethanase with terminal hydroxyl functionality. In this case, the blocking of the isocyanate occurs simultaneously with the synthesis of the polyurethane resin. Alternatively, the polyurethane can be formed by reacting the polyisocyanate and polyol with an OH: NCO ratio of less than 1: 1. In this case, where an excess of isocyanate is used, the polyurethane having unreacted isocyanate functionality is subsequently reacted with a blocking agent. Suitable blocking agents include reactive alcohols or amines. Examples of these are trimethylolpropane, ethanolamine, diethanolamine, Solketal, diols, triols, or a mixture of diols and triols. Preferably, any unreacted socianates are removed before using the polyurethane as the polymer. Suitable carbamate functional polymers can be prepared from an acrylic monomer having a carbamate functionality in the ester portion of the monomer. Such monomers are well known in the art and are described, for example, in U.S. Patents. 3,479,328; 3,674,838; 4,126,747; 4,279,833; and 4,340,497, the descriptions of which are incorporated herein by reference. A synthesis method involves the reaction of a hydroxy ester with urea to form the carboxylate of carbamyloxy .jMMá ^ iiüi ifaáA ^ ^ M (that is, acrylic modified with carbamate). Another synthetic method reacts an ester of unsaturated a, b acid with a hydroxy carbamate ester to form the carboxylate carbamyloxy. Yet another technique involves the formation of a hydroxyalkyl carbamate by reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate. The hydroxyl group in the hydroxyalkyl carbamate is subsequently esterified by reaction with acrylic or methacrylic acid to form the monomer. Other methods for preparing acrylic monomers modified with carbamate are described in the art, and can also be used. The acrylic monomer can subsequently be polymerized together with other ethylenically unsaturated monomers, if desired, by techniques well known in the art. An alternative route for preparing a polymer useful in the coating compositions herein is to react an already formed polymer such as an acrylic polymer with another component to form a carbamate functional group attached to the polymer backbone, as described in US patent 4,758,632, the disclosure of which is incorporated herein by reference. One technique for preparing useful polymers involves thermally decomposing urea (to emit ammonia and HNCO) in the presence of a hydroxy-functional acrylic polymer to form a carbamate-functional acrylic polymer. Another technique involves reacting the hydroxyl group of a hydroxyalkyl carbamate with the isocyanate group of an acrylic or isocyanate-functional vinyl monomer to form the acrylic carbamate-functional. Isocyanate-functional acrylics are known in the art and are described, for example, in the US patent. 4,301, 257, the disclosure of which is incorporated herein by reference. Isocyanate vinyl monomers are well known in the art and include meta-isopropenyl-a-a-dimethylbecil isocyanate. Yet another technique is to react the cyclic carbonate group in cyclic carbonate-functional acrylic with ammonia to form the carbamate-functional acrylic. Cyclic carbonate-functional acrylic polymers are known in the art and are described, for example, in the U.S.A. 2,979,514, the disclosure of which is incorporated herein by reference. A more difficult, but viable way to prepare the polymer is to transesterify an acrylate polymer with a hydroxyalkyl carbamate. The polymer containing reactive functional groups is preferably provided in the form of a latex, the term "latex" is used herein in a broad sense to mean, generally any aqueous dispersion of a water insoluble polymer, the polymer being present in shape of particles. A compound is grafted to the polymer containing a hydrazide group. Preferably, the hydrazide group has the formula: ji ^ sá ik ai? ^ i k where Ri and R2 each independently represents H or substituted or unsubstituted alkyl. In one embodiment, the compound containing a hydrazide group also comprises a hindered amine group, as is frequently found in the compounds, known as hindered amine light stabilizing compounds (HALS). An example of said compound has the formula: In another embodiment, the compound containing the hydrazide group has the formula: wherein R3 and R4 each independently represent H or substituted or unsubstituted alkyl, and R5 represents substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or wherein L represents a divalent linking group, -NH- or -O-. The linking group is preferably aliphatic, but may also be aromatic, cycloaliphatic, or heterocyclic. Preferably, at least one of R3 or R4, and • minus one of R6 and R7 represents hydrogen. In a preferred embodiment, all R3, R4, R5, and Re represent hydrogen. The compounds containing the hydrazide group can be prepared from aliphatic organic acids, such as acetic acid, propionic acid, n-octanoic acid, adipic acid, oxalic acid, sebasic acid and the like. The acid groups typically react with hydrazine, as is known in the art, to produce the hydrazide derivative of the acid. A compound containing the preferred hydrazide group is adipic dihydrazide. Examples of other useful compounds comprising hydrazide groups include hydrazides of the formula R- (CONH-NH2) n; bis-hydrazides the formula NH2-NH-CO-NHNH2; semicarbazides of the formula RNH-CO-NHNH2; thiohydrazides of the formula RNH-CS-NHNH2. In each of the above formulas for the compounds containing the hydrazide group, n is a positive integer of at least 1. In a preferred embodiment n = 2. R can be hydrogen (except for hydrazides or thiohydrazides when n is 1) or an organic radical. Useful organic radicals include aliphatic, cycloaliphatic, aromatic, or heterocyclic groups, preferably 1 to 20 carbon atoms. The R groups must be free of substituents that are reactive with hydrazide groups. adaMdaA || É i | i | Wka | BHBM || H | M Polyhydrazides (eg hydrazides or thiohydrazides where n> 2) are preferably used to inorate the hydrazide groups in the polymer by reacting one of the hydrazide groups with a hydrazide-reactive group in the polymer. The polyhydrazide can react in the polymer by reacting a polyhydrazide with an acrylic or polyester polymer with one or more anhydride or epoxy groups. Alternatively, the hydrazine can react directly with the reactive functional groups in the polymer (eg, with acid groups in an acrylic polymer) to form a functional hydrazide polymer. The conditions for reacting the hydrazide compound with the polymer are within the realm of those skilled in the art. Typically, the hydrazide compound is simply mixed in a dispersion containing the polymer to effect grafting of the hydrazine group in the polymer. If desired, the hydrazide compound can be mixed with a solvent before addition to the polymer dispersion. The amount of the added hydrazide compound is not critical,) but will preferably depend on the number of factors including the degree of substitution of reactive functional groups in the polymer and the desired characteristics of the final coating. Typically, the hydrazide compound will be added in an amount of from about 0.25 to about 10% by weight, preferably from 0.5 to about 5.0% by weight based on the weight of the total solids content of the coating composition. As will be appreciated by those skilled in the art, since in a dispersion the * '*' •• '- * "* - *. I» ti? .. * -m. .i ". * ,. * l *»? * ^ ... ..... a ^ A If the polymer will bend itself to form particles or micelles, the hydrazide compound will react mainly with reactive functional groups located on the outside of the particle or micelle. , the reactive functional groups within the particle or micelle 5 will remain available for entanglement by means of the silane acing to the molecular cleavages of the polymer when removed from the water or other solvent come from the coating composition In particularly useful embodiments, a sufficient number of the reactive groups on the outside of the polymer particle or micelle is made • react with the hydrazide compound to avoid excessive gelation after addition of silane. This will allow the coating composition to be prepared as a package system. To form the coating compositions herein, the hydrazide containing polymers are combined with a silane of the formula wherein n = 1 to 1, 000, preferably 1 to 100, more preferably 1 to 10; R 20 is an optionally substituted hydrocarbon group containing from 1 to 20 carbon atoms (such as, for example, a methyl, phenyl, alkyl or aryl group); Ri is the same or different in each case and is a selected portion of the group consisting of halogen, hydrogen, alkoxy, hydroxy groups, -am amino and epoxy; and R2 may be the same or different in each case and is selected from the group consisting of R and Ri as defined above. Aminosilanes and epoxysilanes are silanes in particular • useful for making the coating compositions herein. The 5 suitable silanes are commercially available from a variety of suppliers. Specific examples of suitable silanes include: allytrimethoxysilane; allyltrimethylsilane; ^ 10 N- (2-aminoethyl) -3-aminopropyl-methyldimethoxysilane; N-2-aminoetyl-3-aminopropyltrimethoxylane; 3-aminopropylmethyldiethoxysilane; 3-aminopropyltriethoxysilane; 3-aminopropyltrimethoxysilane; 15 b1- (dimethylamino) dimethylsilane; bis- (n-methylbenzamide) ethoxymethylsalon; bis (trimethylsilyl) acetamide; n-butyldimethylchlorosilane; t-butyldimethylchlorosilane; Chloromethyltrimethylsilane; 3-chloropropyltriethoxysilane; 3-chloropropyltrimethoxysilane; di-t-butoxydiacetoxysilane; n, n-diethylaminotrimethylsilane; dimethylchlorosilane; dimethyldichlorosilane; • dimethyldiethoxysilane; 5-dimethylethoxysilane; dimethyloctadecylchlorosilane; diphenyldimethoxysilane; 1,3-divinyltetramethyldisilane; 1,3-divinyltetramethyldisiloxane; ^ 10-ethyltriacetoxysilane; (3-glycidoxypropyl) methodoxyethanol; (3-glycidoxypropyl) trimethoxysilane; hexamethyldisilane; isobutyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane; 3-mercaptopropyltrimethoxysilane; 3-mercaptopropyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane; 3-methacryloxypropyltrys (methylsoxy) slan; 20-methylaminopropyltrimethoxysilane; methylcyclohexydichlorosilane; methylcyclohexyldimethoxysilane; methyltriacetoxysilane; . ? * t.? - ~ «, ..,. TO.. , ".,*.., ,._. ,. ^ t ~ ~ tot »» * »« .. »- ^ .. ^. methyltriethoxysilane; methyltrimethoxysilane; • n-methyl-n-trimethylsilyltrifluoroacetamide 5-octadecyltrichlorosilane; octyl trichlorosilane; n-octyltriethoxysilane; phenyltriethoxysilane; phenyltrimethoxysilane; ^ 10 tetra-n-butoxysilane; tetrachlorosilane; tetraethoxysilane (teos); tetrakis (2-ethoxyethoxy) silane; tetrakis (2-methoxyethoxy) silan; 15 tetramethoxysilane; tetrapropoxysilane; trichlorosilane; triethylchlorosilane; triethylsilane; Trimethoxysilylpropyl diethylenetriamine; n-trimethoxy-silicon-propyl-n, n, n -trimethyl ammonium chloride; trimethylbromosilane; trimethylchlorosilane; • fflB-i "", - "trimethylsilylacetamide, trimethylsilylioid, trimethylsilylnitrile, trimethylsilyl trifluoromethanesulfonate, vinyl dimethylchlorosilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, The amount of silane used is not it is critical, but preferably depends on a number of factors including the degree of substitution of reactive functional groups in the polymer and the desired characteristics of the final coating.You can use as little as about 0.25% by weight based on the total weight of the solids content of the coating composition to provide a coating However, if a coating that can withstand 200 rubs with MEK is desired, silane amounts of about 0.25% to about 10.0% by weight can be used to form a cured coating , one or more of the polymers are intertwined as described using a packing system or a two-pack system. In a packaging system, the polymer combines with the silane to form a stable paint system at storage temperatures. In a two-pack system, the polymer and the silane are kept separate just before or in the application of the composition. Usefully, an external catalyst (such as an inorganic acid) is not needed to cure the preferred compositions in accordance with this disclosure. The coating compositions of the present invention can be clear base coat and coating compositions. The composition may be in the form of a substantially solid powder, a dispersion, or in a substantially liquid state. The liquid coatings can go in the solvent or in water. The coatings may also include solvents, pigments, catalysts, hindered amine light stabilizers, ultraviolet light absorbers, rheology control additives, photoinitiators and other additives known to those skilled in the art. The coating compositions can be coated in the article by a number of techniques well known in the art. These include, for example, spray coating, dip coating, flow coating, roll coating, curtain coating 20, vacuum coating, and the like. After an article has been coated with the layers described above, the composition is subjected to conditions for curing the coating layers. The curing action is usually initiated during or after the removal of the solvent and / or the tíriiir. ifh frf "» * - * - "" "'"' * '"" ** - * -' • * - - ^ ... fß j ^ M dispersant, although air curing or at room temperature can be used useful with the coating compositions described herein, heat curing is preferred.

• Heat is carried out when the coated article is exposed to high temperatures. The five cure temperatures will vary depending on the particular compounds employed in the composition, however they generally vary between 20 ° C and about 180 ° C, and preferably between about 50 ° C and about 120 ° C. The healing time will vary depending on the particular components used, and the physical parameters such • 10 as thickness of the coating layers employed, however, typical cure times range from about 0.5 to about 30 minutes. The present invention is illustrated by the following non-limiting examples. 15 EXAMPLE 1 • A coating formulation having the composition shown in Table 1 is prepared by adding the latex emulsion to a stainless steel container. The adipic acid dihydrazide is housed in the container with continuous stirring for one hour to produce "Part A". Water, defoamer and thickeners are added to a mixture of a wetting agent and a stabilizer (diaminosilane). Later, •• - "'• t t" "" - "" - * - * & * '* - * • ". - * t' *." * 'A portion (approximately 20%) of Part A is added under agitation. Next, TiO2 and Kaolin are added. After stirring for approximately 30 minutes, the remainder of Part A is added slowly with • continuous agitation for 15 minutes. Subsequently, a mixture of epoxysilane and water is slowly added, followed by the surfactant solution. Viscosity is adjusted by adding additional thickener, if needed and adding ink. The resulting composition does not contain isocyanate or formaldehyde and is useful as an outer primer. 10 COMPARATIVE EXAMPLE A coating composition was prepared with the formulation shown in Table 1 except that adipic acid dihydrazide, diaminosilane or epoxysilane were not included.

J_úü4naMÉtA¿lliUí littMHtkÜ iatttáitáfÉMiiiriiáHriiilitf MiiÉMláárita TABLE 1 Ingredient Quantity (kilograms) Part A XU41188.51 * 160.77 (40-55% emulsion of a styrene / carboxylated acrylate polymer in water) adipic acid dihydrazide 2.20 Part B Wetting agent 3.93 Hydrosil 2776 (diaminosilane) ** 1.02 Water 53.30 Defoamer 0.83 2% solution of Bentona LT 37.69 (thickener) TiO2 of rutile 20.11 Kaolin 200.79 DYNASYLAN® GLYMO (epoxysilane) ** 3.95 Water 10.42 Water 3.69 Surfactant solution *** 11.32 2% solution of Bentona LT 11.30 ( thickener) Black ink 2.44 Yellow ink 3.59 * Available from The Dow Chemical Company, Midland, Michigan ** Available from Hüls America, Inc., Somerset, N.J. *** SURFYNOL 104 PA (3.85 kg) plus 16.46 kg. deionized water.

COMPARATIVE EXAMPLE B A coating composition having the formula shown in Table 1 was prepared except that 1% of a conventional 5 interleaver (isopropanolamine) was replaced by the adipic acid dihydrazide, diaminosilane and epoxylysilane.

EXAMPLE 2 ^ ßp 10 The physical properties of the coating composition of the example were analyzed as follows: The samples were prepared for analysis, when applying the coating to the fiber cement panels. 2.07 grams of the coating composition was applied to a conventional fiber cement panel of 15.2 cm x 15.2 cm to provide a coating with a thickness of approximately 1 thousand (0.0254 mm). The solvent resistance of the coating was evaluated by exposing the coating to methyl ethyl ketone ("MEK"). Specifically, a ball of cotton dipped in MEK was gently rubbed from one side to the other on the coating immediately followed by drying and cooling. For reproducibility and consistency the test is performed on glass. When a break in the coating is observed, the double number of rubs with MEK is recorded again. If a coating has not failed after 200 ? j ^^^^ J ^^^ i * í? jM ^ w¡ «F ^ ¡¡* gri ^ rubs with MEK, the test is finished and the results are reported as 200+ rubs. A double rub with MEK is when you pass only once from one side to the other with the ball of cotton immersed with MEK. • The water resistance of the coating is tested using a "Cobb test" as described in ASTM # D5795-95, volume 6.01. A lower value indicates greater resistance to water. The Cobb test is performed only after they have been allowed to reach equilibrium to the samples, in this case approximately 5 days. The blocking resistance is analyzed as follows: ^ 10 Following the cooling procedure of the finishing system, three fiber cement panels are placed so that they are in front to front contact and in front to back contact. The panels are placed in a hydraulic press that has previously been heated to a temperature previously selected in the scale of 60 ° C-82 ° C depending on the severity of the test requirements of the finishing system. The pressure rises to 125 psi and is maintained for , 15 minutes. Subsequently, the panels are checked for any fixation or obstruction. The failure rate is recorded. The abrasion resistance of the coating is analyzed at place two fiber cement panels in a gardner debugging tester against the face. The upper panel is attached to a pulley on the gardner debugging tester and weighed with a weight of 2 kilograms. The scrubber tester is turned on and the uncoated surface of the top panel is g ^ s «HMMTMÉH iittifateÜijM MüiM h ^ .- í ^ glides from one side to the other, eroding the painted surface of the lower panel. Each step, from one side to another, is considered a cycle. When a tearing of the paint occurs, the number of cycles is recorded. For purposes of • comparison, the coatings of the comparative examples A and B are also analyzed. The results are given in table II. • 10 As demonstrated by the above data, the coating according to the description herein, shows better solvent resistance, water resistance, blocking resistance and resistance to abrasion compared to the comparative examples. Although the above description contains many specific details of compositions and methods, these specific details should not be considered as limitations • in the scope of any of the described inventions, but as exemplifications of the preferred modalities thereof. The experts in The technique foresees possible variations that are within the scope and spirit of the inventions as defined in the appended claims.

Claims (25)

1. NOVELTY OF THE INVENTION CLAIMS • 5 1. A coating composition characterized in that it comprises: a polymer having at least one reactive group and at least one hydrazide group thereof; and a silane.
2. 2. The coating composition according to claim 1, further characterized in that the polymer is selected from • Starting from the group consisting of acrylic polymers, modified acrylic polymers, polyepoxides, polyesters, polyurethanes, polyamides, polyimides, polysiloxanes, polycarbonates and mixtures thereof.
3. 3. The coating composition according to claim 1, further characterized in that at least one reactive group is 15 selected from the group consisting of carboxyl, hydroxyl, epoxy, amino and amido groups.
4. 4. The coating composition according to claim 1, further characterized in that the silane is a compound of the formula: ^^^ | »^^^« ^ y ^ | gj ^ g ^ ¡^^ | where n = 1 to 100; R is an optionally substituted hydrocarbon group containing from 1 to 20 carbon atoms; R is the same or different in each case and is a portion selected from the group consisting of groups • halogen, hydrogen, alkoxy, hydroxy, amino and epoxy; and R2 may be the same or different in each situation and is selected from the group consisting of R and R1 as defined above.
5. 5. The coating composition according to claim 4, further characterized in that R1 in the silane formula is selected from the group consisting of amino and epoxy groups.
6. 6. The coating composition according to claim 1, further characterized in that it comprises a solvent.
7. 7. The coating composition according to claim 1, further characterized in that the solvent is water.
8. 8. The coating composition in accordance with the 15 claim 1, further characterized in that it substantially does not contain socianate or formaldehyde.
9. 9. A method for coating characterized in that it comprises: providing a composition containing a polymer and a silane, the polymer having at least one reactive group and at least one hydrazide group in the 20 same; and apply the composition to a substrate.
10. 10. The method according to claim 9, further characterized in that the polymer is selected from the group consisting of acrylic polymers, modified acrylic polymers, polyepoxides, polyesters, polyurethanes, polyamides, polmides, polysiloxanes, polycarbonates * and mixtures thereof.
11. 11. The method according to claim 9, further characterized in that at least one reactive group is selected from the group consisting of carboxyl, hydroxyl, epoxy, amino, and amido groups.
12. 12. The method according to claim 9, further characterized in that the silane is a compound of the formula: where n = 1 to 1000; R is an optionally substituted hydrocarbon group containing from 1 to 20 carbon atoms; Ri is the same or different in each case and is a portion selected from the group consisting of halogen, hydrogen, alkoxy, hydroxy, amino and epoxy groups; and R2 may be the same or different in each case and is selected from the group consisting of R and jf R-i as defined above.
13. 13. The method according to claim 12, further characterized in that Ri in the silane formula is selected from the group consisting of amino and epoxy groups.
14. 14. The method according to claim 9, further characterized in that the composition contains a solvent and also 1. ..... J. .-AA ^ A. ... .- .. i. némtrjl ».« .. »« * .... * - -. • ** > «. .. * - ». * > . ! . . , WiiiáBft comprises the step of removing the solvent from the composition after application to the substrate.
15. 15. The method according to claim 9, further characterized in that the solvent is water.
16. 16. The method according to claim 9, further characterized in that the composition does not contain substantially isocyanate or formaldehyde.
17. 17. The method for preparing a coating composition comprising: (a) reacting a polymer having at least one reactive group with a compound having a hydrazide group; and (b) combining the product of step (a) with a silane.
18. 18. The method according to claim 17, further characterized in that the polymer is selected from the group consisting of acrylic polymers, modified acrylic polymers, polyepoxides, polyesters, polyurethanes, polyamides, polyimides, polysiloxanes, polycarbonates and mixtures thereof. same.
19. 19. The method according to claim 17, further characterized in that at least one reactive group is selected from the group consisting of carboxyl, hydroxyl, epoxy, amino, and amido groups.
20. 20. The method according to claim 17, further characterized in that the silane is a compound of the formula: wherein n = 1 to 1000; R is an optionally substituted hydrocarbon group containing from 1 to 20 carbon atoms; Ri is the same or different in each case and is a portion selected from the group consisting of halogen, hydrogen, alkoxy, hydroxy, amino and epoxy groups; and R2 may be the same or different in each case and is selected from the group consisting of R and Ri as defined above.
21. 21. The method according to claim 20, further characterized in that R-i in the silane formula is selected from the group consisting of amino and epoxy groups.
22. 22. The method according to claim 17, further characterized in that step (a) is carried out in the presence of a solvent.
23. 23. The method according to claim 22, further characterized in that the solvent is water.
24. 24. The method according to claim 17, further characterized in that the compound having a hydrazide group is selected from the group consisting of polyhydrazide compounds.
25. 25. The method according to claim 17, further characterized in that the compound having a hydrazide group is adipic acid dihydrazide. ¡¡¡¡¡¡¡¡¡¡¡¡¡! 26. - A coating comprising a polymer interlaced by means of a silane, the polymer having at least one tive group and at least one hydrazide group therein. • 27.- The coating according to claim 26, 5 further characterized in that the polymer is selected from the group consisting of acrylic polymers, modified acrylic polymers, polyepoxides, polyesters, polyurethanes, polyamides, polyimides, polysiloxanes, polycarbonates and mixtures thereof. 28.- The coating according to claim 26, • 10 further characterized in that at least one tive group is selected from the group consisting of carboxyl, hydroxyl, epoxy, amino, and amido groups. 29. The coating according to claim 26, further characterized in that the silane is a compound of the formula: where n = 1 to 1000; R is an optionally substituted hydrocarbon group 20 containing from 1 to 20 carbon atoms; Ri is the same or different in each case and is a portion selected from the group consisting of halogen, hydrogen, alkoxy, hydroxy, amino and epoxy groups; and R2 can be the same or different in each case and is selected from the group consisting of R and Ri as defined above. 30. The coating according to claim 29, further characterized in that Ri in the silane formula is selected from the group consisting of amino and epoxy groups. • * - * - * • «- ^ ¡¡^ - ^ Mfa ** J-