MXPA99004235A - Method of preventing corrosion of metal sheet using vinyl silanes - Google Patents

Abstract

A method of preventing corrosion of a metal sheet, comprising the steps of:providing a metal sheet chosen from the group consisting of coated steel sheet, aluminum sheet and aluminum alloy sheet;and applying a solution containing at least one hydrolyzed vinyl silane to the metal sheet. A coating of paint or other polymer may be applied directly on top of the vinyl silane coating.

Description

- METHOD TO AVOID THE CORROSION OF METAL SHEET USING VINYLSILANOS DESCRIPTION OF THE INVENTION The present invention relates to a method of avoiding the corrosion of metal foil. More particularly, the method comprises applying a solution containing one or more hydrolyzed vinyl silanes to the metal foil. The method is particularly useful as a pretreatment step before painting the galvanized sheet. 10 Most metal sheets are susceptible to corrosion, including the formation of various types of oxides. Such corrosion will significantly affect the quality of such metallic sheets, as well as that of the products produced from them. Although the oxide and the like can often be removed from the metal sheets, such stages are costly and can also decrease metal resistance. In addition, when polymer coatings such as paints, adhesives rubbers are applied to metals, corrosion of the base metal material can cause a loss of adhesion between the polymer coating and the base metal. For example, the metallic cover sheet such as galvanized steel is used in many industries including the automotive, construction and electrical industries. In most cases, the galvanized sheet is painted or otherwise coated with a polymer layer to achieve a durable and pleasantly static product. The galvanized sheet, particularly galvanized sheet particularly submerged in heating, however, often develops "white rust" during storage and transport. White oxide (also called "storage fatigue") is typically caused by condensation of moisture on the surface of the galvanized sheet which reacts with the zinc coating. This white oxide is aesthetically unpleasant and damages the ability of the galvanized sheet to be painted or otherwise coated with a polymer. Thus, before such coating, the zinc surface of the galvanized sheet must be pretreated in order to remove the white oxide which is present, and prevent it from reforming below the polymer layer. Several methods are currently employed to not only prevent the formation of white rust during transport and storage, but also to avoid white rust formation below a polymer coating (eg, paint). In order to avoid white oxide in the hot-dip galvanized sheet during storage and transport, the surface of the sheet is often passivated by forming a thin chromate film on the surface of the sheet. While such chromate coatings provide resistance to white oxide formation, chromium is highly toxic and environmentally undesirable. It is also known to employ a phosphate conversion coating together with a chromate rinse in order to improve the paint adhesion and provide protection against corrosion. It is believed that chromate rinsing covers the pores in the phosphate coating, thereby improving corrosion resistance and adhesion performance. Again, however, it is highly desirable to eliminate the use of all chromate. However, unfortunately, the phosphat conversion coating is generally ineffective without the chromate rinse. Recently, several techniques have been proposed to eliminate the use of chromate. These include coating the galvanized sheet with an inorganic silicate and followed by treating the silicate coating with an organofunctional silan. (U.S. Patent No. 5,108,793). U.S. Patent No. 5,292,549 teaches and rinsing the metal coated steel sheet with a solution containing an organic silane and a cross-linking agent. Several other techniques have also been proposed to avoid the formation of white oxide in galvanized steel, as well as avoiding corrosion in other types of metal foil. Many of these proposed techniques, however, are ineffective, or require time-consuming, energy-inefficient, multi-stage processes. Thus, there is a need for a simple, low cost technique to avoid corrosion on the surface of galvanized steel or other metal foils, particularly where a polymer coating such as paint on the metal is applied. It is an object of the present invention to provide a method for preventing corrosion of the metal sheet. It is another object of the present invention to provide a method for preventing corrosion of coated steel sheet which employs a one stage treatment process. It is another object of the present invention to provide a treatment solution for preventing corrosion of galvanized steel sheet, wherein the treatment composition does not need to be removed before painting. The aforementioned objects can be realized, according to one aspect of the present invention, by providing a method for preventing corrosion of a metal foil, comprising the steps of: (a) providing a foil, the metal chosen from the group that consists of: - steel sheet coated with a metal chosen from the group consisting of: zinc, zinc alloy, aluminum and aluminum alloy; aluminum foil; and aluminum alloy sheet; and (b) applying a solution containing one or more hydrolyzed vinylsilanes to the metal sheet, each of the hydrolyzed vinylsilanes having OR, I a -Si ~ -OR2 OH in one termination and a vinyl group in the opposite ending, wherein Ri and R2 are each selected from the group consisting of hydrogen, alkyl, and acetyl. The total concentration of the non-hydrolyzed vinylsilanes used to prepare the treatment solution is greater than about 4% by volume, based on the total volume of the solution components. The non-hydrolyzed vinylsilanes used to prepare the treatment solution are preferably selected from the group consisting of: wherein X is an alkyl group, and R3, R4, and R5 are each selected from the group consisting of: C1-C4 alkyl, and acetyl. More preferably, X is a C? -C10 alkyl. The other components of the treatment solution preferably include water, and optionally at least one alcohol which can be selected from the group consisting of alcohol which can be selected from the group consisting of: methanol, ethanol, propanol, butanol and isomers of the same. The solution does not need to contain other active components or diluents. Preferably it is substantially free of such additives, for example, silicates and colloidal silica which are included in prior art compositions mentioned above. The pH of the vinylsilane solution should be between about 3 and about 8, more preferably between about 4 and about 6. The vinylsilane solution can be applied to the sheet by immersing the sheet in the solution for about 10 seconds and about one hour, and the sheet can be heat treated after the application of the treatment composition. The metal sheet is coated by hot dip with a metal chosen from the group consisting of zinc, zinc alloy, aluminum and aluminum alloy, and is preferably hot dip galvanized sheet. The non-hydrolyzed vinylsilanes for preparing the treatment solution can be selected from the group consisting of: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyl-taxhoxysilane, vinylacetoxysilane, vinylmethyltrimethoxysilane, vinylethyltrimethoxysilane, vinylpropyltrimethoxysilane, and N- [2- (vinylbenzylamino) -ethyl] - 3-aminopropyltrimethoxysilane. The treated sheet can be coated with a polymer directly on top of the vinyl silane coating, and this polymer can be a paint, an adhesive or a rubber. Suitable paints include polyesters, polyurethanes and epoxies. In the present it has been found that the corrosion of metal foil, particularly galvanized steel, can be avoided by applying a treatment solution containing one or more hydrolyzed vinylsilanes to the metal foil. The corrosion protection provided by the resulting vinyl silane coating is surprisingly superior to the chromate based treatments, and avoids the problem of chromium disposal. In addition, the vinylsilane coating does not need to be removed before painting or applying another polymer (such as adhesives or rubbers), in fact it offers excellent paint adhesion and corrosion protection underneath the paint layer. The treatment method of the present invention can be used in a variety of metal foils, including aluminum foil, aluminum alloy foil, and zinc coated steel foil, zinc alloy, aluminum or aluminum alloy. It should be noted that the term "metal foil" includes both coils as well as cut sections. The treatment method of the present invention is particularly suitable for coated steel such as galvanized steel, GAL ALUME® (sold by Bethelehem Steel), GALFAN® (sold by eirton Steel Corp., of eirton, WV), and similar types of coated steel. More particularly, the treatment method of the present invention provides improved corrosion protection for hot dip galvanized steel. The vinylsilane solution is preferably applied to the metal sheet to transport the end user, it offers corrosion protection during the transport and storage of the metal sheet, including the prevention of white rust in the galvanized steel. The end user can then simply clean with solvent and / or clean the sheet with the alkaline solution in the normal way, and then apply paint or another polymer (for example, adhesive with adhesives or rubber coating) directly on the upper part of the layer of vinylsilane. The vinyl silane coating on the metal sheet not only provides excellent corrosion protection, but also superior paint (or polymer) adhesion. In this way, distinct from many corrosion treatment techniques currently employed, vinyl silane coating does not need to be removed before painting. The preferred vinylsilanes in the treatment solution may be wholly or partially hydrolyzed, and in this form each of the hydrolyzed vinylsilanes has a in one termination and a group vinyl in the opposite ending, wherein Rx and R2 are each selected from the group consisting of hydrogen, alkyl, and acetyl. When they are fully hydrolyzed, Ri and R2 are hydrogen. The non-hydrolyzed vinylsilanes which can be used to prepare the treatment solution include the following. wherein X is an alkyl group, preferably an alkyl of C -.- C10 and R3, R4, and each is selected from the group consisting of: C? -C4 alkyl, and acetyl. The vinylsilanes falling within the above description include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltrimethoxysilane, vinylacetoxysilane, vinylmethyltrimethoxysilane, vinylethyltrimethoxysilane, vinylpropyltrimethoxysilane, and Jsr- [2- (vinylbenzylamino) -ethyl] -3-aminopropyltrimethoxysilane (SAAPS). A particularly preferred vinylsilane is vinyltrimethoxysilane, sold as A-171 by OSI Specialties, Inc., of Tarrytown, NY. The silanes described above must be at least partially, and preferably fully hydrolyzed so that the silane will bind to the metal surface. During hydrolysis, the alkoxy acetoxy groups are replaced with hydroxyl groups. Thus, for example, s completely hydrolyzes vinyltrimethoxysilane according to the following equation: After drying a solution of vinylsilane hydrolysates which have been applied to a metal surface, it is believed that the silane groups condense siloxane structures which are chemically bonded to the metal surface. Hydrolysis of the vinylsilane can be accomplished simply by mixing the vinylsilane with water, optionally including a solvent such as an alcohol in order to improve the solubility of the vinylsilane. The pH of the solution is also preferably maintained below about 8, and more preferably about 4, in order to improve the hydrolysis. The pH can be adjusted, for example, by the addition of a weak acid, such as an acetic acid. In the present application it is believed that the beneficial results of the treatment method of the present invention are due, in part, to the fact that a thin cap of the hydrolyzed vinyl silane monomer is strongly bound to the oxides on the surface of the metal sheet. The metal surface is passivated, and condensation of moisture is prevented by the hydrophobic nature of the vinyl group. In this way, during the preparation of the solution, care must be taken to ensure that the hydrolyzed vinylsilane does not polymerize via a condensation reaction. If the monomer is allowed to polymerize, the coating will not adhere to the metal and therefore a complete film will not form on the metal sheet. The polymerization of the hydrolyzed vinylsilane can be avoided by ensuring that a fresh solution of hydrolyzed vinylsilanes is used, since the reaction occurs slowly over a period of time. More importantly, the polymerization reaction can be inhibited by appropriate pH choice of the solution. The condensation reaction is generally inhibited at a pH below about 8, particularly below about 6, while the same hydrolysis reaction will still occur below a p of 8. The pH of the treatment solution should also be at least about 3, particularly when the hydrolyzed vinylsilane solution is used to treat the galvanized steel, in order to ensure that the base metal and its coatings (eg, zinc) are not attacked. For example, zinc coating in galvanized steel will begin to dissolve at a pH below about 3. Thus, it is preferred that the pH of the treatment solution of the present invention be between about 3 and about 8, and more preferably between about 4 and about 6. In the present application it has been found that the concentration of hydrolyzed vinylsilanes in the treatment solution will affect the degree of corrosion protection. Thus, it is preferred that the solution be prepared using more than about 4% non-hydrolyzed vinylsilanes by volume. It should be noted that the concentration of vinylsilanes discussed and claimed herein are all measured in terms of the ratio between the amount of non-hydrolyzed vinylsilanes employed (i.e., prior to hydrolyzation), and the total volume of components of the vinylsilane solution. treatment (ie vinylsilanes, water, optional solvents and acids that adjust the pH). In addition, the concentrations refer to the total amount of non-hydrolyzed vinylsilanes added, as well as multiple vinylsilanes may optionally be employed. At concentrations below about 4%, it has been found that protection against corrosion will be limited. Greater concentrates (more than about 10%) should be avoided to prevent the condensation reaction from occurring, and to avoid vinyl silane disposal. In addition, treatment solutions containing higher vinyl silane concentrations will produce thick films which are weak and brittle. Since the solubility in water of some vinylsilanes used in the present invention may be limited, the treatment solution may optionally include one or more solvents, such as an alcohol, in order to improve the solubility of the silane. Particularly preferred alcohols include: methanol, ethanol, propanol, butanol, and isomers thereof. The amount employed will depend on the solubility of the particular vinylsilanes, thus the treatment solution of the present invention may contain up to about 95 parts of alcohol (by volume) per 5 parts of water. Methanol is the preferred alcohol. The same treatment method is very simple. Unhydrolyzed vinylsilanes, water, alcohol (if needed), and a small amount of acetic acid (to adjust the pH) are combined together. The solution is then stirred at room temperature in order to hydrolyze the vinylsilane. The hydrolysis can take up to several hours to complete, its completion will be evidenced by the solution becomes clear. In order to ensure that the hydrolyzed vinylsilane monomers do not condense (or polymerize), the solution should be used briefly after the preparation (preferably within one day). The metal sheet is preferably cleaned with solvent and / or alkaline solution by techniques known in the prior art prior to the application of the treatment composition of the present invention. Then the treatment solution can be applied to the clean metal sheet (ie, coating the sheet with the solution) by either immersing the sheet in the solution (also referred to as "rinse") or by spraying the solution onto the metal surface . When the preferred application method of submerging is employed, the duration of the submerging is not critical, as it generally does not affect the resulting film thickness. It is preferred that the submerging time be between about ten seconds and about one hour, preferably only about two minutes to ensure complete coating of the metal sheet. After coating with the treatment solution of the present invention, the metal sheet is air dried at room temperature, and optionally placed in an oven for heat treatment. The heat treatment can take place at temperatures between about 60 ° C and about 200 ° C for between about 5 and about 120 minutes. Preferably, the heat treatment is carried out at a temperature of about 180 ° C for about 10 minutes. While the heat treatment step is not necessary to achieve satisfactory results, this will improve the drying time so that the likelihood of white oxide formation during drying is decreased. Of course the heat treatment stage, on the other hand, will consume large amounts of energy. The treated metal sheet can then be transported to the end user, and even stored for a period of time before use. The coating of the present invention provides significant corrosion resistance during the period of transport and storage. In addition, and as much as significant, the coating does not need to be removed before painting or the application of other polymer coatings. The end user, such as an automotive manufacturer, can directly apply paint on top of the vinyl silane coating without additional treatment such as the application of chromates. Vinylsilane not only provides a surprisingly high degree of paint adhesion (apparently through covalent bonding with vinyl groups), but also prevents delamination and corrosion under the paint even if a portion of the base metal is exposed to the atmosphere . The metal surface, however, must be cleaned with solvent and / or alkaline solution before application of the paint or other polymer coating, using methods well known in the prior art. Suitable polymer coatings include various types of paints, adhesives (such as epoxy automotive adhesives), rubber coatings (e.g., natural, NBR (butadiene and acrylonitrile copolymer), SBR (styrene butadiene copolymer), nitrile or rubber. silicone). Suitable paints include paints based on polyesters, polyurethanes and epoxy. As previously mentioned, the methods of the present invention are particularly useful for the treatment of precoated steel, such as steel which has been coated with either zinc or zinc alloys (eg, hot dipped galvanized steel). Although zinc coating galvanically protects exposed steel, corrosion may occur under a paint box that is applied to zinc-coated steel. This is particularly true if a portion of the painted steel is damaged in such a way that the same steel layer is exposed to the atmosphere. Although the zinc coating will protect the steel from oxidation by sacrificial galvanic action, the zinc coating for corrosion will generate zinc ions that migrate to the exposed steel and combine with hydroxyl ions to form white oxide. Over a period of time, the zinc coating under the paint corrodes slowly, resulting in a delamination of the paint film. While the phosphate / chromate treatments of the prior art tend to reduce delamination of galvanized steel paint to some degree, the results obtained are far from ideal. In this way, corrosion delamination of paint will often displace a small region of exposed steel (ie, a crack in the painted surface) in a period of time (referred to as "run-off" or "back-running"). Hereby it has surprisingly been found that the vinylsilane treatments of the present invention provide an effective undercoating by painting zinc-coated zinc alloy steel, (particularly hot-dip galvanized steel). Importantly, the methods of treatment of the present invention eliminate costly, toxic and environmentally unsuitable methods of treatment of the prior art using phosphates and chromates. The following examples demonstrate some of the superior and unexpected results obtained using the methods of the present invention. EXAMPLE 1 A treatment solution according to the present invention having 5% (by volume) of vinylsilane is prepared as follows: 5 ml of vinyltrimethoxysilane is combined (obtained from OSI Specialties, Inc., as A-171) with 5 ml of methanol, and 0.5 ml of 1 M acetic acid, the solution is then diluted with 100 ml of water, whereby a concentration of vinylsilane is provided. 5% by volume (in terms of the amount of silane initially present). The pH of the solution is 4.4. The treatment solutions having vinyltrimethoxysilane concentrations of 1%, 12%, 3% and 4% are prepared in a similar manner. They are then washed with solvent galvanized hot-dip galvanized steel ("HDG") panels measuring 10 cm x 15 cm for about one minute, removed, air dried at room temperature, and then treated with heat at 185 ° C per approximately 15 minutes. In order to simulate the conditions experienced by the coiled HDG during storage and transport, the HDG panels are then subjected to a "stacking test". Moisture-treated panels are moistened with water, placed in each other in a pile and then placed in a humidity chamber at 60 ° C and 85% RH. The interface surfaces of the panels (ie, surfaces that have contact with another panel) are monitored after one day for the presence of white oxide, and the following results are observed: Solution concentration of Percent of surface vinyl silane (% in volume) covered with white oxide 1 15 2 30 3 15 4 5 5 none The 5% vinyl silane solution-treated panel is then allowed to remain in the humidity chamber, with the interface surfaces of the panel rewetted each day, and not white rust is observed after two weeks. In contrast, untreated HDG panels form white oxide on m 'of 50% of their surface after just one day, and panele coated with a conventional chromate film (treatment with CHEM COTE RF 100, available from Brent America, Inc. ) begin to form white rust after a week (co-rewet of the interface surfaces each day). Thus, the treatment solution and treatment method of the present invention provide protection against white rust, particularly when the vinlsilane concentration is greater than about 4%. EXAMPLE 2 A 5% treatment solution containing vinyltrimethoxysilane is prepared as indicated in Example 1, used to coat the HDG panels in the same manner as in Example 1 (including the heat treatment step). The panels treated in this way are then painted co-powder with polyester and polyurethane paints in the conventional form (Sample C). They are then washed with solvent galvanized steel panels dipped in hot and painted in a similar way (Sample A). Finally, the HD panels are also cleaned with solvent, and then treated with either zinc coating and conversion phosphate (CHEM COTE 3200 coating available from Brent America, Inc.) followed by a rinse with chromate (CHEM SEAL 3603 rinse, available from Brent America, Inc.) (Sample B). The panels of Samples A and B are also painted with powder with polyester and polyurethane paints. In order to measure the shift, which in turn indicates the degree of adhesion of paint to corrosion protection, a writing tool of the type of carbide point pen is used to produce a mark of 3 inches long (7.62 cm) ) in each of the panels. L mark is deep enough to expose the base metal. The marked panels are then subjected to a salt spray test (ASTM B117), as well as a cyclic corrosion test (General Motors GM9540P Test Number). The salt spray test is carried out on the panels painted with polyester powder for one week, while the panels painted with polyurethane powder are subjected to the salt spray test for two weeks. The cyclic corrosion test is carried out for four weeks on all panels. After the end of the test period, a piece of adhesive tape is secured to each mark and then the panel is pulled. The average width of the paint delamination area is measured for each panel, and the following results are obtained.

As indicated by the above results, the treatment method of the present invention provides significant protection against runoff compared to both untreated panels as well as those treated with the phosphate / chromate treatment method. These results clearly indicate that the treatment methods of the present invention not only provide excellent corrosion resistance, but also excellent paint adhesion. The aforementioned description of the preferred embodiments is not an exhaustive means of the variations of the present invention that are possible, and has been presented only for purposes of illustration description. Modifications and obvious variations will be apparent to those skilled in the art in light of the teachings of the aforementioned description if departing from the scope of this invention. For example, various types of polymer coatings other than the paint may be applied to the top of the vinyl silane coating of the present invention. In addition, vinyltrimethoxysilane is simply an example of vinyl silane that can be used. In this way, it is proposed that the scope of the present invention be defined by the appended claims thereto.

Claims (2)

1. CLAIMS 1. A method to prevent corrosion of a metal sheet, characterized in that it comprises the steps of: (a) providing a metal sheet, the metal chosen from the group consisting of: - steel sheet coated with a metal selected from the group It consists of: zinc, zinc alloy, aluminum and aluminum alloy; aluminum foil; and - aluminum alloy sheet; and (b) applying a treatment solution containing at least one hydrolyzed vinylsilane directly to the metal sheet, the treatment solution prepared by hydrolyzing at least one non-hydrolyzed vinylsilane, each of the hydrolyzed vinylsilanes having an OR, I x Si-OR, I OH in one termination and a vinyl group in the opposite ending, wherein Rx and R2 are each selected from the group consisting of hydrogen, alkyl, and acetyl and wherein the total concentration of the non-hydrolyzed vinylsilanes used to prepare the solution of The treatment is greater than about 4% by volume, based on the total volume of the treatment solution, and wherein the pH of the treatment solution is between about 3 and about 8. The method according to claim 1, characterized in that at least the non-hydrolysed vinyl silane is selected from the group consisting of: wherein X is an alkyl group, and R3, R4 and R5 are each selected from the group consisting of: C? -C4 acetyl alkyl. 3. The method according to claim 2, characterized in that X is a Cx-Cio-4 alkyl. The method according to claim 3, characterized in that the at least vinylsilane not hydrolyzed is vinyltrimethoxysilane. 5. The method according to any preceding claim, characterized in that it further comprises the step of applying a polymer coating after the step of applying the treatment solution, the polymer is chosen from the group consisting of: paints, adhesives and rubbers, preferably paintings. 6. The method according to claim 5, characterized in that the paint is a polyester, polyurethane or epoxy. The method according to claim 5, characterized in that it further comprises the step of heat treating the sheet after the application of the treatment solution and before applying the polymer coating. The method according to any preceding claim, characterized in that the treatment solution also comprises water. The method according to any preceding claim, characterized in that the treatment solution further comprises at least one alcohol. The method according to any preceding claim, characterized in that the alcohol is selected from the group consisting of: methanol, ethanol, propanol, butane and isomers thereof. 11. The method according to any preceding claim, characterized in that the treatment solution is applied to the sheet by immersing the sheet in the solution for between about 10 seconds about one hour and the pH of the solution is between about 4 and about 6. 12. A method according to claim 2 and claim 5, characterized in that the metal sheet is a sheet of steel coated with a metal. 13. The method according to claim 12, characterized in that the steel sheet is covered by hot immersion with the metal. 14. The method according to claim 12, characterized in that the steel sheet is steel galvanized hot-dipped. 15. The method of compliance with claim 14, characterized in that the at least vinylsilane n hydrolyzate is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane vinyl ripropoxysilane, vinyl-taxhoxysilane vinylacetoxysilane, vinylmethyltrimethoxysilane vinylethyltrimethoxysilane, vinylpropyltrimethoxysilane, and N- [2 (vinylbenzylamino) -ethyl] -3-aminopropyltrimethoxysilane. 16. The method according to claim 15, characterized in that the at least vinylsilane n hydrolyzate is vinylpropyltrimethoxysilane. 17. A method for preventing corrosion of a metal foil, characterized in that it comprises the steps of: (a) providing a metal foil, the metal chosen from the group consisting of: - sheet of steel coated with a metal selected from the group consisting of of: zinc, zinc alloy, aluminum and aluminum alloy; aluminum foil; and aluminum alloy sheet; and (b) applying a treatment solution consisting essentially of at least unhydrolyzed vinylsilane to the metal sheet, the at least vinylsilane n hydrolyzate is vinyltrimethoxysilane and wherein the total concentration of the non-hydrolyzed vinyltrimethoxysilane used to prepare the solution of The treatment is greater than about 4% by volume, based on the total volume of the treatment solution, wherein the pH of the treatment solution is between approximately 3 and approximately 8. 18. A treatment solution composition characterized by consists essentially of the merchants vinylsilane not hydrolyzed, each of the vinylsilanes n hydrolysates that has in one termination and a vinyl group in the opposite ending, wherein Rx and R2 are each selected from the group consisting of hydrogen, alkyl, and acetyl and wherein the total concentration of the non-hydrolyzed vinylsilanes used to prepare the treatment solution is greater than about 4% by volume, based on the total volume of the treatment solution. 19. The composition according to claim 18, characterized in that the treatment solution also comprises water. 20. The composition according to claim 18, characterized in that the treatment solution further comprises at least one alcohol. The composition according to claim 18, 19 or 20, characterized in that the alcohol is selected from the group consisting of: methanol, ethanol, propanol, butanol, and isomers thereof. 22. The composition according to any of claims 18 to 21, characterized in that the non-hydrolyzed vinylsilane is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyl ributoxysilane, vinylacetoxysilane, vinylmethyltrimethoxysilane vinylethyltrimethoxysilane, vinylpropyltrimethoxysilane, and N- [2 ( vinylbenzylamino) -ethyl] -3-aminopropyltrimethoxysilane. 23. The composition according to any of claims 18 to 22, characterized in that the at least one non-hydrolyzed vinyl silane is vinylpropyltrimethoxysilane or vinyltrimethoxysilane.
2. 2 . The composition according to any of claims 18 to 23, characterized in that the pH is in the range of 3 to 8. The composition according to claim 24, characterized in that it has a weak acid preferably acetic acid, added to the same