Alumina-containing organosilicon resin compositions.

[Detailed Description of the Invention]

The present invention relates to a water constituent effective in preventing or controlling the corrosion of a metal base. In a certain standpoint, the present invention relates to transparent protection coating to a metal base. In another standpoint, a silicone resin matrix indicates the resin composition stable in the state of solution which is not gelled easily, without the oxide of aluminum and silicon precipitating from solution. Although, as for coating resin of a prior art, most gives corrosion prevention or the control characteristic to a metal base, these coating has often lacked required wear resistance when applying some. Therefore, it is the object of the present invention to provide a suitable constituent to coat a metal base, and prevent or reduce corrosion. It is the another object of the present invention to provide a stable water constituent. The annexation thing of various substances in which having been effective as corrosion-proof coating of a metal base was admitted was indicated. Such coating is indicated on the U.S. Pat. No. 3986997 specifications of Clark (Clark) patented on October 19, 1976, for example. Coating is Be formed from the colloid silica in a water alcoholic medium, and the annexation thing of hydrolysis alkoxysilane. Although use of resin on a metal base is mentioned in this indication, the result is not explained in full detail. A U.S. Pat. No. 4027073 specification is treatment intermediary To have about Then and the essentially same general quality of a subject at the divisional application of a U.S. Pat. No. 3986997 specification. On the U.S. Pat. No. 4275118 specification for which a special permission was granted to bunny (Baney) and Chee (Chi) on June 23, 1981, It is colloid about resin of the No. 3986997 specification of an United States patent, and the No. 4027073 specification. It is treatment intermediary To have about generation of purple outdoor daylight line absorption hardening coating used for Chita Near blending. these coating does not contain Chita Near -- receiving a metal base, since the protection against corrosion shown with a metal base by data is slightly good in comparison with the same coating of the constituent of the invention -- some protection -- intermediary To have [ To ]. In the U.S. Pat. No. 3817905 specification patented on June 18, 1974, another coating constituent which raises an operation of Shiroki Sanko Tyng who uses Silang as a base by use of Bad lead metallic powder was indicated. Organotri hydrocarbon Oxy made to hydrolyze this coating and condense Silang and formula Ti (OZ)₄Comprising the becoming hydrolytic titanium compound and granular solid, Z in a formula is a hydroxylation hydrocarbon group of a fatty series with few hydrocarbon groups of a fatty series or an aromatic series, or 20 carbon atoms, or an aromatic series. On the No. 3640093 specification and the No. 3811918 specification of an United States patent for which a special permission was granted to Levene (Levene) on February 8, 1972 and May 21, 1974, respectively, Many annexation things of Silang which has been blended with metal Alkoxide and (or) metal salt and which carried out partial hydrolysis are indicated. Formula SiX whose carbon atom of X is a Alkyl machine from one piece to six pieces in a number of ingredient and whose n is 0, 1, or a numerical value that becomes two in a specification_oY_4-oUse of becoming Silang is mentioned. However, with this specification, it is RSi (OR).₃It is Si (OR), although the example to be used is not shown, either and it is used in all the inner examples in these specifications.₄It is RSi (OR) to Instead of.₃The advantage to be used is not indicated, either. A system of these prior arts of the main differences between Levene's announcement and the present invention is non-aqueous. And these systems are the points that it is not a water colloid system, further. Although examination and an example have mentioned use of water, if it reads carefully, the only water which exists in the system of a prior art is water for hydrolysis, and it is completely clear that this is consumed during a hydrolysis reaction and the non-aqueous system which uses a solvent as a substrate remains. Levene's announcement shows the consecutive reaction method of the efforts which obtains alkoxy functionality oligomer which reacts to metal Alkoxide by their invention next. RSi (OH) whose metal of insolubility [ water ], metal alloy or metallic compounds, and R are organic groups in the European Patent application No. 0035609 specification of September 16, 1981 public notice at the last₃The coating constituent guided from a of colloidal dispersion object is indicated. RSi (OH) in which a formula selects R from the group which comprises the Alkyl machine or phenyl group from one carbon to three pieces in the present invention₃A Which intermediary and at least 10 % of the weight are CH(s).₃Si(OH)₃It comes out and is distributing in the water ―Al call solution of a certain Syros Knoll's partial condensation thing, It is a constituent which comprises the dispersing element of colloid silica and colloid acid-ized aluminum, from solids [ 1 % of the weight of ] to 45 % of the weight is contained, and the solid is essentially from 1 % of the weight of colloid acid-ized aluminum to 60 % of the weight, The water constituent containing from partial condensation things [ 35 % of the weight of ] to [ from 1 % of the weight of colloid silica to 50 % of the weight ] 90 % of the weight is provided. As mentioned above, the non-volatile solid ingredient of a constituent is a mixture of colloid silica, colloid acid-ized aluminum, and the partial condensation thing of Silang. As for Syros Knoll's partial condensation thing, R is usually CH.₃RSi (OH) which comes out and exists₃It is obtained by Condensation. It is RSi (OH) as indicated in the example.₃It generates on that spot by adding the trialkoxysilane equivalent to the acid water dispersing element of Is, colloid silica, and colloid acid-ized aluminum. In effective trialkoxysilane, it is CH at the present invention.₃Si(OCH₃)₃,CH₃Si(OC₂H₅)₃,C₂H₅Si(OCH₃)₃,C₆H₅Si(OCH₃)₃,C₂H₅Si(OC₂H₅)₃And C₃H₇Si(OCH₃)₃of -- Silang [ like ] is included. The most desirable trialkoxysilane for the present invention is CH.₃Si(OCH₃)₃It comes out. If these Silang is contacted in water, it will separate the alcohol which is equivalent to a catalyst precursor alkoxy group in response to a hydrolysis reaction, and will become corresponding Alkyl or Aryl silanol. The alcohol component which exists in the constituent of the present invention is carried out in this way, and is generated. A silanol group is condensed continuously, forms a siloxane bond, and generates a low-molecular quantity hydroxy content polymer for hydroxy content oligomer from it first at the same time Syros Knoll generates. Without [ therefore ] going on until it completes condensation, the substance which is carried out in this way and generated will have many hydroxy groups combined with the silicon atom, and, as a result, Shiroki Sun will dissolve in an alcoholic aqueous agent. If these Shiroki Sun hardens, a hydroxyl machine will be condensed, and they are silsesquioxane and RSiO._3/2, is generated. Generally the diameter of a colloid silica component is a water dispersing element of the particle size of the range from 5mmicro to 30mmicro. In this industry, a silica dispersing element can be manufactured by the well-known method, and can obtain the commercial item of a brand name like "Rudtzsk (Ludox)" and "Narcoag (Nalcoag)." "Rudtzsk" is manufactured at Delaware (Delaware), U.S., and E eye Du Pont de Nemours (E. I.duPont de Nemours and Co., Inc.) of Wilmington (Wilmington). "Narcoag" is manufactured at the Nalco chemical company (Nalco Chemical Company) of Illinois (Illinois), U.S., and Oak Brook (Oak Brook). It is preferred that a particle size uses the colloid silica from 10mmicro to 20mmicro. These substances can obtain the hydrosol of basic and acid both. Colloid silica is SiO of other forms of dispersibility to water like non-granulating poly silicic acid or alkaline metal silicate solution.₂What's -- distinction sticks. An effective aluminum oxidation thing is a colloid aluminum oxidation thing in the present invention. These substances can obtain a commercial item. One of such the substances is colloid acid-ized aluminum of sale by registered trademark Nalco ISJ-614. This aluminum oxide can be obtained at 10 % of the weight of underwater concentration, and a particle size is about 2mmicro. Generally these aluminum oxide solution means that PH is [ Then and this ] completely useful for the present invention immediately in the acid range. aluminum of versatility [ aluminum / colloid acid-ized ] again for example doria -- it can also manufacture by the well-known method in this industry from Leucoxide. Low-grade fatty series alcoholic solution is made to distribute colloid silica and an aluminum oxide in the solution into which the partial condensation thing was put for the present invention. In suitable low-grade fatty alcohol, methanol, ethanol, n ―Propanol, isopropanol, n ―Butanol, Iso― butanol, and the third butanol are included. The mixture of these alcohol is preferred, although it can be used and the present invention is actually carried out. When using a constituent for coating, it is preferred to use 50 % of the weight of isopropanols at least into an alcoholic mixture, and to make wearing of coating the optimal. When using a constituent as coating to a metal base, it is also preferred to use a polar coexistence solvent. In such polar solvents, they are monoethyl ether acetic acid glycol and ethylene glycol. Although dimethyl ether etc. are included, it does not limit to this. A solvent system is made to contain the alcohol from about 20 % of the weight to 75 % of the weight, and the solubility in the inside of the constituent of a partial condensation thing should be secured. Depending on the case, an alcoholic above-mentioned solvent and polar solvents with water miscibility another together can be used. These solvents should use 20% of the weight of the solvent in small quantities. Then of these solvents is also good at acetone, butyl cello Sorb, methyl ethyl ketone, etc., for example. Generally a constituent is RSi (OCH).₃)₃of -- generally trialkoxysilane [ like ] is added and manufactured to water colloid silica and colloid acid-ized aluminum by PH lower than 7. When there is already no PH of sol in the acid range, in order to maintain sol stably, it is preferred to add one of organic or inorganic acid to sol, and to make it PH of the acid range. In higher PH, it is publicly known that early gelling tends to take place. for example, PH makes a system gel within 1 hour in about 10.5 -- on the other hand -- PH -- about 8 -- both solid ingredients -- comparatively -- a fixity solid -- comparatively -- and -- in several hours or several days, depending on the situation of a solvent system currently used, sol is stability -- intermediary To have. However, when a reaction object is contacted first and hydrolysis takes place, it is preferred to maintain a system into acidity. Since the one where PH is lower promotes maintenance of the stability of a constituent, such acid PH should be preferably made less than 5. That is, before mixing an ingredient, acid can be added to either Silang or a colloid substance. the present invention -- an intermediary -- an effective thing is organic acid [ like formic acid and acetic acid ] whose I and Acid are, or mineral acid like chloride. It is hydrolyzed and the alkoxy group of Silang generates corresponding alcohol at the same time it contacts water in existence of acid. An additional solvent or water can be added to a constituent, and the solid in the last constituent can be made into a desired percentage. For hydrolysis of alkoxysilane, it generates heat slightly at the time of mixture. Since the alcohol of suboutput carries out azeotropy after all and cools the reaction principal part even though it is, generation of heat is controlled easily. Probably, it will be preferred to add cooling. A reaction mixture should be mixed enough, and it should be made to ripe for a short time, and the partial condensation thing should be made to generate certainly. At this time, the constituent is clear, or it is Floating(ing) slightly, and viscosity is low. When it is going to use a constituent as coating, milder curing conditions can be used, and a buffering potential condensation catalyst can be added to a constituent so that the last coating can be made into the optimal frictional resistance. Alkali metal salt of carboxylic acid like potassium formate is one kind of such a potential catalyst. Amine Carboxylate salt and the fourth ammonium carboxylate salt are the another kind of such a potential catalyst. needless to say -- a catalyst -- a coexistence solvent system -- solubility -- or it must be miscibility at least. At room temperature, a catalyst is not shortened so that the bath life of a constituent can be accepted, but a constituent is the latency of the grade hardened simultaneously with heating. A buffering catalyst is used for avoiding the operation exerted on PH of a constituent. The colloid silica dispersing element of a certain kind which can obtain a commercial item contains the alkali-metal-salt machine of organic acid and the isolation which generates [ be / it / under / adjustment / of PH / reaction ] a carboxylate salt catalyst on that spot. This guesses right, especially when PH begins using the sol of 8 or 9. Dimethylamine acetate, ethanol amine acetate, Dimethyl aniline Formate Carboxylate salt like carbolic acid tetraethyl ammonium, acetic acid sodium, sodium propionate, sodium formate, or benzyl acetate trimethylammonium can be added, and a catalyst can be made to act on a constituent. although the quantity of a catalyst can be changed based on desired curing conditions -- a catalyst -- the inside of a constituent -- about 1.5 % of the weight -- a bath life -- short Nuclear -- and the coating optical characteristic may be spoiled. It is preferred to use the catalyst from about 0.05 % of the weight to 1 % of the weight. In order to make stability of a dispersing element into the maximum at the same time it makes hardening output into the optimal characteristic, It is based on the solid in which it is preferred with which that PH uses Then and the constituent containing the solid from 5 % of the weight to 25 % of the weight for the ranges from 4 to 5, and a silica component exists in a mixture, It exists from 5 % of the weight to 28 % of the weight, and a particle size is a range from 5mmicro to 30mmicro, and colloid acid-ized aluminum exists on the basis of a total solid from 2 % of the weight to 25 % of the weight, and a particle size is a range from 10mmicro to 20mmicro, and it is CH.₃Si(OH)₃Partial condensate exists in methanol, isopropanol, and the coexistence solvent of water in the quantity of within the limits from 70% of the weight of a total solid to 90 % of the weight, and alcohol is from 30% of the weight of a coexistence solvent to 60 % of the weight. As for a catalyst, when asking for the catalyst for coating constituents, it is preferred to select from the group which comprises acetic acid sodium and benzyl acetate trimethylammonium, and to exist in the quantity from 0.05% of the weight of a constituent to 1 % of the weight. Such a constituent is comparatively stable and Then and the bath life can generate surface coating which it will be made to harden comparatively at the temperature of the range from 50degreeC to 150degreeC for a short time if There and a base are coated for about one month, and has transparent wear resistance, and has corrosion resistance. The coating constituent of the present invention can be poured, can be applied to a metal base by a usual method like spraying or immersion, and can make a continuation surface film. A constituent can be applied to other bases like wood, a plastic, the printing surface, the skin, glass, ceramics, and textiles although a metal base is improved to the utmost by the application of coating. A plastic like acrylic or poly carbonic ester glasses A lens can be coated with the constituent of the present invention. In the fixed application which needs advanced optical resolving, before applying a coating constituent to a base, it is sometimes preferred to filter this. In application like corrosion-proof coating to metal, since the slight cloudy weather (5% or less) which arises since a fixed prescription article like the prescription article containing citrate and sodium acid citrate was used is not harmful, it is not necessary to filter. Coating can be substantially stuck on the surface of all the solids by selecting an appropriate prescription which includes a pretreatment (it is an implication about use of a primer) of a solvent, application conditions, and a base. By removing a solvent and volatile matter, it can be made hard solvent resistance surface coating. If a constituent is air-dried, it will be in the state where there is no adhesiveness, but in order to make remains Syros Knoll in a partial condensation thing condense, the range from 50degreeC to 150degreeC needs to be heated. It is this last hardening and a formula is RSiO._3/2of silsesquioxane will be generated and wear resistance of coating is reinforced remarkably. Although the thickness of coating can be changed by a peculiar application technique, generally thickness uses coating from 2micro to 10micro preferably from about 0.5micro to 20micro. It can be especially made thin coating by spin coating. The following example is a thing for explanation, and evaluated the constituent using the following test method. Corrosion test The used corrosion test is a copper-acetic acid promotion salt spray test (the Copper-acetic-acid Accelerated Salt Spray[CASS] test) given in ASTM B-368. As for examination solution, the sodium chloride of 3.2±1 (it adjusts by addition of acetic acid) is 5±1% of the weight of solution, and PH which contains the second copper 1g of chlorination per 1 gallon of examination solution is Oh. Resin of the experimental object was coated, and in the testing laboratory, the stiffened metal panel was abbreviation 15 * Leaned from Vertical, and then was exposed to a detailed fog of examination solution during various time by temperature 120 *±2 *F. The end of the panel was protected with the waterproof tape. 1.5±0.5 ml of solution is 1 hour, and it is 80 cm.²of -- the density of fog was adjusted so that it might be brought together in a level area. Time to expose to fog was changed, the panel was examined, and corrosion was observed. By a predetermined sample, once corrosion starts, corrosion will advance quickly and will cover the great portion of surface of a panel. The used metal panel (3 inch x4.5 inch x0.025 inch) is aluminum by Ohio (Ohio), U.S., and the Kew panel company (Q-Panel Co.) of Cleveland (Cleveland), and is Oh. EXAMPLE Triisopropoxy It is CH about 0.5 g of aluminum.₃Si(OCH₃)₃It mixes with 8.7 g, acetic acid 0.2g, 9.1 g of isopropanol, water 4.0g, 1.0 g of 2 ―Butoxy ethanol, and 1.5 g of Narcoag 1034A colloid silica (Nalco chemical company manufacture of Illinois, U.S., and Oak Brook, 34% of solid), and is weight ratio aluminum.₂O₃/CH₃SiO_3/2/SiO₂Resin of But 2.5 / 87.1/10.3 was manufactured. The opaque resin composition which contains To shake and about 20 % of the weight of solids for these substances together for several minutes in a small glass bottle was obtained. The aluminum panel was coated with this substance and it was made to harden by 120 degreeC for 6 hours. CH using the panel which carried out the double-sided application, examine a panel by the CASS examining method, and non-according to the present invention₃SiO_3/250 % of the weight of colloid silica and CH independent of resin containing Only, and another present invention₃SiO_3/2It compared with resin containing 50 % of the weight. Both the resin compositions (CH) independent of the present invention₃SiO_3/2Resin and CH₃SiO_3/2/SiO₂After exposing resin for 48 hours, it showed corrosion. The constituent by the present invention (a ratio is aluminum of 2.5/87.1/10.3)₂O₃/CH₃SiO_3/2/SiO₂After exposing resin by CASS examination for 72 hours, it showed corrosion slightly. aluminum of weight ratio 2.6 / 77.1/20.3₂O₃/CH₃SiO_3/2/SiO₂The resin to contain was manufactured and it examined in the similar way. Aluminum which coated with hardening resin A panel began to show corrosion by CASS examination in 48 hours.