GB1593217A - Coating composition - Google Patents

Description

(54) COATING COMPOSITION (71) We, UNION CARBIDE CORPORATION, a corporation organized and existing under the laws of the State of New York, United States of America, whose registered office is, 270 Park Avenue, New York, State of New York 10017, United States of America. (Assignees of THOMAS GINSBERG, LAWRENCE GEORGE KAUFMAN), do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- Background of the Invention This invention pertains to single-package zinc-rich coatings and more particularly to blends of zinc, partially hydrolyzed alkyl silicates and an arninosilane.

Zinc-rich coatings are effective in protecting steel against corrosion. The principle of this protective action is attributed to the fact that zinc, being higher than iron in the electromotive series of the elements reacts first in any environment conducive to the ionic dissolution (oxidation) of metals, thereby protecting the steel substrate.

As the name implies, zinc-rich coatings contain a high concentration of zinc in the dry film. This is required so as to provide the electrical continuity and, therefore, the conductivity necessary for the electro-chemical process to take place.

In order to obtain these zinc-rich coatings on a ferrous substrate, a paint formulation containing very fine zinc dust produced by distilling the metal under controlled conditions of condensation is used. When the paint is applied, the metallic powder is held in place on the surface by a binder matrix. Zinc-rich coatings are classified, according to the nature of the binder, into organic or inorganic coatings.

Organic zinc-rich coatings utilize synthetic polymers as binders, Although such coatings afford effective corrosion protection, their heat and solvent resistance are limited.

Inorganic binders do not have these limitations. Such binders include water soluble silicates, which are insolubilized by a curing composition after application, and alkyl silicates which do not require post cure. Although alkyl silicates contain organic chains, the resulting zinc-rich coatings are classified as inorganic because it is believed that, upon drying, a totally inorganic matrix of SiO2 is formed. This reaction takes place slowly and proceeds through continuous stages of hydrolysis.

The alkyl silicates that may be used in zinc-rich coatings may vary in their level of hydrolysis. If an alkyl silicate having a very low level of hydrolysis is used, the curing reaction is so slow that the film remains uncured for prolonged periods of time. Using alkyl silicates hydrolyzed to higher levels reduces the time necessary to obtain dry films. Unfortunately as the drying time decreases due to the higher degree of hydrolysis, the stability of the product in turn decreases. This lower stability is manifested in various ways. One is an increasing tendency for the paint to gel in the container upon storage. Another is a diminished pot life when alkyl silicate is mixed with the zinc dust in which case gelling usually occurs in a few hours.

One way to avoid instability of the paint composition in the container and premature gellation with the zinc, is to package the zinc separately from the alkyl silicate and mix the two components just prior to application.

This is done commercially in the so-called 2-package zinc-rich coating compositions and the field has adapted its working methods to this characteristic of the product or paint used to provide the coatings. However, the problems inherent in a 2-component coating composition, viz., doubled production, warehousing, stocking and inventory, as well as metering and mixing on site coupled with limited pot life makes a single-component zinc-rich paint primer composition very desirable.

If zinc-rich coatings are made with alkyl silicates of low degrees of hydrolysis.

stability of the alkyl silicate in its container as well as the pot life of primer composition after addition of the zinc dust to the alkyl silicate improves considerably. The price of this improved stability, however, is a much lengthened drying time. The problem facing the formulator is therefore how to obtain curing of a single-package alkyl silicate, zinc-rich paint primer composition in a reasonably short time, while maintaining good package stability in conjunction with nonreactivity of the alkyl silicate with the zinc dust.

Several proposed solutions for this problem have been put forth in the prior art. Thus, for example in U.S. 3,653,930 a single-package, zinc-rich coating was obtained by the addition of low molecular weight amines to ethyl silicate hydrolyzed to about 40% together with nitro compounds to prevent gassing. The same general approach was also described in Netherlands Patent No. 6,900,729.

In U.S. 3,660,119 film formation of a 40% hydrolyzed alkyl silicate was obtained through the use of strong bases, such as, sodium or potassium methoxide or ethoxide.

U.S. 3,859,101 discloses use of zinc chromate instead of nitro compounds as anti-gassing additives in a mixture of alkyl silicate and zinc dust.

U.S. 3,917,648 utilizes a reaction product of alkyl silicates with polyols to form a product which is stable in the presence of zinc.

U.S. Serial No. 710,737 provides a single package alkyl silicate-zinc primer composition containing fatty and amido amines to impart stability.

The prior art references recited above suffer the following disadvantages: 1. Low molecular weight amines are volatile and therefore alkyl binders containing them lose effectiveness upon storage.

2. Low molecular weight amines are water-soluble therefore introducing a factor of water sensitivity into a coating primarily intended for corrosion protection.

3. Low molecular weight amines have high chemical reactivity. Thus they react with acids such as those produced by absorbed carbon dioxide during storage.

This may account for their loss of effectiveness with time.

Low molecular weight amines present in the coating formed on the ferrous substrate have adverse effects on the resistance of the zinc-rich film to environmental agents and interfere with the adhesion and chemical resistance of top coats applied to the primer coat.

5. Low molecular weight amines are toxic, representing a potential safety hazard to those coming in contact with the coating compositions.

6. Strong bases such as alkali metal alkoxides or their corresponding hydroxide by-products adversely affect a metal of amphoteric character such as zinc.

7. The alkali metal alkoxides or their corresponding hydroxide by-products remain in the zinc-rich film formed on the ferrous substrate, introducing an element of water and chemical sensitivity which may affect the performance of top coats applied to the primer coat.

8. Polyol silicate zinc-rich coatings produce films which are softer than desirable.

According to the present invention there is provided a composition for protecting ferrous metals from corrosion, comprising particulate zinc, an unhydrolyzed or a partially hydrolyzed organic silicate and a hardening amount of hydrolyzable silicon compound selected from: (a) aminosilanes of the formula:

wherein: t is an integer having values of 0 to 10; each of M, Y, Q and Z are R or

R is H, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 2 to 3 carbon atoms, R' is -C2H4-, C3H6- or -R2-O-R2- and R2 is an alkylene radical having 1 to 8 carbon atoms; a is an integer having values of 1 to 3; b is 0, 1 or 2 and the sum of a+bA3; with the proviso that at least one of M, Q, Y or Z is

X is an hydrolyzable organic group; (b) quaternary ammonium salts of the aminosilanes in (a); and (c) the hydrolyzates and the condensates of the aminosilanes in (a).

The hydrolyzable organic group X may be, for example, an alkoxy group or an alkoxyalkyl group e.g. -OC2H4OCH3. Preferred values of R and H and CH3 and preferred values of a and b are 1 and 0 respectively. The organic silicate may be, for example, an alkoxyalkylpolysilicate e.g. ethoxyethylpolysilicate or a tetra-alkyl orthosilicate e.g. tetraethyl orthosilicate.

The hydrolyzable silicon compound for use in the compositions of this invention may conveniently be selected from (a) amino silanes is of the formula

wherein: t isO, 1, 2 or 3, a is an integer having values of 1 to 3, b is O, 1 or 2, and the sum of a+b is 43.

each of R is H, alkyl having I to 4 carbon atoms or hydroxyalkyl having 2 to 3 carbon atoms, R1 is -C2H4-, C3H6-, or -R3 -O-R3-, wherein R3 is an alkylene radical having 1 to 8 carbon atoms, R4 and R5 are each H or -CH3, and X is a hydrolyzable organic group; (b) quaternary ammonium salts of the aminosilanes in (a); and (c) the hydrolyzates and condensates of the aminosilanes in (a).

The zinc-rich coating composition containing an alkyl silicate may be used as a primer paint coating composition and may remain stable when packaged for prolonged periods of time. The coating compositions of the invention which upon application to a ferrous substrate may rapidly form a dry, hard, corrosion-resistant protective primer film.

The compositions described above are stable for prolonged periods of time in a closed container. Thus separate packaging is not required. When applied on a ferrous substrate, the zinc-rich formulations dry rapidly with the result that a hard, continuous, smooth film is formed having excellent corrosion protecting properties.

The alkyl silicates used in this invention are known in the art comprising unhydrolyzed alkyl and alkoxyalkyl silicates and alkyl and alkoxyalkyl silicates hydrolyzed up to about 40 per cent by weight. Alkyl silicates are produced by the reaction of silicon tetrachloride and alcohols and alkoxy alcohols, generally in a reactor equipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-product is removed by reflux which may be carried out at reduced or atmospheric pressure. Through this process, the most common products TEOS (tetraethylorthosilicate), and Cellosolve (Trademark of the Union Carbide Corporation for monoalkyl ethers of ethylene glycol) silicate are made.

Subsequently these products may be partially hydrolyzed by the addition of water and an acid catalyst. The amount of water added determines the degree of hydrolysis in the final product. Commercially available products derived from ethanol include the unhydrolyzed TEOS, Condensed Ethyl Silicate (about 7 per cent hydrolysis), Ethyl Silicate 40 (40 per cent hydrolysis containing 4Q SiO2), and Ethyl Silicate P-18, having an 80 to 85 per cent hydrolysis level.

The hydrolyzable silicon compounds used in this invention are also known in the art and include a wide variety of compounds. Typical examples are gammaaminopropyltriethoxysilane having the formula:

and N - beta(aminoethyl) - gamma - aminopropyltrimethoxysilane having the formula:

Other exemplary aminosilanes include:: aminomethyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-methylaminopropyltrimethoxysilane, gamma-aminopropyltripropoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylethyldiethoxysilane, gamma-aminopropylphenyldiethoxysilane, gamma-aminoisobutyltrimethoxysilane, delta-aminobutyltriethoxysilane, delta-aminobutylmethyldiethoxysilane, beta-aminoethyltriethyoxysilane, epsilon-aminopentylphenyldibutoxysilane, N - (beta - aminoethyl) - gamma - aminopropyltrimethoxysilane, N - (beta - aminoethylaminoethyl) - gamma - aminopropyltrimethoxysilane, N - (gamma - aminopropyl) - gamma - aminoisobutylmethyldiethoxysilane, N - (beta - aminoethyl) - gamma - aminopropyltriethoxysilane.

In addition to the above-enumerated aminosilanes which contain one silane group one can also use related aminosilanes containing two or more silane groups.

Representative examples are: N - (beta[N' - gamma(trimethoxysilylpropyl) - amino - ethyl] - gamma aminopropyltrimethoxysilane

N,N - betatbislN' - gamma - (trimethoxysilylpropyl)aminoethyli - gamma aminopropyltrimethoxysilanel

and N,N - beta[bis(N',N' - gamma - bis(trimethoxysilylpropyl)aminoethyl)} gamma - aminopropyltrimethoxysilane]

A typical preparation of an alkoxysilylpropylamine is contained in U.S.

2,832,754 wherein gamma - chloropropyltriethoxysilane and liquid ammonia in a ratio of about 1 to 20 are charged into a pressure vessel heated at a temperature of about 100"C. for 12 hours. After cooling, filtering, washing and fractionally distilling the mixture approximately 50 per cent of the desired product is obtained.

Another method for the preparation of aminoalkyl - trialkoxysilane is described in U.S. 2,930,809 wherein a cyanoalkyltrichlorosilane described in U.S.

2,837,551 is prepared followed by alcoholysis and hydrogenation. For example, hexachlorodisilane and acrylonitrile in a 1:1 molar ratio are sealed in an autoclave heated to a temperature of about 200"C. for 2 hours. One of the products obtained upon fractional distillation of the mixture is beta-cyanoethyltrichlorosilane.

Ethanolysis of this compound yields beta - cyanoethyltriethoxysilane. The latter compound is charged to a stainless steel pressure vessel together with Raney nickel. The temperature of the vessel is then cooled to -780C. and an excess of liquid ammonia added. Hydrogen gas is charged into the system and the mixture heated at a temperature of 100"C. for 16 hours in a rocking autoclave. The mixture is then cooled to room temperature, filtered, washed with diethyl ether and fractionally distilled. One of the products obtained is triethoxysilylpropylamine.

The hydrolyzates and condensates of the aminosilanes described above can be prepared by the conventional known methods of hydrolysis and condensation. As is well known in the art, hydrolyzates represent the metathetical reaction products of water and corresponding hydrolyzable aminosilanes, while condensates represent the siloxane products obtained upon condensation of the hydrolyzate reaction mixture. The amount of water employed is not critical and merely depends upon the degree of hydrolysis and condensation desired. Accordingly, completely hydrolyzed as well as partially hydrolyzed products can be provided.

The preparation of quaternary salts of aminosilanes is disclosed in U.S.

3,389,160 incorporated herein by reference.

The term "hardening amount of a hydrolyzable silicon compound" is used in this invention to mean an amount sufficient to afford a dry film of the coating composition when placed on a ferrous substrate under ambient conditions. It has been found that at least 5% by weight of hydrolyzable silicon compound, based on the weight of partially hydrolyzed organic silicate, is required to obtain a dry film within a practical exposure time, that is, in about 5 to 10 minutes. There is no critical upper limit but for practical purposes there is no advantage in using more than 50% by weight of hydrolyzable silicon compound. It is preferred to use 15 to 45% by weight of hydrolyzable silicon compound.

Although not essential for the practice of this invention, it is preferred that metal protective compositions of this invention include a water scavenging agent.

Suitable water scavenging agents are, for example, zeolites, silica gel, tetra-alkyl silicates, and trialkyl borates. Zeolites are preferred because unlike the others given above the scavenging or water removal action does not produce a reaction product.

The zeolite water-scavenging agent can be any of the well known threedimensional crystalline zeolites of the molecular sieve type, either naturallyoccurring or synthetically prepared by conventional hydrothermal crystallization, and which have pore dimensions large enough to permit the passage of water molecules. Typical of the naturally occurring zeolites are clinoptilolite, chabazite, gmelinite, mordenite, erionite, offretite, phillipsite and faujasite. Illustrative of the synthetic molecular sieve zeolites are zeolite A, U.S.P. 2,882,243; zeolite X, U.S.P.

2,882,244; zeolite R, U.S.P. 3,030,181, zeolite S, U.S.P. 3,054,657; zeolite T, U.S.P.

2,950,952; zeolite F, U.S.P. 2,996,358; zeolite B, U.S.P. 3,008,803; zeolite M, U.S.P.

2,995,423; zeolite H, U.S.P. 3,010,789; zeolite J, U.S.P. 3,011,809; zeolite Y, U.S.P.

3,130,007; and zeolite L, U.S.P. 3,216,789. Advantageously the zeolite selected will have a framework molar SiO2/A12O3 ratio of less than 50, and preferably less than 20, since the highly siliceous zeolites tend to exhibit organophilic properties to the detriment of their hydrophilic characteristics. Particularly suitable, because of their extremely high water-sorption capacity are the various cation forms of zeolite A. The potassium cation form of zeolite A, moreover, has an effective pore diameter of between 3 and 4 Angstroms and thus is capable of readily adsorbing water but effectively excludes most other molecules in the system on the basis of molecular size.

For use as adsorbents, the zeolites should be at least partially dehydrated, preferably fully dehydrated, by heating in air or vacuum at moderate temperatures of 250 to 3500C. for several hours. Since zeolite crystals are small, seldom larger than 10 micrometers, they can suitably be admixed in the coating compositions without adversely affecting its essential properties. Alternatively, the zeolite crystals can be formed into shaped agglomerates with conventional binders such as clays and enclosed in the container in which the product is stored.

The invention is described in the Examples which follow.

All parts and percentages are by weight unless otherwise specified.

Example 1 Single-package Zinc-rich Coating with Ethyl Silicate 40 and Gamma aminopropyltriethoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40 per cent by weight of SiO with 5 grams of gamma - aminopropyltriethoxysilane and 30 grams of finally divided zinc having a particulate size of about 2 to about 15 microns (American Smelting and Refining Co. ASARCO L-15).In addition, in order to maintain the mixture in an anhydrous state, 5 grams of a water scavenging agent (Union Carbide Corp. molecular sieves 4 A) were added and the composition was thinned with 50 grams of a hydrocarbon solvent consisting of a mixture of 61% by volume of paraffinics and 39% by volume of naphthenics having a boiling range of about 158--196"C. of (American Mineral Spirits Company Mineral Spirits 66-3). The resultant liquid protective coating or primer paint had a package stability of over six months.

When this paint was applied by spraying to sand blasted, cold-rolled steel panels measuring approximately 4 inches by 4 inches by 1/8 inch, there was obtained a smooth film which dried in less than ten minutes. The steel panel so coated was subjected for 1000 hours to salt spray (ASTM Method B-l 17) and 1000 hours in fresh water immersion (ASTM Method B-870). There was no evidence of corrosion or other signs of failure on the panel so coated.

Example 2 Single-package Zinc-rich Coating with Ethyl Silicate 40 and N-beta-(aminoethyl) gamma-aminopropyltrimethoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% by weight of SiO2 with 5 grams of N - beta(aminoethyl) - gamma - aminopropyltrimethoxysilane and 300 grams of finely divided zinc dust (ASARCO L-15), 5 grams of a water scavenging agent (Union Carbide molecular sieves 4A) and 50 grams of Amsco Mineral Spirits 66-3.

The resultant primer paint was stable for over six months in storage. When applied to sand blasted steel panels as in Example 1, the coating dried to a hard film in less than ten minutes. When these panels were subjected to a salt spray and water immersion for 1000 hours, they showed no evidences of corrosion or other failure.

Example 3 Single-package Zinc-rich Coating with Tetraethylorthosilicate and N-beta(aminoethyl)-gamma-aminopropyltrimethoxysilane A ferrous metal protective composition was prepared by mixing 45 grams of tetraethylorthosilicate with 5 grams of N- beta(aminoethyl) - gamma aminopropylmethoxysilane and 300 grams of ASARCO zinc dust L-15, 5 grams of molecular sieves 4A, and 50 grams of Amsco Mineral Spirits 66-3. The resultant primer paint was stable in storage for over six months. When applied as a spray coating to a sand blasted steel panel, a dry film formed in less than ten minutes.

When panels were exposed as in Example 1 for 1000 hours in the salt spray and water immersion test, there was no evidence of corrosion or other failure.

Example 4 Single-package Zinc-rich Coating with Cellosolve Silicate and Gamma-aminopropyltriethoxysilane A ferrous metal protective paint primer composition was prepared by mixing 45 grams of partially hydrolyzed ethoxyethylpolysilicate containing 19% SiO2, 5 grams of gamma - aminopropyltriethoxysilane, 300 grams of ASARCO L-15 zinc dust, 5 grams of molecular sieves 4A and 50 grams of Amsco Mineral Spirits 66-3.

The resultant primer paint composition had a package stability of over six months.

When applied as a spray over sand blasted panels, the composition dried to a hard film in less than ten minutes. The panels, when subjected to the salt spray and water immersion test described in Example 1 for 1000 hours, showed no evidence of corrosion or other failures.

Example 5 Single-package Zinc-rich Coating with Tetraethylorthosilicate and Poly(aminoalkyl)dimethylpolysiloxane A ferrous metal protective composition was prepared by mixing 45 grams of tetraethylorthosilicate with 5 grams of a poly(aminoalkyl) dimethylpolysiloxane, 300 grams of ASARCO zinc dust L-15, 5 grams of molecular sieves 4A, and 50 grams of Amsco Mineral Spirits 66-3. The resultant paint was stable in storage for over six months. When this coating composition was applied to sand blasted steel panels, it formed a dry film in less than ten minutes. When similar panels were exposed for 1000 hours to salt spray and water immersion as in Example 1, there was no evidence of corrosion or other failure.

Example 6 Single package Zinc-rich Coating with Ethyl Silicate 40 and an Aminoalkylalkylalkoxysilane A ferrous metal protective composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40 weight % of SiO2 with 5 grams of an aminoalkylalkylalkoxysilane (Union Carbide Silane A-1902), 300 grams of ASARCO zinc dust L-15, 5 grams of molecular sieves 4A and 50 grams of Amsco Mineral Spirits 66-3. The resultant paint was stable for over six months on storage.

When this coating composition was applied to sand blasted steel panels, it formed a dry film in less than ten minutes. When similar panels were exposed for 1000 hours to salt spray and water immersion as in Example 1, there was no evidence of corrosion or other failure.

Example 7 Single package Zinc-rich Coating with Cellosolve Silicate and N-beta (aminoethyl)gamma-aminopropyltrimethoxysilane A ferrous metal protective composition was prepared by mixing 45 grams of partially hydrolyzed ethoxyethylpolysilicate, containing 10% SiO2, 10 grams of N beta(aminoethyl) gamma - aminopropyltrimethoxysilane, 300 grams of ASARCO zinc dust L-15, 5 grams of molecular sieves 4A, and 50 grams of Amsco Mineral Spirits 66-3. The resultant paint was stable upon storage for over six months. When this coating composition was applied to sand blasted steel panels, it formed a dry film in less than ten minutes. When similarly coated panels were exposed for 1000 hours to salt spray and water immersion, as in Example 1, there was no evidence of corrosion or other failure.

Example 8-11 Single package Zinc-rich Coatings with Ethyl Silicate 40 and Varying Concentrations of N-beta(am inoethyl)gamma-aminopropyltrimethoxysilane Ferrous metal protective compositions were prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% by weight of SiO2, 2 grams of molecular sieves 4A, 300 grams of ASARCO zinc dust L-15 and 2, 5, 10 and 20 grams respectively of N - beta(aminoethyl) gamma aminopropyltrimethoxysilane. In each Example the resultant paints were stable for over six months. When these paints were applied to sand blasted steel panels, they formed dry films in less than ten minutes. When similarly prepared panels were exposed for 1000 hours to salt spray and water immersion, as in Example 1, there was no evidence of corrosion or other failure.

Examples 12-15 Single package Zinc-rich Coatings with Varying Ratios of N-beta(aminoethyl) gamma-aminopropyltrimethoxysilane and Mica Ferrous metal protective compositions were prepared by mixing the following components: EXAMPLE Component 12 13 14 15 ASARCOZincDustL-15 600g 600g 600g 600g Mica 40g 40g 40g 40g Molecular Sieve 4A 4g 4g 4g 4g Partially hydrolyzed ethyl silicate containing40%SiO2 109g 105.5g 102g 98.5g Union Carbide Silicone A-1120'"' lg 22.5g 33g 45g (a) N - beta(aminoetlhyl) gamma - aminopropyltrimethoxysilane.

The resultant paints were stable for over six months. The resultant paints when applied to sand blasted panels formed a dry film in less than ten minutes. These coated panels when exposed for 1000 hours to salt spray and water immersion, as in Example 1, showed no evidence of corrosion or other failure.

Example 16 Single package Zinc-rich Coating with Ethyl Silicate 40 and N-(beta-ethylene diaminoethyl)-beta-aminoethyltrimethoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicates containing 40% SiO2, 10 grams of N (beta - ethylenediaminoethyl) - beta - aminoethyltrimethoxysilane, 300 grams of ASARCO zinc dust L-15, and 5 grams of molecular sieves 4A. The resultant paint was stable for over six months.

When the resultant coating composition was applied to sand blasted steel panels, a dry film was obtained in less than ten minutes. Panels so coated and subjected to salt spray and water immersion, as in Example 1, showed no evidence of corrosion or other failure.

Example 17 Single package Zinc-rich Coating with Ethyl Silicate 40 and Gamma-N-(gamma butylamino)propyltrimethoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% SiO2, 10 grams of gamma N - (gamma - butylamino)propyltrimethoxysilane, 300 grams of ASARCO zinc dust L-15, and 5 grams of molecular sieves 4A. The resulting paint was stable for over six months.

When this coating was applied to a sand blasted steel panel, a dry film was obtained in less than ten minutes. These panels, so coated, and subjected to salt spray and water immersion, as in Example 1, showed no evidence of corrosion or other failure.

Example 18 Single package Zinc-rich Coating with Ethyl Silicate 40 and N,N-beta-(bis hydroxyethyl)gamma-aminopropyltriethoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% SiO2 with 10 grams of N,N beta - (bis - hydroxy - ethyl) - gamma - aminopropyltriethoxysilane, 300 grams of ASARCO zinc dust L-15, and 5 grams of Molecular Sieves 4A. The resultant paint was stable for over six months.

When this coating was applied to a sand blasted steel panel, a dry film was obtained in less than ten minutes. Panels so coated subjected to salt spray and water immersion for 1000 hours, as in Example I, did not show evidence of corrosion or other failure.

Example 19 Single package Zinc-rich Coating with Ethyl Silicate 40 and Polyaminoalkyltrialkoxysilane A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% SiO2 with 10 grams of polyaminoalkyltrialkoxysilane, 300 grams of ASARCO zinc dust L-15, and 5 grams of molecular sieves 4A. This paint was stable for over six months.

When this coating was applied to a sand blasted steel panel, a dry film was obtained in less than ten minutes. Panels so coated subjected to salt spray and water immersion for 1000 hours, as in Example 1, did not show evidence of corrosion or other failure.

Example 20 Single package Zinc-rich Coating with Ethyl Silicate 40 and Gamma-N,N dimethylammoniumpropyltrimethoxysilane Acetate A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% SiO2 with 10 grams of gamma - N,N - dimethylammoniumpropyltrimethoxysilane acetate, 300 grams of ASARCO zinc dust L-15, and 5 grams of Molecular Sieves 4A. The resulting paint was stable for over six months.

When this coating was applied to a sand blasted steel panel, a dry film was obtained in less than ten minutes. Panels so coated subjected to salt spray and water immersion for 1000 hours, as in Example 1, did not show evidence of corrosion or other failure.

Example 21 Single package Zinc-rich Coating with Conductive Extender Pigment A ferrous metal coating composition was prepared by mixing 45 grams of partially hydrolyzed ethyl polysilicate containing 40% SiO2 with 5 grams of Union Carbide Silane A-l 120, 200 grams of ASARCO zinc dust L-15, 100 grams of ferrous phosphite (an electrically conductive extender pigment available commercially as "Ferrophos" 2131, from Hooker Chemical Co., with a mean particle size of 6 microns), 5 grams of molecular sieves 4A, and 50 grams of Amsco Mineral Spirits 66-3. The resulting paint was stable for over six months.

Example 22 Single Package Zinc-rich Coating with Ethyl Silicate 40 and N-beta[N' gamma(trimethoxysilylpropyl)-aminoethyll-gamma aminopropyltrimethoxy Silane A ferrous metal coating composition was prepared by mixing 155.2 grams of partially hydrolyzed ethyl polysilicate containing 40 percent by weight of SiO2 with 38.8 grams of N - beta[N' - gamma(trimethoxysilylpropyl) - aminoethyll - gamma aminopropyltrimethoxy silane and 892.5 grams of finely divided zinc having a particulate size of about 2 to about 15 microns (America Smelting and Refining Co.

ASARCO-L-15), and 74 grams of a finely divided extender (Water-Ground Mica 325, of The English Mica Co.). In addition, in order to maintain the mixture in an anhydrous state, 7.5 grams of a water scavenging agent (Union Carbide Corp.

molecular sieves 4A) were added and the composition was thinned with 293.5 grams of ethylene glycol monoethyl ether (Cellosolve). An antisettling agent was used to prevent hard settling (24 g of MPA-60-X, a hydrogenerated castor oil, of NL Industries) and 15.5 g of a thickener (Ethocel Medium Premium 100, of Dow Chemical Co., was added to give desired viscosity). The resultant ethyl silicate liquid protective coating or primer paint had a package stability of over 3 months.

When this paint was applied by spraying to sand blasted, cold-rolled steel panels measuring approximately 4 inches by 8 inches by 1/8 inch, there was obtained a smooth film which dried in less than ten minutes. The steel panel so coated was subjected for 500 hours to salt spray (ASTM Method B-117) and there was no evidence of corrosion or other signs of failure on the panel so coated.

Example 23 Single-package Zinc-rich Coating with Ethyl Silicate 40 and N-beta[N'- gamma(trimethoxysilylpropyl)-Aminoethyl]-Gamma Aminopropyltrimethoxy Silane A ferrous metal coating composition was prepared by mixing 174.6 grams of Ethyl Silicate 40 with 19.4 grams of N - beta[N' - gamma(trimethoxysilylpropyl) aminoethyl] - gamma aminopropyltrimethoxy silane, 892.5 grams of finely divided zinc dust (ASARCO L-15), 7.5 grams of a water scavenging agent (Union Carbide Molecular Sieves 4A) 74 grams of Mica 325, 24 grams of MPA-60-X, 15.5 grams of Ethocel Medium Premium 100, and 293.5 grams of Cellosolve.

The resultant primer paint was stable for 3 months in storage. When applied to sand blasted steel panels as in Example 1, the coating dried to a hard film in less than 10 minutes. When these panels were subjected to a salt spray and water immersion for 500 hours, they showed no evidences of corrosion or other failure.

WHAT WE CLAIM IS: 1. A composition for protecting ferrous metals from corrosion comprising particulate zinc, an unhydrolyzed or a partially hydrolyzed organic silicate and a hardening amount of hydrolyzable silicon compound selected from (a) amino silanes of the formula

wherein: t is an integer having values of 0 to 10; each of M, Y, Q and Z are R or

R is H, alkyl having I to 4 carbon atoms or hydroxyalkyl having 2 to 3 carbon atoms; R' is -C2H4-, -C3H6- or -R2-O-R2- and R2 is an alkylene radical having 1 to 8 carbon atoms; a is an integer having values of 1 to 3; b is 0, 1 or 2; and the sum of a+bA3 with the proviso that at least one of M, Q, Y or Z is

X is a hydrolyzable organic group; (b) quaternary ammonium salts of the aminosilanes in (a); and (c) the hydrolyzates and condensates of the aminosilanes in (a).

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (22)

**WARNING** start of CLMS field may overlap end of DESC **. ASARCO-L-15), and 74 grams of a finely divided extender (Water-Ground Mica 325, of The English Mica Co.). In addition, in order to maintain the mixture in an anhydrous state, 7.5 grams of a water scavenging agent (Union Carbide Corp. molecular sieves 4A) were added and the composition was thinned with 293.5 grams of ethylene glycol monoethyl ether (Cellosolve). An antisettling agent was used to prevent hard settling (24 g of MPA-60-X, a hydrogenerated castor oil, of NL Industries) and 15.5 g of a thickener (Ethocel Medium Premium 100, of Dow Chemical Co., was added to give desired viscosity). The resultant ethyl silicate liquid protective coating or primer paint had a package stability of over 3 months. When this paint was applied by spraying to sand blasted, cold-rolled steel panels measuring approximately 4 inches by 8 inches by 1/8 inch, there was obtained a smooth film which dried in less than ten minutes. The steel panel so coated was subjected for 500 hours to salt spray (ASTM Method B-117) and there was no evidence of corrosion or other signs of failure on the panel so coated. Example 23 Single-package Zinc-rich Coating with Ethyl Silicate 40 and N-beta[N'- gamma(trimethoxysilylpropyl)-Aminoethyl]-Gamma Aminopropyltrimethoxy Silane A ferrous metal coating composition was prepared by mixing 174.6 grams of Ethyl Silicate 40 with 19.4 grams of N - beta[N' - gamma(trimethoxysilylpropyl) aminoethyl] - gamma aminopropyltrimethoxy silane, 892.5 grams of finely divided zinc dust (ASARCO L-15), 7.5 grams of a water scavenging agent (Union Carbide Molecular Sieves 4A) 74 grams of Mica 325, 24 grams of MPA-60-X, 15.5 grams of Ethocel Medium Premium 100, and 293.5 grams of Cellosolve. The resultant primer paint was stable for 3 months in storage. When applied to sand blasted steel panels as in Example 1, the coating dried to a hard film in less than 10 minutes. When these panels were subjected to a salt spray and water immersion for 500 hours, they showed no evidences of corrosion or other failure. WHAT WE CLAIM IS:

1. A composition for protecting ferrous metals from corrosion comprising particulate zinc, an unhydrolyzed or a partially hydrolyzed organic silicate and a hardening amount of hydrolyzable silicon compound selected from (a) amino silanes of the formula

wherein: t is an integer having values of 0 to 10; each of M, Y, Q and Z are R or

R is H, alkyl having I to 4 carbon atoms or hydroxyalkyl having 2 to 3 carbon atoms; R' is -C2H4-, -C3H6- or -R2-O-R2- and R2 is an alkylene radical having 1 to 8 carbon atoms; a is an integer having values of 1 to 3; b is 0, 1 or 2; and the sum of a+bA3 with the proviso that at least one of M, Q, Y or Z is

X is a hydrolyzable organic group; (b) quaternary ammonium salts of the aminosilanes in (a); and (c) the hydrolyzates and condensates of the aminosilanes in (a).

2. Composition as claimed in claim 1 wherein X is an alkoxy group having I to

2 carbon atoms.

3. Composition as claimed in claim 1 wherein X is an alkoxyalkoxyl group.

4. Composition as claimed in claim 3 wherein the alkoxyalkoxyl group is OC2H4OCHs.

5. Composition as claimed in any one of the preceding claims wherein R is H.

6. Composition as claimed in any one of claims 1 to 4 wherein R is CH3.

7. Composition as claimed in any of the preceding claims wherein a is I and b=0.

8. Composition as claimed in any one of the preceding claims wherein the organic silicate is an alkoxyalkylpolysilicate.

9. Composition as claimed in claim 8 wherein the alkoxyalkypolysilicate is ethoxyethyl polysilicate.

10. Composition as claimed in any one of claims 1 to 7 wherein the organic silicate is a tetra-alkyl orthosilicate.

11. Composition as claimed in claim 10 wherein the tetraalkyl orthosilicate is tetraethyl orthosilicate.

12. Composition as claimed in any one of the preceding claims wherein the amount of hydrolyzable silicon compound is in the range of 5% to 45% by weight based on the weight partially hydrolyzed organic silicate.

13. Composition as claimed in any one of the preceding claims wherein X is -OCH

14. Composition as claimed in any one of the preceding claims wherein the hydrolyzable silicon compound is selected from (a) amino silanes of the formula

wherein: t is 0, 1, 2 or 3, a is an integer having values of 1 to 3, b is 0, 1 or 2, and the sum of a+b is A3.

each of R is H, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 2 to 3 carbon atoms, R' is -C2H4-, -C3H6-, or -R3 -O-R3-, wherein R3 is an alkylene radical having 1 to 8 carbon atoms, R4 and R5 are each H or -CH3, and X is a hydrolyzable organic group; (b) quaternary ammonium salts of the aminosilanes in (a); and (c) the hydrolyzates and condensates of the aminosilanes in (a).

15. A composition as claimed in claim 14, substantially as hereinbefore described in any one of Examples 1 to 21.

16. A composition as claimed in claim 1, substantially as hereinbefore described in either of Examples 22 and 23.

17. A substrate coated with a composition as claimed in any one of claims 1 to 13 and 16.

18. A substrate as claimed in claim 17 which is a ferrous substrate.

19. A substrate coated with a composition as claimed in claim 14 or claim 15.

20. A substrate as claimed in claim 19 which is a ferrous substrate.

21. A substrate as claimed in claim 17, substantially as hereinbefore described in either of Examples 22 and 23.

22. A substrate as claimed in claim 19, substantially as hereinbefore described in any one of Examples 1 to 21.