Compositions: coating or plastic – Coating or plastic compositions – Silicon containing other than solely as silicon dioxide or...
Reexamination Certificate
2001-02-08
2002-08-13
Brunsman, David (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Silicon containing other than solely as silicon dioxide or...
C106S287110, C106S287140, C106S287150
Reexamination Certificate
active
06432191
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to compositions useful for coating various surfaces, including, metals, especially aluminum, steel and galvanized steel, and various metal alloys, such as brass, alkali metal silicate coatings, priming metals, painted finishes, marine finishes, and the like. More particularly, this invention relates to silane-based, coating compositions which are catalyzed with acid and/or base metallic and/or non-metallic compounds and which form strongly adherent, corrosion resistant coatings on a wide range of painted and non-painted surfaces, including metals, plastics, concrete and alkali metal silicates. Coating compositions of this invention provide hard, transparent, durable coatings which do not suffer noticeable degradation in gloss nor concurrent yellowing over long periods of time under exposure to corrosive, e.g., acidic or alkaline conditions.
2. Discussion of the Prior Art
It is well known to catalyze silanes with acids. However, acid catalyzed aqueous silane coating compositions are not considered useful for coating steel; the acid conditions, e.g., pH below 7, promote corrosion of the steel substrate.
U.S. Pat. Nos. 3,944,702, 3,976,497, 3,986,997 and 4,027,073 describe coating compositions, which are acid dispersions of colloidal silica and hydroxylated silsequioxane in an alcohol-water medium.
U.S. Pat. No. 4,113,665 discloses chemically resistant ambient curable coatings based on a binder of which the major portion is prepared by reacting, in an acidic solution, trialkoxysilanes (e.g., methyltriethoxysilane) with aliphatic polyols, silicones or both. Barium fillers, such as barium metaborate, may be added to provide resistance to sulfur dioxide. Zinc oxide or metallic zinc may be included for further corrosion resistance. The compositions may be applied to, e.g., steel petroleum tanks, by spraying, concrete, vitreous surfaces.
U.S. Pat. No. 4,413,086 describes water reducible coating compositions containing organosilanepolyol which is a reaction product between certain hydrophilic organic polycarbinols and organosilicon material, e.g., organosilane, curing agent (e.g., aminoplast resin), organic solvent (optional), essentially unreacted polyol (optional), essentially unreacted hydrolyzed and condensed organosilane (optional), water (optional) and pigment (optional).
U.S. Pat. No. 4,648,904 describes an aqueous emulsion of (a) hydrolyzable silane, inclusive of methyltrimethoxysilane, (b) surfactant (e.g., Table I, col. 4) and (c) water. The coatings may be used for rendering masonry water repellant.
U.S. Pat. No. 5,275,645 is purported to provide an improvement to the acid-catalyzed organosilane coating compositions of the above-mentioned U.S. Pat. No. 4,113,665. According to this patent a protective coating is obtained at ambient temperature from a coating composition containing organosilanes having an Si—O bond, using an amine catalyst and an organometallic catalyst.
U.S. Pat. No. 5,879,437 describes a coating composition containing a tetraalkyl silicate or monomeric or oligomeric hydrolysis product thereof, present in a proportion of 40-90% by weight based on the non-volatile content of the composition and a hydrous oxide sol (Type A or Type B), in an amount such that the oxide constitutes 10-60% by weight of the non-volatiles. According to the patentees, this coating composition is suitable for the pretreatment of solid surfaces such as metals generally, including steel, titanium, copper, zinc and, particularly aluminum, to improve adhesion properties of the pretreated surface to subsequently applied coatings, such as paint, varnish, lacquer; or of adhesive, either in the presence or absence of a lubricant.
U.S. Pat. No. 5,882,543 describes methods and compositions for dehydrating, passivating and coating HVAC and refrigeration systems. The compositions include an organometalloid and/or organometallic compound, which reacts with water in the system. The sealing function of these compositions is apparently obtained by introducing the composition to the fluid enclosure and upon exiting from an opening, the composition (i.e., organometallic) reacts with atmospheric moisture to seal the opening.
U.S. Pat. No. 5,939,197 describes sol-gel coated metals, especially titanium and aluminum alloys. The sol-gel coating provides an interface for improving adhesion, through a hybrid organometallic coupling agent at the metal surface, between the metal and an organic matrix resin or adhesive. The sol is preferably a dilute solution of a stabilized alkoxyzirconium organometallic salt, such as tetra-i-propoxy-zirconium, and an organosilane coupling agent, such as 3-glycidyloxypropyltrimethoxysilane, with an acetic acid catalyst.
U.S. Pat. No. 5,954,869 discloses an antimicrobial coating from water-stabilized organosilanes obtained by mixing an organosilane having one or more hydrolyzable groups, with a polyol containing at least two hydroxyl groups. This patent includes a broad disclosure of potential applications and end uses, e.g., column 4, lines 35-53; columns 23-25.
U.S. Pat. No. 5,959,014 relates to organosilane coatings purported to have extended shelf life. Organosilane of formula R
n
SiX
4-n
(n=0-3; R=non-hydrolyzable group; X=hydrolyzable group) is reacted with a polyol containing at least three hydroxyl groups, wherein at least any two of the at least three hydroxyl groups are separated by at least three intervening atoms.
U.S. Pat. No. 6,057,040 relates to novel bis-aminosilanes and coating compositions containing the bis-aminosilanes.
In my recently issued U.S. Pat. No. 5,929,129, there are described corrosion resistant coatings provided by aqueous-alcoholic dispersions of the partial condensate of monomethyl silanol (obtained by hydrolysis of monomethyl alkoxysilane) alone or in admixture with minor amounts of other silanol, e.g., gamma-glycidyloxy silanol, wherein the reaction is catalyzed by divalent metal ions, e.g., Ca
+2
, typically from alkaline earth metal oxides. When these coating are applied to, e.g., boat hulls, such as aluminum hulls, they are highly effective in preventing corrosion from salt water for extended periods.
The coating compositions of this earlier patent, have also been found to be very highly effective in providing strongly adherent, corrosion resistant coatings on a variety of other substrates and products, including, especially, air conditioning and other HVAC systems (see, e.g., Provisional Application 60/181061, filed Feb. 8, 2000, in the names of Anthony Gedeon, et al.).
In my Provisional Application, Ser. No. 60/185,354, filed Feb. 28, 2000, silane-based, aqueous coating compositions are described which are especially adapted for coating or overcoating refurbished painted finishes, especially as a gel-coat restorative for fiberglass-reinforced epoxy and polyester resins, particularly, for boat hulls and other marine finishes. According to this Provisional application, an acidic aqueous silane based coating composition is described which is obtained by admixing (A) at least one silane of the formula (1)
R
1
Si(OR
2
)
3
(1)
wherein
R
1
is a lower alkyl group, a phenyl group or an
N-(2-aminoethyl)-3-aminopropyl group, and
R
2
is a lower alkyl group;
(B) acid component selected from water-soluble organic acids, H
3
BO
3
and H
3
PO
3
; and
(C) water.
Other ingredients which can be used in these compositions include silicates, mono-lower alkyl ethers of ethylene glycol, lower alkanol, ultraviolet light absorbers, colloidal aluminum hydroxides and metal alcoholates.
In my provisional application Ser. No. 60/185,367, filed Feb. 28, 2000, I described non-aqueous coating compositions containing, for example, (A) silanes represented by formula (1):
R
1
nSi(OR
2
)
4-n
(I)
where R
1
is a lower alkyl group, phenyl group, 3,3,3-trifluoropropyl group, &ggr;-glycidyloxypropyl, &ggr;-methacryloxypropyl group, N-(2-aminoethyl)-3-aminopropyl group or aminopropyl group,
R
2
is a lower alkyl group; and
n is a number of 1 or
Brunsman David
Sherman & Shalloway
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