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WO1987007627A1 - Composition de revetement anti-corrosion pour metaux - Google Patents

Composition de revetement anti-corrosion pour metaux Download PDF

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Publication number
WO1987007627A1
WO1987007627A1 PCT/US1987/001322 US8701322W WO8707627A1 WO 1987007627 A1 WO1987007627 A1 WO 1987007627A1 US 8701322 W US8701322 W US 8701322W WO 8707627 A1 WO8707627 A1 WO 8707627A1
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Prior art keywords
oil
corrosion
drying
drying oil
composition
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PCT/US1987/001322
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English (en)
Inventor
Harold H. Christhilf
Steven D. Clark
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Witco Corp
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Witco Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Definitions

  • Our present invention is concerned with the preparation of novel liquid corrosion-inhibiting coating compositions, of the type hereafter described, which are effective, when applied in thin films on ferrous and non-ferrous, particularly ferrous, metals and steels, and which, when dried and/or cured, form hard, non-tacky dry films, which are highly effective for the prevention or inhibition of corrosion or rusting of such of said metals which are susceptible to corrosion or rusting.
  • compositions which have been suggested, or which have been or are currently being commercially used fall, generally speaking, into two classes, one being compositions which form coatings in relatively thin films and which are soft, and are commonly of a character such that they may readily be stripped off or removed from the metal surfaces, for example. by organic solvents, where it is necessary to remove the coatings at periodic intervals to carry out repairs or the like on the metal surfaces, after which they are recoated; and the other comprises compositions which form coatings in relatively thin films and which are hard and of a character such that they are, and are intended as, essentially permanent coatings and are removable only with great difficulty.
  • the coating compositions of our present invention are of the type which involve the use of inorganic-organic complexes which comprise thixotropic overbased alkaline earth metal organic sulfonates complexed with inorganic alkaline earth metal carbonates, as one of the essential ingredients of 3aid coating compositions, it is to be noted that the prior art has long known of such inorganic-organic complexes, and of corrosion-inhibiting coating compositions which contain, as one of the ingredients thereof, the aforesaid inorganic-organic complexes.
  • corrosion-inhibiting coating compositions which contain thixotropic, or grease-like or gel-like thixotropic, alkaline earth metal organic sulfonates complexed with alkaline earth metal carbonates, with or without admixture with polymers, petrolatums, microcrystalline or other waxes, plasticizers, and resins, in a carrier or diluent of non-volatile or volatile (or mixtures of non-volatile and volatile) hydrocarbons and/or other organic liquid solvents, is well-known to the art and is disclosed in such U.S. Patents as Nos.
  • corrosion-inhibiting compositions are known to have a certain utility for a variety of purposes, some including float coating or flotation coating of the insides of tanks, e.g., ballast tanks for ships, barges, off-shore oil rigs, etc., wherein, for instance, the tank is filled with water, the lighter-than-water corrosion-inhibiting composition is poured onto the surface of the water, and the water is then drained from the tank, and the floating layer of anti-corrosion agent deposits on the .side walls and bottom of the tank as the water drains out.
  • Other uses for various of said corrosion-inhibiting compositions include, for instance, automobile and truck body undercoatings, maintenance coatings, and others for use in other environments.
  • Patent No. 3,925,087 discloses corrosion-inhibiting compositions which comprise (a) about 10 to about 30% by weight of a rust-inhibitive grease-like concentrate comprising a thixotropic inorganic-organic complex stably dispersed in an essenti-all inert liquid oil phase in an amount not to exceed 4 parts, per part of said complex, said inorganic-organic complex comprising a thixotropic overbased alkaline earth metal, particularly calcium, organic sulfonate complexed with calcium carbonate; (b) about 2 to about 10%, by weight, of a drying oil, particularly tung oil, or synthetic drying oil, said drying oil or synthetic drying oil being mis ⁇ ible with a diluent oil selected from the group consisting of aliphatic hydrocarbon diluents, cycloaliphatic hydrocarbon diluents, aromatic hydrocarbon diluents, and mixtures thereof boiling at temperatures above 150° C; and (c) from at least 60% by weight to essentially
  • SACI products are stated to constitute formulations containing the aforementioned thixotropic overbased calcium organic sulfonates complexed with calcium carbonate, namely, the inorganic-organic complexes used as one of the ingredients of the corrosion-inhibiting compositions of said Patent No. 3,925,087, but that the "SACI” products generally are not the inorganic-organic complexes per se.
  • the patent discloses the use of the "SACI"-200 and “SACI”-300 products, as they are commercially marketed and sold, in the production of the corrosion-inhibiting or rust-inhibiting compositions of said patent.
  • the active ingredients are in a fc complex/drying oil ratio of about 1:1-3:1; and that dilution of the active ingredients to, for example, the 50-300 cps level, permits deposition of at least 1.0 gram of these active ingredients per square meter of metal to be protected.
  • the said Patent No. 3,925,087 contains 25 Examples, exclusive of four Examples (C-l to C-4) which contained only a "SACI” product and a naphthenic oil, without any drying oil, as Control Formulations; of the Nos. 1 to 25 Examples, some contain only a naphthenic oil solution of tung oil without any "SACI”; others contain a naphthenic oil solution of "SACI”-200, or “SACI”-300 (Examples 2 and 17-19) and tung oil with no drier, falling withi-n the scope of the invention of said patent; others contain a naphthenic oil solution of "SACI"-200 and linseed oil, with or without driers, apparently falling within the scope of said invention; and others comprise a naphthenic oil solution of "SACI”-200, and tung oil in amounts of 20 and 30 wt.% of the formulation (Examples 14 and 15) and falling outside of the scope of the invention of said patent.
  • compositions of the invention may contain petroleum resins or waxes, which may be added, or which-may be present in the particular "SACI” product utilized, as, for instance, "SACI"-300 (see Column 1, last paragraph thereof, and Example 2).
  • SACI SACI-300
  • Saltspray Tests of the aforementioned Examples 14, 15 and 16 show time periods of 5, 6 and 28 hours, respectively, before Failure, which are tantamount to utter failure or inoperativeness of such compositions in corrosion resistance in standard Saltspray tests.
  • Table I in Column 10 of said patent Saltspray Tests of the aforementioned Examples 14, 15 and 16 show time periods of 5, 6 and 28 hours, respectively, before Failure, which are tantamount to utter failure or inoperativeness of such compositions in corrosion resistance in standard Saltspray tests.
  • the corrosion-inhibiting compositions of said Patent are stated to form solid protective coatings which are soft or tacky, rather than brittle, and have little or no tendency to crack. They are stated to be particularly adapted for the coating of the inside of tanks and can be applied by spraying but are best applied by a flotation coating procedure, and that they possess the advantageous property of the entire protective coating on a metal surface of said corrosion-inhibiting compositions being easily stripped off with unheated degreasing solvents.
  • Patent No. 3,453,124 discloses, among other things, the preparation of inorganic-organic complexes in the form of thixotropic overbased alkaline earth metal (such as calcium) organic sulfonates complexed with alkaline earth metal (such as calcium) carbonates, dispersed, in the form of colloidal particles, in oil carriers such as mineral oils or other non-volatile carriers or media, as well as other carriers or media which are volatile, such as mineral spirits, and, also, mixtures of non-volatile and volatile carriers or media.
  • alkaline earth metal such as calcium
  • alkaline earth metal such as calcium carbonates
  • corrosion-inhibiting coating compositions for the treatment of ferrous and non-ferrous metals which comprise, as essential components of the invention of said patent, reaction products of the aforesaid inorganic-organic complexes, colloidally dispersed in said carriers or media, with phosphoric acid esters of alcohols.
  • Patent No. 3,453,124 also discloses, in Columns 43 and 44, the results of comparative corrosion tests with illustrative corrosion-inhibiting compositions of said patent and with commercial automobile undercoating compositions, which latter include an identified petrolatum undercoating composition; an undercoating composition not specifically identified, but stating that it comprised SAE 40 oil, a rust-inhibitor, and a drying oil; a petroleum base translucent film (otherwise unidentified); and an asphalt cutback undercoating composition (also otherwise unidentified) ; in which comparative tests of corrosion-inhibiting compositions made in accordance with the claimed invention of said patent are shown to be superior to those corrosion-inhibiting compositions with which comparison was made.
  • Patent No. 3,492,231 discloses methods for the preparation of the inorganic-organic complexes and their utility in the production of corrosion-inhibiting compositions for use on metals.
  • Various of such inorganic-organic complexes have long been known to the art, and they are illustrative of certain of the many compositions which heretofore have been known to the art dealing with corrosion-inhibiting compositions containing said complexes.
  • Patent No. 3,565,672 discloses methods for the preparation of mineral oil solutions of inorganic-organic complexes, which are disclosed as possessing utility as corrosion-inhibitors, the complexes, as such, being but one of the ingredients which can be used in the particular combination of ingredients which, in certain proportions, constitute the novel and highly-improved corrosion-inhibitor compositions of our present invention.
  • Patent No. 3,565,843 discloses organic rust-inhibiting compositions which form hard coatings which are almost tack-free to the touch by spraying on metal surfaces, which compositions comprise (a) about 10 to 35 wt.% of an inorganic-organic complex in the form of an overbased alkaline earth metal organic sulfonate which has been admixed with aqueous ammonia under conditions to form a gel, which is, in fact, a thixotropic gel; (b) about 5 to 15 wt.% of a coating material selected from the group consisting of a hydrocarbon polymer resin and a combination of a hydrocarbon polymer resin, an ethylene-vinyl acetate copolymer having a specified melt index, and a wax, and wherein said hydrocarbon polymer resin has a specified molecular weight and a specified softening point; and (c) about 55 to 85 wt.% of a hydrocarbon solvent having a boiling point range of about 270° to 450
  • Patent No. 3,661,622 discloses, among other subject matter, the preparation of thixotropic overbased alkaline earth metal, particularly calcium, organic sulfonates, complexed with an alkaline earth metal, particularly calcium, carbonate; the admixture therewith of certain polymers such as low-density polyethylene, polypropylene, etc.; copolymers of the foregoing with vinyl monomers such as ethylene-vinyl acetate; polymethyl methacrylate and others; and the preparation of corrosion-inhibiting primer coating compositions containing the aforesaid ingredients.
  • the inclusion of the polymers, as is pointed out in Column 11, Lines 45-65, serves, among other functions, to produce films which are harder, tougher and less tacky than primer compositions which do not contain such polymers.
  • the primer compositions are stated to be desirably applied to metal surfaces to be coated in the form of a volatile organic solvent solution, said primer composition solution being applied by brush coating or by spraying, and evaporating the volatile organic solvent from the primer composition film, after which a conventional paint is applied.
  • Patent No. 3,746,643 discloses viscous, high-melting point corrosion- or rust-inhibiting coating compositions for metals which comprise a solution in a volatile hydrocarbon solvent, such as Stoddard solvent, which solution may also contain some mineral oil, of an inorganic-organic complex in the form of a thixotropic overbased alkaline earth metal organic sulfonate complexed with an alkaline earth metal carbonate, and which coating compositions contain certain proportions of macrocrystalline wax.
  • a volatile hydrocarbon solvent such as Stoddard solvent
  • the novelty in this patent resides in the incorporation of macrocrystalline wax into the composition, which imparts an unexpected marked increase in the resistance to rusting of dip-coated steel panels, as demonstrated by Weatherometer testing, over similar coating compositions not containing microcrystalline wax, or over similar coating compositions containing ordinary paraffin waxes.
  • Patent No. 3,816,310 discloses methods for the preparation of coating compositions which have particular utility as rust-inhibitors, as well as rust-inhibitor greases.
  • This patent discloses methods of preparing inorganic-organic complexes in the form of thixotropic overbased alkaline earth metal, particularly calcium, organic sulfonates, complexed with an alkaline earth metal, particularly calcium, carbonate, dissolved or dispersed in a non-volatile carrier, such as mineral oils, or a volatile organic solvent, such as Stoddard solvent, or a mixture of non-volatile carriers and volatile - organic solvents.
  • Compositions made in accordance with this patent can be applied, by spraying or painting, to a metal surface to coat said surface and protect it against rusting, and it is stated that such
  • compositions have particular utility for rust-proofing automobile underbodies.
  • Such corrosion-inhibiting compositions are in the form of hot-melt compositions and are radically different from the corrosion-inhibiting compositions of our present invention not only because they are hot-melt compositions but, also, because the compositions set instantly, for instance, within about 10 seconds, on the ferrous metal substrate and the coatings formed are soft.
  • the corrosion-inhibiting compositions of our present invention are particularly advantageous and highly effective, as, for instance, as pipe varnishes in steel mills which produce steel pipe, the compositions of said patent would have no commercial utility; and the same is true in regard to many other uses which the corrosion-inhibiting • compositions of our present invention are especially satisfactory and for which uses the compositions of said patent would be of no commercial value.
  • Patent No. 4,495,225 which is generally somewhat related to the above-mentioned Patent No. 3,925,087, discloses corrosion-inhibiting compositions which contain a corrosion-inhibiting grease-like concentrate of a thixotropic overbased calcium sulfonate-calcium carbonate complex dispersed in a mineral oil, the mineral oil constituting from 20 to 60 wt.% of the compositions; from about 5 to 25% of a drying oil; and specified low ranges of special drier compositions, to-wit, those selected from two different groups of driers, namely, (1) a first metal drier selected from the group consisting of copper carboxylate compounds, rare earth carboxylate compounds and mixtures thereof, and (2) a second metal drier consisting of zinc carboxylate compounds.
  • this patent states that the coating compositions of said patent cure to a "solid but soft protective layer. "
  • the patent discloses that the corrosion-inhibiting comositions of this patent may contain petrolatums, oxidized petrolatums, hydrocarbon diluent oils, polyisobutylenes to provide improved adhesion to.metal surfaces, pigments such as aluminum pigments and carbon black, and skin-preventing agents.
  • SACI Structure-based calcium organic sulfonate/ ⁇ alcium carbonate complexes
  • SACI thixotropic overbased calcium organic sulfonate/ ⁇ alcium carbonate complexes
  • the aforesaid "SACI” products contain a thixotropic overbased calcium organic sulfonate/calcium carbonate complex colloidally dispersed in a volatile hydrocarbon solvent (mineral spirits), or in a paraffinic mineral oil, or in a mixture of said mineral spirits and said mineral oil.
  • the organic sulfonate part of the thixotropic overbased calcium organic sulfonate-cal ⁇ ium carbonate complexes of the aforesaid "SACI" products is derived from the use of branched chain or linear/straight chain monoalkylbenzene or dialkylbenzene sulfonic acids or mixtures of such sulfonic acids, the alkyl radical or radicals each containing at least 12 carbon atoms and generally in the range of from 12 to 30 carbon atoms.
  • SACI-100 and 100A concentrates are colloidal dispersions of said complex in a mixture of mineral spirits and a paraffinic mineral oil.
  • SACI also contains oxidized petrolatums for improved anti-corrosion properties.
  • SACI products contain 60, 50 or 40 wt.% solids. Coatings made with its listed basic compositions are generally stated to be formulated with waxes (refined and unrefined); petrolatums; oxidized petrolatums, those having an Acid No. of 15-20 being recommended; pigments; resins; and asphalts. Coatings made with "SACI"-100 and 100A concentrates are stated to produce films which are soft, oily and self-healing.
  • Salt fog tests on "SACI"-100 and 100A show 500 hours to failure for "SACI”-100; 600 hours to failure for "SACI”-100A with a dry film thickness of 0.5 mil; 1000 hours to failure for "SACI”-100 and 1200 hours to failure for "SACI”-100A with a dry film thickness of 1.0 mil.
  • SACI-200 and 200A are ' colloidal dispersions of said complex in a paraffinic mineral oil.
  • SACI paraffinic mineral oil.
  • SACI contains 36 wt.% of said complex and 64 wt.% mineral oil.
  • SACI also contains oxidized petrolatum. The other statements made as to "SACI"-100 and 100A are applicable to "SACI"-200 and 200A.
  • SACI-300 is a colloidal dispersion of a thixotropic overbased inorganic-organic complex in mineral spirits containing about 35 wt.% of said complex and about 37 wt.% of said mineral spirits, with minor proportions of a microcrystalline wax and a paraffinic mineral oil to provide corrosion-inhibiting compositions which are stated to have exceptional protection properties in salt water immersion and salt atmospheres; that typical applications include outdoor parts storage, automobile body rust protection, coatings for underground pipe, marine applications and protection of overseas shipments; that "SACI” 300 wax-like coatings can be used in organic solvent dilutions or in combination with asphalts or petrolatums where long-term protection and relative ease of removal are important; and that the films resulting from using the basic formulation of SACI are firm and waxy.
  • “SACI”-300A is similar to “SACI”-300; but it also contains oxidized petrolatum. Salt fog tests on “SACI”-300 and “SACI”-300A show, among other thicknesses of dry films, 300+ hours to failure for "SACI”-300 with a 0.5 mil dry film thickness and 800+ hours to failure with "SACI”-300A with the same film thickness; and, where the film thickness is 1.0 mil, 800+ hours to failure for "SACI"-300 and 1500+ hours to failure for "SACI”-300A. With films of 5.0 mil thickness, “SACI”-300 showed failure after 2000+ hours, and "SACI"-300A showed failure at 3000+ hours.
  • SACI commercial "SACI” products are, as noted above, "SACI”-2400, “SACI”-2452 and “SACI”-2460. These “SACI” products are all corrosion-preventive concentrates in the form of mineral spirits-wax colloidal dispersions. They are stated to have a high content of the thixotropic inorganic-organic complex (65 wt.% solids in “SACI”-2400, 52 wt.% in “SACI”-2452, and 60 wt.% in “SACI”-2460) .
  • Salt fog data are presented utilizing dry film thicknesses of 0.5 mil and 1.0 mil, hours to failure with 0.5 mil being 500, and hours to failure with.1.0 mil_being 1100.
  • SACI-700 is a colloidal dispersion of said complex in mineral spirits, the non-volatile solids content of which, namely, the thixotropic overbased complex (TBN is 250), is substantially 50 wt.%, and the mineral spirits content of which is substantially 50 wt.%. It is stated in “SACI”-700 Technical Data sheets that the “SACI”-700 must be used with an added plasticizer or resin for effective protection; and, generally, that “SACI”-700 can be formulated with hydrocarbon resins, asphalts, waxes, mastics, petrolatums and oils to produce a variety of effective coatings. Also shown are the results of salt spray and humidity cabinet corrosion tests.
  • SACI-760 is a colloidal dispersion in mineral spirits of a thixotropic overbased calcium organic sulfonate complexed with calcium carbonate (TBN is 265), the non-volatile solids content of which, namely, the thixotropic overbased complex, is substantially 60 wt.%, and the mineral spirits content of which is substantially 40 wt.%.
  • the organic portion of said organic sulfonate is derived from a linear alkylbenzene sulfonic acid.
  • SACI various "SACI” products are stated to be capable of being formulated with one or more of refined and unrefined waxes, petrolatums, resins, polymers, asphalts, oils, and aliphatic and aromatic solvents to achieve various levels of solids, activity, and/or viscosity.
  • Our present invention is based upon discoveries that novel improved corrosion-inhibiting coating compositions can be obtained which are characterized by a combination of particular properties and which have enhanced utilities over various of the corrosion-inhibiting coating compositions which have heretofore been known to the art.
  • compositions are in the form of free-flowing liquids which are capable of being applied as thin films on the surfaces of metal substrates which are to be protected against corrosion or rusting, and contain, as essential ingredients, (a) inorganic-organic complexes in the form of thixotropic overbased alkaline earth metal, particularly calcium, organic sulfonates completed with alkaline earth metal, particularly calcium,- carbonates; (b) synthetic drying oils particularly per se, or mixtures of synthetic drying oils with drying oils, in which latter case it is especially advantageous that such mixtures contain substantially predominating proportions or amounts of the synthetic drying oils over the proportions or amounts of the drying oils; (c) driers, commonly and desirably of the type of paint driers; and (d) volatile organic solvents, particularly volatile hydrocarbon solvents; the aforesaid (a), (b) and ( ⁇ ) ingredients being dissolved and
  • novel and improved corrosion-inhibiting compositions of our ** present invention are generally characterized by the following properties: These include the production, on drying and/or curing, at room temperatures or ambient temperatures, of thin liquid films of said compositions, for instance, from about 0.5 to 6 mils, or even appreciably greater, but preferably about 1 to about 3.5 mils, in a drying and/or curing time of about 1 to about 6 hours, particularly about 1 to 2 hours; the dry and/or cured films are characterized by being firm or hard, but generally not brittle, and are non-oily or essentially non-oily and free or essentially free of tack to the human touch* they have a strong adherence to the metal substrate and possess a permanence so as not to be readily removable or stripped off from the metal substrate by means of unheated usual degreasing solvents; and, generally speaking, are removable by other means only with substantial difficulty in those instances where removability may be sought without damaging the underlying surfaces of the metal substrate.
  • the foregoing combination of ingredients are used
  • inorganic-organic complexes are, as is well-known, water-insoluble but are colloidally dispersible in volatile organic solvents, most commonly of hydrocarbon aliphatic or cycloaliphatic character. As previously noted, they are disclosed in the various patents referred to above.
  • the aforesaid complexes are most desirably derived from the use of branch chain or linear or straight chain monoalkylbenzene sulfonic acids or dialkylbenzene sulfonic acids, or mixtures of such sulfonic acids in which the dialkylbenzene sulfonic acids advantageously predominate, and the alkyl groups of which contain predominately from 12 to 30 carbon atoms, more particularly predominately from 12 to 22 carbon atoms.
  • postdodecylbenzene sulfonate
  • sulfonic acid of a bottoms product from the manufacture of dodecylbenzene in which the alkyl groups are branch chain
  • another is a sulfonic acid of a generally corresponding bottoms product but in which the alkyl groups are linear or straight chain and which bottoms are commonly known as "NAB” bottoms.
  • NAB bottoms of bottoms.
  • inorganic-organic complexes in the case of the calcium compounds, are commonly characterized by the formula (RSO3)2Ca:CaC ⁇ 3, where R is an akylbenzene radical of the foregoing type.
  • any thixotropic overbased calcium sulfonate/calcium carbonate complex is acceptable or reasonably satisfactory in the production of the novel corrosion-inhibiting compositions of our present invention, particularly advantageous as a convenient commerce source of such c ⁇ mplexes is "SACI"-760.
  • synthetic drying oil is intended to mean materials which have good to excellent drying properties- at room temperatures or ambient temperatures and which, generally speaking, may be in the form of resins or resinous materials, and which comprise polymers or copolymers, illustrative examples of which are ethylenically-unsaturated polycarboxylic acid esters of aliphatic polyhydric alcohols, in which said polyhydric alcohols contain at least three hydroxyl groups and examples of which polyhydric alcohols are glycerine, trimethyol propane and pentaerythritol, and in which the polycarboxylic acids are preferably phthalic acid or phthalic anhydride, or maleic acid or maleic anhydride, and with ethylenically-unsaturated oils such as linseed oils or similar drying oils or the long oil fatty acids thereof, such as linseed oil fatty acids or tall oil fatty acids (TOFA) .
  • synthetic drying oil is intended to mean materials which have good to excellent drying properties
  • alkyds include long oil alkyds or oil-modified alkyd resins, and phenolic-modified alkyds.
  • the hydroxyl values of such alkyds are variable, those having hydroxyl values in the range of about 60 to about 125 being particularly preferred.
  • synthetic drying oils also includes resins or resinous materials, having good to excellent relatively fast drying properties at room temperatures or ambient temperatures, which are chemically structurally modifications of the alkyd resins or are chemically structurally different from the long oil alkyd resins.
  • Modified alkyd resins which have good to excellent drying properties include acrylic and vinyl modified alkyds.
  • Alkyd resin or resinous driers can also be modified by a post addition of phenolics, acrylics and vinyls in which the drying characteristics of the starting alkyds are varied, but, so long as the thus-modified alkyds have good to excellent drying properties reasonably akin to those of the long oil alkyds, their use is within the scope of our invention.
  • Other resin or resinous materials which have good to excellent drying properties include certain epoxy esters and certain polybutadienes.
  • thermoplastic resins of the type which form such films through volatile solvent evaporation.
  • thermoplastic resins which may be of the type of acrylic, vinyl and hydrocarbon resins, when admixed with convertible resins, improve drying and/or curing times, film hardness, and resistance to organic solvents and various chemicals. No novelty is claimed by us per se in synthetic drying oils.
  • post-modified alkyds are generally employed as a minor part of the convertible resins, such as the long oil alkyds, and a minor part of the corrosion- inhibiting compositions, such post-modified alkyds constituting from about 2 to 15 wt.%, preferably about 2 to about 6 wt.%, of the corrosion-inhibiting compositions.
  • Synthetic drying oils are sold under various trademarks illustrative of which are “BECKOSOL” (Reichhold Chemical Company); "AROPLAZ”, for example, “AROPLAZ 1266-M-60, 1266-M-70 and 1271 (Ashland Chemical Company); epoxy ester resins such as those sold under the trademarks “EPOTUF”, preferably “EPOTUF” No. 37- 004, and “UROTUF” (Reichhold Chemical Company); and certain of the "RICON” resins, preferably “RICON” 100 and/or 156 (Colorado Chemical Specialties, Inc.).
  • drying oils which per se are well-known to the art, is intended to mean natural drying oils which have good to excellent drying properties at room temperatures or ambient temperatures which, generally speaking, comprise ethylenically-unsaturated triglycerides of.
  • higher fatty or other ethylenically-unsaturated monocarboxylic acids illustrative of which are linseed oil, soya bean oil, dehydrated castor oil, tung oil, walnut oil, oiticica oil, safflower oil and fish oils, as well as such modified oils exemplified by oxygenated drying oils such as, for instance, oxygenated or blown or heat-bodied or polymerized or isomerized oils of the foregoing natural drying oils.
  • drying oils In place of glycerin, other aliphatic polyhydric alcohols containing at least 3, generally from 3 to 6, hydroxyl groups can be reacted with higher molecular weight ethylenically-unsaturated monocarboxylic acids containing mainly from 16 to 22 carbon atoms to produce said drying oils.
  • the preferred drying oils which are used in conjunction or together with the synthetic drying oils, are raw linseed oil or bodied linseed oils per se, as they are and long have been known to the art.
  • the driers which are utilized in the corrosion-inhibiting compositions of our invention can be and • desirably are driers which, typically, are of the paint drier type. They are, generally speaking, polyvalent, usually divalent, metal salts of soap-forming carboxylic acids.
  • Illustrative examples of such driers are naphthenates, tallates, and octoates of such metals as cobalt, zirconium, lead, nickel, zinc, chromium and manganese, or mixtures of two or more of such driers.
  • the drier is used in distinctly small proportions, generally in the range of about 0.3 to about 2 wt.% of the corrosion-inhibiting composition, the amount depending, in part, on the wt.% of the synthetic drying oil, or the above-described mixtures of synthetic drying oils and drying oils, used in any of the corrosion-inhibiting compositions of our present invention.
  • volatile organic solvent such solvents can be of aliphatic, cycloaliphatic or aromatic character, and include hydrocarbons, chlorinated hydrocarbons, alcohols, ketones and ethers which are compatible in the .system.
  • Preferred volatile organic solvents are aliphatic solvents, especially suitable being odorless mineral spirits because of its low toxicity and relatively low cost as well as its advantageous flash point; and, also, VM&P.
  • Other volatile organic solvents which can be used are disclosed in the above-mentioned Patent No. 3,453,124, in Column 3, the dis ⁇ losure of which volatile solvents is herein incorporated by reference.
  • Petrolatums and/or oxidized petrolatums, and, also, microcrystalline waxes, crude and refined, can be used in the corrosion-inhibiting compositions of our invention. They are, as indicated above, per se, well-known to the art and are articles of commerce. Illustrative of the oxidized petrolatums are those sold by ALOX Corporation under ALOX Nos. 100D, 102, 600 and 601. Those oxidized petrolatums where the extent of oxidation is such as to provide acid numbers in the range of about 10 to 130 are most suitable for the purposes of our present invention-, particularly oxidized petrolatums having acid numbers in the range of 15 to 60.
  • SOCCO-R-H-15 Metal Lubricants Co., Harvey, Illinois
  • SOCCO-R-H-15 Metal Lubricants Co., Harvey, Illinois
  • the petrolatums, the oxidized petrolatums, and the microcrystalline wax act, in certain respects, generally as self-healers, they serve to inhibit or prevent overcuring and embrittlement of the coatings, and they also function to lower water-sensitivity. Where utilized, they may be employed in variable minor proportions, generally in the range of about 2 to about 6 wt.% of. the corrosion-inhibiting compositions of our invention.
  • epoxidized oils which may be used in the corrosion-inhibiting compositions made in accordance with our invention are, per se, well-known to the art. When used, they serve to promote compatibility and to improve flexibility of the coatings on metals and, also, to enhance the adhesion of the coatings to the metal surfaces. They have little effect on salt fog performances.
  • Illustrative epoxidized oils are those prepared by the epoxidation of triglyceride oils, particularly, drying oils of natural or synthetic character, among which are tung oil, dehydrated castor oil, corn oil, cottonseed oil, soya bean oil, walnut oil, and fish oils.
  • epoxidized linseed oil exemplified by the product sold under the trademark "DRAPEX” (Argus Chemical Corporation), in which the epoxide equivalent is 10.4.
  • epoxidized oils which have high oxirane contents. They may be utilized in distinctly minor proportions, generally from about 2 to 6 wt.% of our corrosion-inhibiting compositions.
  • Non-drying oil type resins and. certain waxes can also be incorporated into the corrosion-inhibiting compositions of our invention, and they can be of otherwise diversified types. Those which fall into this category are hard resins and hard waxes which are water-insoluble and soluble or colloidally-dispersible in volatile organic solvents.
  • hydrocarbon resins include, by way of illustration, hydrocarbon resins (petroleum and non-petroleum), unmodified or modified, and sold under such trademarks as “PICCOPALE” (Hercules, Inc.), “BETAPRENE” (Reichhold Chemical Company); and thermoplastic resins of various types such as acrylic resins and some of which are sold under the trademark “ACRYLOID”-acrylic resins (Rohm & Haas Co.); and vinyl resins such as those sold under the trademark "GEON” (B.F. Goodrich Chemical).
  • Illustrative hard waxes are polyethylene waxes, carnauba wax and montan waxes as well as certain synthetic waxes.
  • An illustrative ultraviolet absorber useful in corrosion-inhibiting compositions made in accordance with our present invention, particularly where exposure to outdoor sunlight is involved and the coatings are clear, is the product sold under the trademark "TINUVIN” (Ciba-Geigy Corporation). Its use is generally in proportions of less than 1 wt.% of the corrosion-inhibiting compositions.
  • Pigments represent another of the optional ingredients of the corrosion-inhibiting compositions of our invention. Generally, they have the property of enhancing to a substantial extent the ability of the corrosion-inhibiting coatings produced by the compositions of our invention to withstand any adverse effects of ultraviolet rays which may be encountered in outdoor exposure environments.
  • Illustrative examples of such pigments are titanium dioxide, zinc oxide, iron oxides, carbon black, lamp black, Moly Orange; and organic dyes such as Phthalo Greens, Phthalo Blues, and organic reds and yellows. If used in our corrosion-inhibiting compositions, the proportions thereof may range * from a fraction of 1 to about 18 wt.% of our i. compositions.
  • Extenders also are optional ingredients in the corrosion-inhibiting compositions of our invention. They are generally similar in the functions which they perform in our corrosion-inhibiting compositions to the pigments except that certain of said extenders do not impart any color or impart only relatively little color to our compositions. They tend to have a favorable effect in salt fog and QUV test results, reducing film drying time, enhancing film hardness, and increasing resistance to ultraviolet rays.
  • Illustrative examples of extenders are clays, talcs, calcium carbonates, mica, and silicas. If used, the proportions thereof are variable but may conveniently range, for instance, up to about 35 wt.% of our corrosion-inhibiting compositions.
  • Polybutenes can be used in the corrosion-inhibiting compositions of our invention. If used, they serve to improve compatibility, play a favorable role in preventing or reducing any tendency of embrittlement in the coating, and they also enhance adhesion of the cured films to the metal substrate. If used, the proportions thereof are variable, but may conveniently range, for instance, from 2 to about 6 wt.% of our corrosion-inhibiting compositions.
  • plasticizers generally of the type which are used in paint compositions. They have the properties of tending to reduce embrittlement of the films or coatings produced by the compositions of our invention.
  • plasticizers are phthalate esters, for example, dioctyl phthalate; trimellitates, for instance, trioctyltrimellitate; and adipates, for instance, dioctyl adipate. If used, the proportions thereof may range up to about 12 wt.%, generally from about 2 to 5 wt.% of our corrosion-inhibiting compositions.
  • compositions anti-skinning agents particularly suitable being that sold under the trade designation "Exskin II" (Methyl Ethyl*Ketoxime) which is used in very minor proportions, generally well less than ' l wt.%, usually about 0.3 to 0.4 wt.%.
  • the corrosion-inhibiting compositions of our present invention do not contain any mineral oils, paraffinic or naphthenic. Small proportions may be used, but not in sufficient amounts to adversely affect the hard, non-tacky, essentially non-oily coatings produced in the use of the corrosion-inhibiting compositions of our present invention. If used, the proportions, based on the weight of our corrosion-inhibiting compositions, are distinctly minor, generally in the range of about 1 to about 3%.
  • EXAMPLES of corrosion-inhibiting coating compositions made in accordance with the present invention are given by way of illustration only and not by way of limitation as numerous other compositions can readily be prepared in light of the teachings and guiding principles disclosed above. (Also included with said EXAMPLES are Ranges of Wt.% modifications of said EXAMPLES without any material changes in the properties and utilities of said illustrative EXAMPLES proper). All parts listed are by wt.% of said compositions. They include preferred embodiments of the invention.
  • EXAMPLES 1 and 5 as constituting, generally, the best embodiments of our invention for use as pipe varnish compositions, although they have many other areas of usage as highly effective corrosion-inhibiting compositions.
  • EXAMPLE 2 we consider EXAMPLE 2 as the best embodiment of our invention for overall use, in a variety of environments such as automotive maintenance, industrial and, also, various non-automotive environments such as on bridges, where fast-drying, hard, non-tacky, essentially non-oily highly-permanent coatings are an important desideratum; as well as effective corrosion resistance in aggressive salt environments, where the corrosion-inhibiting compositions of our invention are applied to somewhat rusted or poorly-prepared metal substrate surfaces, primarily but not limited to different grades of carbon steel.
  • Our corrosion-inhibiting compositions also allow, in many instances, for good film build and application even on the bottom side of horizontal surfaces without any appreciable dripping or loss of.the applied liquid coating prior to at least partial drying and/or curing occurring.
  • compositions which function best in certain environments may not, though reasonably or highly effective, necessarily be the best embodiments when used in other environments.
  • Overall, what has been set forth above as being considered the best embodiments of our invention is, generally speaking, correct. All of said compositions are, however, highly advantageous in various environments or for various corrosion-inhibiting uses.
  • SACI-760 is used as the source of the inorganic-organic complex, in this case the thixotropic overbased calcium sulfonate/calcium carbonate complex which, as has been noted above, contains 60 wt.% of said non-volatile (N.V.) complex and 40 wt.% of mineral spirits, it also being pointed out that the TBN of the complex is approximately 265.
  • blending order is in order only to exclude the drier(s), and epoxidized oils if used in the compositions; and, after the stripping, then to add the drier(s) and the epoxidized oil.
  • the heat reached during stripping would cause or tend to cause gelling if the driers and/or the epoxidized oil were present in the composition when the stripping step was carried out.
  • SACI Thixotropic Overbased Calcium Sulfonate/Calcium Carbonate Complex
  • Phenolic Modified Alkyd (50 N.V. ) 2.89 2-4
  • Anti-Skinning Agent 0.44 0.3-0.6
  • Anti-Skinning Agent 0.35 0.3-0.5
  • Anti-Skinning Agent 0.4 0.3-0.5
  • Phenolic Modified Alkyd (50 N.V.) 2.8 2-3.2
  • corrosion-inhibiting compositions, and/or films produced by the use of such compositions on metal substrates, made in accordance with our present invention have definitely improved properties or advantages, or various combinations of improved properties or advantages, in relation to one or more of at least the following considerations set forth below, over corrosion-inhibiting compositions and/or films utilizing overbased thixotropic inorganic-organic complexes as one of the ingredients of said compositions but where such compositions do not contain synthetic drying oils or natural drying oils and driers, as well as over corrosion-inhibiting compositions and/or films utilizing as one of the ingredients thereof overbased thixotropic inorganic-organic complexes, which compositions also contain drying oils, synthetic or natural, as shown in the above-cited Patent No.
  • corrosion-inhibiting compositions of our invention have a wide range of uses in environments in which their properties are such that they overcome problems which various prior art and prior-known corrosion-inhibiting compositions have not been adequately satisfactory.
  • a number of particular problems which has long plagued the steel pipe industries which has centered around seeking satisfactory or even reasonably satisfactory so-called pipe varnish compositions for steel pipe during storage under atmospheric or weather conditions or the like.
  • so-called varnish compositions which are commercially used are commonly characterized, when applied to the steel pipe, by the usual spraying or otherwise coating of presently-used pipe varnish compositions, by sagging which results in an uneven film build.
  • the application of the pipe varnish compositions produces a film thickness of as little as 0.5 mils at the top of the pipe while, at the bottom of the pipe, there is an overbuild of film thickness, as well as literal dripping, creating undesirable "housekeeping" problems.
  • high rejection rates after outdoor storage of the varnished or coated steel pipe are encountered, being not uncommonly in excess of 30% after 6 months of outdoor storage. Such deficiencies have caused the rejection of appreciable amounts of steel pipe after outdoor storage with consequent substantial economic loss.
  • Traditional pipe varnishes comprise or consist of low-cost, quick-drying alkyd resins cut back to about 50% solids with volatile organic solvents. Due to better solvency and a relatively fast evaporation rate, a solvent such as xylene is commonly used. This choice of such solvents creates an extreme fire hazard in plant operations as the flash point is generally in the range of 70-85° F.
  • Such traditional pipe varnish compositions commonly have marginal corrosion resistance. They commonly give only 100-200 hours salt fog protection at 1 mil dry film thickness. The relatively low solids content gives traditional pipe varnish compositions bad film build and application characteristics. When spray applied to a hopefully consistent 2 mils film thickness, such pipe varnish compositions, as indicated above, display very bad film sag (running) on curved surfaces.
  • compositions of our present invention which are of especial utility as pipe varnishes in steel mills are characterized by particularly effective corrosion resistance, water displacement, thixotropy, U.V. resistance and film hardness and effective short dry time of the films
  • the inventions disclosed in each of said Patent Applications are concerned with corrosion-inhibiting compositions which are of the type which include, as constituents thereof, (a) an inorganic-organic complex in the form of a thixotropic overbased alkaline earth metal organic sulfonate complex with an alkaline earth metal carbonate, (b) a drying oil or a synthetic drying oil, and ( ⁇ ) a drier, in certain proportions, with or without various other ingredients, which compositions, after application in the form of a thin film on a metal surface and drying and/or curing, form a hard, essentially non-oily coating.
  • the corrosion-inhibiting compositions disclosed and claimed in said copending Applications constitute various definite improvements over corrosion-inhibiting compositions previously known to the art.
  • the corrosion-inhibiting compositions disclosed and claimed in our present Application constitute further improvements not only over the prior art patents and publications discussed above but also constitute further improvements and provide additional advantages for various corrosion-inhibiting purposes over the corrosion-inhibiting compositions disclosed in said
  • MRT Stands for MAGNAFLUX RETENTION TEST METHOD which is a method which actually measures the cracks and defects in an iron or steel member usually before coating and commonly after coating with a corrosion-inhibiting coating.
  • the Magnaflux test is a test of the pipe itself. If free from cracks or similar defects, the Magnaflux particles should not adhere to the coating at the end of testing the steel pipe for defects. This Test Method is a

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

Composition anticorrosion constituée d'un complexe inorganique/organique, sous forme d'une solution et/ou d'une dispersion colloïdale dans un solvant organique volatil d'un métal alkalino-terreux thixotrope surbasé, par exemple le calcium, un sulfonate organique, mélangé avec un métal alkalino-terreux, par exemple le carbonate de calcium; et une huile siccative synthétique, comme par exemple des alkydes d'huiles fortement polymérisées, ou un mélange de ladite huile siccative synthétique avec une huile siccative naturelle (modifiée ou non), comme par exemple l'huile de lin normale ou épaisse, ladite huile siccative synthétique représentant environ 15 à 60 % en poids de ladite composition ou lorsque ladite huile siccative naturelle est utilisée pour constituer jusqu'à 40 % en poids de l'huile siccative synthétique, avec en plus un siccatif pour peintures.
PCT/US1987/001322 1986-06-12 1987-06-04 Composition de revetement anti-corrosion pour metaux Ceased WO1987007627A1 (fr)

Applications Claiming Priority (2)

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US87335586A 1986-06-12 1986-06-12
US873,355 1986-06-12

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WO1987007627A1 true WO1987007627A1 (fr) 1987-12-17

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WO (1) WO1987007627A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9249339B2 (en) 2013-12-30 2016-02-02 Matthew Watson Auto reconditioning solution
DE102015216701A1 (de) * 2015-09-01 2017-03-02 Bayerische Motoren Werke Aktiengesellschaft Korrosionsschutzmittel und Verfahren zum Konservieren eines Hohlraumes
US10538676B2 (en) 2015-07-01 2020-01-21 Nippon Paint Holdings Co., Ltd. Surface layer-peelable composite coating film, coating composition for forming composite coating film, and method
US11220607B2 (en) 2018-12-18 2022-01-11 Fuchs Petrolub Se Anticorrosive agent for cavity preservation, and use thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017002885A1 (fr) * 2015-07-01 2017-01-05 日本ペイントホールディングス株式会社 Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé
TWI861427B (zh) * 2021-07-30 2024-11-11 戴龍文 金屬磨損修復組成物及其製法

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3565843A (en) * 1967-12-20 1971-02-23 Rudolph Kassinger Organic rust inhibiting composition
US4495225A (en) * 1984-03-21 1985-01-22 Economics Laboratory, Inc. Method and composition for the prevention or inhibition of corrosion
US4631083A (en) * 1985-06-17 1986-12-23 Witco Corporation Pipe varnish compositions and use thereof

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US3925087A (en) * 1974-04-04 1975-12-09 Economics Lab Corrosion inhibition or prevention with inorganic-organic complexes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3565843A (en) * 1967-12-20 1971-02-23 Rudolph Kassinger Organic rust inhibiting composition
US4495225A (en) * 1984-03-21 1985-01-22 Economics Laboratory, Inc. Method and composition for the prevention or inhibition of corrosion
US4631083A (en) * 1985-06-17 1986-12-23 Witco Corporation Pipe varnish compositions and use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0309472A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9249339B2 (en) 2013-12-30 2016-02-02 Matthew Watson Auto reconditioning solution
US10538676B2 (en) 2015-07-01 2020-01-21 Nippon Paint Holdings Co., Ltd. Surface layer-peelable composite coating film, coating composition for forming composite coating film, and method
DE102015216701A1 (de) * 2015-09-01 2017-03-02 Bayerische Motoren Werke Aktiengesellschaft Korrosionsschutzmittel und Verfahren zum Konservieren eines Hohlraumes
US11220607B2 (en) 2018-12-18 2022-01-11 Fuchs Petrolub Se Anticorrosive agent for cavity preservation, and use thereof

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JPH02500450A (ja) 1990-02-15
EP0309472A4 (en) 1992-03-18
EP0309472A1 (fr) 1989-04-05

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