JPH02500450A - Corrosion inhibiting composition for coatings on metals - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Corrosion inhibiting composition for coatings on metals Technical field Our invention provides novel liquid coating corrosion inhibiting compositions of the type described below. Regarding. The coating corrosion inhibiting composition is suitable for coating on ferrous and non-ferrous (especially ferrous) metals and steel. Effective when applied as a thin film and dried and/or cured. forms a hard, non-stick dry film and is not susceptible to corrosion or rust. It is very effective for preventing or suppressing corrosion or rust of the above-mentioned metals.

Background of conventional technology Over a very long period of time, many coating compositions have been proposed, and many of them However, if ferrous metals or non-ferrous metals are susceptible to rust or corrosion, have been used commercially for coatings to prevent or inhibit corrosion. known for a long time As previously mentioned, rust or corrosion is caused by water and air (especially humid air). gold by various chemicals or other materials in contact with metal surfaces. Occurs due to environmental conditions such as surface contact. In most cases, iron, steel, etc. While ferrous metals represent an area where rust and corrosion problems are particularly problematic, various non-ferrous metals metals, such as aluminum, are also subject to corrosion.

has been suggested or has been or is currently in commercial use. Corrosion inhibiting compositions currently available can be broadly divided into two types. One is relative They form a thin film-like coating on the gold and are soft. properties such that they can be easily peeled off or removed from metallic surfaces, e.g. by organic solvents; The composition is

In such cases, it is necessary to periodically remove the coating in order to repair the metal surface, etc. Then recoat them.

The other composition forms a relatively thin film coating and hard, hard, and intended to be and have the properties of an essentially permanent coating; and , consisting of a composition that can be removed only with great difficulty.

The coating composition of our invention contains as one of the essential components of the coating composition: Thixotropic overbased alkaline earth complexed with inorganic alkaline earth metal carbonate A type that involves the use of inorganic-organic complexes consisting of metal organic sulfonates. Therefore, in the prior art, such an inorganic-organic complex and a component of a corrosion-inhibiting composition for a coating are used. As such, corrosion inhibiting compositions for coatings containing the inorganic-organic complexes have long been known. You should be aware of what is being done to you.

chickentrope or grease-like complexed with alkaline earth metal carbonates is a gel-like Chintorog alkaline earth metal organic sulfonate, polymers, Trolatums, microcrystalline or other waxes, thinning agents, and resins; Non-volatile or volatile (or mixtures of non-volatile or volatile) hydrocarbons and and/or other liquid organic solvent vehicles or diluents. The use as corrosion inhibiting compositions for coatings is well known in the art, containing and U.S. Patent Nos. 3,925,087, 3,453,124, 3.4 No. 92.231, No. 3,565,672, No. 3,565°843, No. 3.6 No. 61.622, No. 3,746,643, No. 3,816,310 and No. 4. No. 495.225, as well as those referenced in the specifications of these patents. Disclosed in other patent specifications, etc. These various coating corrosion inhibiting compositions are for various purposes, e.g. tanks (e.g. marine ballast tanks, barges, offshore oil wells) including some float coating or flotation coating inside the It is known to have a certain degree of utility. Now, for example, fill the tank with water. However, a corrosion inhibiting composition that is lighter than water is poured onto the surface of the water, and then the water is drained from the tank. The floating layer of anti-corrosion agent is removed from the tank at the same time as the water is removed. Attach to both walls and bottom of. Other uses of the various corrosion inhibiting compositions include, e.g. For use in car and truck body primers, conservation paints, and other environments. There are other uses for rice.

No. 3,925,087 discloses (a) 4 parts in an essentially inert liquid oil phase; Chicken complexed with calcium carbonate, stably dispersed in an amount not exceeding from overbased alkaline earth metal (especially calcium) organic sulfonates. about 10% of a rust-inhibiting, grease-like concentrate containing a thixotropic inorganic-organic complex. ~30% by weight; (b) aliphatic hydrocarbon diluent, alicyclic hydrocarbon diluent, aroma consisting of group hydrocarbon diluents and mixtures thereof boiling at temperatures above 150°C Drying oil (particularly tung oil) or synthetic drying oil which is miscible with the diluting oil selected from the group and (c) from 60% to essentially the balance of said composition. A corrosion inhibiting composition comprising a diluent oil is disclosed.

In column 6, lines 36-43 of the above-mentioned U.S. Pat. No. 3,925,087, it is stated that Too much drying oil leads to the formation of cracks in the film...'' Describe it. A drying oil of 3 to 9% by weight is suitable, with 6 to 8% by weight being preferred.

The above-mentioned U.S. Pat. No. 3,925,087 specifies that In column 2, line 21, a gel-like thixotropic persalt complexed with calcium carbonate One commercially available source of an inorganic-organic complex composition comprising a calcium-based organic sulfonate The compositions are all petroleum resins or waxes distributed in a hydrocarbon solvent. or may contain. References are made to the City under the trademark rsAcIJ. Two such rsAcIJ products, viz. , rsAcIJ products including rsAcIJ-200 and rsAcIJ-300 Specifically disclosed as an example. (rsAcIJ is a registered trademark, 197 Liteco Corporation, New York, New York, from 3 years onwards. owned. ) The rsAcIJ product is complexed with calcium carbonate as described above. Formulation containing a thixotropic overbased calcium organic sulfonate It is stated that it consists of That is, the inorganic-organic complex is No. 25,087 as a component of the corrosion inhibiting composition. Therefore, the l5A(, rJ product is not generally an inorganic-organic complex itself. stomach. The patent specification states that rSACIJ-200 and rSACIJ-300 products are Since it has been commercialized and is commercially available, the production of the corrosion inhibiting or rust inhibiting composition of the patent is Discloses the use of rsAcI'-200 and rsAcI'-300 products in ing.

Column 4, lines 40 to 56 of the patent specification describes typical inorganic-organic complex greases. concentrates, such as 15AC■ products, in amounts greater than 25% by weight, and typical Since it contains 50 to 70% by weight of the complex itself, the corrosion inhibiting composition of the patent invention The proportions of the essential components of the composition are: a, about 5-15% by weight of the inorganic complex: b, about 2% to about 10% by weight drying oil; and C9 essentially the balance up to 100% (e.g. , at least 75% by weight) as a hydrocarbon oil diluent. It has been removed. The specification then states that the active ingredient thus represented is about 1 = complex/drying oil ratio of 1 to 3:1, e.g. activity to about 50 to 300 cps. The dilution of the ingredients is at least 1.0 g per square meter of metal to be protected. If it adheres, it will be described.

The '087 patent contains rsAcIJ and rsAcIJ as control formulations. Four examples (C-1 to C-4) containing only naphthenic petroleum and no drying oil are included in the account. 25 Examples: Among the 1 to 25 Examples, some have no rs Contains only naphthenic petroleum solution of tung oil without AcIJ; others , rsAcIJ-200 or rsAcIJ-300 (Examples 2 and 17 to 19) and naphthenic petroleum solution with dryer-free tung oil. Those within the permitted range: Others include rsAcIJ-200 and hair dryer. The scope of the patent includes naphthenic petroleum solutions of linseed oil with or without Those clearly within the range: and the others are rSACI''-200 of naphthenic petroleum solution and tung oil in amounts of 20 and 30 wt% of the formulation. (Examples 14 and 15), which are outside the scope of the patent. The patent specification is Whether the corrosion inhibiting composition of the invention contains or is added petroleum resin or waxes. , or the particular rsAcIJ product utilized, e.g., rsAcIJ-300, (See the final paragraph in column 1 and Example 2) . As shown in the last paragraph of column 8 of Patent No. 3,925,087 Compositions 14.15 and 16 each disclose the following formulations: Ingredients in weight% Example Naphthenic petroleum rsAcTJ 200 Tung oil +4 75.0 5. 0 20 +5 65.0 5.8 30 16 75.0 15.0 10 According to Table 1 in column 10 of the said patent, the salt water spray of the aforementioned Examples 14, 15 and 16 The tests show 5.6 and 28 hours respectively before failure, which are similar to the standard salt spray test. equivalent to complete failure or ineffectiveness of such compositions in corrosion resistance.

In fact, the March 1975 lO date in the packaging of Patent No. 3.925.087 has been amended. In the first paragraph of page 9 of the sound, [increasing the proportion of tung oil at the expense of rSACIJ] It also causes “rapid damage to the coating”! Please make a specific reference to This specific reference is made to the aforementioned Examples 14-16 of the patent. Ru. In fact, 10% of the mixed state with naphthenic petroleum and rsAc IJ-200 of tung oil (Example 16 of the patent), as the amendment states on page 9 of the patent. , failure of the salt spray test that occurs at the end of 28 hours is ``claimed; (i.e., 10% tung oil: The amount of tung oil is about 10% or less, more preferably When the amount of drying oil exceeds about 9% or less showed a substantial decline in performance. Examples 5.6 and 7 show I; salt spray test results Even from a practical standpoint, the corrosion inhibiting compositions of Examples 1, 2, and 3, and most Other sets which possibly form part of said invention except for not having valid salt spray test values In contrast to commercial products, it had no commercial value.

The patent's corrosion-inhibiting compositions are soft or sticky, rather than brittle, and have a tendency to crack. It is described as forming a solid protective coating with little or no oxidation. They are , is described as being particularly suitable for coating the inside of tanks, and by spraying Although it can be applied, it is best applied using the flotation coating method. And that et al., the corrosion inhibiting composition was easily removed from metal surfaces in non-heated degreasing solvents. It is described as having the advantageous properties of a complete protective coating on the surface.

The above-mentioned prior art mentioned in column 2 of the above-mentioned patent No. 3,925,087 Disclosure of Technical Patent No. 3,453,124 and No. 3,565,843 Regarding the invention of the patent No. 3,925,087, thixotope that is stably dispersed in the essentially inert liquid oil phase component of the control composition. Patent No. 3゜92 as a rust-inhibiting grease-like concentrate consisting of rope inorganic/organic complexes 5.087 is disclosed as an exemplary description. Said Patent Nos. 3,453,124 and 3,565,843 and their A more complete discussion of the disclosures of the other above-listed patents is believed to be here in turn, and that and is shown below.

Patent No. 3,453,124 discloses, among other things, oil vehicles such as mineral oil. or other non-volatile vehicle or medium, or mineral spirits, etc. Other vehicles or media of volatile nature, and even more volatile and volatile Aluminum dispersed in the form of colloidal particles in a mixture of aqueous vehicle or medium. Thixotropic overbased alkali complexed with carbonates of potassium earth metals (such as calcium) The production of inorganic-organic complexes in the form of earth metal (calcium, etc.) organic sulfonates has been developed. Show. The patent also describes corrosion inhibiting compositions for coating processing sump of ferrous or non-ferrous metals. disclosed that the composition comprises the vehicle or medium as an essential ingredient of the patented invention. The above-mentioned inorganic-organic complex colloidally dispersed in aluminum and phosphoric acid of alcohols Consists of reaction products with esters. In column 40, lines 48 to 75 of the patent, certain The addition of hydrocarbon resins of the type to the reaction product results in particularly useful corrosion inhibiting compositions. and that the resin is soft and non-greasy in coating compositions. Rather, it imparts the property of forming a robust coating on the metal, and this robust coating resists wear and tear. , provides additional resistance to dust absorption, gravel absorption, etc.; and Avoids the disadvantages of soft, grease-like coatings that easily peel off on contact Therefore, it is stated that there are advantages.

Said patent No. 3,453,124 also states that in columns 43 and 44, Comparative Corrosion Using Exemplary Patented Corrosion Inhibition Compositions and Commercial Automotive Primer Compositions Disclose test results. Commercial automotive primer compositions include specified petroleum primers. Composition: Not specified, but contains 5AE40 oil, rust inhibitor and drying oil. Undercoat compositions described as; petroleum-based translucent films (others not specified); ); and asphalt cutback primer compositions (and other specified not made in accordance with the claimed invention of the patent. Comparative testing of corrosion inhibiting compositions has shown that they are superior to the corrosion inhibiting compositions to which they are compared. It is disclosed that it has been shown that the

Patent No. 3,492,231 describes a method for producing an inorganic-organic complex and its use in metals. The utility of the complex in the preparation of corrosion inhibiting compositions for use is disclosed. these A variety of inorganic-organic complexes have been known in the art for a long time, and they These complexes are illustrative of compositions previously known to those skilled in the art dealing with corrosion inhibiting compositions containing such complexes. known from.

Patent No. 3,565,672 describes a method for producing a mineral oil solution of an inorganic-organic complex. disclosed that the complex has utility as a corrosion inhibitor, and here the complex itself is complex. It is disclosed that it is only one component among several components. The complex consists of multiple components with specific Can be used in combination, and in certain proportions, our invention's novel and highly Features an improved corrosion-inhibiting composition Patent No. 3,565,843 discloses that by spraying onto metal surfaces, An organic chain-suppressing composition is disclosed that forms a hard coating with little tack. the composition (a) In fact, ammonia under conditions that form a gel that is a chickentrope gel Inorganic-organic in the form of an overbased alkaline earth metal organic sulfonate mixed with water. about 10 to 35 wt% of the organic complex; (b) carbonization having a specific molecular weight and a specific softening point; Hydrogen polymer resins as well as hydrocarbon polymer resins with specific melt index. ethyl vinyl acetate copolymer and a combination with wax, about 5 to 15 wt% of the selected coating material; and (c) about 270° to 450'F. about 55 to 85 wt% of a hydrocarbon solvent having a boiling point in the range of .

Patent No. 3,661,622 describes, among other subject matter, alkaline earth Thixotropic overbased alkaline earth complexed with metal (especially calcium) carbonates Production of metal-based (especially calcium) organic sulfonates: and low-density polyethylene , with certain polymers such as polypropylene; Copolymerization with vinyl monomers such as vinyl, polymethyl methacrylate and others remers: as well as the production of corrosion-inhibiting primer coating compositions containing the above-mentioned components. Disclose. As pointed out in column 11, lines 45-65, the content of polymers is , among other functions, compared to primer compositions that do not contain such polymers. This produces a harder, tougher and less tacky film. The primer The composition is preferably applied to the metal surface to be coated in the form of a solution in a volatile organic solvent. The primer composition solution can be applied by brushing or spraying. The volatile organic solvent is evaporated from the applied primer composition film and then typically It is stated that the paint should be applied.

Patent No. 3,746,643 discloses a viscous, high melting point coating for metals. Alternatively, a rust inhibiting composition is disclosed.

The composition comprises a solution of a volatile hydrocarbon solvent such as Stoddard solvent, the solution comprising: Thixotropic overbased alkaline earth metal rusted with alkaline earth metal carbonate Certain mineral oils consisting of inorganic-organic complexes in the form of organic sulfonates may also be included; The coating composition then contains a certain proportion of microcrystalline wax. This special The novelty lies in the inclusion of microcrystalline wax in the composition; Types that do not contain microcrystalline waxes as shown in the esalometer test Similar coating compositions or similar coating compositions containing conventional paraffin wax Dip-coated steel panels exceed expectations in their resistance to rust. Does not give a significant increase.

Patent No. 3,816,310 discloses rust inhibitors and also rust inhibitor greases. Disclosed is a method of making a coating composition that has particular utility. This patent applies to mineral oil or volatile organic solvents such as Stoddard solvents; an alkali dissolved or dispersed in a mixture of a volatile organic solvent and a volatile organic solvent. Thixotropic overbased alkaline complexed with earth metal (especially calcium) carbonates Preparation of inorganic-organic complexes in the form of lithium metal (especially calcium) organic sulfonates Disclose a method to do so.

Compositions made according to this patent can be applied to metal surfaces by spraying or painting. and can be applied to metal surfaces to protect them against rust; Such compositions are stated to have particular utility for the rust prevention of automobile undercarriages. There is.

Chicken Toro, as shown by U.S. Pat. No. 4,150,192. overbased calcium sulfonate/calcium carbonate complex; loratum; non-volatile diluent oil represented by mineral oil; microcrystalline wax: powder a Particulate fillers such as aluminum, basic lead silicone chromate, zinc molybdate, etc. : a mixture containing a hydrocarbon-derived thermoplastic resin; a phosphorescent pigment; and a plasticizer. It is also known in the art to prepare corrosion inhibiting compositions or rust inhibitors. prepared As used herein, such corrosion inhibiting compositions are in the form of true melt compositions. and not only is it a true melt composition, but the composition is ready to use, e.g. Because it cures within about 10 seconds on a ferrous metal substrate and the coating formed is soft, we is fundamentally different from the corrosion inhibiting composition of the present invention. Our corrosion inhibiting composition of the present invention , for example, as a pipe varnish for steel factories that manufacture steel pipes. The patented compositions have advantages and are highly effective for many important applications. would have no commercial utility: and the same is true for the corrosion inhibition of our invention. This is true for many other applications for which control compositions are particularly suitable; In contrast, the compositions of the patent would have no commercial value.

Patent No. 4,495,225 is based on the above-mentioned patent No. 3,925,087. Although the specification is relevant, a corrosion inhibiting composition is disclosed, the composition comprising: Mineral oil comprising 20-60 wt% of the composition: about 5-25% drying oil; A thixotropic overbased component dispersed in a low range specialty dryer composition. Corrosion-inhibiting grease-like concentrate of lucium sulfonate-calcium carbonate complex contains. That is, the dryers are selected from two different groups. That is, (1) A group consisting of copper carboxylate compounds, rare earth carboxylate compounds, and mixtures thereof. and (2) a zinc carboxylic acid compound. The second metal dryer is selected. From the third line from the bottom of the second column to the third column, The patent specification states that the coating composition of the patent cures into a "solid but soft protective layer." Then write it down. The patent specification states that the corrosion inhibiting composition of this patent contains petrolatum, Can contain petrolatum oxide, hydrocarbon diluent oil, polyisobutylene, metal surfaces, For pigments such as aluminum pigments, carbon black, and anti-skin agents Provides improved tack.

One of several components in the preparation of our novel corrosion inhibiting compositions of the present invention For the known rust-inhibiting thixotropic inorganic-organic complexes used as For certain rsAcIJ products, as a commercial source of products containing Disclosure of Patent Nos. 3,925,087 and 4,495,225 In addition, there are other rSACIJ corrosion control products known in the industry, including: The product is disclosed in Patent Nos. 3,925,087 and 4,495. , No. 225, disclosed in certain rsAcIJ products mentioned in US Pat. Contains various thixotropic inorganic-organic complexes. Such rsAcIJ products may also be advantageously used in the preparation of the novel corrosion inhibiting compositions of the present invention. This way Additional rsAcIJ products such as Disclosed in the tasheet.

Below we refer to various other rSAcIJ products, which contains the chickentrope overbased calcium according to our invention as one of its ingredients. Sources of Siium Organosulfonate/Calcium Carbonate Complexes for Use of the Complexes as a practical matter, the expediency or attempted use of the use or attempted use. or the complexes mentioned above, independently of any disadvantages.

rsAcIJ-100 and 100A, rSACIJ-200 and 200A, r sAcIJ-300 and 300A, rsAcIJ-2400, rsAcIJ -2452 and rsAcIJ -2460. Regarding further technical data sheets relating to AcIJ products are manufactured in volatile hydrocarbon solvents (mineral spirits) or in paraffin. colloidally dispersed in mineral oil, or in mineral spirit and mineral oil. Thixotropic overbased calcium organic sulfonate/calcium carbonate complex contains. The thixotropic overbased calcium organic salts of the rSACIJ products mentioned above. The organic sulfonate moiety of the sulfonate-calcium carbonate complex is branched or is a linear/linear monoalkylbenzene or dialkylbenzene sulfonic acid or sulfonic acid, an alkyl group or at least 12 carbon atoms, generally from 12 to It is derived from the use of a mixture of groups each containing 30 carbon atoms.

rsAcIJ-100 and 100A concentrates are mineral split and paraffin A colloidal dispersion of the complex in a mixture of mineral oils. rsAcIJ-1 00A also contains oxidized petrolatum for modified anti-corrosion properties. Ru. rsAcIJ-100 product contains 60.50 or 40 wt% solids . Coatings made with the listed basic compositions are generally waxes (refined and petrolatum: oxidized; petrolatum (with an acid value of 15 to 20); (Recommended): Pigments; Resins; and Asphalt. has been done. Coatings made with rsAcI''-1oo and -10OA concentrates were Produces a soft, oily and self-healing film. It is stated that it will be done. , rsAcIJ-100 and -10OA, salt Haze test is 500 hours to failure of rSACIJ-100: 0.5 mil "5ACIJ-100A failure for 600 hours on dry film of thickness; 1 ．． 1 for failure of rsAcIJ-100 in O mil thick dry film. 000 hours and 1200 hours for failure of rsAciJ-100A.

rsAcIJ-200 and 200A are colloids of pre-complexes in paraffinic mineral oil. It is a do-like dispersion. rsAcIJ-2'OOA contains 36 wt% of the above complex and 64 Contains wt% mineral oil. rsAcIJ-200A is oxidized petrolatum Also contains. Other things done for I'5ACIJ-100 and 100A The description is applicable to rSACIJ-200 and 200A.

rSACIJ-300 is a thixotropic overbased inorganic in mineral splints. A colloidal dispersion of an organic complex, comprising about 35 wt% of the complex and about 37 wt% of the complex. containing the mineral split and a small proportion of microcrystalline wax and paraffinic mineral oil. and provides a corrosion inhibiting composition. The composition is exceptionally resistant to seawater immersion and salt atmospheres. listed as having protective properties; typical applications include outdoor parts storage, automotive Protects against body rust, covers underground pipes, and protects vessels for marine applications and foreign routes; sAcIJ 300 wax-like paint with organic solvent dilution or long-term protection and relative in combination with asphalt or petrolatum where ease of removal is important and the film obtained from using a basic formulation of 5ACI. is solid and wax-like. rsAcIJ -300A is rsAcI''-3 Similar to 00; but it also contains oxidized petrolatum. rsAcI J-300 and rsAcIJ-300A salt haze test Among other thicknesses, rsAcIJ-300 breaks at 0.5 mil dry film thickness. rSACIJ-300A at 300+ hours and same film thickness for loss 800+ hours to failure; rsAc for 1.0 mil film thickness 800+ hours for IJ-300 failure and rsAcIJ-30OA failure Shows 1500 medium hours for losses. In a 5.0 mil thick film, rsAcIJ -300 shows damage after 2000+, rSACIJ-300A at 3000+ It showed damage in between.

As mentioned above, other commercially available rsAcIJ products include rsAcI''-2400, , rsAcIJ-2452 and rsAcIJ-2460. These rS All ACN products are mineral splint-wax colloidal dispersions. It is an anti-food concentrate. They have a high content of thixotropic inorganic-organic complexes. Then, it is described that (65 wt% solid content in rsAcr"-2400, r 52 wt% in SACIJ-2452, 60 wt% in rsACIJ-2460 ). They effectively achieve the desired solidity, activity and/or viscosity level. both refined and unrefined waxes, petrolatum and oxidized petrolatum, Compatible with resins, polymers, asphalts, oils, and aliphatic and aromatic solvents It is stated that. Salt haze data for dry film thicknesses of 0.5 mil and 1.0 mil. The time to breakage is 500 at 0.5 mil. , and the time to failure at 1.0 mil is 1100.

rsAc TJ-700 is the colloidal form of said complex in mineral split. and its non-volatile solids content, i.e. thixotropic overbased complex ( TBN is 250), is substantially 50 wt%, and the mineral supplement The content is substantially 50 wt%.

The rsAcIJ-700 technical data sheet states that the rSACN-700 does not have a valid warranty. It is stated that it must be used with additional plasticizers or resins for protection: In general, rsAcI''-700 can be used to produce a variety of effective coatings. Hydrocarbon resins, asphalt, waxes, mastics, petrolatum and oils It is stated that it can be mixed with. In addition, the results of the salt spray test and the wet chamber corrosion test were The results are also shown.

rsAcIJ-760 is a chickentrope overbased complexed with calcium carbonate Mineral splint colloid of calcium organic sulfonate (TBN 265) It is a solid dispersion whose non-volatile solids content, i.e. body, is substantially 60 wt%, and its mineral split content is substantially It is 40Wj%. The organic portion of the organic sulfonate is a linear alkylbenzene. Derived from sulfonic acid.

Generally speaking, different rsAcIJ products have varying degrees of solidity, activity, and/or or one or more refined and unrefined waxes to achieve viscosity; Petrolatum, resins, polymers, bitumen, oils, and aliphatic and aromatic It is stated that it can be prepared with a solvent.

Summary of the invention Our invention is characterized by a combination of specific properties and features previously known in the art. New and Improved Applications with Enhanced Utility over Various Coating Corrosion Control Compositions The present invention is based on the discovery that corrosion inhibiting compositions for coatings can be obtained.

The corrosion-inhibiting composition of our invention (hereinafter referred to as "composition" or "coating" for convenience) sometimes referred to as "composition". ) are metal supports to be protected against corrosion or rust. It is a free-flowing liquid that can be applied as a thin film onto the surface of the body. And the group The composition contains as essential components (a) an alkaline earth metal (especially calcium) carbonate; Thixotropic overbased alkaline earth metals (especially calcium) complexed with salts inorganic-organic complexes in the form of organic sulfonate salts; (b) synthetic drying oils, especially as such; or a mixture of synthetic drying oil and drying oil, in the case of such a mixture, the proportion of drying oil or It is particularly advantageous to contain a substantial proportion or amount of synthetic drying oils exceeding the amount (C) The type of dryer and paint dryer is normal and desirable; and (d) containing a volatile organic solvent, especially a volatile hydrocarbon solvent. Said ( Components a), (b) and (c) are dissolved in the solvent (d) and/or in colloidal form. dispersed and applied by conventional application methods, e.g. by brushing, but more preferably or spray drying to provide a free-flowing, homogeneous composition that can be deposited onto a metal support. Ru.

Our new and improved corrosion inhibiting compositions generally exhibit the following properties: more characterized: i.e., these characteristics include about 1 to about 6 hours, specifically about During the drying and/or curing period for a drying and/or curing time of 1 to about 2 hours, or at ambient temperature, e.g., about 0.5 to 6 mils, or suitably even thicker, but Preparation of a thin liquid film of the composition, preferably from about 1 to about 3.5 mils; drying and and/or the cured film is robust or hard, but generally not brittle, and Non-oily or essentially non-oily and non-sticky or essentially non-oily to the touch Non-stick; they can be removed from metal supports by unheated conventional degreasing solvents. Strongly attached to the metal support so that it cannot be easily removed or peeled off. adhesive and durable; and, generally speaking, the surface underneath the metal support. of substantial difficulty where removability may be required without damaging the surface. It includes that it can only be removed by some other means. Advantageously, various The above-mentioned combinations of components may include one and especially one or more auxiliary components or Used with several ingredients as detailed below.

detailed description We have identified the components that we consider to be essential to our novel corrosion inhibiting compositions. disclosing the above combination of minutes and that the ingredients are used in a range of proportions; Describe it. The proportions in the foregoing ranges, in terms of wt% of the corrosion inhibiting composition, are approximately as follows: It is: Synthetic drying oil and drying In particular, 20-40% (Synthetic drying oil standard) (c) Dryer (single or multiple) 0.3 to 2 preferably 30-50 】, based on solid content Regarding component (a), complexed with alkaline earth metal (especially calcium) carbonate Thixotropic overbased alkaline earth metal (especially calcium) organic sulfonic acids Various inorganic-organic complexes in salt form can be used in accordance with our invention. like this As is well known, inorganic-organic complexes are water-insoluble, but are soluble in volatile organic solvents. solvents, most commonly of hydrocarbon-aliphatic or cycloaliphatic character, in which colloidal It can be dispersed into As mentioned above, they are disclosed in the various patent specifications mentioned above. It is shown. As also indicated above, the complex may be branched or linear. or linear monoalkylbenzenesulfonic acids or dialkylbenzenesulfonic acids. Preferably the predominant amount is phonic acids or dialkylbenzenesulfonic acids. and 12 to 30 carbon atoms, more particularly 12 to 30 carbon atoms. most preferably derived by the use of alkyl groups containing primarily 22 carbon atoms. Ru. One well-known source of such This material is commonly referred to as the distillation residue from the production of dodecylbenzene. sulfonic acid of the bottoms product, where the alkyl group is a branched chain. And the other one is generally the corresponding distillation residue sulfur. fonic acid, but its alkyl group is linear or linear, and the residue is known as total rNABJ potmus. These inorganic-organic complexes are In the case of calcium compounds, the formula (R5Os)ICa: CaC05 (wherein R is It is an alkylbenzene group of the type mentioned above. ) is usually characterized by Yo A broader formula is shown, for example, in the aforementioned U.S. Pat. No. 3,453,124. There is. The patent specification discloses thixotropic compounds useful in preparing the corrosion inhibiting compositions of our invention. Discloses Rope Alkaline Earth Metal Organic Sulfonate/Alkaline Earth Metal Carbonate Complex do. Those inorganic-organic complexes that are particularly useful in the practice of our invention include approximately 200 or with respect to their metal ratio, they have a base number in the range of ~350: at least 4.5, and specifically in the range of about 7 to about 12. It is listed. Any thixotropic overbased calcium sulfonate/cal Siium carbonate complexes are also amenable to the production of our novel corrosion inhibiting compositions. or suitably satisfactory, with any convenient commercial source of said complex. Of particular interest is rsAcIJ-760. If our invention for use in the manufacture of corrosion inhibiting compositions made according to It is desirable to use it as a starting material containing a low content of mineral splits. Then all you have to do is take a certain amount of rsAcI'-760. and heat it, e.g., at 225° F., to remove less than 40 wt. the desired amount to give the complex having the desired wt% based on the full mineral split. is to evaporate the mineral split.

(b) With respect to ingredients, i.e., synthetic drying oil, or synthetic drying oil that is larger than the drying oil; Regarding the mixture of synthetic drying oil and drying oil, which accounts for the major amount, we first consider the following: It can be pointed out that: As used herein by us, the term "synthetic drying oil" means or a material with good to excellent drying properties at ambient temperature. and, generally speaking, in the form of a resin or resin-like material. and consists of polymers or fupolymers, illustrative examples of which are aliphatic An ethylenically unsaturated polycarboxylic acid ester of a polyhydric alcohol, where the Polyhydric alcohols contain at least three hydroxyl groups; Examples include glycerin, trimethylolpropane (irimelbyol pro pane) and pentaerythritol, and among polycarboxylic acids, preferred or phthalic acid or phthalic anhydride, or maleic acid or maleic anhydride. acid, and ethylenically unsaturated oils such as linseed oil or similar drying oils or linseed oils. These long oil fatty acids, such as dioleic acid fatty acids or tall oil fatty acids (TOFA), Ru. These include long oil alkyd resins or oil-modified alkyd resins, and phenolic alkyd resins. There are modified alkyd resins. The hydroxyl values of the alkyd resins vary. and they are about 60 to about 125" oils that are good to good at room temperature or ambient temperature. Also encompasses resins or resin-like materials that have outstanding relatively fast drying properties, It is a chemically and structurally modified product of long oil alkyd resin, or it is a chemically and structurally modified product of long oil alkyd resin. different. Modified alkyd resins with good to excellent drying properties include acrylic There are vinyl-modified alkyd resins and vinyl-modified alkyd resins. alkyd resin or resin Similar dryers are also available through the post-addition of phenolic resins, acrylic resins and vinyl resins. The drying properties of the starting alkyd resin can be varied, but However, it is important to note that such modified alkyd resins are suitably similar to those of long oil alkyd resins. Their use is within the scope of our invention as long as they have good to excellent drying properties. Ru. Other resins or resin-like materials with good to excellent drying properties may be epoxy esters and certain polybutadienes. Some of these resins have drying properties, but these may have negative effects or costs as described below. may not be industrially useful. For example, polybutadienes have a certain Although due to its physical properties it cannot be used in the proportions necessary for use in accordance with our invention. , they are used in small proportions, for example, 1 to 2 or 3%, and special effects, such as long-oil alkyd resins (which contain at least 15w of the corrosion-inhibiting composition) t%) can be used to obtain. During oxidation, it hardens , forming or producing a non-tacky, essentially non-oily film; good to At least some of the aforementioned resins or resin-like materials having excellent drying properties. are commonly referred to as convertible resins or binders. Others are In the category of thermoplastic resins that form the above-mentioned films by evaporation of emitting solvents. enter. Such thermoplastic resins include acrylic resin, vinyl resin, and hydrocarbon resin. When mixed with the convertible resin, drying and/or Improved curing time, film hardness, and resistance to organic solvents and various chemicals do. Synthetic drying oils, by themselves, are not claimed by us as novel. aftereffects In those cases where polyalkyd resins are utilized, they generally include, e.g. Used as a minor part of convertible resins such as long oil alkyd resins, and corrosion inhibiting Used as a minor part of the composition. Here, such post-modified alkyd resin is corrosion inhibiting. It constitutes about 2 to 15 wt% of the composition, preferably about 2 to about 6 wt%.

Synthetic drying oil is manufactured by BECKOSOLJ (Richhold Chemical Company). -), rAROPLA2J, for example, rAROPLAX1266-M-60 , 126 Roth 70 and December” (Ashland Chemical Company) ; Various rEPOTUFJ, preferably rEPOT[]F JNo, 37 -004, and rUROTIIFJ (Richhold Chemical Company ) as well as rR1cONJ resin, Preferably, rRIcOJ 100 and/or 156 (Colorado Chemical Certain of Pennyarytes, Inc., marketed under various descriptive trademarks of There is.

As used by us in the specification, the term "drying oil" does not refer to the term itself. Well known in the industry to have good to excellent drying properties at room or ambient temperatures is intended to mean natural drying oils. Generally speaking, the drying oil is Ethylenically unsaturated trigs of fatty acids or other ethylenically unsaturated monocarboxylic acids Examples include linseed oil, soybean oil, dehydrated castor oil, tung oil, and lycerides. Examples of lumi oil, oiticica oil, safflower oil and fish oil, as well as the natural drying oils mentioned above. For example, oxidized or blown oils or heat-thickened or polymerized oils or There are modified oils represented by oxidized drying oils such as isomerized oils. of glycerin Alternatively, others containing at least 3, generally 3 to 6 bitroxyl groups High molecular weight aliphatic polyhydric alcohols containing mainly 16 to 22 carbon atoms It can be reacted with an ethylenically unsaturated monocarboxylic acid to produce the drying oil. generally In other words, preferred drying oils are those used in conjunction with or in conjunction with synthetic drying oils, but those skilled in the art As is known in the industry and has been known for many years, raw linseed oil or thickened linseed oil itself.

Regarding component (C), i.e., the dryer, dryers are well known in the art, and Various types of compositions containing drying oils or corrosion inhibiting compositions in which drying oils are utilized commonly used in products. Drivers utilized in the corrosion inhibiting composition of our invention The ear can be a dryer, typically of the paint dryer type; and desirable. Generally speaking, they are polyvalent, common, soap-forming carboxylic acids. It is a divalent, metal salt. Illustrative examples of said dryers include cobalt, silyl Such metals as conium, lead, nickel, zinc, chromium and manganese etc. phthenates, talate salts and octanoates, or such dryer There are mixtures of two or more types. Cobalt naphthenates and diyl octoate Mixtures of coniums are preferred. Dryers have a clearly small proportion, generally corrosion inhibition. It is used in the range of about 0.3 to about 2 wt% of the control composition; Synthetic drying oils used in any of the corrosion inhibiting compositions of the present invention, or as described above. It depends on the wt% of the synthetic drying oil and the drying oil mixture. Cobalt naphthenate vs. It is preferred to use a mixture of zirconium ctanoate in a weight ratio of about 1:13.3. Yes.

Regarding component (d), ie volatile organic solvents, the solvents may be aliphatic, cycloaliphatic or aromatic. Can have aromatic properties, including hydrocarbons, chlorinated hydrocarbons, alcohols, keto and system-compatible ethers. Preferred volatile organic solvents are fatty family of solvents, particularly due to its low toxicity and relative low cost, as well as its advantageous flash point. Therefore, odorless mineral splits are suitable: as well as VM&P.

Other volatile organic solvents that can be used are those described in the aforementioned Patent No. 3,453,124. Volatile solvent disclosure is included herein.

Now we obtain certain effects and give certain properties to the corrosion inhibiting composition of our invention. one or more compounds that can be used to prepare the corrosion inhibiting composition. Let's move on to consideration of auxiliary ingredients. In general, each of the following ingredients are conventionally known in the art: , the inorganic-organic complexes described in the aforementioned prior art patents and technical data sheets. Used in certain corrosion-inhibiting compositions of the type utilized as one of its ingredients .

In the corrosion inhibiting composition of our invention, petrolatum and/or oxidized petrolatum, Also, unrefined and refined microcrystalline waxes can be used. They are, As mentioned above, they themselves are well known in the art and are commercial products. Oxidized Examples of petrolatum include ALOX No. 100D, 102.600 and 601. This is the kind sold by the ALOX company. I For purposes of each invention, those oxidized petrolatums have a degree of oxidation of about 1 It is most suitable for cases where the acid value is in the range of 0 to 130, and specifically oxidized Petrolatum has an acid number ranging from 15 to 60.

Trademark rsOcco-R-H-ISJ (Metal Lubrigand Corporation) The products sold under the United Nations University of California, Harvey, Illinois) are synthetically oxidized Pel An example is Tam, which is used and sold for use in rust inhibitor formulations. Corrosion inhibitors are prepared by mixing with metals or synthetic sulfonates.

Petrolatum, oxidized petrolatum and microcrystalline waxes are common in certain respects. act as self-healers, and they prevent overhardening of the coating. oxidation and embrittlement, and they also act on low water sensitivity. . If used, they can be used in variable small proportions and, roughly, our invention from about 2 to about 6 wt% of the corrosion inhibiting composition.

Epoxidized oils that can be used in corrosion control compositions made in accordance with our invention are As such, it is well known in the industry.

When used, they promote compatibility and improve the flexibility of coatings on metals. , and also enhances the adhesion of the coating to metal surfaces. They are somewhat Effective against salt fogging performance. Exemplary epoxidized oils include triglyceride oils, Drying oils of natural or synthetic nature, among them tung oil, dehydrated castor oil , corn oil, cottonseed oil, soybean oil, walnut oil and fish oil, but these epoxidized It can be prepared by Particularly satisfactory is the use of epoxidized It is mani oil and has the trademark rDilAPEXJ (Argus Chemical Corporation). The epoxide equivalent is 10.4. It is. Preference is given to using epoxidized oils with a high oxirane content. So These can be used in distinctly smaller proportions, generally accounting for about 2-6w of our corrosion-inhibiting compositions. It can be used at t%.

Non-drying oil type resins and certain waxes are also incorporated into the corrosion control compositions of the invention. Yes, and they can be of different diversified types. this Those that fall into this category are water-insoluble, soluble in volatile organic solvents or colloids. These are hard resins and hard waxes that can be dispersed in different shapes. They include, by way of example, Modified or modified hydrocarbon resins (petroleum-based and non-petroleum-based), rPlc cOPALEJ (Harkle's Inc.), r BETAPRENEJ (Rinhi) Products sold under the trademark Hold Chemical Company Various types of thermoplastic resins such as lyre resins, some of which are rAcRYLOIDJ acrylic resin (Rohm & Haas Company) Sold under: and the trademark rGEoN” (BF Goodlin There are vinyl resins such as those sold under the trade name Chi Chemical. exemplary rigid Waxes include polyethylene wax, carnauba wax and montan wax. and certain synthetic waxes. Regarding the extent to which the resin or wax is used. The percentages can vary somewhat, but they should not exceed 5wt%. Preferably, it is not used in high amounts, generally from about 1% to about 3% of our corrosion inhibiting compositions. It is.

Corrosion-inhibiting coatings are used in environments where they are exposed to ultraviolet light and are subject to UV degradation. If a coated metal surface is used, it should be Including the reagent in the appropriate amount or proportion in the corrosion inhibiting composition of our invention Can be done. Ultraviolet absorbers useful in corrosion inhibiting compositions made according to our invention , particularly if it involves outdoor sun exposure and the coating is transparent. The UV absorber has the trademark rTINOVINJ (Tiver-Geigy Corporation). There are products sold under the Its use is largely due to corrosion-inhibiting compositions. It accounts for less than 1 wt% of the total weight of the substance.

Pigments are another optional component of the corrosion inhibiting compositions of our invention. general In particular, they demonstrate the ability of the corrosion inhibiting coatings produced by the compositions of our invention to To withstand the harmful effects of ultraviolet rays that may be encountered in outdoor exposure environments, It has the property of increasing strength to a certain degree. Illustrative examples of such pigments include titanium dioxide, acid Zinc oxide, iron oxide, carbon black, lamp blank, Mori Orange (Mel y Orange); and phthalo green, phthalo blue, and orange red. There are organic dyes such as red and yellow. When used in our corrosion inhibiting compositions, The proportion can range from decimal to 18 wt% of our composition.

Extenders are also optional components of the corrosion inhibiting compositions of our invention. those Generally speaking, one of the extenders in the function it serves in our corrosion inhibiting composition. The fixed ones impart no hue to our compositions, or relatively little color. It is similar to pigments except that it only provides a phase. They are salt haze test and QUV test. experiment, reduce film drying time, enhance film hardness, and It tends to have a positive effect on increasing resistance to UV radiation. workman Illustrative examples of xistenders include clay, talc, calcium carbonate, mica, and There is silica. If used, the proportions may vary, but for example: Our corrosion inhibiting compositions can conveniently range up to about 35 wt%. Ru.

Polybutene can be used in the corrosion inhibiting compositions of our invention. If used, it are useful in improving compatibility and preventing or reducing the tendency of coatings to become brittle. and they play a favorable role in the curing process for metal supports. It also increases the stickiness of the lume. If used, the proportion may vary, but However, for example, in the range of 2 to about 6 wt% of our corrosion inhibiting composition, can be extended.

Yet another optional ingredient that can be included in our corrosion inhibiting compositions of the invention includes Generally, there are types of plasticizers used in coating compositions. They are the spoilers of our inventions. Characteristics that tend to reduce embrittlement of films or coatings made with food inhibiting compositions have sex. Illustrative examples of such softeners include phthalates, e.g. dioctyl trimellitate; trimellitates, such as trioctyl trimellitate; and adipates, such as dioctyl adipate. If used, its Proportions can range up to about 12 wt% of our corrosion inhibiting compositions, approximately It is approximately 2 to 5 wt%.

In certain cases, it may be preferable to include anti-skinning agents in our compositions; The appropriate one is the trademark rExskio Ill (methyl ethyl ketoxy It is sold under a very small proportion, approximately less than 1wt%. It is also used in considerably lower amounts, usually about 0.3 to 0.4 wt%.

Our corrosion inhibiting composition of the present invention contains mineral oil (paraffinic or naphthenic). Not having one is desirable in certain cases. However, our Hard, non-stick, essentially non-oily coatings made with the corrosion inhibiting compositions of the present invention. It cannot be used in sufficient quantities to adversely affect the quality of the product. If used, its proportion (corrosion) (based on weight of the food suppressant composition) is a distinctly small proportion, generally in the range of about 1% to about 3%. It is surrounded. They prevent or reduce possible over-hardening or embrittlement of the coating, Other points, e.g. to bleed out the cured film and prevent corrosion in damaged areas. prevents or suppresses water sensitivity, enhances or increases the prevention of water leakage by reducing water sensitivity, and improves the It may have other minor effects, such as the ability to increase wetting to the genus. I As mentioned above, many people are fully aware of the properties of mineral oil, and in fact, Very high percentages are used in various prior art corrosion control compositions to achieve industrial efficiency. However, in the novel composition of our invention, the use of mineral oil is unnecessary. is necessary.

The following examples of coating corrosion control compositions made in accordance with the present invention are for illustrative purposes only. In the light of the above essential teachings and guidelines, many such This is not intended to be limiting as other compositions can be readily prepared. (Also, the example Any material may be subject to change in the properties and utility of the illustrative and suitable embodiments. However, variations in the wj% range are included. ) All parts listed refer to the composition. It is wt% of the standard. They include preferred embodiments of the invention. Example 1 and 5. Optimal embodiment of our invention for use as a pipe varnish composition We generally think of them as consisting of It has many other areas of use as a corrosion inhibiting composition. Example 2 was dried quickly. A durable, hard, non-stick, essentially non-oily and highly durable coating is an important requirement. In some cases, automotive maintenance, industry, and also various non-automotive environments such as bridges. Additionally, the corrosion inhibiting composition of our invention for general use in various environments such as metal surface supports that are somewhat rusty or poorly manufactured (mainly (but not limited to different grades of carbon steel), salt-affected rings We believe that this is the best embodiment of our invention for effective corrosion resistance in ing. In many cases, our corrosion inhibiting compositions can even be used at the bottom of horizontal surfaces. , before at least partial drying and/or curing occurs. provides good film formation and application with no loss of applied liquid coating.

Compositions that perform best under certain circumstances are suitable and highly effective; Understand that when used below, it may not necessarily be the best implementation. Bede. Throughout, we believe that this is the best embodiment of our invention. What I said above is generally correct. However, all of the above compositions have different environment or for various corrosion control applications.

In the following example, thixotropic overbased calcium sulfonate/calcium For carbonate complexes, use rsAcI, 1-760 as the inorganic-organic complex source. do. The complex contains 60 wt% of the non-volatile (N) as described above.

V,) complex and 40 wt% mineral splint, the TBN of the complex is about 2 It has also been pointed out that it is 65.

of the inorganic-organic complex present in the coating corrosion inhibiting composition of the example; Mineral splint and rsAcIJ-760 are shown as separate ingredients. Mineral sprigs present in the coating composition can be removed by adding The wt % of the total amount of particles can be easily determined by simple arithmetic calculations. Before separately prepared, free or essentially free of organic solvents, as shown in A thixotropic inorganic-organic complex is used as the complex component of our corrosion inhibiting composition of the present invention. However, certain rsAcIJ products, especially For this purpose, use commercially available products such as rs'AcI''-760 or rsAcIJ-700. It is clearly more convenient to

For example, in the case of other ingredients used in the preparation of our inventive corrosion inhibiting compositions: This also applies, for example, to the addition of desired ingredients to our various corrosion inhibiting compositions of the present invention. , when achieved in a predetermined specific proportion, for example, in the state of a solution of an organic solvent. Synthetic drying oils or pastes such as those manufactured and sold industrially use the fee. Generally speaking, synthetic drying oils and aluminum pigment pastes, etc. Metallic pigments are mixed with volatile organic solvents such as mineral splits. and has been commercially marketed. For example, aluminum pigment paste is 7ON , V, is generally commercially available as a mixture.

The order of mixing or blending the ingredients is not important; any convenient additions may be made. Overall, I'm satisfied.

Stripping of volatile organic solvents in the production of our inventive corrosion-inhibiting compositions When used in a composition, the order of arrangement is After stripping, except for dryer(s) and epoxidized oil only: , then add the dryer(s) and epoxidized oil. The stripping process When carried out, if dryers and/or epoxidized oil were present in the composition. In some cases, the heat reached during stripping causes or tends to cause gelation.

overbased calcium Sulfonate/ calcium carbonate Complex (60N, V,) (rsAclJ-760) 33.9 32-31 long oil alkyd resin (7 [IN, V,) 26.71 28-32 phenolic resin modification Alkyd resin (SON, V,) 2-89 2-4 Coarse microcrystalline wax 4. H 2-6 Miraru Sprint 31. Og 28-32 paint dryer 0.7 0. 3-1 anti-skin agent 0.6.1 0j-0.8 performance +QUV-330 hours Marking: 1.5 mil DFT*-500 hours-1mm undercut Film: hard; cures after 1 hour of contact* (dry film thickness) Example 2 overbased calcium Sulfonate/ calcium carbonate Complex (6’ON, V,) (rsAcIJ-760) 5G, 35tg-51 long oil alkyd resin (70N, V,) 27.32 25-30 boiled linseed oil ILO7B~12 Coarse and fine crystalline wax 5.16 4-6 Polybutene 5.16 4-6 Paint dryer 0.9L6-1.2 Anti-skinning agent 0.44 0.3-0.6 Performance: QUV-420 hours average Salt cloudy: 0.5ml DFT*-700 hours: 1.0mil DFT*-950 Time opening Sharpening: 3.5 mil DFT*-500 hours-1mm undercut Drying time: 4 hours *(Dry film thickness) Example 3 overbased calcium Sulfonate/ calcium carbonate Complex (60N, V,) (rsAclJ-760) N, 8 40-43 long oil alkyd resin (70N, V,) 22.63 20-25 Boiled linseed oil 8.5 7.5-10 Coarse microcrystalline wax 4, 34-6 Polybutene 4.3 4-6 Powdered iron oxide pigment 17.75 1s~20 Paint dryer 0.37 0.3 ~0.5 Anti-skin agent 0.35 0.3~0.5 Performance: Approximately 1000 hours open leg eating test Tests were carried out and no corrosion was observed. The test is still ongoing.

Example 4 overbased calcium Sulfonate/ calcium carbonate Complex (60N, V,) (rsAcIJ-760) 17.0 15-50 long oil alkyd resin (70N, V,) 25.5 24-27 Boiled linseed oil 9.48-10 Coarse microcrystalline wax 5.14-6 Polybutene 5.2 4-6 aluminum pigment Paste (70N4.) 6.6 6-8 paint dryer 0. B O, 5~ l Anti-skin agent 0.4 0.3~O-S Performance: QUV-4000 hours, no rust, salt cloudy: 1. Oml DFT*-1, 296 hours scribing: 3,5 mil DFT*-500 hours-1rnm undercut to Film: Hard: For 1 hour contact *(Dry film thickness) Example 5 overbased calcium Sulfonate/ calcium carbonate Complex (60N, V,) (rsAcIJ-760) 32.72 30-35 Nagaike alkyd resin (70N, V,) 25.9 24-27 phenol resin modified Alkyd resin (50N, V,) 2.8 2-3.2 Coarse microcrystalline wax 4. 0 2-6 Volibutadiene (rRIcONJlO+ and/or +56) L, 8 1.5-2.5 bahts 31.5 28-32 Carbon black 0.25 +1.2~0.35 Paint dryer 0.68 K1.5-0.75 Anti-skin agent 0.35 0.3-0. (Performance: QUV- 330 hours Salt cloudy: 1ml DFT*-720 hour marking: 1.5mil DFT*-50 0 hours - 1~2mm undercut *(Dry film thickness) Example 6 overbased calcium Sulfonate/ calcium carbonate Complex (60N, I',) (rsAclJ-760) 27.9 25-30 Evogisiesester (60N, L) (37-001) 20.9 u-H boiled linseed oil 7.06-8 Talc (extender) 27.9 26-30 Coarse microcrystalline wax 2.8 2-4 My Larsbritt 10.3 9-12 Epoxidized linseed oil 2.82-3 ．． 2 Paint dryer 0.4 0.3-0.6 Performance: QUV-665 hours Salt cloudy: 1. Oml DFT*-450 hours Drying time: Approximately 1/2 hour Hardness: very hard *(Dry film thickness) In the performance tests reported above, the salt haze test ASTM B-117 except that Q panels coated with a mil thickness of film were used. I obeyed and went. Some coatings I; score the panel below the center of the panel. , 500 hours in an Earthaw sprayer containing a 5% salt solution. Tested for a while. The damage was caused by more than 3mm of creep from the scribe line due to rust. It was decided when.

Generally speaking, at least in most cases, the corrosion inhibiting compositions and/or corrosion caused by the use of such compositions on metal supports. The film clearly improved properties or advantages, or various combinations of improved properties or advantages; , the above composition except that it does not contain a synthetic drying oil or a natural drying oil and a dryer. Corrosion inhibition using an overbased tigisotrope inorganic-organic complex as a component of Beyond the control compositions and/or films, as well as the above-listed U.S. Pat. No. 3. Drying oils (synthetic or natural) as shown in US Pat. No. 925,087 4,495,225, or as shown in the above-listed patent specification No. 4,495,225. a composition containing a drying oil, as in Corrosion inhibiting compositions and/or films utilizing thixotropic inorganic-organic complexes have: i.e. salt spray and salt fog test procedures, or accelerated weathering tests (immediate Corrosion resistance as proven by QUV); film hardness: abrasion resistance Properties: Adhesion of the film to the surface of the metal support; and generally a high degree of durability. having the improved properties or advantages described above or various combinations thereof.

The many corrosion inhibiting compositions disclosed in the prior art listed above have enabled many young or most of the above-specified auxiliary ingredients have traditionally been alkaline earth metal carbonates. of thixotropic overbased alkaline earth metal sulponate forms complexed with salts Inorganic - organic 8! Corrosion inhibiting compositions of the type containing complexes, as well as drying oils (Patent No. 4.4) 95.225) or drying oil or synthetic drying oil (Patent No. 3,925.0) No. 87) for use in various corrosion inhibiting compositions, including those containing What has been achieved is acknowledged and clearly demonstrated. Therefore, we follow Within the scope of the prior art, the use and utility of corrosion inhibiting compositions indicates the use of known auxiliary ingredients. patentable novelty in aspects of the use of said adjunct components in corrosion inhibiting compositions; It's not what I'm looking for. Said prior art compositions incorporate said auxiliary ingredients into said compositions. does not disclose our new and improved corrosion inhibiting compositions. stomach.

As previously mentioned, the corrosion-inhibiting compositions of our invention have wide-ranging applications in the environment. and within this environment, the properties of the composition are controlled by conventional techniques and conventionally known corrosion inhibitors. To overcome problems that could not be fully satisfied with the composition. Thus, for example, atmospheric conditions For stale pipes in storage due to unfavorable conditions or weather conditions, Or you can focus on putting together a fairly adequately satisfying so-called vibrator varnish composition. There are a number of specific problems that have long plagued the steel pipe industry. now Even in the days when large steel mills manufactured steel pipes, among other things. The so-called varnish compositions used commercially are Ordinary spray or other applications of vibrator varnish compositions currently in use. Due to the sagging which results in uneven film formation when applied by cloth, characterized. In the illustrative case, application of the pipe varnish composition Forms a film as thick as 0.5 mil at the tip of the tube, but only However, at the bottom of the pipe, there is an overformation of the film thickness, as well as an undesirable There is literal dripping that creates management problems. In addition, various current Potential protective properties and variations and inhomogeneities of pipe varnish compositions used. Because of the uniform film formation, varnished or coated pipes are stored outdoors. After 6 months of outdoor storage, there was an unusually high failure rate of over 30%. Ru. Such drawbacks result in the rejection of a significant amount of stale pipe after outdoor storage. It has resulted in substantial economic losses.

Traditional pipe varnishes are reduced to about 50% solids with volatile organic solvents. Made of low-cost, quick-drying alkyd resin. Better solving power and relatively faster Due to the rate of evaporation, solvents such as xylene are commonly used. This selection of such solvents has a flash point generally in the range of 70 to 85'F, so it can be used in plant operations. , poses an extreme fire hazard. The traditional pipe varnish compositions are typically Extremely corrosion resistant. They typically have a dry film thickness of 1 mil and a Provides only 0-200 hours of salt fog protection. The relatively low solids content makes traditional This results in poor film formation and application properties in pipe varnish compositions. successfully When spray applied to a consistent 2 mil film thickness, the above As such, such pipe varnish compositions are very bad on curved surfaces! : Rumi (Ran) ning) to show.

solve the problem and create a suitable or at least nearly suitable pipe varnish composition. Many efforts have been made over a considerable period of time to reach this goal. This way Those with such efforts are thixotropic overbased compounds complexed with calcium carbonate. Known volatile organic solvent-based wax-modified castings of the lucium organic sulfonate type. or hydrocarbon water such as the corrosion-inhibiting composition ESCORE2 (Exxon Company). Use in mixtures with base resins and, in certain cases, petrolatum; Latam; slack wax and crude or refined microcrystals Waxes such as crystalline wax (unoxidized or oxidized); etc. one or more additional ingredients selected from the group, in particular more than one ingredient This included use in collaboration with The use of the proposed pipe varnish composition is , properly refining the film with reduced sagging problem, and various other However, there are other drawbacks, such as ultraviolet (0, V) ), as well as insufficient degree of resistance to degradation and film hardness in connection with disadvantages, such as cost factors, etc., do not make it commercially satisfactory to meet the problem. stomach.

The corrosion inhibiting properties of our invention are particularly useful as pipe varnishes in steel plants. In particular, those of the control composition have effective corrosion resistance, water exclusion, chicken tropism, U, V , characterized by its resistance to film hardness and effective short drying time of the film. It will be done.

We file Continuing Patent Application No. 705.148, filed February 25, 1985, and successors. Reference is made to the following patent application No. 745,762, filed June 17, 1985. However, we are aware of these patent applications. Because among us is one of the co-inventors for each of said patent applications. The said patent application, in common with our present application, is owned by the same assignee. Ru. The inventions disclosed in each of the above patent applications relate to corrosion inhibiting compositions. and the composition comprises, as its constituents, a certain proportion of (a) an alkaline earth metal; in the form of chickentrope overbased alkaline earth metal sulfonate complexes with carbonates. an inorganic-organic complex, (b) a drying oil or a synthetic drying oil, and (c) a dryer, and seeds. It is a type of substance that may or may not contain other ingredients. After the composition is applied in a thin film onto a metal surface and dried and/or cured, Forms a hard, essentially non-oily coating. Disclosed and claimed in said continuation patent application The corrosion-inhibiting compositions described herein are the same as corrosion-inhibiting compositions previously known in the art. Exceeding; constitutes various distinct improvements. Disclosed and claimed in our present application The corrosion-inhibiting compositions disclosed herein are subject to further improvements beyond the prior art patents and publications discussed above. It not only constitutes a good corrosion inhibiting composition, but also exceeds the corrosion inhibiting composition disclosed in said continuing application. Contains further improvements in various corrosion-inhibiting compositions for various purposes! gives additional benefits to I can do it.

Beyond the corrosion inhibiting compositions disclosed in said continuing application, As an illustration of improved corrosion inhibiting compositions for use as pipe varnishes, One of the two essentially equivalent optimum compositions of our present application and the said continuation publication. Use as a pipe varnish specifically disclosed by Application No. 745.762 The following table shows a comparison of the characteristics of the best implementations known to us for this purpose.

2. Example 23 of Continuing Application No. 745,762, Example 5 of our present application *, MRT is a corrosion-inhibiting coating that is commonly applied to iron or steel before and after coating. MagnaFranks Retention, a method to actually measure cracks and defects in parts MAGNAFL[IX RETENTION TES T means METIIOD). The Magnafranks test is a test of the pipe itself. It is an experiment. If there are no cracks or similar defects, the Magnaflux particles will No adhesion to the coating at the final point of testing the steel pipe. This test method is It is a well-recognized and published test. It is implemented by us as follows. Performed: 1. Knife coat the Q panel with a corrosion inhibiting composition to a dry film thickness of 1.5 mils. Ru.

2. Air dry the panel for 24 hours.

3. Immerse the panel in the Magnaflux iron filling and shake off the excess.

4. Brush lightly to remove excess fill that is not tightly bonded.

5. Arbitrary evaluation on a scale of 0 to 5.

〇　 - Complete release - No filler present.

1- Excellent – only a trace amount remains 2 - Barely Pass - Some filling is observed.

3-Failure at the last minute-Some filling remains.

4- Poor - Many covered surfaces 5- Very poor - almost completely covered surface.

3 to 5 is a failure.

In many respects, the exemplary corrosion inhibiting composition of Example 5 of our present application differs from ours. is known to be the best composition for use as a pipe varnish. In the tests of It is clear from the clothing that it is superior in the , and MRT tests.

Our present application also addresses the corrosion control methods disclosed and claimed in said continuing patent application. clearly distinguishable from the composition.

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Claims (23)

[Claims] 1. in the form of a liquid solution and/or colloidal dispersion, comprising essentially the following ingredients: The following composition wt% ratio: (a) alkaline earth metal carbonate The thixotropic complex complexed with Basified alkaline earth metal organics Inorganic-organic in the form of sulfonate Complex 20-50 (b) Synthetic drying oil or synthetic drying oil A mixture containing drying oil along with drying oil and the synthetic dryness in the mixture Oil is in considerable excess of the proportion of drying oil and synthetic drying oil alone. When using: 15-60 ; Or synthetic drying oil and drying. Drying oil: 15-50 It can be up to about 40% of synthetic drying oil. (c) Dryer (single or multiple) 0.3-2 (d) a corrosion inhibiting composition comprising a volatile organic solvent of 10 to 70; , the corrosion inhibiting composition is applied as a thin film to a ferrous or non-ferrous metal surface. After drying and/or curing at room or ambient temperature for about 1 to about 6 hours, a hard, non-tacky to form a substantially non-oily coating, which can be applied to most organic solvents without heating. is not inherently removable, or if it is otherwise removable. For example, the removability may be difficult and potentially damaging to the metal surface. The corrosion inhibiting composition is achieved by: 2. The composition according to claim 1, wherein the alkaline earth metal is calcium. 3. Calcium organic sulfone in which an inorganic-organic complex is complexed with calcium carbonate It is an acid salt and the organic moiety is alkylbenzene, and the alkyl is 12 to 30 3. A composition according to claim 2, containing 5 carbon atoms. 4. The composition according to claim 2, wherein the synthetic drying oil (b) is a long oil alkyd. . 5. The composition of claim 2, wherein component (a) comprises about 15 to about 30 wt%. thing. 6. The composition of claim 3 comprising about 2 to about 6 wt% microcrystalline wax. . 7. 4. The composition of claim 3 comprising from about 2 to about 6 wt% polybutene. 8. Claim 3 comprising about 2 to about 6 wt% phenolic resin modified alkyd. composition. 9. The volatile organic solvent is a member of the group consisting of mineral split and VM&P. The composition according to claim 4. 10. in the form of a liquid solution and/or colloidal dispersion, containing substantially the following ingredients: , the following composition wt% proportion: (a) complexed with calcium carbonate; thixotropic overbasing Lucium organosulfonate form the inorganic-organic complex of the body, where the The organic part of the sulfonate is mono Alkyl- and dialkylben It is a mixture of zenes and the alkyl is mainly composed of 12 to 18 carbon atoms. The complex contains about 200 with a base number of ~350 (b) in the range of about 60 to about 125 long oil with a hydroxyl value of Alkyd drying oil or long oil Contains drying oil along with Lucid drying oil. Mixture containing long oil alkyd alone When used in: 15-3 5; or with long oil alkyd Drying oil: 15-50 The sex oil is up to about 40% of the long alkaline oil. Configuration (c) Dryer (single or multiple) 0.3 -2(d) A corrosion inhibiting composition comprising a volatile hydrocarbon solvent 10-70; Yes, the corrosion inhibiting composition is applied in the form of a thin film to the surface of ferrous or non-ferrous metals. and after drying and/or curing at room or ambient temperature for about 1 to about 6 hours, a hard, non-viscous Forms an adhesive, substantially non-oily coating that is compatible with most organic solvents without heating. is essentially not removable, or if not removable If so, the removability would be with substantial difficulty and without the possibility of damage to the metal surface. The above-mentioned corrosion inhibiting composition. 11. Claim 10, wherein the long oil of the long oil alkyd resin drying oil is tall oil. Compositions as described. 12. The volatile hydrocarbon solvent is of the group consisting of Mineral Split and VM&P. 11. The composition of claim 10, which is a member of the composition. 13. 12. The set of claim 11 comprising about 2 to about 6 wt% microcrystalline wax. A product. 14. The percentage of the components listed below: i.e., component (a) 32-34% (b) Long oil alkyd resin drying oil 28-32% (c) Volatile hydrocarbon solvent Gami Neural split and VM&P selected from the group consisting of approximately 28-32%; 2-6% microcrystalline wax and 2-4% phenolic resin-modified long oil alkyd 11. The composition of claim 10, comprising a resin drying oil. 15. The proportions of the ingredients listed below: i.e. component (a) 47-52 (b) Long oil alkyd resin drying oil 25-30 (c) Mi neral split and selected from the group consisting of VM&P The volatile hydrocarbon solvent present is approximately 18 to 25%, and the drying oil is boiled linseed oil, and the boiled linseed oil constitutes 8-12%, and the composition comprises 4% Claim 10 comprising ~6% polyptene and 4-6% microcrystalline wax. Compositions as described. 16. The proportions of the ingredients listed below: i.e. component (a) 38-43(b) Long oil alkyd resin drying oil 20-25(c) Mi neral split and selected from the group consisting of VM&P The volatile hydrocarbon solvent present is approximately 15 to 20%, and the drying oil is boiled linseed oil, and the boiled linseed oil constitutes 7-10%, and the composition comprises 4% Claim 10 comprising ~6% polybutene and 16-19% iron oxide pigment. composition. 17. The proportions of the ingredients listed below: i.e. component (a) 45-50 (b) Long oil alkyd resin drying oil 22-28 (c) Mi neral split and selected from the group consisting of VM&P The volatile hydrocarbon solvent present is approximately 16 to 20%, and the drying oil is boiled linseed oil, and the boiled linseed oil constitutes 7-11%, and the composition comprises 4% ~6% polybutene, 4-6% microcrystalline wax, and 5-8% aluminum 11. The composition according to claim 10, comprising a pigment paste. 18. The proportions of the ingredients listed below: i.e. component (a) 30-35 (b) Long oil alkyd resin drying oil 24-28 (c) Volatile 40 to 45%, and the composition contains 2 to 4% phenolic resin modified long oil alkyd resin drying oil, 1-3% polybutene, 4-6 % microcrystalline wax, and 0.2-1% carbon black. Composition according to item 10. 19. The proportions of the ingredients listed below: i.e. component (a) 25-30 (b) Epoxy ester drying oil 18-22 (c) Mi neral split and selected from the group consisting of VM&P Volatile hydrocarbon solvent present in the range of 18 to 23, and the drying oil boiled linseed oil, and the boiled linseed oil constitutes 6 to 8% and the composition comprises 2 to 8%; Claims containing 4% epoxidized linseed oil and 2-4% microcrystalline wax Composition according to item 10. 20. A film of the composition according to claim 1 is deposited on a metal surface, and then A method for inhibiting corrosion of a metal surface, the method comprising drying the film. 21. A film of the composition according to claim 10 is deposited on a metal surface, and then A method for inhibiting corrosion of a metal surface, the method comprising drying the film at a temperature. 22. Deposition of the composition according to claim 1 on the surface of a metal article, and then the composition Said metal article protected against corrosion by drying the article. 23. Deposition of the composition according to claim 10 on the surface of a metal article, and then the assembly. Said metal article protected against corrosion by drying of the composition.