ACID BASED VARIABLE VISCOSITY COMPOSITIONS SUCH AS CORROSION AND GREASE REMOVERS AND POLISHERS

Abstract: An improved, highly penetrating rust remover and/or degreaser composition for metallic surfaces, which is chemically inhibited to substantially prevent oxidation-reduction reactions with a metal substrate and limit the action of the composition to a chemical attack on corrosion. The composition is preferably a single phase dispersion and includes respective quantities of an acid such as hydrochloric acid and phosphoric acid, an organic compound containing a nitrogen, oxygen or sulfur atom such as N-(2-hydroxyethyl) oxazolidine, an alcohol or other organic solvent for grease removal, water and one or more emulsifiers (e.g., a derivative of hydrogenated tallow) for stabilizing and lowering the surface tension of the resultant composition. The compositions may be formulated as liquids or with a viscosity control agent such as a polylmer of vinyl pyrrolidone to give a paste-like consistency permitting easy use thereof on vertical surfaces. In other forms, the compositions hereof may include a mild abrasive such as activated silica gel.

Description: ACID BASED VARIABLE VISCOSITY COMPOSITIONS SUCH AS CORROSION AND GREASE REMOVERS AND POLISHERS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is concerned with improved, acid-based corrosion, grease removal and polishing compositions for treating metallic surfaces and objects. More particularly, it is concerned with such compositions which are compounded so as to substantially prevent oxidation-reduction reactions that would normally take place at a metallic surface, and allow only- acid attack of the oxides on the metal. In preferred forms, the compositions hereof may include polyvinyl pyrrolidone as a viscosity control agent and inhibitor, a derivative of hydrogen tated tallow as an emulsifier, and an N-substituted oxazolidine as an acid inhibitor. 2. Description of the Prior Art Compositions for removing corrosion (metal oxides) from metallic surfaces and objects have long been available. Generally speaking, such materials are acid based, i.e., they rely upon an acidic attack in order to remove corrosion. A persistent problem encountered in connection with prior corrosion removal compositions and polishes stems from the fact that oxidation- reduction reactions can occur between the compositions and the underlying metal surfaces to be cleaned and decorroded. Hence, while many of these prior compositions were effective in corrosion removal and/or polishing, they often were prone to attack the metal substrate and leave the same pitted and unattractive. Another problem with such prior compositions stems from the fact that they are ineffective as grease removers. Accordingly, if the metallic surfaces desired to be decorroded had substantial amounts of fatty organic (oil) films thereon, the effectiveness of the compositions was reduced, and the acidic and aqueous components thereof hindered in removal of corrosion. Furthermore, such solutions were of uncontrolled viscosity, either being too viscous to prevent OMPI appliσation by spray or brush, or too low in viscosity to cling on vertical surfaces. SUMMARY OF THE INVENTION The present invention overcomes the problems noted above, and provides greatly improved, flowable, aqueous, highly penetrating compositions of acidic pH which are effective for polishing and removal of corrosion from metallic surfaces, and also to degrease the same. The compositions of the present invention may include respective quantities of an acid, an organic compound having a nitrogen, oxygen or sulfur atom therein, an alcohol* or other organic solvent, water and at least one emulsifier. In preferred forms, the acid component is selected from the group consisting of hydrochloric, sulfuric, phosphoric, acetic, citric, nitric, boric and mixtures thereof. The acid is further preferably present at a level of from about 2% to 95% by weight, and more preferably from about 5% to 37% by weight. The organic compound is advantageously selected from the group consisting of N-substituted oxazo- lidines (most preferably N- (2-hydroxyethyl) oxazolidine) , the p-alkyl benzyl pyridine chlorides, phenylthiourea, 2-mercaptobenzothiazole, di-ortho- tolyl-thiourea, pyridine, quinoline, decylamine, the dibenzyl sulf oxides, 2-butyne-l, 4-diol, 1-hexyne- O PI 3-ol, 4-ethyl-l-octyne-3-ol, decyclamine, soyaamine, oσtadecylamine, trimethylsoyaammonium chloride, trimethyloctadeσyla monium chloride, trimethyldo- decyl ammonium chloride, trimethyltallowammonium chloride, N-coco-1, 3-diamino ropane, the tetraalkyl- ammonium bromides having an alkyl group with at least 10 carbon atoms therein, the mono-, di-, and tri- butylamines , hexamethylenediam ne, polyvinyl pyrroli- done, 2- (bis) 2-hydrox ethyl (amino)-l, 3-propane- diol, 2- (bis)2-hydroxyethyl (amino)-methanediamine, l,6,8-triaza-4, 10-dioxabicyclo [5,5,0] dodecane, and mixtures thereof. Such compounds should be used at a level of from about 0.01% to 20% by weight, and more preferably from about .5% to 5% by weight. » The alcohol component is most preferably 1-proρanol, but other alcohols could also be employed. As used herein, other alcohols refers to an alcohol having an alkyl group with from about 1 to 10 carbon atoms, inclusive. The alcohol should be used at a level of up to 40% by weight, and most preferably at a level of about 1 to 8% by weight. The water should be present at a level of from about 30% to 80% by weight, and most advantageously at a level of from about 50% to 80% by weight. The most preferred emulsifiers for use in the invention are selected from the group consisting of the derivatives of hydrogenated tallow (e.g., N, N 1 , N'-tris (2-hydroxy- ethyl)-N-tallow-1, 3-diamino- propane or amine acetate hydrogenated tallow) , polyoxyethylene ethers, polyoxyethylene ester alcohols, polyoxyethylene esters of mixed fatty and resin acids and mixtures thereof, although other specific types referred to hereinafter also have utility. The total amount of emulsifier present in the composition should be from about 0.1% to 15% by weight, and more preferably from about .5% to 5% by weight. A viscosity control agent (thickener) can also be used ' in the compositions hereof to ' give variations in viscosity. Such viscosity control has heretofore proved to be difficult or impossible to obtain in acidic compositions, inasmuch as most conventional thickeners tend to flocculate at low pH. The control agents of the invention should be selected from the group consisting of polyvinylpyrrolidone and the allylamine emulsion polymers. The pyrrolidone is preferred, however, inasmuch as it also acts as a corrosion inhibitor on metallic surfaces. The viscosity control agent should be used at a level of up to about 35% by weight, and most preferably at a level of from about 0.5% to 5% by weight. A synergistic ef ect is observed by the use of the mixture of polyvinyl pyrrolidone, Ethoduσπteen T/13, and N-(2-hydroxyethyl)-oxazolidine as a corrosion inhibitor in preventing base metal attack, inasmuch as the attack with the preferred mixture is less than that of any of the individual corrosion inhibitors. In further forms of the invention, a mild abrasive such as activated silica gel (at a level of up to about 10% by weight) can be employed. Perfumes and coloring agents can be added as desired. In addition the system can be modified for corrosion removal on metal surfaces having a heavy grease or oil coating by preparing a two-phase emulsified system fay the addition of toluene or related organic solvents . BRIEF DESCRIPTION OF THE DRAWING The single feature is a graphical representation depicting the extent of base metal attack when using a commercially available corrosion remover, 10% HC1, and the preferred corrosion removing composition of the invention. DESCRIPTION OE THE PREFERRED EMBODIMENTS The most preferred rust removal compositions in accordance with the present, invention contain commercial hydrochloric acid, commercial phosphoric acid , 1-ρropanol, N- (2 hydroxyethyl) oxazolidine, water, a thickening agent, and N,N* , N' -tris (2-hy- dro xy ethyl )-N-ta 11 ow-1, 3-diaminopropane as an emulsifier. The following table sets forth the single most preferred rust removal composition, as well as ranges of use of the above identified components . TABLE I Amounts (% by Weight) Component Range Preferred Commercial hydro¬ chloric acid (37%) 2 -35% 27% Commercial phosphoric acid (85%) 0 -10% 4% N- (2-hydroxyethyl) oxazolidine 0.01-20% 1% Ethoduomeen T/13***- 0.01-15% 1% 1-propanol 0 -20% 5% Polyvinyl-. pyrrolidone 2 0 -15% 3% Water 30 -90% 59% 100% λ N f N' ,N'-tris(2-hydroxyethyl)-N-tallow-l,3- diamino ropane, Sold by Armak Industrial Chemical Division, Chicago, Illinois. 2 Purchased from Sigma Chemical Co., St. Louis, Missouri, and reported to have a molecular weight of 360,000. OMPI The oxazolidine base metal inhibitor component of Table I is prepared by slowly adding, with mixing, 435.7 grams of formaldehyde to a beaker containing 564.3 grams of diethanolamine. After all for alde- hyde is added, the mixture should be stirred for an additional hour. In other contexts , a base metal inhibitor component can be produced as the reaction product of a lower aldehyde (i.e., containing from about 1-4 carbon atoms) and an alkanolamine (containing one or more alkyl group each having from about 2-8 carbon atoms ) . In formulating the preferred composition of Table I, a beaker containing 590 grams of water is provided. Ten grams of the Ethoduomeen T/13 hydro¬ genated tallow emulsifier, 270 grams hydrochloric acid, 40 grams phosphoric acid, and 50 grams of 1-propanol are all added to the beaker, with con¬ tinual mixing. The mixture is then heated to 50° C. f and 30 grams polyvinylpyrroli ine is slowly added thereto. Mixing is continued until all of the polymer has dissolved. The drawing graphically illustrates the inhibition against base metal attack provided with the preferred composition of Table I. Specifically, a commercially available corrosion remover sold under the designation "Naval Jelly" was tested, along with OMPI a solution of 10% hydrochloric acid, and the preferred composition hereof. In all cases, testing conditions were identical, and the extent of attack on a base metal substrate was measured. As can be seen, the extent of such attack is very high with the Naval Jelly and hydrochloric acid, but is significantly lower with the preferred inhibitor composition of the invention. In the case of a cleaner/polish for brass and copper, the most preferred compositions, and the ranges of use of components, are set forth below: TABLE II Amounts (% by Weight) Component Range Preferred Commercial hydro¬ chloric acid (37%) -37% 13.5% Commercial phosphori c acid (85%) 0 -85% 2. 0% N- (2-hydrox ethyl) oxazolidine 0.01-20% 0.5% Ethoduomeen T/13***- 0.01-15% 0. 5% 1-P ropanol 0 -20% 2. 5% Polyvinyl- pyrrolidone 2 0 -35% 1.5% Water 30 -90% 79. 5% 100.0% 1'2 Same as in Table I In preparative procedures all of the components save the polyvinylpyrrolidone are simply admixed as a single phase dispersion or solution, whereupon the mixture is heated to 50° C. (although such heating is optional) and the polymer is slowly added thereto with mixing to give a thickened, viscous composition. As noted above, a number of different materials can be employed for the various components. With respect to the e ulsifier (s) , surfactants available from ICI Americas, Inc., Wilmington, Delaware, and Armak Chemicals Division, Chicago, Illinois, can be employed in lieu of or in addition to the preferred tallow based emulsifiers. An exemplary list of such surfactants is provided in Table III. TABLE III Trade Name Class & Formula HLB Arlatone 285 Polyoxyethylene fatty acid ester 14.4 Arlatone 298 Polyox thylene fatty acid ester 14.4 Arlatone G Polyox ethylene fatty glyce ide 10.8 Arlatone 970 Polyoxyethylene so bitan fatty acid ester - 14.3 Atlox 1285 Polyoxyethylene triglyceride 14.4 TABLE III Trade Name Class & Formula HLB Brij 35 Polyoxyethylene (23) lauryl ether 16.9 Brij 58 Polyoxyethylene (20) cetyl ether 15.7 Brij 78 Polyoxyethylene (2) stearyl ether 15.3 Brij 98 Polyoxyethylene (20) oleyl ether 15.3 Brij 99 Polyo xy ethyl ene oleyl ether 15.3 Atlas G-263 N-cetyl-N-ethyl morpholinium ethosulf ate 30.0 Atlas G-271 N-soya-N-ethyl morpholinium ethosulf ate 30.0 Atlas G-1285 Polyoxyethylene triglyceride 14.4 Atlas G-1288 Polyoxyethylene triglyceride 16.0 Atlas G-1300 Polyoxyethylene triglyceride 18.1 Atlas G-1304 Polyoxyethylene triglyceride 18.7 Atlas G * 1795 Polyo x et yl ene lanolin derivative 17.0 Atlas G-2079 Polyoxyethylene palmitate 15.5 Atlas G-2109 Polyoxyethylene coconut fatty acid 13.3 Atlas G-2162 Polyoxyethylene propylene glycol stearate 16.0 OMPI TABLE III Trade Name Class & Formula HLB Atlas G- 3634 A Quaternary ammonium derivative 18.5 Atlas G-3707 Polyo xy ethyl ene- lauryl-ether 12.8 Atlas G-3816 Polyo ethyl en e- cetyl- ether 14.9 Atlas G-3820 Polyo xy ethyl en e- cetyl-ether 15.7 Atlas G-4905 Polyo x ethyl ene- sorbitan-monoleate 15.0 Atlas G-4 32 Polyo x ethyl ene- lauryl- ether 16.0 Atlas G-4938 Polyo xy ethyl en e- stearyl-ether 15.3 Atlas G-4961 - Polyo xy ethyl ene- alky- ami ne 15.5 Atlas G-8916P Polyo x ethyl ene- sorbi tan- ester 14.6 Myrj 49 Polyoxyethylene stearate 15.0 Myrj 51 Polyox ethylene stearate 16.0 Myrj 52 Polyo x ethylene stearate 16.9 Myrj 52C Polyoxyethylene stearate 16.9 Myrj 52S Polyoxyethylene stearate 16.9 Myrj 53 Polyo xy ethyl ene stearate 17.9 Myrj 59 Polyo x ethylene stearate 18.8 OMPI -u- TABLE III Trade Name Class & Formula HLB Renex 20 Polyoxyethylene ester of mixed fatty and resin acids 13.5 Renex 30 Polyoxyethylene ether alcohol 14.5 Renex 649 Polyo xy ethyl ene alkyl aryl- ether 16.0 Renex 650 Polyoxyethylene alkyl aryl- ether 17.1 Renex 678 Polyo xy e hyl ene alkyl aryl- ether 15.0 Renex 679 Polyo xy ethyl ene ' alk l aryl- ether 14.4 Renex 682 Polyoxyethylene alkyl aryl-ether 13.9 Renex 690 Polyo xy ethyl ene alkyl aryl-ether 13.3 Renex 698 Polyoxyethylene alky laryl-et her 13.0 Renex 707 Polyoxyethylene fatty acid alcohol 12.2 Renex 709 Polyoxyethylene fatty acid alcohol 12.5 Renex 711 Polyoxyethylene fatty ' acid alcohol 13.9 Renex 714 Polyoxyethylene fatty acid alcohol 14.9 Renex 720 Polyoxyethylene fatty acid alcohol 16.2 Tween 20 Polyo xy ethyl ene- sorbitan monolaurate 16.7 TABLE III Trade Name Class & Formula HLB Tween 20 SD Polyo yethyl en e- s o bit an monolaurate 16.7 Tween 40 Polyo xyethyl ene- sorbitan-monopalmitate 15.6 Tween 60 Polyo xyethylene- sor bi tan-monos tear ate 14.9 Tween 60 SD Polyo xy ethyl ene- sor bi tan-monos tear ate 14. 9 Tween 80 Polyo xyethyl ene- sor bitan-monooleate 15.0 Tween 80 SD Polyo xyethyl en e- sor bitan-monooleate 15.0 Atlas G 3300 Alkyl aryl sulfonate 11.7 The compos itions of the invention are eff ective to remove corrosion from base metallic surfaces while substanti ally preventing oxidation-reduction reactions with the metal itself . In addition, grease removal is enhanced by virtue of the pres ence of a single phase , aqueous system . Use of the pref erred single phase system also enhances the penetration of corrosion where the latter is present . Representati ve metals which can be cleaned and/ or degreased using the compositions hereof include iron and steel , bronze , brass , copper , monel , nickel, chromium plated metals and aluminum. A cleaner for tubes of boilers may also be provided by incorporting in the formulation a high foaming agent plus thickeners such as polyvinyl¬ pyrrolidone to improve wall adherence. This allows the corrosion remover to be circulated and foamed in place throughout the system by pumping or by an air blast. An -additive such as Arlatone G may also be included as desired to help prevent surface rerusting. This type of corrosion remover is advantageous in that a small amount will cover a large surface area and does not require heating to permit the corrosion removal action to take place. Also, since all components are water soluble, removal of the corrosion remover can be performed by flushing water through the system. An exemplary formulation of a- composition containing at least one foaming agent and a thickener is as follows: TABLE IV Pref erred P ermissible Composi tion Components Range ' (% by Weight) Water 30 -90% 69.5% Commercial hydro¬ 2 -37% 27. 0% chloric acid (37%) N (2 -hydro xyethyl) 0.01-20% 1.0% oxazolidine ' Ethoduomeen T/131 0.01-15% 1.0% TABLE IV Pref erred Permissible Composition Coup *— on en ts Range (% by Weight) Polyvinyl¬ 0.1 -15% 1.0% pyrrolidone 2 Arlatone G-3 0.1 - 2% 0.5% 100. 0% 1 , 2 Same as in Table I . 3 See Table III . The preferred boiler tube cleaner is prepar ed in the same manner as the rust remover and cleaner/ polisher descr ibed above . The Arlatone G component is added initially with the HC1 , oxazolidine and Ethoduomeen . An additional use and formulation for the removal of carbonate deposits and scales for the application of salts to non-metallic surfaces can be made by using the above formulations with the deletion of the base metal corrosion inhibitor . This formulation enhances surface deposit removal without penetration to the base . An exemplary formulation of a composi tion containing at least one degreasing agent and a thickener is as follows: OMPI • 1/- TABLE V Preferred Permissible Composition Components Range (% by Weight) Water 25-95% 77.0% Commercial hydro¬ 2-37% 15.0% chloric acid (37%) Rennex 30 0-10% 1.0% Polyvinyl pyrrolidone 1-35% 5.0% Ammonium chloride 0-40% 2.0% 100.0% Other acids such as sulfuric, nitric, phos¬ phoric, acetic, citric, boric, or mixtures thereof can be substituted as well as other salts such as sodium perborate, tri-sodium phosphate, ammonium acetate, sodium chloride, etc. - JKEAl OMPI WIPO

Claims: CLAIMS The embodiments of the invention in which an exclusive property or privilege is claimed, are defined as follows: 1. In a flowable, aqueous composition containing sufficient acid to give the composition an acidic pH, the improvement which comprises a minor amount of viscosity control agent in the composition selected from the group consisting of polyvinyl pyrrolidone and the allylamine emulsion polymers. 2. The composition as set forth in Claim 1, said agent being present at a level of up to about 35% by weight. 3. The composition as set forth in Claim 2, said level being from about 0.5 to 5% by weight. 4. The composition as set forth in Claim 1, said composition including an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, acetic, boric and mixtures thereof. 5. The composition as set forth in Claim 1, said acid being present at a level from about 2 to 95% by weight. 6. The composition as set forth in Claim 5, said level being from about 5 to 37% by weight. 7. The composition as set forth in Claim 1, said composition further including at least one emulsifier. 8. The composition as set forth in Claim 7, said emulsifier being present at a level of from about 0.01 to 15% by weight. 9. The composition as set forth in Claim 8, said level being from about 0.5 to 5% by weight. 10. The composition as set forth in Claim 7, said emulsifier comprising a derivative of hydrogenated tallow. 11. The composition as set forth in Claim 10, said emulsifier being N,N* ,N'-tris- (2-hydro yethyl) -N- tallow-l,3-diaminopropane . 12. The composition, as set forth in Claim 1, including a quantity of an organic compound having a nitrogen, oxygen or sulfur atom therein. 13. The composition as set forth in Claim 12, said compound being selected from the group consisting of N-substituted oxazolidines , the p-alkyl benzyl pyridine chlorides, phenylthiourea, 2-merca tobenzo- thiazole, di-ortho-tolyl-thiourea, pyridine, quinoline, decylamine, the dibenzyl sulfoxides, 2-butyne-l,4-diol, l-hexyne-3-ol, 4-ethyl-l-octyne- 3-ol, decylamine, soyaamine, octadecylamine, trimethylsoyaammonium chloride, trimethylocta- OM?l decylammonium chloride, trimethyldodecylammonium chloride, trimethyltallow ammonium chloride, N-coco-1, 3-diaminopropane, the tetraalkyl ammonium bromides having an alkyl group with at least 10 carbon atoms therein, the mono-, di-, and tributylamin ' es , he amethylenediamine, polyvinyl pyrrolidone, 2- (bis)2-hydroxyethyl (amino)-l,3-propanediol,2- (bis) 2-hydro xyethyl (amino)-methane-diamine,l,6,8- triaza-4,10-dioxabicyclo[5,5,0] dodecane, and mi xtur es the r eo f . 14. The composition as set forth in Claim 13, said compound being N- (2-hydroxyethyl) oxazoladine. 15. The composition as set forth in Claim 12, said compound being present at a level of from about 0.01 to 20% by weight. 16. The composition as set forth in Claim 15, said level being from about 0.5 to 5.0% by weight. 17. The composition as set forth in Claim 12, said compound being the reaction product of a lower aldehyde and an alkanolamine. 18. The composition as set forth in Claim 1, including an alcohol having an alkyl group containing from about 1 to 10 carbon atoms. 19. The composition as set forth in Claim 18, said alcohol being 1-propanol. 20. The composition as set forth in Claim 18, said alcohol being present at a level of up to about 20% by weight. 21. The composition as set forth in Claim 20, said level being from about 1 to 8% by weight. 22. The composition as set forth in Claim 1, said composition having water present at a level of from about 30 to 90% by weight. 23. The composition as set forth in Claim 22, said level being from about 50 to 80% by weight. 24. A flowable composition comprising respective quantities of water, acid, an organic compound having a nitrogen, oxygen or sulfur atom therein, a viscosity control agent selected from the group consisting of polyvinyl pyrrolidone and the allylamine emulsion polymers, and a derivative of hydrogenated tallow. 25. The composition as set forth in Claim 24, said derivative being N,N' ,N' -tris- (2-hydro yethyl) -N- tallcw-l,3-diaminopropane. 26. A flowable composition comprising respective quantities of water, acid, a viscosity control agent, an emulsifier, and an N-substituted oxazolidine. 27. The composition as set forth in Claim 26, said oxazolidine being N- (2-Hydroxyethyl) oxazolidine. . 1PO 28. A flowable composition comprising respective quantities of water, acid, a viscosity control agent, an emulsifier, and a cca-pcund which is the reaction product of a lower aldehyde and an alkanolamine. O PI

Inventors: VITEK RICHARD K, VITEK, RICHARD, K.
Applicants: FOTODYNE INC, FOTODYNE, INC.
Application year: 1983
Main classification: C11D7
IPC codes: C11D7, C23G1, C23G5