United States Patent (19) 11 Patent Number: 4,540,442 Smith et al. 45 Date of Patent: Sep. 10, 1985

(54) COMPOSITIONS AND METHODS FOR 4,284,434 8/1981 Lingmann et al...... 252/117 REMOVING SEALANT COMPOSITIONS FOREIGN PATENT DOCUMENTS (75) Inventors: Timothy J. C. Smith, Colmar, Pa.; Jirgen Geke, Disseldorf, Fed. Rep. 1143976 2/1969 United Kingdom . of Germany; Robert Q. Cooper, Primary Examiner-Paul Lieberman Lansdale, Pa. Assistant Examiner-John F. McNally Attorney, Agent, or Firm-Ernest G. Szoke; Henry E. 73) Assignee: Amchem Products, Inc., Ambler, Pa. Millson, Jr.; Mark A. Greenfield (21) Appl. No.: 580,965 (57) ABSTRACT 22 Filed: Feb. 16, 1984 Aqueous compositions containing as essential ingredi (51) Int. Cl...... C03C 23/00; B08B7/00; ents; an alkanolamine, an aliphatic con C11D 9/30 taining 5 to 18 carbon atoms, and an arylenetriazole (52) U.S. Cl...... 134/2; 134/3; have been found effective in removing resin-containing 134/38; 252/89.1; 252/524; 252/173; 252/117 sealants from the surfaces of zinc containing metals, (58) Field of Search ...... 134/3, 38, 41; 252/117, such as galvanized steel, without causing changes in the 252/89.1, 524, 529, 542, 548, 173 surfaces of the metal, so that phosphate coatings which are subsequently applied to said surfaces are neither (56) References Cited streaky nor spotty. U.S. PATENT DOCUMENTS 3,337,471 8/1967 Levy et al...... 252/153 25 Claims, No Drawings 4,540,442 1. 2 rinse, application of a pre-coat (a phosphate coating), a COMPOSITIONS AND METHODS FOR water rinse, and drying. The pre-wipe or pre-cleaning REMOVING SEALANT COMPOSITIONS with these detergent compositions not only removes the sealant, but also other undesirable materials and thus This invention relates to the removal from metals of 5 helps in preventing or delaying the contamination of the sealants used in the automotive and other fields. It par cleaner composition which is subsequently used. ticularly relates to compositions and methods for re These detergent compositions were found to be satis moving sealants and other extraneous materials such as factory in pre-treating automotive bodies which were oils, dust smudges and the like which are deposited or constructed of steel. However, when the metal used in otherwise formed on automobile bodies. 10 these bodies included sections of galvanized steel, prob BACKGROUND OF THE INVENTION lems appeared. This occurred, for example, when Gen eral Motors began the manufacture of the 1982 Citation One of the most difficult problems in cleaning auto hatch-back since this new hatch-back had an all ultra motive bodies prior to the finishing steps leading to the smooth galvanized steel hatch-back lid; the rest of the application of automotive paint is in the removal of 15 body being formed of the type of steel previously used. unwanted sealants commonly used in sealing and water Except for the hatch-back lid, very uniform precoats proofing joints and openings between metal parts. (i.e. phosphate coatings) were obtained on automobile When such sealants are applied, usually by means of bodies treated as described above; however, the phos extrusion through grease guns, excess quantities of seal phate coatings on the metal of the lid were streaky and ant are often inadvertently extruded or dripped onto the 20 covered with white spots. Good siccative coatings can adjacent metal parts. Frequently, dust or other undesir not be obtained on such streaky and spotted surfaces. able material settles on and adheres to this sealant. The Apparently, some component or components in these excess sealant must be removed from the metal before detergent compositions is reacting with the zinc in the the application of a conversion coating prior to paint galvanized steel thereby causing the undesirable streak ling. 25 ing and spotting. The sealants commonly used in the automotive and Accordingly, it is an object of this invention to pro allied industries are compositions containing a resin vide a composition for the removal of undesired sealant such as an epoxy resin or a vinyl resin, e.g. polyvinyl from automobile bodies the use of which will not result chloride resin; a heavy blending oil such as linseed oil, in streaking or spotting on galvanized steel when a dioctylphthalate, diethylphthalate, dibutylphthalate, 30 phosphate precoat is subsequently applied. etc.; a fixotrope, e.g. CARBOSIL; and a filler such as It is another object of this invention to provide a calcium carbonate or limestone. Such sealants are of composition for the removal of undesired sealant from course water-insoluble, since their purpose and use as the surface of galvanized steel without affecting the sealants is to seal and waterproof the joints and open surface of the steel. ings in which they are used. These sealants are also used 35 Other objects will appear from the description which in allied industries, such as the aviation industry, in the follows. manufacture of trucks and buses, and in the manufac ture of tractors and other motorized farm equipment. DESCRIPTION OF THE INVENTION One method for removing such unwanted sealants is In accordance with this invention, there are provided by the use of kerosene. However, kerosene has many compositions for the removal of sealant and other unde disadvantages, including toxicity to the workers using it sirable materials from the surfaces of galvanized steel on prolonged exposure; flammability problems; un and other zinc containing metals without affecting the pleasant odor; and the problem of removing excess surface of the metal so streaking or spotting does not kerosene from the metal parts, since kerosene has low occur when phosphate precoats are subsequently ap water solubility and cannot be readily removed by use 45 plied to the metal treated with said compositions. In of a water rinse. In fact, when automotive bodies con addition, the compositions of the invention provide taining areas coated with kerosene are immersed or meaningful temporary corrosion protection. It should sprayed one after the other in a standard cleaning solu be noted that the present compositions can also be ap tion prior to the application of a conversion coating to plied advantageously to the surfaces of metals other the metal bodies, the bath becomes contaminated rela 50 than zinc containing metals, for example, to ferrous tively rapidly and rendered ineffective by the kerosene, metals, such as steel, and to aluminum. The composi requiring frequent down time and expense in draining tions are aqueous solutions containing as essential ingre the kerosene-contaminated bath and making up a fresh dients an alkanolamine, an aliphatic carboxylic acid bath. The use of emulsifiable kerosene was an improve containing 5 to 18 carbon atoms, and an arylenetriazole; ment but did not satisfactorily eliminate the above prob 55 the amount of alkanolamine being at least sufficient to lems. Hence, until commercially alternative means were react with the carboxylic acid to form a water-soluble developed for removing the sealant the use of kerosene salt, had to be tolerated. The compositions desirably contain in approximate Aqueous detergent compositions have been devel percent by weight: oped to remove the undesirable sealant and these com 60 positions are now replacing kerosene. Such composi tions have been disclosed and claimed in copending % By Preferred 2 Most Preferred application Ser. No. 379,108, filed May 17, 1982 to Ingredient Weight By Weight % By Weight Plante et al. These detergent compositions are used as an alkanolamine 1-55 2-6 2.5-3.5 65 an aliphatic 0.9-40 i.S.-3.0 2.0-2.5 prewipe or precleaner to remove the undesirable sealant carboxylic acid before the body is subjected to the sequential treatment containing 5 to prior to the application of a siccative coating. This 18 carbon atoms sequential treatment comprises a cleaning step, a water an arylenetriazole 0.01-10 0.02-0.07 0.03-0.05 4,540,442 4. -continued PEGOSPERSE 700-TO (Glyco Chemicals, Inc.) a nonionic surfactant which is an abietic acid con % By Preferred 26 Most Preferred Ingredient Weight By Weight % By Weight taining approximately 14 to 16 moles of ethoxylation; surfactant 0-5 0.3-5 0.6-1.5 IGPAL CA-630 (GAF Corp.) a nonionic surfactant, water qs. 100 qs, 100 qs. 100 which is an alkyl phenoxy poly(ethyleneoxy) ethanol; TRYCOL LF-1 (Emery Industries, Inc.) a nonionic surfactant which is an alkyl poly ether; The pH of these compositions range from about 7.5 to RENEX 20 (I.C.I. United States, Inc.) a nonionic, about 10.0, preferably from about 7.8 to about 8.5. polyoxyethylene ester of mixed fatty acids and resin The alkanolamine can be a mono-, di-, or trialkanola O acids; mine or mixtures thereof. Preferably, the alkanol group MIRAWET B (Miranol Co.) an anionic surfactant, or groups therein each contain from 1 to 5 carbon sodium 2-butoxyethoxyacetate; atoms. Triethanolamine is most preferred. Triethanol SURFONICLF-7 (Texaco Chemical Co.) a nonionic amine is usually added in the form of commercial prod surfactant which is an alkyl polyethoxylated ether; uct containing 85% triethanolamine and the balance 15 TERGITOL ANIONIC-08 (Union Carbide Corpo diethanolamine. ration) an anionic surfactant which is sodium 2-ethyl The aliphatic carboxylic acids include saturated and hexyl sulfate; unsaturated acids which can be straight chained or PETRO ULF (Petrochemicals Co., Inc.)-Linear branched. Such acids include , isovaleric alkyl naphthalene-anionic; and acid, angelic acid, tiglic acid, , t-butylacetic 20 CHEMEEN C-12G (Chemex, Inc.) an ethoxylated acid, heptanoic acid, 2-ethyl-hexanoic acid, 4-ethyl-hex coco amine. anoic acid, , valproic acid, pelargonic acid, HYAMINE 3500 (Rohm & Haas Co.) a cationic sur isononanoic acid, and the like. Also included within the factant which is lauryl dimethyl benzyl scope of the invention are mixtures of two or more such chloride. acids. 25 The surfactant can be anionic, cationic or nonionic. The surfactants serve to enhance the cleaning effect Mixtures of two or more surfactants can be used, except of the composition and facilitate the removal of shop that mixtures of anionic and cationic surfactants should dirt, lubricating and treating oils, marks from highlite not be used. Suitable surfactants include: marking pens, etc. Low foaming non-ionic surfactants POLY-TERGENT S-205LF (Olin Mathieson Com 30 are preferred. pany), a polyoxyethylene-polyoxypropylene alcohol; The arylenetriazoles are compounds of the formula TRITON DF-16 (Rohm & Haas Co.) a nonionic surfactant which is a modified polyethoxylated straight chain alcohol; POLY-TERGENT S-505LF (Olin Corp.) a nonionic 35 surfactant which is a modified polyethoxylated straight chain alcohol; SURFONIC LF-17 (Texaco Chemical Co.) a non ionic surfactant which is an alkyl polyethoxylated ether; where Ar is o-phenylene, mono-alkyl-o-phenylene, po PLURAFAC RA-30 (BASF Wyandotte Corp.) a 40 lyalkyl-o-phenylene, o-naphthylene, and alkyl-o- nonionic surfactant which is a modified oxyethylated naphthylene wherein the alkyl group has from 1 to 4 straight chain alcohol; carbon atoms. The preferred compound is a 4-methyl PLURAFAC D-25 (BASF Wyandotte Corp.) a non benzotriazole of the structure. ionic surfactant which is a modified oxyethylated straight chain alcohol; 45 TRITON X-120 (Rohm & Haas Co.) a nonionic sur CH3 factant which is an octyl phenoxy polyethoxy ethanol; N GENAPOL PN-30 (American Hoechst Co.), a non I ionic surfactant which is composed of ethylene diamine N containing about 30 moles of ethylene oxide and about SO NH1 60 moles of propylene oxide; ETHOMEEN C/20 (Armak Co.), a nonionic surfac The triazoles act as inhibitors in preventing attack by tant which is a coconut oil amine containing about 10 the alkaline solution on the zinc in the galvanized steel. moles of ethylene oxide; If the composition will not be used within a few days ANTAROXBL 330 (GAF Corp.) a nonionic surfac 55 after its preparation, but at later time, it is preferable to tant which is an alkyl poly (ethyleneoxy) ethanol; add a preservative to the composition to prevent micro TRITON CF-10 (Rohm & Haas Co.) a nonionic sur bial growth, e.g. sodium pyrithione which acts as both factant which is an alkylaryl polyether having a carbon a fungicide and bacteriacide. It is added in a concentra chain of about 14 carbon atoms and approximately 16 tion in percent by weight of about 0.1 to about 1.0, moles of ethoxylation; 60 preferably from about 0.2 to about 0.3%. SURFACTANT AR 150 (Hercules, Inc.) a nonionic Additional ingredients which can be added to the surfactant which is an ethoxylated abietic acid deriva present compositions include water soluble dyes to aid tive with approximately 15 moles of ethoxylation; in identification, small amounts of fragrances, e.g. PLURONIC L061 (BASF Wyandotte, Inc.) a non lemon oil, to mask or improve the odor, and alkalibo ionic surfactant which is a condensate containing only 65 rates to improve the cleaning power. The alkali borate ethylene oxide and propylene oxide chains; can be added per se, or as boric acid plus an alkali hy ANTAROX LF-330 (GAF Corp.) a nonionic surfac droxide, e.g. sodium or potassium hydroxide, in a con tant which is an alkyl poly(ethyleneoxy) ethanol; centration of about 3 to about 7% by weight. 4,540,442 5 6 The aqueous compositions of the invention can be formulated as such or, preferably, prepared as concen -continued trates and then diluted with appropriate quantities of Sodium pyrithione 0.20 water prior to use. Useful concentrates can contain the Water qs. 100.00 above ingredients in the following approximate percent by weight: EXAMPLE 6

Preferred 2% Same ingredients and quantities thereof as in Example Ingredient % by weight by weight 10 5 except that PETRO ULF was used in place of CHE an alkanolamine 10-30 13-7 MEEN C-12G. an aliphatic carboxylic 9-13 10-12 acid containing 5 to EXAMPLE 7 18 carbon atoms an arylenetriazole 0.1-0.35 0.15-0.25 Same ingredients and quantities thereofas in Example surfactant 0-10 3-17 15 5 except that MIRAWETB was used in place of CHE watet qs. 100 qs. 100 MEEN C-12G. The above concentrates can be used without dilution EXAMPLE 8 or diluted with water, e.g. to a 20% concentration. Same ingredients and quantities thereofas in Example The invention will become clearer from the examples 20 which follow. These examples are given by way of 5 except that ETHOMEEN C20 was used in place of illustration and are not to be regarded as limiting. CHEMEEN C-12G. In preparing the aqueous compositions of this inven EXAMPLE 9 tion the desired quantities of the materials comprising the compositions were dissolved with stirring in the 25 required amount of water at room temperature. Alter Triethanolamine 15.00 natively, the compositions can be formed with less than 4-Ethylhexanoic acid 11.00 the required amount of water, and after solution is com CHEMEEN C-12G 4.00 Tolyltriazole 0.20 plete, additional water is then added to bring the solu Sodium omadine 0.20 tion to the desired concentration. 30 In the examples, the numerical amounts refer to Water qs. 100.00 weight percent. EXAMPLE 1. EXAMPLE 10 35 Same ingredients and quantities thereof as in Example Triethanolamine 15.00 9 except that caprylic acid was used in place of 2-ethyl Isononanoic acid 11.00 hexanoic acid. Tolyltriazole" 0.20 Water q.s. 100.00 EXAMPLE 11 "a mixture of 4- and 5-methylbenzotriazole 40 While ordinary tap water is satisfactory, as a matter Triethanolamine 15.00 of practice deionized water was used. Caproic acid .00 - CHEMEEN C-12G 4.00 EXAMPLE 2 Tolyltriazole 0.20 45 Sodium pyrithione 0.20 Water qs. 100.00 Triethanolamine 15.00 Isononanoic acid 1100 CHEMEEN C-12G 4.00 Tolyltriazole 0.20 EXAMPLE 12 Water q.s. 100.00 50

Triethanolamine 15.00 EXAMPLE 3 Valeric acid 1.00 CHEMEEN C-12G 4.00 Same ingredients and quantities thereof as in Example Tolyltriazole 0.20 2 except that benzotriazole was used in place of tolyl 55 Sodium pyrithione 0.20 triazole. Water qs. 100.00 EXAMPLE 4 Same ingredients and quantities thereofas in Example EXAMPLE 3 2 except that PETRO ULF was used in place of CHE 60 MEEN C-12G. Triethanolamine 5.00 EXAMPLE 5 Isononanoic acid 11.00 CHEMEEN C-12G 3.50 65 GENAPOL PN30 0.50 Triethanolamine 15.00 Tolyltriazole 0.20 Isononanoic acid 1100 Water qs. 100.00 CHEMEEN C-12G 4.00 Tolyltriazole 0.20 4,540,442 7 8 EXAMPLE 4 H Same ingredients and quantities thereofas in Example 13 except that the composition contained 0.20% by 5 /N weight of sodium pyrithione. Ar N aN EXAMPLE 5 N where Ar is o-phenylene, monoalkyl-o-phenylene, po Triethanolamine 15.00 O lyalkyl-o-phenylene, o-naphthylene and alkyl-o- Isononanoic acid 1100 naphthylene where the alkyl group has from 1 to 4 Eit hydroxide carbon atoms, wherein the alkanolamine and the ali CHEMEEN C-2G 3.50 phatic carboxylic acid are present in the composition in GENAPOL PN30 0.50 amounts sufficient to remove the resin-containing seal Tolyltriazole 0.20 15 ant when the aqueous composition is applied thereto Sodium pyrithione 0.20 and wherein the arylenetriazole is present in a quantity Water qs. 100.00 sufficient to prevent attack on the metal surfaces by the aqueous alkaline solution. The compositions of the above examples were found 2. A composition according to claim 1 wherein the to be effective in removing from metallic surfaces such 20 aliphatic carboxylic acid is an alkanoic acid which is resin-containing sealants as: straight chained or branched. GM 998-1263, a polyvinyl chloride plastisol sealer 3. A composition according to claim 2 wherein the manufactured by Union City Industries, Union City, alkanoic acid is isononanoic acid. Mich.; 4. A composition according to claim 3 wherein the GM 998-1553, a polyvinyl chloride plastisol sealer 25 arylenetriazole is tolylenetriazole. manufactured by Hughes Chemical Co., Madison 5. A composition according to claim 1 which con Heights, Mich.; tains in approximate percent by weight: GM 998-1301, a red sealer having a linseed oil base, manufactured by J. W. Mortell, Warren, Mich.; an alkanolamine 1-55 M4G145C, a pink sealer used by the Ford Motor an aliphatic carboxylic acid 0,9-40 Company; containing 5 to 18 carbon atoms M4G161C, a white sealer used by the Ford Motor an arylenetriazole 0.0-1.0 Company; and surfactant 0-1S GM 998-1981, a black sealer used by the General 35 water qs. 100. Motors Corporation; - readilywhich hadand been effectively placed onremoved the metal. by Thecontacting sealants themwere tains6. Ain compositionapproximate percentaccording by toweight: claim 5 which con with the composition, such as by wiping with a rag which had been dipped into the composition being 40 an alkanolamine 2-6 tested. In addition to wiping, the sealant was also effec- an aliphatic carboxylic acid 1.5-3.0 tively removed by spraying the composition onto the containing 5 to 18 carbon atoms metal or dipping the metal into the composition. The a retriazole 907 compositions can be used at full strength or in diluted water q.S. io0. form of about 2 to 5 fold dilution. The diluted composi- 45 tion." substantially as effective as those at full 7. A composition according to claim 5 which con When the metal from which the sealant was removed tains approximate percent by weight: was galvanized steel, it was then treated as described above and a phosphate precoat applied. These phos- 50 an alkanolamine 2.5-3.5 phate precoats were not streaky and showed no spot- an aliphatic carboxylic acid 2.0-2.5 ting. containing 5 to 18 carbon The compositions were also tested under field condi- s arylenetriazole 0.3-0.05 tions in the factory on automobiles in which certain 55 Surfactant 0.6-1.5 parts of the bodies were composed of galvanized steel. Water qs. 100. The Sealant was readily removed by wiping or spraying leaving a clean surface, and the phosphate precoat 8. A composition according to claim 5 wherein the which was subsequently applied as described above aliphatic carboxylic acid is an alkanoic acid, the alkyl showed no streaking or spotting. 60 portion of which is straight chained or branched. What is claimed is: 9. A composition according to claim 8 wherein the 1. A aqueous alkaline composition which is effective alkanoic acid is isononanoic acid. in removing a resin-containing sealant from ferrous and 10. A composition according to claim 9 wherein the Zinc containing metals without adversely affecting the arylenetriazole is selected from the group consisting of Surfaces of the metal, containing as essential ingredients: 65 phenylenetriazole, tolyltriazole, dimethylbenzotriazole, an alkanolamine, an aliphatic carboxylic acid containing and naphthylenetriazole. 5 to 18 carbon atoms, and an arylenetriazole having the 11. A composition according to claim 10 wherein the formula arylenetriazole is tolyltriazole. 4,540,442 10 12. A composition according to claim 11 wherein the surfactant is anionic, cationic, nonionic, or a mixture of an alkanolanine 0-30 two or more of such surfactants, provided that the mix an aliphatic carboxylic acid 9.13 ture does not include both cationic and anionic surfac containing 5 to 18 carbon atoms tants. an arylenetriazole 0.1-0.35 13. A composition according to claim 12 wherein the surfactant 0-10 surfactant is nonionic. water q.S. 100, 14. A composition according to claim 13 which con tains a preservative to prevent microbial growth. O 22. A composition according to claim 21 which con 15. A composition according to claim 14 wherein the tains approximate percent by weight: preservative is present in from about 0.1 to about 1.0% by weight. an alkanolamine 13-17 16. A composition according to claim 15 wherein the an aliphatic carboxylic acid 10-12 15 containing 5 to 18 carbon preservative is present in about 0.2 to about 0.3% by atons weight. An arylenetriazole 0.15-0.25 17. A composition according to claim 16 wherein the surfactant 3-7 preservative is sodium pyrithione. water q.S. 100. 18. A composition according to claim 17 which con tains a water-soluble dye. 23. A process for removing a resin-containing sealant 19. A composition according to claim 18 which con from the surface of a zinc containing metal which com tains a fragrance. prises contacting the sealant with the composition of claim 1. 20. A composition according to claim 17 which con 24. A process according to claim 23 wherein the tains about 3 to 7% by weight of an alkali metal borate, 25 metal is galvanized steel. the alkali metal being sodium or potassium. 25. A process according to claim 23 wherein the 21. An aqueous composition containing in approxi contacting is achieved by spraying, dipping or wiping. mate parts by weight: sk : k + k, 30

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