Patented May 23, 1950 2,509,174

UNITED STATES PATENT OFFICE 2,509,174 PROCESS OF WATERPROOF NG TEXT LE FABRICs Milton J. Scott and Stuart H. Rider, Springfield, Mass, assignors to Monsanto Chemical Com pany, St. Louis, Mo., a corporation of Dela No Drawing. Application May 22, 1947, Serial No. 49,880 10 Claims. (C. 117-161) This invention relates to waterproofing con melamine containing about 2 mols of stearyl al positions and to materials treated therewith. cohol per mol of hexamethylol melamine. More particularly, the invention relates to cer tain aminotriazine-aldehyde-alcohol reaction Ecample I products and to cellulosic and proteinaceous ma 314 parts of spray dried crystalline hexa terials treated therewith. methylol melamine of Example I were mixed An object of this invention is to prepare water with 320 parts (10 mols) of anhydrous methanol proofing compositions. and 0.5 part of ethyl phosphoric acid. The mix A further object is to prepare aqueous emul ture was refluxed for 30 minutes at atmospheric sions of aminotriazine-aldehyde-alcohol reaction O pressure and then 404 (1.5 mols) parts of stearyl products. alcohol were added and refluxing continued for Another object is to provide waterproof coat 30 minutes. The solution was concentrated by S. vacuum distillation at about 25 inches of mercury Still another object is to provide Waterproof until the temperature rose to about 130 C. The textiles. S resulting material was a methyl stearyl ether of These and other objects are attained by pre hexamethylol melamine containing about 1.5 paring a liquid reaction product of an amino mols of stearyl alcohol per mol of hexamethylol triazine, an aldehyde, and two alcohols one of melamine. which is an aliphatic Saturated alcohol contain Eacample IV ing 6 carbon atoms or less and the other of which 20 Example III was repeated except that about is a saturated or unsaturated aliphatic alcohol 15 molls of cetyl alcohol were substituted for the containing at least 12 carbon atoms, and then steary alcohol. A methyl cetyl ether of hexa treating water-receptive materials with the liquid methylol melamine was obtained. reaction product to render then Water-repellent. In making the mixed ethers of alkylol amino The following examples are given in illustration 25 triazines, each of the components may be re and are not intended to limit the scope of this placed by analogous materials and the amounts invention. Where parts are mentioned, they are of the components may be varied Over a wide parts by Weight. range. ECarple Instead of melamine shown in Example I other 30 aminotriazines may be used. Typical examples 126 parts (1 mol) of melamine were mixed with of aminotriazines are: melamine, formoguana 480 parts of Formalin (equivalent to about 6 mois mine, melam, melem, aminotriazines in which 1 of formaldehyde). The pH of the mixture was or 2 amino groups are substituted by hydroxy, adjusted to about 8-9 and the mixture was then halogen, alkyl, aryl or aralkyl groups such as 2 refluxed at atmospheric pressure for 30 minutes. 35 hydroxy-4, 6-diamino-1,3,5-triazine, 2,4-dihy The resultant solution of hexamethylol melamine droxy-6-amino-1,3,5-triazine, 2 - chloro-4,6-di in water was cooled to crystallize the hexamethyl amino-1,3,5-triazine, 2-phenyl - 46 - diamino ol melamine thus producing an aqueous slurry. 1,3,5-triazine, 6-methyl-2,4-diamino - 13,5-tri The slurry was spray dried and the crystals were azine, aminotriazines in which the hydrogen recovered for further reaction. 40 atoms of the amino groups are partially Sub Eacample II stituted by amino, alkyl, aryl, or aralkyl groups such as 2,4,6-trihydrazino-1,3,5-triazine, mono-, 314 parts (about 1 mol) of spray dried crystal di-, or trialkyl melamines, e. g., 2,4,6-triethyl line hexamethylol melamine of Example I Were triamino-1,3,5-triazine, mono-, di-, or triaralkyl mixed with 504 parts (6 mols) of anhydrous n 45 melamines, mono-, di-, or triaryl melamines, e.g., butanol and 0.5 part of concentrated hydrochlo 2,4,6-triphenyl-triamino-1,3,5-triazine, etc. Mix ric acid. The mixture was refluxed for 30 mini tures of two or more of the above may also be utes at atmospheric pressure and then 538 parts employed. (2 mols) of stearyl alcohol were added and re The formaldehyde shown in Example I may be fluxing continued for 30 minutes at atmospheric 50 replaced in whole or in part by saturated or pressure to obtain a clear Solution. The Solu unsaturated aliphatic, allicyclic or aromatic al tion was concentrated by distillation at a vacuum dehydes. Typical examples of aldehydes which of 25 inches of mercury until a temperature of may be used are: formaldehyde, acetaldehyde, 130° C. Was obtained. The resulting material was propionaldehyde, butyraldehyde, hexaldehyde, a mixed steary n-butyl ether of hexamethylol SS octaldehyde, benzaldehyde, furfural, acrolein, 2,509,174 w 3 4. w methacrolein, crotonaldehyde, cinnamaldehyde, sufficient to activate the etherification reaction etc. For economic considerations, under present and does not interfere therewith. day conditions, the lower aliphatic aldehydes, The etherification catalysts include such acids especially formaldehyde, constitute a preferred as sulfuric, hydrochloric, acetic, phosphoric acids, class for use in making the resins of this inven etc. The acids are used in concentrated form tion. The aldehydes may be used in propor and contain a relatively minor percentage of tions ranging from 1 to 6 or more nois per mol of water. aminotriazine. The mixed alcohol ethers of alkylol aminotri The preliminary reaction to produce the al azines are liquid resins insoluble in Water and kylol aminotriazines as typified by Example I is soluble in organic solvents such as alcohols, ke carried out preferably under alkaline condi 0. tones, esters, toluene, benzene, mineral spirits, tions, i. e., a pH of 8-10 under refluxing conditions etc. They are water-white or slightly yellow in at atmospheric pressure. In the preferred emi color. They may be used to waterproof cellul bodiment of this invention the reaction under losic or proteinaceous materials such as paper, reflux is stopped by cooling as soon as a clear cotton, wood, wool, silk, viscose and cellulose Solution is obtained. The alkylol aninotriazine acetate rayons, etc. is then crystallized and freed from water and The liquid resins may be cured to an insolu excess aldehyde. It is, however, within the SCOpe ble, infusible state by the application of heat at of this invention to add the alcohols and etherifi about 100 to about 300° C. for a short period with cation catalysts to the Water solution of the out the addition of a curing catalyst. Acid cur alkylol melanine and then carrying out the eth ing catalysts may be used, if desired. erification step in an aqueous medium. The mixed ethers may be applied as a water In the second step of this invention, as illus proofing composition from a solution in organic trated in xamples II, III and IV, the n-butanol solvents or from an aqueous emulsion. and methanol may be replaced in whole or in part by other saturated aliphatic alcohols con Eacample W taining 6 carbon atoms or less, e. g., ethanol, 70 parts of a butyl-stearyl ether of hexameth propanol, isopropanol, isobutanol, pentanols, hex yol melamine made as shown in Example II arols, etc. To obtain the best results, the lower were dissolved in 30 parts of mineral spirits and alcohol should be a straight chain alcohol but then emulsified with 100 parts of Water in the branched chain alcohols such as isopropanol or presence of ammonium oleate as emulsifying isobutanol may be used to obtain specific prop agent. The resulting emulsion was an oil-in erties in the final resin. The amount of satu water type emulsion containing 36% solids by rated aliphatic alcohol to be used will depend on weight and 15% solvent by Weight. the process used and the product desired. From A portion of the emulsion was diluted with i to 6 mols of alcohol are used in the reaction water to about 10%. Solids (liquid resin) by with the alkylol aminotriazine and it is conven weight. Cotton cloth was drawn through the di ient to use a substantial excess of alcohol to act ute emulsion, partially dried by wringing and as a solvent for the resins produced. An excess then dried for a few minutes at approximately of alcohol is particularly desirable if the sub 100° C. followed by treatment for about 20 min stantially anhydrous process shown in Examples 40 utes at 145-155° C. The resin pick-up was found III and IV is used. If desired, the solvent may to be between 3 and 4%. The treated cloth had be removed by vacuum distiliation to obtain the substantially 100% resistance to water as meas pure liquid resin. ured by ASTM Test Method D583 40T using the . The stearyland cetyl alcohols shown in Exam Water Absorption (Spray) Method. After re ples II, III and W may be replaced in whole peated launderings with soap and hot water, a or in part by other saturated or unsaturated sample of the treated cloth still had excellent aliphatic alcohols containing at least 12 car water repellence and had not shrunk materially. bon atoms and preferably not more thari 35 car Moreover, repeated treatment with dry cleaning bon atoms, e. g., carnaubyl alcohol, heptadec solvents did not appreciably alter the water re ano, nondecanol, eicosanol, melissic alcohol, pellency of the treated fabric. etc. The long chain alcohols which may be A further portion of the emulsion made ac either straight or branched chain compounds, cording to Example W and diluted to about 10% may be used in proportions ranging from 1 to 4 solids with water was used to treat a Woolen mols of alcohol per mol of alkylol aminotriazine. fabric in substantially the same manner and They partially replace the lower alcohols on thie with substantially the same results. alkylol aminotriazine, thus releasing the lower Quite unexpectedly, it was found that even alcohols to act as Solvents for the reaction prod though more than the minimum amount of resin uct. The waterproofing properties of the new res to produce water repellency was used, the hand ins are attained as soon as from about 1 to about of the fabric was as soft and in Some cases softer, 2 molls of higher alcohol have reacted with 1 than the hand of the untreated fabric. no of the alkylol aminotriazine. If from 2 to 4 Still another portion of the emulsion prepared nols of the higher alcohol react with 1 mol of according to Example V was diluted with water aminotriazine-aldehyde reaction product, the to about 6% solids by weight. The dilute emul waterproofing properties of the product are very sion was then roll-coated on thin kraft paper. slightly increased over a resin containing only 1 The coated paper was dried at about 100 C. and to 2 mols of higher alcohol. then heated at 140-160° C. for about 5 minutes. In the preferred embodiment of this invention, The treated paper was substantially 100% wa water-free crystalline hexamethylol melamine ter repellent and was not noticeably stiffer than made as shown in Example I is reacted first with O the untreated paper. an excess, i. e., more than 6 mols, of an anhy drous lower aliphatic alcohol and then with 1 Ecample VI to 2 naos of a higher aliphatic alcohol using an An emulsion similar to that of Example V was acidic condensation catalyst. The small amount made using the resin of Example IV. When ap of water normally associated with the catalyst is s plied to cotton and wool fabric and to paper 2,600,174 5 similar results were obtained, i. e., substantially tiles which have been treated with the resins of 100% water-repellency as measured by ASTM this invention. "Mark-off is the appearance of Test Method D583 40T. The water repellency marks on a treated fabric when scratched or of the fabric was substantially unaffected by roughly treated. The marks are unsightly and laundering or dry cleaning. The hand of the not easily removed. Nylon and other fabrics fabric and stiffness of the paper were not sub treated with the mixed ethers of this invention stantially altered by the resin. do not "mark-off.' Aqueous emulsions of the resins of this inven Eacample VII tion are particularly valuable since they may be 5 parts of a butyl-stearyl ether of hexamethyliol O made Originally with a relatively high per cent melamine made as in Example II were dissolved by weight of resin in which condition they may in 95 parts of mineral spirits. Cotton cloth was be easily diluted to relatively low resin content drawn through the solution, partially dried by as desired for other uses. For example, in treat Wringing and then dried for a few minutes at ing textiles, the emulsion may be diluted until approximately 100° C. The cloth was then heat 5 it contains from about 1% to about 6% by weight ed to 145-155 C. for about 20 minutes. The resin of resin to regulate the subsequent resin pickup pick-up was about 4%. The results obtained in of the fabric within desired limits, i. e., generally water repellency tests were similar to those ob 2 to 6% by weight based on the weight of the tained as shown in Example W. fabric. In the preferred embodiment of this invention, 20 It is obvious that many variations and altera the liquid resin is emulsified with water. It is tions may be made in the products and processes convenient, but not necessary, to thin the resin of this invention without departing from the with a solvent such as mineral spirits prior to spirit and scope of this invention as set forth in the emulsification step. Warious emulsifying the appended claims. agents may be used such as soaps, salts of styrene What is claimed is: maleic anhydride copolymers, salts of aryl su i. A process for Waterproofing textile fabrics fonic acids, etc. A preferred group of emulsify which comprises impregnating said fabrics with ing agents are ammonium or amine salts of oleic an aqueous emulsion of a mixed ether comprising acid including ammonium oleate, morpholine an aminotriazine condensation product etherified oleate, ethanolamine oleate, etc. Conveniently, 30 with (1) from 5-2 mois of a Saturated unsubsti an emulsion containing about 35% by weight of tuted monohydric aliphatic alcohol containing liquid resin is prepared which can be further from 1-6 carbon atoms and (2) from 1-4 mols of diluted to suit the particular requirements of an alcohol taken from the group consisting of the material to be waterproofed. unsubstituted monohydric saturated and unsatu The resins of this invention, whether used in 35 rated aliphatic alcohols containing from 12-30 the form of a solution in volatile solvents, or as carbon atoms, and thereafter heating the in aqueous emulsions provide substantially 100% pregnated fabric at from 100 C. to 300 C. water repellency for the treated materials. In 2. A process as in claim 1 wherein the 1-6 cases of cellulosic or proteinaceous materials, such carbon atom alcohol is n-butanol. aS paper, Cotton, wood, wool, silk, cellulose AO 3. A process as in claim 1 wherein the 1-6 acetate rayons, etc., they become bonded so firm carbon atom alcohol is methanol. ly that they cannot be removed by washing with 4. A process as in claim 1 wherein the 1-6 Soap and water or by cleaning with dry cleaning carbon atom alcohol is methanol and the 12-30 Solvents. This property is of especial advantage carbon atom alcohol is steary alcohol. for the protection of textiles which must be fre 45 5. A process as in claim 1 wherein the 16 quently washed or dry cleaned. A typical ex ample of the valuable properties of textiles treat carbon atom alcohol is stearyn-butanol alcohol. and the 12-30 ed by the emulsions of this invention is the re 6. A process as in claim 1 wherein the 1-6 sistance of a treated white cotton cloth to a carbon atom alcohol is n-butanol and the 12-30 Water-Soluble ink. In a laboratory test, a large 50 carbon atom alcohol is cetyl alcohol. Spot of Water-soluble ink was placed on a sample 7. A process for waterproofing textile fabrics of treated white cotton cloth. The stained which comprises impregnating said fabrics with sample was then placed in a stream of cold water an aqueous emulsion of a mixed ether comprising and the ink vanished almost immediately, leave 1 mol of hexamethylol melamine etherified with ing no colored stain. The cloth was shaken 55 from 5-2 mols of methanol and from 1-4 mols of vigorously and then was found to be substantially stearyl alcohol, and thereafter heating the ims dry. pregnated fabrics at temperatures of from 100 A further advantage of the resins of this in C. to 300° C. vention is their, lack of original color and their 8. A process for waterproofing textile fabrics resistance to the development of color on aging. 60 which comprises impregnating said fabrics with This property permits them to be used on white an aqueous emulsion of a mixed ether comprising and delicately tinted textiles without impairing 1 mol of hexamethylol melanine etherified with the Color of the textile. from 5-2 mols of n-butanol and from 1-4 mols of Still another advantage of these resins is that Stearyl alcohol, and thereafter heating the im they do not change the physical characteristics 65 pregnated fabrics at temperatures of from 100' of materials treated therewith, i. e., they do not C. to 300° C. increase the harshness of hand of textiles, nor 9. A process for waterproofing textile fabrics the stiffness of paperS. which comprises impregnating said fabrics with Still another advantage is that they do not an aqueous emulsion of a mixed ether comprise deteriorate on long aging to generate acidic type 70 ing 1 mol of hexamethylol melamine etherified materials which tender the fabric as is the case With from 5-2 molls of n-butanol and from 1-4 With many other types of permanent water re mos of cetyl alcohol, and thereafter heating the pellents. impregnated fabrics at temperatures of from 100 An important advantage is the resistance to C. to 300° C. 'mark-Off' of textiles and especially nylon texa 75 10. A process for waterproofing textile fabrics 8,80024 7 . which comprises impregnating said fabrics with REFERENCES C TED from 2-6% by weight, based on the weight of The following references are of record in the thean aminotriazine-aldehydefabric, of a mixed ether comprisingcondensation 1 molprod of file of this attent: uct etherified with (1) from 5-2 mols of Satu- 5 UNED STATES PATENS rated unsubstituted monohydric alcohol contain- Number Name Date ing from 1-6 carbon atoms and (2) from 1-4 2,197,357 Widmer ------Apr. 16, 1940 mols of an alcohol taken from the group consist- 2329,622 Johnstone ------Sept. 14, 1943 ing of unsubstituted monohydric saturated and 2,357,273 Thurston ------Aug. 29, 1944 unsaturated aliphatic alcohols containing from to 2,371,892 Hood ------Mar. 20, 1945 12-30 carbon atoms, said mixed ether being de- 2,420,157 West ------May 6, 1947 posited on the fabrics from aqueous emulsion, 2,426,770 Grin ------Sept. 2, 1947 and thereafter heating the impregnated fabrics at 100° C. to 300 C. MILTON J. SCOTT. 5 STUART, ROIR,