United States Patent Streck (15) 3,635,652 (45) Jan. 18, 1972 54 PROCESS FOR DYEING Du Pont Dyes & Chem. Tech. Bulletin, Vol. 18 (2) 1962, pp. POLYURETHANE FOAM IN 89-93. NONAQUEOUS DYE BATH (72) Inventor: Primary Examiner-George F. Lesmes Clemens Streck, Loudonville, N.Y. Assistant Examiner-T.J. Herbert, Jr. 73 Assignee: GAF Corporation, New York, N.Y. Attorney-George L. Tone, Walter C. Kehm and Samson B. (22) Filed: July 5, 1968 Leavitt (21) Appl. No.: 742,523 (57) ABSTRACT A composition of matter comprising polyurethane foams and (52) U.S. Cl.................................................. 8/4, 260/2.5 AK articles foamed therefrom, having applied thereto an essen (51 int.C. ......................................................... D06p3/24 tially water-insoluble dyestuff of the class known as spirit or (58) Field of Search............................................... 814, 178 E solvent-soluble dyestuffs; particularly those dyestuffs of this class which are formed by the reaction of water-soluble dyes 56 References Cited which contain water-solubilizing sulfonic or carboxylic acid groups with water-insoluble amines which are free from such UNITED STATES PATENTS solubilizing groups. In addition to the amine-salt-type of spirit 2,384,00l 9, 1945 Wesson.................................. 8/73 X or solvent-soluble dyestuffs, the metallized O,O'-dihydroxy 3,120,423 2/1964. Herschler et al. azo-type of spirit or solvent soluble-dyestuffs may be used. 3,337,289 8/1967 Manwaring...... The invention is also concerned with a method for the produc 3,432,251 3f 1969 Fisher............................................ 814 tion of dyed polyurethane foams which comprises applying to the polyurethane foam or article a solution of a water-insolu OTHER PUBLICATIONS ble, spirit or solvent-soluble dyestuff in a volatile organic sol Colour Index 2nd Ed. 1956, Vol. 2 pp. 2815 and 28 16, Publ. went AATCC, Lowell, Mass. 6 Claims, No Drawings 3,635,652 2 PROCESS FOR DYEING POLYURETHANEFOAMN final color of the foam is effectively controlled and which NONAQUEOUS DYE BATH serves to mitigate or otherwise overcome the several problems faced by prior art processes. BACKGROUND OF THE INVENTION Other objects and advantages of the present invention will The class of polymers known as polyurethanes are well 5 become apparent as the description thereof proceeds. known in the art and are commonly produced by reacting In satisfaction of the foregoing objects and advantages, diisocyanates, such as toluene diisocyanate, with glycols, there is provided by this invention compositions of matter polyols, hydroxyl-rich polyesters and various polyethers. In comprising polyurethane foams, and articles formed the production of these polymers, several methods are availa therefrom, having applied thereto essentially water-insoluble ble to produce foams by taking advantage of various aspects of 10 dyestuffs. Such spirit or solvent-soluble dyestuffs comprise (I) the reaction. For example, if high acid values are present in dyestuffs formed by the reaction of water-soluble dyes which the compound to be reacted with the isocyanate, a gas-form contain water-solubilizing sulfonic or carboxylic acid groups, ing reaction occurs which results in the production of a foam. with amines which are free from such solubilizing groups, and it is also known to produce foams based on castor oil formula (II) spirit and solvent-soluble dyestuffs of the metallized, 0,0'- tions as outlined in U.S. Pat. No. 2,787,601 or by the so-called 15 dihydroxy-azo type. The novel dyed compositions of this in "one-shot' method wherein a glycol, a polyacid and a diiso vention are characterized by good color fastness and color cyanate are reacted in the presence of an activator mixture to uniformity, effect foaming. There is also provided by the present invention a process for Flexible foams formed by the methods outlined above are the production of dyed polyurethanes which comprises dis well known to be useful for filling and insulation purposes but 20 solving a water-insoluble, spirit or solvent-soluble dyestuff of in recent years have become useful in many other areas where the above types (I) or (II) in an organic solvent, and applying color is an important characteristic. Thus polyurethane foams the resulting product to the polyurethane foam. are now in common use in the production of clothing, cleaning brushes and sponges, cushions for weather stripping, lamina 25 DESCRIPTION OF THE PREFERRED EMBODIMENTS tion to fabrics to produce various materials such as synthetic It has now been discovered that certain essentially water-in leathers and the like. It has, therefore, become important to soluble, spirit or solvent-soluble dyestuffs may be employed to provide means for coloring the foams to enhance their ap provide colored articles of the class of materials commonly pearance. referred to as polyurethane foams by dyeing, padding or print Various procedures have been attempted heretofore in an 30 ing the foams with organic solvent solutions of the dyestuffs to effort to devise suitable methods for dyeing polyurethanes in a be described hereinafter. The resultant products have been satisfactory manner. One method which has been employed found to be characterized by good fastness properties and involves incorporating a pigment dye into the reaction mass uniformity of color. The process of this invention has been prior to the production of the foam. However, this method has found extremely suitable where dyeing with bright colors is the disadvantage that the final coloration cannot be carefully 35 desired. Moreover, it has been found that the present inven controlled as it is dependent on reaction conditions. tion provides a procedure wherein the final color of the foam Moreover, it is difficult to obtain a uniform dispersion of the may be easily and carefully controlled. pigment in the reaction mass so as to obtain a uniformly The polyurethane foams to which the invention is applica colored product. ble are specifically set forth hereinabove. In general, it may be It has also been suggested to dye the polyurethane foams 40 said that the products commonly referred to as "polyurethane with direct dyes such as, for example, by the method described foams' and the various articles produced therefrom, are in U.S. Pat. No. 3, 197,268. However, this method has not susceptible to excellent dyeing employing the dyes and been entirely satisfactory because of the problem of obtaining processes of this invention. suitable color fastness. The dyes employed in the present invention in one embodi It is, therefore, apparent that a distinct need remains in the 45 ment generally comprise () water-insoluble, spirit-soluble art for a suitable method of dyeing polyurethane foams and ar amine salts of acid and direct dyes. These water-insoluble salts ticles produced therefrom. are generally spirit-soluble and are preferably produced by SUMMARY OF THE INVENTION reacting a water-soluble dye molecule containing at least one 50 sulfonic or carboxylic acid group with an equivalent amount It is accordingly one object of the present invention to pro of a water-insoluble amine. In a further embodiment, there vide compositions of matter comprising dyed polyurethane may also be employed (II) metallized 0,0'-dihydroxy-azo-type foams, and articles formed therefrom, and processes for dye spirit or solvent soluble dyes. ing the same, which overcome or otherwise mitigate the disad The amine-salt dyes may also be formed from metallized vantages of prior art methods of dyeing. 55 salts of water-soluble dyes which contain at least one sulfonic It is a further object of the invention to provide composi acid or carboxylic acid group which may be converted into the tions of matter comprising dyed polyurethane foams, and arti spirit-soluble salts. It is contemplated that any colored dye cles produced therefrom, wherein the polyurethane foams are molecule which contains at least one acidic group of the class dyed with essentially water-insoluble, spirit or solvent soluble indicated may be employed to produce the water-soluble dyestuffs dissolved in an organic solvent, the dyed products 60 amine salt. resulting therefrom being characterized by good fastness pro Among the acidic and direct dye molecules which have perties particularly in the bright colors. been found to be operable to react with the amine to form the A still further object of the present invention is to provide amine salts are those of the following specific formulas, and methods for the dyeing of polyurethane foams, whereby the Color Index name and number identification: I---------- Acid Yellow 23; C.I. 1940. Hois-K X-N-N-g-g-cooliHo N / N SOH 6153 0 1 019 037 3,635,652 3. 4 ll... th 8olvent Orange 20. N- Y. N. N. ( - (|| ' ('ll E() -- (' N N() N 1 N SOH III. C2H5 --- phs4. Acid Blue 83; C.I. 42660. S ( ) SOE N O C2Hs IV-------- Acid Blue 59; C.I. 50315. rol N- SOH HN- =N- NH V--------- Sulfonated copper phthalocyanine.-------------------------------------------------------------------------- Direct Blue 86; C.I. 74180. WI. - - {No. D-N-N-g-g-ch, Acid Orange 72; C.I. 18740. HO-C N.4 Cr OH N / N SOH WII----- CH Acid Yellow 99; C.E. 13900. SOH OH Ho C=O NO N VIII.----- (It Edirect Red 81; C.I .28160. HO3S- -NHC o–K X IX -- . OH, SOs Solvent Red 31; C.I. 27.306. HOSS 6S4 1009 O38 3,635,652 A -- - - - - - - - so H Acid Yellow 36; C.I. 13065. N. Stilbene dye - - - - - - - - - - -------------------------------------------------------------------.. - - - - - - - - - - - - - - - - - - Direct Yellow ll; C.I. 4000. X O 2. (N / role Solvent Red 49; C.I. 451703. \/ -COOH In addition, any dyes of the anthraquinone, triphenyl wherein R is a long carbon chain alkyl radical and R and R. methane and phthalein type are also considered operable in are alkyl radicals of one to two carbon atoms. Illustrative of this aspect of the invention so long as they contain at least one this class of amines is diethyloctadecylamine, described in acid group of the sulfonic or carboxylic acid type.