||||||||||||||| US0051 12930A United States Patent (19) (11) Patent Number: 5,112,930 Liidemann et al. 45 Date of Patent: May 12, 1992 54 MODIFIED POLYURETHANES 4,469,840 9/1984 Alberts et al. ...................... 524/500 CONTAINING PERFLUOROALIPHATIC 4,559,056 12/1985 Leigh et al.............................. 8/581 GROUPS AND USE THEREOF 4,739,013 4/1988 Pinchuk et al. ....... ... 525/10 4,748,215 5/1988 Lindner et al. ........... ... 525/479 75 Inventors: Simpert Liidemann, Bobingen; 4,851, 176 7/1989 Christiansen et al. ... 264/268 4,851,475 7/1989 Federici et al. ....................... 528/2 Michael Bernheim, Aystetten; Bernhard Sandner, Diedorf; Erich 4,935,480 6/1990 Zdrahala et al. ..... ... 528/28 Rössler, Stadtbergen-Leitershofen; 5,019,428 5/1991 Ludemann et al. ................... 528/38 Hans-Burkhardt Vogel, Brombach, FOREIGN PATENT DOCUMENTS all of Fed. Rep. of Germany 298.364 1/1989 European Pat. Off. 73) Assignee: Ciba-Geigy Corporation, Ardsley, WO86/02115 4/1986 PCT Int'l Appl. N.Y. OTHER PUBLICATIONS (21) Appl. No.: 667,721 Patent Abstract of Japan-JP-A-60-81-278. (22 Filed: Mar. 11, 1991 Product Bulletin-DD1 1410-Henkel Corp., Minneapo lis, MN. Related U.S. Application Data Primary Examiner-Melvyn I. Marquis (62) Division of Ser. No. 301,681, Jan. 25, 1989, Pat. No. Attorney, Agent, or Firm-Marla J. Mathias; Edward 5,019,428. McC. Roberts 30 Foreign Application Priority Data 57) ABSTRACT Jan. 29, 1988 (DE) Fed. Rep. of Germany ....... 3802633 Modified polyurethanes containing perfluoroaliphatic Sep. 16, 1988 (DEl Fed. Rep. of Germany ... 383.1452 groups which are obtained by reacting oligo(poly)ure thanes containing free hydroxyl or isocyanate groups 51) Int. Cl............................................... C08G 77/04 and perfluoroaliphatic groups with di/polyfunctional 52 U.S. Cl. ........................................ 528/28; 528/18; polysiloxanes at elevated temperatures with conversion 528/21; 528/26; 525/440, 525/446; 525/453 of all the reactive groups of the urethane are used for 58 Field of Search ....................... 528/28, 26, 18, 21; the oil- and water-repellent finishing of fiber materials, 525/446, 453, 440 conferring on these materials thus treated not only laun 56) References Cited dering- and drycleaning-stable effects but also in partic U.S. PATENT DOCUMENTS ular a very soft, full hand of very good surface smooth ness, these excellent hand effects being further opti 3,968,066 7/1976 Mueller .............................. 260/29.6 4,054,592 10/1977 Dear et al............................. 560/25 mized by the addition of a polyethylene dispersion and 4,098,742 7/1978 Mueller ............................... 428/42 /or of further customary textile assistants, in particular 4,421,783 12/1983 Marwitz et al. ................... 427/54.1 water-repellent fluorocarbon compounds. 4,433,007 2/1984 Marwitz et al. ................... 427/54.1 4,463,127 7/1984 Alberts et al. ...................... 524/731 1 Claims, No Drawings 5, 112,930 1. 2 from Henkel Corp.), including mixtures with one an MODIFIED POLYURETHANES CONTAINING other. The formulations produced therefrom are free of PERFLUOROALPHATIC GROUPS AND USE self-color. THEREOF The crucial factor for the subject-matter of the inven tion, then, is that the equivalence ratio in the prepara This is a divisional of Ser. No. 301,681 filed Jan. 25, tion of the oligo(poly)urethanes be chosen in such a 1989, now U.S. Pat. No. 5,019,428. way that, following the reaction, either free OH groups The present invention relates to modified polyure (compound la) or free NCO groups (compound 1b) thanes containing perfluoroaliphatic groups (Rf) and remain. In addition, the reaction can be controlled the use thereof for the oil- and water-repellent finishing 10 within wide limits. For instance, usable starting sub of fiber materials. In addition, there is also described the stances for preparing the novel modified polyurethanes conjoint use thereof together with textile assistants for containing perfluoroaliphatic groups are obtained the oil- and water-repellent finishing of fiber materials. within the OH: isocyanate group ratio of from 3:2 to Polyurethanes which contain perfluoroaliphtic 15:14 as well as in the range from 2:3 to 14:15, conse groups are already known in the art (U.S. Pat. Nos. 15 3,968,066 and 4,054,592). It is also known to use these quently forming polyurethanes which contain per compounds for the oil- and water-repellent finishing of fluoroaliphatic groups and free OH or NCO groups by fiber materials. These finishes, however, have the disad block formation, the latter being used particularly ad vantage that the water repellency is on the whole unsat vantageously, since thereby the end reaction with the isfactory. DE-A-2,802,392 in addition discloses poly polysiloxanes is determinable in a simple manner, for urethanes composed of perfluoroalkyl-containing seg 20 example by IR spectroscopy. ments and siloxane-containing segments, these polyure The other starting compounds are di- or polyfunc thanes being usable for treating textiles. It is true that tional polysiloxanes (compounds 2). Depending on these finishing agents represent a certain improvement whether, then, compound (1) has free OH groups (com as far as the fabric hand is concerned, but they are like pound 1a) or free NCO groups (compound lb), differ wise still unsatisfactory in respect of oil and especially 25 ent compounds (2) will be used. Suitable for the reac water repellency and their laundering and dry cleaning tion with the free OH groups are in particular those stability (see examples). having epoxy and carboxyl groups, and for this reason It has therefore already been proposed in PCT Appli there are used as compounds (2) those polysiloxanes cation WO 86/02115 to remove this disadvantage by having at least two functional groups that contain such using selected extenders, namely NCO-containing com groups (compound 2 a), preferably in the a, co-position. pounds having a molecular weight of at least 450 in Free NCO groups by contrast react in particular with blocked form. Indeed, this addition brings about a laun OH and amine or amide groups, so that compounds (1 dering- and drycleaning-stable water repellency, but the b) should be reacted in particular with those compounds fabric hand does not always meet present-day require 35 (2) which are OH-functional, in particular carbinol ments, since the fabric hand obtainable by the prior art functional (OH group bonded to silicon via carbon is frequently excessively dry and comes nowhere near chain) or amine/amide-functional (compound 2b). Simi the desired soft hand effect of inherent softness and larly, of compounds (2b), those which are difunctional pleasant fullness and surface smoothness. and have the functionality in the a, co-position are again We have now found modified polyurethanes which contain perfluoroaliphatic groups and which meet all used preferably. Otherwise, the structure of the polysi the stated requirements. loxanes is not subject to any particular conditions, other The present invention thus provides the modified reactive groups being largely excluded and otherwise polyurethanes containing perfluoroaliphatic groups the customary constituents such as ethyl, phenyl and in (Rf) described in. more detail below. particular methyl radicals being present. Examples of The oligourethanes and/or polyurethanes used as 45 such compounds are without claim to completeness, starting compounds which contain free hydroxyl or a,c)-carbinol-functional dimethylpolysiloxane having a isocyanate groups and perfluoroaliphatic groups (com molecular weight of from 600 to 10,000, pounds 1) are in principle known from the cited prior o,c)-epoxy-functional dimethylpolysiloxane having a art (U.S. Pat. Nos. 3,968,066 and 4,054,592). They are molecular weight of from 600 to 10,000, obtained by reacting diols which contain perfluoroali 50 a,c)-dihydroxy-functional dimethylpolysiloxane having phatic groups and have from 1 to 18, in particular from a molecular weight of from 1200 to 15,000, silicones 6 to 16, carbon atoms in the perfluoroalkyl radical with of the formula di/polyisocyanates. Details may be found in the two cited U.S. patents. Particularly suitable diols with per fluoroaliphatic groups have proved to be those of the 55 Hs Hs formula (CH3)3Si o oil OSi(CH3)3 CH3 X R-CH-CH-S-H-CH-OH n R-CH2-CH2-S-CH-CH2OH = -(CH2)3-O-CH2-CH-CH2) i.e. 2,3-bis(1,1,2,2-tetrahydroperfluoroalkylthio)butane N/ 1,4-diols (R?--C16F33 to -C6F13). Suitable di/- polyisocyanates are in particular aliphatic diisocya having a viscosity of from 30 to 100 mPa.s at 20° C. nates, for example 1,6-hexamethylene diisocyanate or 65 Compounds (1 a) and (1 b) are preferably reacted trimethylhexamethylene diisocyanates and isophorone with compounds (2 a) and (2b) in such amounts that a diisocyanate and also a diisocyanate derived from a small excess of the di/polyfunctional groups of the dimeric fatty acid containing 36 carbons (DDI (R) 1410 polysiloxane is present. However, it is perfectly possible 5, 112,930 3 4. to have the two reactants react in approximately equiv obtained contain about 10 to 40% by weight of active alent amounts. In general, the reaction is carried out in substance. an organic solvent, in particular in esters, such as butyl The aqueous dispersions thus obtained are like the acetate, or in fluorinated hydrocarbons, such as hexa organic solutions of the reaction products according to fluoroxylene, thereby obtaining systems which give the invention highly suitable for the oil-in-water repel good further processing. The reaction itself may be lent finishing of fiber materials, in particular textiles. carried out under atmospheric air pressure in the ab The amounts used therein are chosen in such a way, sence of atmospheric humidity, but preferably it is car assuming a customary liquor pickup, that the finishing ried out under an inert gas, in particular nitrogen.