CA2110488A1 - Fluorochemical water- and oil-repellent treating compositions - Google Patents

Abstract

This invention relates to a treating composition containing 0.3 to 30 % by weight of a fluoroaliphatic radical containing poly(oxyalkylene) compound, 0.3 to 30 % by weight of an anti-soiling agent and 0 to 60 % by weight of an environmentally acceptable water-miscible organic solvent and water for the use for imparting excellent water- and oil repellency, stain resistance and dry soil resistance to textiles, carpets, concrete, paper, leather and wool.

Description

2i~488 FLUOROCHEMICA~ WATER- AND OIL- REPELLENT
TREATING COMPOSITIONS

This invention relates to a ~reating composition containing a fluoroaliphatic radical and an anti-soiling agen~ for imparting water and oil repell~ncy as well as soil resistance to textiles and 10 other ma~erials trea~ed therewith.
Furthermore, the invention relates to a process for preparing the treati~g composition and to sub~trates treated with the treating composition.
The need for the removal of spots and stain~
15 from fabrics and carpets and a variety of other substrate surfaces is well known.
The treatment of textiles with fluorochemicals containing fluoroaliphatic radicals to impart water and oil repellency has b~en known for some 20 time. For example U.S. Pat. No. 3,57~,791 (Sherman and Smith) and U.S. Pat. No. 3,728,~51 (Sherman and ~mith disclose relat.ively high mole~ular weight materials which include block or graft copolymers, or block and gra~t copolymers, which have at least two 25 different segments, one of whi~h is highly fluorinated and ole~phobic and the other o~ which is water ~: solYatable or hydratable. The water solvatable or ~: hydratable segment ~ears pluralities o~ structural units containing characteristic solvatable polar groups 30 such as ether oxygen atoms. U.S. Pat. No. 3,816,167 (Schultz and Sherman) discloses applying a treatment of fluoroaliphatic comonomer and polyalkylene gylcol cross-linked in situ ~y an aldehyde-containing prepolymer to provide stain release to synthetic fibers 35 during laundering. U.S. Pat. No. 4,043,964 (Sherman and Smith) discloses a coating which provides durably : soil-resistank carpet which contains (a~ at least one phase of a specified water-insoluble add~tion polymer WO 93/01348 PCl~tUS92/05531 2110~38 - 2 -derived from a polymerizable ethylanically unsaturated monomer free of non~vinylic fluorine and (b) at least one phase of a ~pecified water-in~oluble fluorinated compon~nt containing a fluoroaliphatic radical of at 5 least 3 carbon a~oms. The monomer from which the fluorinated component is formed may contain dicarboxylic acid, glycol, diamine, hydroxyamine, etc.
U.S. Pat. No. 4,264,434 (Patel) disclos~s a li~uid carpet treating composition containing a 10 water-insoluble addition polymer derived from polymerizable ethyl2nically unsaturated monomer free of nonvinylic fluorine and having at least one major transition temperature higher than about 25C and a water--insoluble fluoroaliphatic radical- and aliphatic ,.--15 chlorine containing ester having at least one major transition temperature higher than about 25DC. Such treating compositions, however, are mainly intended for mill treatment of *h~ textile where treatment steps, such as heating are generally applied.
U.S0 Pat. No. Re. 30,337 and U.S. Pat. No.
4,160,777 ~Loudasj discloss compositions containing deterg~nt ompatible organic fluorochemical compounds and an anti-redepo~ition agent e.g. an ammonium salt of the hydrolyzed copolymer of styrene and maleic 25 anhydrlde for imparting water and oil repellency and soil resi~tance to textiles and to detergent solutions containing such compositions for cleaning textiles simultaneously with imparting the water and oil repellency and soil resistance.
U~S. Pat. No. 3,654,244 (Pittman et al.) disclo~es polymers for providing both 50il repellency and soil releasability to ~ibrous materials~ The polymers are copolymerization products of at least two different monomers, one imparti~g oleophobic properties 35 which is an acrylate or methacrylate which contains a . terminal perfluoroalkyl group of 3 to lB perfluorinated carbon atoms, .and the other hydrophilic properti~

WO93/01~8 PCT/US92/05531 ~ _ 3 _ 21~ 8~
which is an acrylate or methacrylate of a specified hydrocarbon alcohol.
U,S. Pat. No. 3,787 r 351 (Olson) discloses oligomers which act as wetting agents in filled or 5 reinforced synthetic resin composites, the oligomers having a plurality o.f fluoroaliphatic radicals linked to solubilizing poly(oxyalkylene) moietie~.
U.S. Pat. No. 3,920,614 (Kirimoto et al~) discloses an oil- and water-repellent copolymer having lo high soil release properties which is prepared by copolymeri7.i~g at least 25 weight percent o~ a polymerizable fluoroalkyl monomer and 5-50 weight percent of a polymerizable acrylate or methacrylate containing poly(oxyethylene) units. ~he copolymer may ~5 optionally contain comonomer and/or a acrylonitrile or methacrylonitrile.
U.S. Pat. No. 4,289,892 (Soch) discloses preparing rigid or flexible polyurethane foams with high or low d2nsity and uniform cellular structure 20 using fluoroaliphatic radical-~ubstituted poly(oxyalkylene) polyols as foam stabilizers.
: U.S. Pat. No. 4,859,754 (Maekawa et al.) discloses a water and oil repellent having desoiling properties composed of a polyfluorinated 25 group-con~aining copolymer obtained by copolymerizing a polyfluorinated ~roup-containing monomer which can be an acrylate or m~thacrylate and an:amphipathic mo~omer having a hydrophilic moiety and a lipvphilic moiety which can hav~ as the hydrophilic moiety a 30 polyoxyalkylene chain.
U.S. Patent No. 4,795,793 (Amimoto et al.) discloses fluorine-containing copolymers comprising 30 to 90% by weight of the constituting unit derived from . (a) a polymerizable compound having a perfluoroalkyl 35 group of 4 to 20 carbon atoms, 10 to 59% by weight of he constituting unit derived from (b) cyclohexyl or benzyl e~ter of acrylic acid or methacrylic acid and 0.1 to 10% ~ 9ght of the constituting unit derived from (c) at least one selected from the group consisting of polyethylene glycol diacrylate and N-methylolacrylamide.
U.S. Pat. No. 3,74~,268 (Loudas) describes a stable one-phase composi~ion which is useful as a spot and stain remover comprising a hydrocarbon solvent of low volatility, water, surfactan~, organic co-solvent and an anti-soiling agent. As organic co-solvents are 10 used chlorinated alkylenes like trichloroethylene or perchloroethylene or aromatic hydrocarbons like benzene, toluene and xylene. Useful anti-so~ling agents include brittle polymeric resins, such ~s styrene-maleic anhydride copolymers, colloidal alumina, 15 colloidal suspensions of silica, polyvinylpyrollidone, polyacrylate/acrylic acid copolymers, vinyl acetate/maleic a~hydride copolymers, carboxymethylcellulose, carboxyl-containing resins and water-soluble melamineformaldehyde condensates.
~0 U.S. Pat. No. 3,901,727 (Lo~das) discloses a conta.iner stabl~, water-dilutable alkaline cleaning composition which ha~, in an aqueous medium (a) a water-di~persible detergent which is capable of drying to a non-oily, non-tacky reæidue, (b) a 25 water-dispersible organic carboxyl~containing material which can be the ammonium salts of styrene maleic anhydride copolymers, a water-dispersible Lewi~ ba~e, (d) a zinc or zirconium coordination complex, (e) a ` fluorochemical compound which is water-dispersible at 30 or about pH 8, has acid functionality and forms zinc or zirconium salts which are capable of imparting water and oil repellency.
U.S. Pat. No. 4,419,298 (Falk) discloses ammonium and amlne salts of acids ha~ing 35 gem-di-perfluoroalkyl groups useful for providing oil and water r~pellency to cellulosic and polyamide materials. Styrene/maleic anhydride polymers are W093/0134~ PCT/~S92/05531 _ 5 _ 2ii~38 disclosed as sizing agents useful in aqueous emulsions for topical application which contain the ammonium or amine salts of the gem-di-perfluoroalkyl group containing acids.
U.S. Pat. No. 4~107,055 tSukornick) describes a fabric coating compo~ition including a polymer having a glass transition temperature above room temperature such as a styrene/maleic anyhdride copolymer, an ionic non-polymeric fluorinated surfac~ant and a carri~r.
U.S. Pat. No. 4,681,790 (Fong) describes a treating composition to imp rt water- and oil . repellency as well as soil `resistance containing ~luorochemical compound A, a fluorochemical compound known to have utility with surfactants and/or i5 detergents for providing oil and water repellency, and fluorochemical ~ompound B, a fluoroaliphatic radical-containing poly(oxyalkylene), and an organic water-mi~cible solYent.
U.S. Pat. No. 4,668,726 (Howells~ describes a 20 blend of the mixture of a cationic and nonionic fluorochemical, a fluorochemical poly(oxyalkylene) and/or a hydrocarbon non-ionic surfactant.
U.S. Pat. No. 4,788,287 and U.S. Pat. No.
4,792,354 (Matsuo et al.~ disclose a water and oll 25 repeIlent compound having at least two terminal segments and an intermediate segment connecting the terminal segments and having a molecular weight of from 800 to 20,000, each terminal s~gment containing at least one polyfluoroalkyl group connected by a -CONH-30 linking group, the intermediate se~ment being aurethane oligomer containing at least two -CONH-linking groups in one molecule, and said terminal segments and intermediate ~egment being connected by a -CONH- linking group. The urethane olig~mer of matsuo 35 et al. 1354 further contains a hydrophilic molecular chain.

The above re:f erences disclose f luorochemical compounds or treating composi~ions which may ~e applied to textiles. These known fluorochemical treating agents have the disadvantage that they contain 5 chlorina~ed solvents which are no longer acceptable from a toxicological and environmental standpoint.
Those treatment agents which do not rontain chlorinated solvents and which are environmentally more acc~ptable have insufficient water and oil repellent properties.
The present invention provides, in one aspect, an aqueous ~reating composition for providing . water~ and .stain repèllency and dry-soil resistance to fibrou~ materials without the need for thermal cure, said composition comprising a) 0.3 ~o 30% by wei~ht of a water soluble or dispersible fluoroaliphatic radical-containing poly(oxyalkyl~ne) compound, or a composition comprising a mixture of such poly(oxyalkylene) ~0 compounds having one or more mono~alent fluoroaliphatic radicals a~d on~ or more poly~oxyalkylene) moieties, said fluoroaliphatic radicals and poly(oxyalkylene) moi~ties being bonded together by hetero atom-containing groups or organic ~i~king groups or combinations of such groups; and b) 0.3 ts 30% by weight of solid, non-tacky, water-soluble or water dispersible anti-soiling agent which, upon drying of the composition, is capabla of rendering the substrate non-tacky and resistant to soiling; and G) water, 35 with the proviso that ~he ratio of component (a) to component (b) be 1:20 to 20:1~ The compositions may optiona-ly contain up to 60% by weight of at least one WO93/01348 P~T/~S92~0S~31 _ 7 _ -c~ l 10 ~ ~
environmentally acceptable water-miscible organic solvent.
The fluoroaliphatic radical-containing poly(oxyalkylene) compound can be a fluoroaliphatic 5 oligomer or pol~mex (the tçrm oligomer hereinafter including polymer unless otherwise indicated) pres~nted by the general formula:
~R~Z[(R3)yZ'B]t II
(Rf~Zc(R3)yzlB~]t]w III
where Rf is a fluoroaliphatic radical, Z is a linkage through which Rf and tR33y moieties ' are covalently bonded together, is a poly(oxyalkylene) moiety, R3 being an oxyal~ylene group with 2 to 4 carbon atoms and y is an integer (where the above fox~ulas are those of individual compounds) or a : number (where the above form~las are those of mixtur~s) at least 4, preferably 15 to 125 and can:be a~ high as 180 or higher, B is a hydrogen atom or a monov~lent terminal organic radical, B' is B or a valence bond, with tbe proviso that at least one B' is a ~alence bond interc~nnecting.a Z-bond~d R3 radi~al to another Z, Z' is a linkage through which B:, or B', and R3 are covalently bonded together, s is an integer or number of at Ieast l and can be as high as 25 or higher, t is an integer or number of at least 1, and can be a~ high a6 60 or~higher, and - w is an integer or ~umber greater than 1, and can be as high as 30 or higher.
In formulas II and III, where there were a : plurality of Rf radicals, they are either the same or WO ~3~0t348 PCr/US92/05531 different. This also applies to a plurality of Z, Z ', R3, B, B', and, in formula III, a plurality of s, y and t.
Rf is a stable, inert, nonpolar, pref erably 5 saturated monovalent moiety which is both oleophobic and hydrophobic: . A f luorinated oligomer preferably comprises from ~ to about 25 R~ group~; arld preferably comprises about 5 pers::ent to about 30 p~rcant, and more prsferably about 8 percen~ to about 20 percent fluorin~3 10 by weight based on the total weight of the oligomer, the loci of the f luorine being essentially in the Rf group~; . Rf pref erably con~a-ins at leas~ about 3 carbon atomc, more pref erably 3 to about 2 0 carbon atoms, and ~, most preferably about 6 to about 12 carbon atoms. Rf 15 can contain straight chain, }:~rant::hed chain, or cyclic alkyl group~ is preferably free of polymerizable olef inic unsaturation and can c~ptionally contain catenary heteroatoms such as oxygen, divalerlt or hexavalent sulfur, or nitroge~n. It is pr~ferred that 20 each Rf c:ontaln about 40~6 tc, about 78% fluorine by weight, more pre~erably about 50% to about 78% fluorine by weight. ~he terminal portion of the Rf group contains a fully i~luorinated terminal group. This terrainal group preferably c:onkains at least 7 f luorine 25 atoms, e.g., CF3C~2CF2, (CF3)2CF, CF2SF2, or the like.
Perf luorinated aliphatic ~roups , i . e ., those of the f ormula CnF2n~l, are the most pref erred embodiments of Rf ~
Generally, the oligomers will contain about 5 30 to 40 weight percent, preferably about 10 to 30 weight E~ercent, Of carbon-bonded f luorine, If the f luorine content is less than a~Dout 19 weight perc:ent, impractical large amounts of the oligomer will generally be requirQd, while f luorine contents greater 35 than about 35 weight percent result in oligomers which have too low a solubility to be efficient.

WO 93/0134~ PCI/US92/0~531 9 2 1 1 ~ ~ ~ 8 In the poly (oxy~lkylene) r~dical, ~R3) y~ R3 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCH2CH2-, OCH2CH2CH2-, OCH(CH3)CH2-, and -OCH(CH3)CH(CH3~ , the oxyalkylene units in said 5 poly(oxyalkylene) being the same, as in poly(oxypropylene), or present as a mixture, as in a heterir straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a straight or branched chain of blocks of oxyethylene 10 units and blocks of oxypropylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages. Where said catenary linkag~s have three or more valences, they provide a means for obkaining a branched chain of 15 blocks of oxyalkylene units. The poly(oxyalkylene) radical~ in the oligomers can be the same or different, and they can be pendent. The molecular weight of the poly~oxyalkylene) radical can be about 500 to 2,500 and higher, e.g., 100,000 to 200,000 or higher.
~he function of th~ linkages Z and Z' is to covalently bond the fluoroaliph~tic radicals, Rf~ the poly(oxyalkylene) moieties, (R3)~ and radicals B and B', together in the oligomer Z and Z' can be a valence bond, for example, where a carbon atom of a 25 fluoroaliphatic radical is bonded or linked directly to a carbon atom of the poly(oxyalkylene) moiety. Z and Z' each can also compri~e one or more linking groups such as polyvalent aliphatic and polyvalent aromatic, oxy, thio~ carbonyl, sulf~ne, sulfoxy, phosphoxy, 30 amine, and combinations thereof, such as ox~alkylene, iminoalkylene, iminoarylene, sulfonamide, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, urea, and ester. The linkages Z and Z' for a specific oligomer will be dictated by the ease of preparation of 35 such an oligomer and the availability of necessary precursors thereof.

10~88 Illustrativ~ linking groups z are alkylene groups, such as ethylene, isobutylene, hexylene, and methylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as -CH2C6H4CH2- and 5 -C6H4CH2C6H4-, having Up to 20 carbon atoms, arylene groups, such as tolylene, -C6H3(CH3)-, poly(oxya~kylene3 groups, such as -(C2H40)yC2H4~ where y is 1 to about 5t and various combinations of these groups. Such groups can also include other hetero moieties (besides -O-), lO including -S- and -~-. Ho~ever, Z is preferably free of groups with active hydrogen atoms.
From the above description of ~ and Z' it i5 apparent that these linkages can have a wide variety of structures, and in f~ct where either is a valence bond, 15 it does not even exist as a structure. However large Z
or Z' is, the fluori~e content (the locus of which i~
Rf) is in th~ aforementioned limit~ set forth in the above deccription, and in general the total Z and Z' content of the oligomer is preferably less than lO
20 weight pe~cent of the oligomer.
~: The monovalent ~erminal organic radical, B, ` i5 one which is covalently bonded through z t ~ to the ~:~ poly(oxyalkylene) radicalO
Though the natur~ of B can vary, it 25 preferably is ~uch that it complements the poly(oxyalkylene) moiety in maintaining or establishing the desired solubility of the oxyalkylene~ The radical B can be a hydrogen atom, acyl, such as C6HC(O)-, alkyl, preferably lower alkyl, such as methyl, 30 hydroxyethyl, hydroxypropyl, mercaptoethyl and aminoethyl, or aryl, such as phenyl, chlorophenyl methoxyphenyl, nonylphenyl~ hydroxyphenyl, and aminophenyl. Generally, Z'B will be less than 50 weight percent of the (R3)yZ~B moiety.
The ~luoroaliphatic radical-containing oxyalkylene polyurethanes used in this invention can be prepared by a variety of known methods, such as by WO93/0134X ~CT/US92/05531 condensation, free radical, or ionic homopolymerization or copolymerization using solution, suspension, or bulk polymerization techniques, e.g~, seP "Preparative methods of Polymer Chemistry", Sorenson and Campbell, 5 2nd e~., Interscience Publishers, (196~).
The polyaerylates are a parti~ularly useful class of oxyalkylenes and they can be prepared, for example, by free radical initiated copolymerization of a fluoroalîphatic radical-con~aining acrylate with a 10 poly(oxyalkyl~ne) acrylate, ~.g., monoacrylate or diacrylate or mixture~ thereof. As an example, a fluoroaliphati-c acrylate, Rf-R " -O2C-CH=CH2 (where R "
is, for example, sulfonamido alkylene, ~.carbsnamidoalkylene, or alkylene), e~g., 15 C8F17S~2N(~4Hg)CH2C~202CCH=CH2, can be copolymerized with a poly(oxyalkyléne~ monoacrylat~, CH2=CHC~o)(R3)XoCH3, to produce a polyacrylate oxyalkylene.
Further description of fluoroaliphatic radical-containing poly(oxyalkylene) compounds useful 20 in this invention and their preparation are known from U.S. Pat. No. 3,787,351 (Olson), U.S. Pat. No.
: 4,289p892 (Soch), U.S. Pat. No. 3,654,244 (Pittman et al.~, U.S. Pat. No. 3,920,614 (Kirimoto et al.), U.Sv Pat~ No. ~,681,790 (Fong), U.S. Pat. No O 4 ~ 795 / 793 (Animoto et al.), U.S. Pat. No. 4,859,754 (Maekawa et al.) and U.S. Pat. No. 4,792,3S4 (Matsuo et al.).
: In a preferred embodiment of the invention the fluoroaliphatic radical-containing poly(oxyalkylene) compound contains a fluoroalkyl 30 radical having 3 to 20 carbon atoms, wherein perfluoroalkyl radicals are particularly preferred.
In a further preferred embodiment the poly(oxyalkylene) compound can contain 4 to 180, preferably 15 to 125, ethylene and/or propylene 35 radicals.
The most preferred compound of the fluoroaliphatic radical-containing poly(oxyalkylene) WO ~13/01348 PCI /US92/OS531 2~ O ~L~8 compound is a poly (oxyalkylene) copolymer of (a) CBFl7so2N(cH3)c2H4oco~H=~H2 (b) CH2=C(CH3)cOO(cH2cH20)soH
(c) CH2=c(cH3)~oo(cH2~H2o~9ococ(cH3)=cH2 5 preferably in a 1:l weight ratio of a:(b + c) and a 3:1 weight ratio of b:c.
The anti-soiling agents are defined as those materials which are solid, non-tacky water soluble or water dispersible and which upon drying of the lO composition are capabl~ of rendering the ubstrate non-tacky and re~istant to soiling~ Also mixtures of the anti-soiling agents ~an be used.
Useful anti-soiling agents include brittle polymeric resins such as styrene-maleic anhydride 15 copolymers and salts thereo~ ~e.g. SMA~ Resins available from AtQchem) r col~oidal alumina (e.gO
Catapal~ and Di~pal~ aluminas available ~rom Vista Chemical Com~any), colloidal suspensions of silica (e.g. Nalco~, silicas available from Nalco Chemical 20 Company), polyvinylpyrrolid~ne, polyacrylate/acrylic arid copolymers (e.g. Rhople~ resins available ~rom ~ohm and Haas), vinyl acetate/maleic anhydrid~
copolymers (e.g. VAMA resins availabIe from Monsanto)~
carboxymethylcellulose, carboxyl-containing resins (e.g. Carboset~ resins from B. F. Goodrich) and water-soluble melamine formaldehyde condensates.
: The preferred compounds are styrene/maleic anhydride resin salts, which are low molecular weight copolymers of styrene and maleic anhydride.
30 Styrene/maleic anhydride resin salts are readily hydrolyzed in aqueous ammonia and used as such as anti-s~ g agents.
The typical chemical structure of the aqueous solutions is as follows:
with m = l - 3 n = 6 - 8 W093/0l34X PCT~US92/05~31 - 13 _ 2~`0~8 c-o lc-o These products are commercially available from Atochem as SMA~ - resins.
The environmentally acc~ptable water-miscible 5 organic solvents, if used, pref~rably have low toxicity, e.g. the solvents ax~preferably classified in Gexmany according to class II or class III of the German emission control regula~ion (TA-Luft)~
The organic solvent, if us~d, preferably has lO an ade~uate rate of evaporation which is lower than 2,000 with diethylether ha~ing 1 to permit remo~al : after application~
Use~ul organic solvents are those which are at least partially wat r-mlscible such as alcoh~ls, 15 water-misci~le ~thers~(e.g. di@thylene glycol diethylether, diethylene glycol dimethylether, propylene ~Iy ol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene g:lycol 20 monopropylether, propylen~ glycol monobutylether, ethylene glycol monobutylether, dipropylene ~lycol monomethylether, diethylen~glycol monobutylether), lower esters of monoalkylethers of ethyleneglycol or propylene glycol (e.g. propylene glycol monomethyl 25 ether acetate) all commercially available from Union Carbide, Dow Chemicals or Hoechst. Mixtures of organic solvents can also be used.
Furthermore, the treating compositions according to the invention may contain other WO~3/01348 PCT~IJS92/05531 2 ~ 8 _ 14 -ingredients which increase effectiveness or impro~e physical appearance. For example, these compositions may contain ingredi~nts which make the compositions more suita~le for use and less susceptible to 5 degradation or alteration, Such ingredients include corrosion inhibitors such as sodium nitrite and/or - morpholine to inhibit storage andJQr shipping container corrosion, a chelating agent such as that available under the trade designation Versenol~ 120 to inhibit 10 metallic contamination caused by leaching of the storage container wall during long term storage.
Minor amounts of additives such as about 1%
by weight ~f 3,5-dimethyl-1-hexyne-3-ol available under the trade designation sulfonyl 61, n pentanol, or 1~ cyclohexanol to stabilize the composition to improve shelf-life and prevent precipitation ~nd sedimentation.
Other ingredients such as fragrances, germicidal materials~ defoamers and the like may also be added.
The viscosity of the novel composîtion can be 20 modified over a wide range by addition of various ~: common thickeners, e.g. carboxymethyl cellulose thickéners, hydroxypropylmethyl cellulose thic:keners, acrylate thickeners.
Substrates which can be treated in accordance 25 wi~h this invention are textile fibers or filaments, and finished or fabricated fibrous article~ such as : textiles, carpet, paper, paperboard, leather and the like. The textiles include those made of natural fibers, such as cotton and wool and those made of 30 synthetic organic f ibers, such as nylon, polyolefin, acetate, rayon, acrylic and polyester fibers.
The treatment compositlon according to the invention can be conveniently applied to a fibrous 35 substrates and other surfaces by spraying, dipping, coating, paddin~, foam or roller coating application, or by a combination of two or more of these methods.

WOs3tO134X PCT/US92~05~31 - 15 ~ 2 ~ 8 The treatment composition is used for imparting excellent water- and oil repellency, stain resistance and dry soil resistance to textiles, carpets, concrete, paper, leather and wood.
The invention i6 further illustrat~d by the following ~xamples wherein all parts are par~s by weight unless otherwise indicat2d.
The starting materials used in the examples were prepared as follows a) fluoroaliphatic radical-containing poly(oxyalkylene) compound (Component A~, was prepar-d by mixing together the following ingredients in the following portions _ Parts by weiqht Inqredient r hybrid copolymer of equal parts of A and B monomer~
(A~ C8Fl7SO2N(C~3)C2H4OCOCH=CH2;
and ; ~B) methacrylate esters of a : polyethylene qlycol of molecular weight of about 4,000 (Carbowax 4,000) comprising (a) ~H2=c(cH3)coo(cH2cH2o)soH
and (b) CH2-c(cH3)cO~(cH2cH2o)9o-COC(CH3)=CH2 in a ratio of a:b of about 3:1.

WO 93/0134X Pcr/US92/05531 0~88 _16-Parts by wei~ht ~sE~s!i~

7 Polyethylene glycol having a molecular weight of about 4, 000 Carbowax 4, 000) Water 7 Ethylene glycol acetate b) - Anti coiling agent Procedure for preparing. a 1~% solids solution of anti-soiling agent, Component B:
- Charge vessel with 533 g water and add lOo g styrene maleic anhydrid~ copolymer ( SMA 3 OoO, commerciallLy available from Atochem Inc. ) while maintaining ~igoroUs stirring.
- Slowly add ammonium hydroxide (28%) 34 g, a slight exotherm occurs.
~0 - Heat to 70 - 75OC maintain ~emperature and agitation until solution is ::omplete.
After cooling to room temperature, a slightly yellow viscous s~lution ~f pH 8 . 5 - 9 . 3 containing approximately 15% active anti-soiling agent is 2 5 obtained .
The example according to the present inYentiori and the comparative eYamples were used on test Xabric samples which were evaluated for water- and ~: ~ oil repellency also a spray rating test, an abrasic)n 30 resistance test and a dry soil test were per~ormed~
The test fabric: samples are further described in the following table:
:~ .
~ .
. 35 WO 93/0134X PCI/USg2/05531 2 1 ~ S~ ~

Substrate Wei~ht /m2 Pile hei~ht Cotton/Viscose (50/50) 280g Gobelin*I ( 100% Cotton) 326g Gobelin*II ( 100% Cotton) 320g Cotton-flat (100% Cotton) 166g Cotton-pile ( 100% Cotton) 565g + 1 mm - Wo~l (100%) 520g Acrylic (100%) 510g + 2 mm Polyester (100%) 229g 10 Viscose (100%3 335g + 0.5 mm Cotton/A~rylic (6~/40) 310g . Cotton/Polyester (65/35) 277 * Gobelin - woven cotton upholstery fabric.

The test methods are described as follows:

A. Water Repellency test ~WR) The a~ueous stain or water repellency of treated samples is measured using a water/isopropyl 20 alcohol test, and the result i5 ~xpres~ed in terms of a water repellency rating of the treatefl fabric. Treated fabrics which are p~netrated by or resistant only to a 100 percent water/zero percent isopropyl alcohol mixture (the least pene~rating of the test mixtures) 25 are given a rating of 0, whereas treated fabrics resistant to zero percent waterll00 percent isopropyl alcohol mixture (the most penetrating of the test mix~ures) are given a rating of 10. Other intermediate values are de~ermined by use of other water/isopropyl 30 alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10.
Results are reported as an average of replicate t~sting. The water repellency rating corresponds to the most penetrating mixture which does ~lOt penetrate 35 or wet the fabric after 30 seconds contact.

B. Oil~ ency test (OR) The oil repellency of treated carpet and textile samples is measured by the Amexican A5sociation of Textile Chemists and Colorists (AATCC) Standard Tast 5 Method No. 118-1983, which test is based on th~
resistance of treaked fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to Nujol~, a brand of mineral oi~ and the least penetrating of the test oils, are given a rating of 1, 10 whereas treated fabrics resistant t~ heptane (the most penetrating of the test oils) are given a value of 8.
Other intermedia~e values.are determined by use of other pure oils or mixtures of oils, as shown in the following table:

Standard Test Liquids AATCC OIL
Repellency Ratinq Number Com~osit~a 1 Nujol~
. 2 65:35 Nujol~ : hexadecane by volume 70F (21C) 3 n-he~ade~ane 4 n-tetradecane n-dodecane 6 n-decane 7 n-octane 8 n-heptane The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does 35 not penetrate or wet the fabric after 30 seconds contacts. HighPr numbers indicate better oil repellency.

C. Spray Rating test (SR) The spray rating, i.e., resistance of a treated substrate to wetting with water, was measured ~9 2L1~3~
using AATC~ Test Method 2~ - 1977, "Water Repellency :
Spray Test" as described in American Association of Textile Chemists and Colorists and Colorists ~echnical Manual, 1977, 53/ 245. Samples are rated on a scale of 5 0 to 100, with 0 indicating complete wetting of the upper and lower surfaces of the substrate and with 100 indicating no wetting.

D. Accelerated Dry Soil test (ADS) This accelerated dry soil test measures the tendency of a fabric to resist dry soil during use. A
total of four samples,.sized 14 cm x 17 cm are soiled in an accelerated soil tester, filled with sixty felt cubes (1.5 cm sides), using a 3M standard carpet dry 15 soil (commercially available from 3M Company) during a ten minutes run. After removal of the samples from the soil tester, the excess soil is r~moved by blowing with compressed air. Evaluations are made by comparing to a 3M Soil Resistance Rating Board (available from 3M
.20 Company) in an 7'Evaluation Area~' (reference AATCC Test method 124-1984) with an "Overhead Lighting Arrangement" as indicated in AATCC Test Method 124-1984, Section 4.3 and f iqure 1 i5 recommended.
A dry soil rating of 5 indicates that there 25 is no increase in soiling versus a blank, a dry soil rating of 1 refers to ~evere soiling.

E. ~brasion Oil Repellency (AOR) This test measures the durable effectiveness 30 of a protective fluorochemical fini~h by evaluating its : resistance to abrasion and wear. It provides a simple, rapid method to measure the oil repellency of the finish after a specified abrasion method.
.The durable effectiveness of a fluorochemical 35 treatment to abrasion and wear is measured by abrading 5 cm x 12.5 cm samples of fabric back and forth 20 times by making 10 turns of the crank at the rate of 1 turn pe~ ~ ~ ~ with WETODRY TRI-M-ITF~ Abrasive paper no. 600 (co~mercially available from 3M Company3 on an AATCC crockmeter model CM-l (available from Atlas Electric Devices Co.). The above described OR
5 repellency test i~ perormed on the abraded samples and the repellency ratings recorded as ~OR valu~s.

F. Stain Release Test The staining agen s were left on the fabric l0 for 5 minutes, blotted off with a dry paper towel, then cleaned with diluted household detergent (brushed) rinsed with pure water (brushed) and dried at room temperature. The remaining stain was evaluated for its intensity with the 3M stain release rating scale (l =
15 se~ere stain, ~ = no stain).

G. "Walk on" Test (WOS) In this test, specimens of textile and selected control samples were exposed to normal foot 20 traffic in a controlled test area. The test specimens and controls were remov~d at predetermined intervals corresponding to different degrees of soiling or : exposure to soiling~ Rating of these test results is similar to that described in the Accelerated Soiling : 2 5 TPSt method.
~: The invention is further illustxated by the following examples wherein all parts are parts by weight unless or otherwise indicated in the examples.
Examples O - 8 Composition according to the invention are described in Table I, the amounts of Components A and B
being those of ~he solutions prepared a~ove. The organic svlvents listed in Table I are identified as follows:
BC : Ethyleneglycolmonobutylether PnP: Propyleneglycol mono-n-propylether DPM: Dipropyleneglycol monomethylether W~93/013~8 PCT/US~2/05531 - 21 - 21~
PnB: Propyleneglycol mono n-butylethe~ `t ., _:
PM : Propyleneglycol monomethylether PE: Propyleneglyc:ol monoethylether DMM: Propyleneglycol dimethylether IPA: I~opropanol Table I

~ _ . . . ~
Component A compon~nt B Organic l0 Ex. Fluoro- Anti-soil SO1VBnt No. chemical resin * Water 0 5.8 5 --~ 89.2 l ~ 5.8 5 25 BC 64.2 15 2 5.8 5 25 PnP 64.2 ~~ 3 5D8 5 5G DPM 39.2 4 5.8 5 25 DPM 49.2 15 PnB
5.~ 5 25 PM 54,2 l0 PnB

6 5.8 5 22.5 PE 59.2 :: 7.5 PnB
: 7 5.8 5 l0 BC 54.2 ~; 25 D~M
Z5 8 5.8 5 44.6 IPA 44.6 ..
These solutions were æprayed onto cotton-flat, cotton pile and wool fabric test sampl~s ; at approximately 50% wet pick up, and were left to dry 30 for 24 hr~ at ambient temperature before the samples were tested. Oil repellency, water repellency, spray rating, abrasion oll repellency and accelerated dry soiling were evaluated on the cotton-flat, cotton-pile and wool fabrics, the results being set forth in Tables 35 IIa, IIb and IIc, respectively.

:

WO 93tO134~ PCl/US92/05~31 TABLE IIa ( Cotton-f lat ) Example OR WR SR AOR ADS
O 6 8 50 5 2.5 5 1 6 10 70 5 2.5 4 6 9 7~ 4 2.5 $ 70 5 2.`5 7 3 9 5~ 3 4 TABLE IIb (Cotton-pile) Exam~le OR WR SR AOR ADS

1 4 4 70 3 2.5 ~O 2 4 2 70 2 2 4 3 2 ~ 0 2 2 . 5 ~ 2 70 4 3 25 7 O 2 70 O 3 ~ 5 8 3 2 70 2 3.S
~::

:~

WO 93/0134~ PCI/US92/05531 -- 2 3 -- 2 1 1 ~ ~ 8 ~
TABLE IIc (woc~l ) Example OR w~ sR AOR ADS
O 3 1 50 1 2.5 1 ~; 3 70 3 2 3 6 4 ~5 5+ 3 4 ~ 3 70 1 2 2 7g 7 4 ~ 75 3 3 ,~_.Examples 9 - 13 In the f ollowing exampIes, the ratios of fluoropolymer (Component A) to anti-soil agent (Component B) are varied as shown in Table III.

; ; Table III
~: ~ 20 Ex~ Component Component t)rganic ; No. A B Solvent Water 9 2 . 50 11. 67 10PnES/25 PM 50 . 83 ~ 25 10 3 . 33 10 . O 10PnB j25 PM 51. 6 : 11 4 .16 8 c 33 10PnB/25 PM 52 . 5 ~: 12 5 . 00 6. 67 10PnB/25 PM 53 . 3 13 6.67 3.33 10PnB/25 PM 55.0 ::
3 0 These solutions were sprayed onto the di~f erent f abric test samples, dried at ambient temperature and test~d as in Examples 1 - 8.
Perf ormanc:e results on the cotton-f lat, cotton-pile and wool fabrics are set forth in Table IVa, IVb and IVc.

~: :

WO ~3/01348 PCr/US92/05531 ....
2 L10 48~ - 24 TA13LE IVa (Cotton f lat) Exam~le O~ WR SR AOR ADS

4 ~ 50 2+ 3 11 4 ~ 50 3 2 . 5 12 ~ 9 50 4 2.5 13 5 9 so 5 2 . 5 TABLE IVb (Cotton -pile) ExamDle OR WR SR AOR ADS

~ 2 70 1 4 11 4 2 7~ 3 3.5 1~ ~ 2+ 70 4 2 . 5 13 5 4- '75 4 2 . 5 TABLE IVc wool ) Example OR ~3 ~B ~ ADS
9 4 1 50 o 2.5 ~0 ~ S ~ 70 1 2 11 4~ 3 70 1 2 12 ~ 3 70 2 2 ~
13 6 : 3 70 1~ 1.5 30 Examples 14 - 20 and Comparative Examples A - G
;In ` order to demongtrate ~ompositions arcording to this invention have excellent performance on various textile substrate~, and that furthermore the : overall per~ormance is equa~ to or better than ~:3 5 trichloroethane based f ormulations, in Examples 14 20, the composition described in Example 5 was applied to ~arious textile substrates set forth in Table V and WOg3/Ot348 PCT/US42/~5531 - 25 - 2 ~ 8 tested as described in Examples 1-8. The results are set forth in Table Va. In Comparative Examples A-G, these substrates were treated with a fluorochemical - urethane acrylate terpolymer which is the reaction 5 product of 3~ parts C~Fl7SO2N(CH3)C2H~OCOCH=CH2, CONHC3H60CO~H=CH2 19 parts C8F17~02N(CH3)c2H4NHcO ~ and 10 parts C4HgOCOCH-CH2 and which is provided as 0.7%
solids in l,l,l-trichloroethane as in Example 14-20.
The treated substrate6 were tested as in Exampl~s ~ 14-20. The results are set forth in Table Vb.
Table Va Ex~ Substrate OR ~R SR AOR A~S
14 Acryli~ 6 3 50 5 3 Polyester 6 3 50 6 3.5 20 16 Viscose 6 3 70 5 3.5 17 Polyester~cotton 6 4~ 50 2 3 : 18 Viscose/cotton 5 3 70 2 2 19 Gobelin I 5 4 70 3 2.5 Gobelin II 5 ~ 70 4 3.5 2~

Table Vb Comp.Ex~ Substrate OR WR SR AOR ADS
A Acrylic 5 5 75 5 3 B Polyester 4 7 70 3 2 C Viscose 5 6 75 4 2 D Polyester/cotton 2 3 50 0 E Viscose/cotton 4 10 70 3 2 F Gobelin I 4 5 70 3 2.5 G Gobelin II 3 4 75 1 2 Examples 21 - 30 and Comparative Examples H - Q
.

WO93/0134R PCT/US92/0553i Besides oil-, water-, and dry soil repellency, an important feature of an upholstery treatment is its "Stain Relea~e~' characteristics. In ca~e a treated upholstery fabric gets stained, it is a 5 major advantage if the stain can be removed easily.
In order to evaluate khe stain release properties, in Examples 21 - 30, 10 different upholstery fabrics were treated with the composition Example No. 5 (see table 1) as in Examples 1 - 8.
10 These treated fabrics were then stained with 13 different stains of different classes: oily-, aqueous-, and viscous staining agents. The s~ain release results are set forth în Tables VIa and VIb.
~ In Compara~iYe Examples H - Q, the untreated 15 fabric were evaluated for stain rel~ase. The results are set forth in Tables ~IIA a~d VIIB.

Table VIa 20 Example 21 22 23 24 25 FabricCQtton Cotton Poly-Stain. pile flat AcrYli~ es~er Viscose Wine 8 7 7 8 8 25 Coffee 8 8 8 8 7.5 Thee 8 B 8 8 6.5 Juice 8 8 8 8 8 Cola 8 8 8 8 Z
Kool aid 8 7 7 8 6 30 Butter 7.5 7 7 6 7 Mayon~aise 7~5 6 8 8 8 Mustard 8 7 7 8 6 Ketchup 8 8 8 8 8 3S Curry 6 3 6 ~ 3 Chocolate 8 7 8 WO 93/01348 Pcr/US92/05~3~
- 27 _ 211~g8 Table VIb Example 2~ 27 ~8 29 30 Fabric Cotton/ cottonl Cotton/ Gobelin 5 Gobe 1 in Stain: Acrylic PolYester Viscose I II

Wine ~ 8 4 8 8 lO Cof f ee 7 7 4 8 B
Thee 7 ~ 7 8 6 Juice ~ 8 7 8 8 Cola 8 8 7 8 8 Kool aid 7 ~ 5 7 8 lS Butter 8 7 8 8 6 . 5 Mayonnaise 8 7 ~ 8 8 Mustard 8 7 8 ~ 7 . 5 Ketchup 8 7 8 g 8 2 0 Curry ~ 6 ~ 5 6 Chocolate 8 7 7 8 7 Table VIIa Example H I J K L
2 5 Fabric Cotton Cotton Poly-Stain: Pile Flat Acr~lic ester Viscose Wine S 3 3 6 2 Cof f ee 6 6 3 8 4 Thee ~ 4 5 8 3 . 5 Juice 6 ~ 4 8 7 Cola 8 ~ 7 8 7 Kool aid 7 3 6 . 7 Butter 6 7 7 7 3 Mayonnaise 6 8 8 8 7 ~ustard 3 3 3 7 4 Ketchup 3 4 4 8 6 Curry 2 2 2 5 4 O Chocolate 2 3 5 5 WO 9~/013~ PCI /US92/05531 2~ 8 - 28 -Table VIIb Example M N 0 P Q
Fabric Cotton/ Cotton/ Cotton/ Gobelin Gobelin Stain: Acrylic Polyester Viscose I II
Wine 6 l 4 7 6 Cof f ee 7 4 4 7 8 The~ 8 l 7 8 6 Juice 8 8 7 8 lO Cola 8 7 7 8 8 Kool aid 6 7 5 6 8 Butter 6 l ~ 6 6 Mayonnaise 8 6 8 8 7 DMC) 2 1 3 2 3 ~qu tard 3 6 8 3 7 Ketchup 3 7 8 3 Curry 2 4 ~ 2 3 Chocolate 2 3 7 5 3 20 Example 31 and Comparative Examples R - S
The compositions according to the present invention were also tested under normal foot traffic in a controlled test area. In Table VIII the "Walk on"
results of wool fabric (520 g/m2) treated with a 25 composition acc:ording to this invention without anti-soil resin (Comparative Example R) fabrics without any treatment ( Comparative Example S ) .

WO 93/01348 PCr~U~92/05531 2 1 1 ~ 8 Table VIII
Example Treatment composition WOS _ 31 5. 8 Component A
5 Component B

1 0 PnB
54 . 2 water S
R 8 . 3 Comp~nent 10 PnB
56.7 water 3 - 4 S no treatment 3 ,~_ A dry soîl rating of 5 îndîcat2s that there is ho 15 încrease in soiling versus a fabrîc whîch was not subj ec:ted to f oot traf f ic .

Example 3~ and ComparatiYe :5:xamples T - tJ
Cotton-flat, co~ton-pile and wool fabrie:s 2 O were treated and tested as in Examples I - 8 using the composition of Example ~ of thîs invention (Example 32) and Example lO oP U. S. Pat. No. 4, 681, 790 ~Fon~) ( C:omparative E5xamp?e T) . For Comp~rativ~ Example U, the fa~3rie~ were untreated. The results :of the 2~ cotton-flat, cotton-pile~ and wool are set forth irl : Table~ IXa, Ixb and IXc, respectively.
.~: :
TABLE IXa ~: (Cotton-f lat~
3 0 Example OR WR SR AOR ADS

~1 . O O O U 2 ' :: -WO 93/0134X Pcr/US92/05531 2 ~ 88 ~ 30 -TABLE IXb (Cotton-pile) Example OR WR SR AOR ADS

T 2 l+ 50 l 3 l O TABLE XXc (ws:~ol ) E~ple OR WR ~ AOR ADS

32 6 3 7~ S 2 From Tabl~s IXa, IXb and l~;c, it can ~be se~n that the composition according ~o the il~Yentiorl has a better:
20 perforraance on ::o~on and wool textiles than the composition of U,t S. Pat. No. ~a, 681, 790 ., Examples 3 3 and 3 4 Commercially available f luc~roc:hemic:al . .
2 5 polyoxyalkylene compounds wers evaluated in compositiorls of the pre~ent inv~3ntion as set f orth in Table X.
~:: :
~ 30 ;
:
~ 3~
:
:

~ 40 : .

W~93/01348 . P~T/US92/QSS31 21~ll88 - 31 - . .
Table Component A Component B
fluorochemical anti-soil Organic 5 Ex. No polyoxyalkylene resin _ solvent Water 33 5.8 20nyl 7910* 5 25 BC 64.2 34 5.8 AG-780** 5 50 PnP 39.2 10 * Zonyl 7910 is a fIuorochemical polyurethane comprising polyoxyalkylene moieties (available from Du Pont).
*~ AG-780 is a fluoroaliphatic radical containing polyoxyalkylene compound according to U.S. Pat. No.
15 3,920,61~ (available from Asahi Glass).

The compositions were applied to fabrics and tes~ed as de~cribed in Examples 1-8. The results are set f orth in Tables XIa, XIb and XIe:: .
T~ble XIa : : (Cottor:~f lat) Exam~le OR WR SR AOR ADS

2~ 34 5 2 0 4 3 ~ ..
T~BLE XIb tCotton-pile) ~83~ QB WR SR AOR ADS

3~ 4 2 70 3 3 TABLE XIc (wool) Exa~El~ OR WR SR AOR ADS
33 7 2 7~ 4 3 34 6 2 70 ~ 3 WO ~3/01348 PCI/US92/05531 Various modif ications and alterations of this invention will become apparent to those skilled in the art without departing from the scope of thi~; invention.

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Claims (14)

CLAIMS:

1. An aqueous treating composition for providing water- and oil repellency, stain resistance and dry soil resistance to fibrous materials comprising a) 0.3 to 30% by weight of a water soluble or dispersible fluoroaliphatic radical-containing poly(oxyalkylene) compound, or a composition comprising a mixture of such poly(oxyalkylene) compounds having one or more monovalent fluoroaliphatic radicals and one or more poly(oxyalkylene) moieties, said fluoroaliphatic radicals and poly(oxyalkylene) moieties being bonded together by hetero atom-containing groups or organic linking groups or combinations of such groups; and b) 0.3 to 30% by weight of solid, non-tacky, water-soluble or water dispersible anti-soiling agent which, upon drying of the composition, is capable of rendering the substrate non-tacky and resistant to soiling; and c) water, with the proviso that the ratio of component (a) to component (b) be 1:20 to 20:1.

2. The treating composition of claim 1 further comprising to 60% by weight of at least one environmentally acceptable watermiscible organic solvent.

3. Treating composition of claim 1 wherein the fluoroaliphatic radical containing poly(oxyalkylene) compound has the general formula:

(Rf)sZ[(R3)yZ'B]t II
(Rf)sZ[(R3)yZ'B']tlW III

where Rf is a fluoroaliphatic radical, Z is a linkage through which Rf and (R3)y moieties are covalently bonded together, (R3)y is a poly(oxyalkylene) moiety, R3 being an oxyalkylene group with 2 to 4 carbon atoms and y is an integer (where the above formulas are those of individual compounds) or a number (where the above formulas are those of mixtures) at least 4, preferably 15 to 125 and can be as high as 180 or higher, B is a hydrogen atom or a monovalent terminal organic radical, B' is B or a valence bond, with the proviso that at least one B' is a valence bond interconnecting a Z-bonded R3 radical to another Z, Z' is a linkage through which B, or B', and R3 are covalently bonded together, s is an integer or number of at least 1 and can be as high as 25 or higher, t is an integer or number of at least 1, and can be as high as 60 or higher, and w is an integer or number greater than 1, and can be as high as 30 or higher.

4. Treating composition of claim 1 wherein the fluoroaliphatic radical containing poly(oxyalkylene) compound contains a fluoroalkyl radical having from 3 to 20 carbon atoms.

5. Treating composition of claim 1 wherein the poly (oxyalkylene) compound contains 4 to 180 ethylene and/or propylene radicals.

6. Treating composition of claim 1 wherein said poly(oxyalkylene) compound is a copolymer of (a) C8F17SO2N(CH3)C2H4OCOCH=CH2 (b) CH2=C(CH3)COO(CH2CH2O)90H
and (c) CH2=C(CH3)COO(CH2CH2O)90COC(CH3)=CH2

7. Treating composition of claim 1 wherein the weight ratio a:(b+c) is 1:1, and b:c is 3:1.

8. Treating composition of claim 2 wherein the water-miscible organic solvent has low toxicity and flammability and an adequate rate of evaporation to permit removal after application.

9. Treating composition of claim 2 wherein the water-miscible organic solvent is an alcohol, a water-miscible ether, a glycol ether, a lower ester of monoalkyl ether, of ethylene glycol or of propylene glycol, and mixtures thereof.

10. Treating composition of claim 1 wherein the anti-soiling agents include brittle polymeric resins, styrene-maleic anhydride copolymers and salts thereof, colloidal alumina, colloidal suspensions of silica, polyvinyl-pyrrolidone, polyacrylate/acrylic acid copolymers, vinyl acetate/maleic anhydride copolymers, carboxymethylcellulose, carboxyl-containing resins and water soluble melamineformaldehyde condensates.

11. A process for providing a substrate with water- and oil-repellency, stain resistance and dry soil resistance comprising the steps of (a) contacting said substrate with the aqueous treating solution of claim 1 and (b) allowing the treated substrate to dry at ambient temperature.

12. The process of claim 11 wherein said substrate is a textile fabric, carpet, concrete, paper, leather or wood.

13. A treated substrate having water- and oil-repellency, stain resistance and dry soil resistance comprising a coating of the composition of claim 1 on said substrate.

14. A treated substrate of claim 13, wherein the substrate is textile, carpet, concrete, paper, leather or wood.