CA1248273A - Blends of fluorochemicals and fibrous substrates treated therewith - Google Patents

Abstract

ABSTRACT

Blends of fluoroaliphatic radical-containing compounds and fluoroaliphatic radical-containing poly(oxyalkylenes) useful in the form of organic solutions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers, to impart oil and water repellency.

Description

BLENDS (~F FL~OROCHE~IC~LS
AND F~BXCUS S~lBSTR~TES TREATED T~EREWITH
, This invention relates to the treatment of fibrous substrates~ such as textile fibers, paper, and leather, with fluorochemical compositions to impart oil and water repellency, and to the resulting treated substrates.
In another aspect, it relates to the treatment of carpet fiber ~ith a finish comprising a fluoroaliphatic radical-containing composition to impart oil and water rspellency and soil resistance to such fiberO In another aspect, i~
relates to fluoroaliphatic radical-containing compositions, and their preparation, which are useful in such treatment.
In the industrial production of textiles, such as carpet and apparel, and such other fibrous substrates as paper and leather, it is common to treat such substrates with fluorochemicals containing luoroaliphatic radicals (often designated by the symbol "Rf") to impart oil and water repellency to the surface of such substrates. ~luoro-chemicals of this tyue and theix application to fibrous substrates are described in various prior art publicdtiorls, e.g., U.~. Patent Nos. 3,329,661 (Smith et al), 3/458j57 (Tokoli), 3,574,791 ~Sherman et al), 3,728,15i (Sherman et al), 3,916,053 (Sherman et al), 4,144,367 (Lar,duccij, 3,896,251 (Landucci), 4~024,178 (Landucci), 4,165~33 (Katsushima et al), 4,190,545 (Marshall), 4,215,205 (~anducci), 4,013,627 (Temple), 4,264,484 (Patel), 4,029,585 (Dettre), 3,462,296 (Raynolds et al), and 4,325,857 (Champaneria et al), and Banks, R. E., Ed~
"Organofluorine Chemicals and their Industrial Applications", Ellis Horwood, Ltd., West ~ussex, En~land, 226-230 (1979).
Althou~h some Eluorochemicals are useful in many applications and many are commercial products, some ara relatively expensive to prepare and apply, others are difEicult to apply, and others are not durable or do not impart the required properties to the extent desirad.

--2~ 3 Conventionally, fluorochemical compositions have been coJ~mercially applied as a top coating to the finished fibrous article, such as carpet~ Recently, several fluorochemical compositions have been commercially applied to textile fiber or yarn during its manufacture before it is woven or fabricated into the finished art~cle. However, some of these fluorochemical compositions have had limited success for various reasons including incompatibility or reactivity of the fluorochemical with fiber finish compo-10 nents such as lubricants, lack of durability of thefluorochemical on the treated fiber to dyeing or other fiber manufacturing operations, and insufficient water and oil repellency and soil resistance in the finished article.
It is an object of this invention to provide 15 blends of (a) fluoroaliphatic radical-containing compounds which impart oil and water repellency, such as fluoro-aliphatic radical-containing carbodiimide (hereinafter often called fluorochemical carbodiimides for brevity), or fluoroaliphatic radical containing esters (hereinafter ~0 call~d fluorochemical esters), or fluoroaliphatic radical-containing carbonylimino compounds (hereinafter often called fluorochemical carbonylimino compounds for brevity), and (b) fluoroaliphatic radical-containing poly(oxyalkylenes) (hereinafter often called fluorochemical 25 oxyalkylenes for brevity), said blends being useful for treating textile fibers and other fibrous substrates to impart oil and water repellency thereto.
Another object of this invention is to provide blends of fluorochemical carbodiimide, carbonylimino, or 30 ester compounds and fluorochemical oxyalkylenes, which blends can be used to treat textile ibers in cornbination with or as a component of fiber finishes, e.g. spin-finish lubricants, such blends being compatible with said fiber finishes and not interfering with normal textile fiber 35 processing steps.
A further object of this invention is to provide fluorochemical-treated textile fiber with a high percentage l.~f~

of the fluorochemical retained on the fiber through ~iber processing and dye~ng steps, and with durable water and oil repellency and soil resistance properties.
It is yet another object of this invention to 5 provide blends of fluorochemical carbodiimide, car-bonylimino, or ester compounds and flurochemical oxy-alkylenes which can be used in the form of organic solutions or aqueous dispersions to treat fibrous substrates such as textile fibers, filaments, yarns, or finished fibrous articles, e.g. carpets, and other fibrous substrates such as paper and leather, to impart oil and water repellency thereto.
Briefly, this invention provides, in one aspect, compositions comprising blends of: (a) normally solid, 15 water-insoluble, fluorochemical compositions which impart oil and water repellency to fibrous substrates and are fluoroaliphatic radical-containing compounds such as carbodiimide, carbonylimino, or ester compounds, or compositions comprising or consisting essentially of 20 mixtures of said compounds, which compounds have one or more monovalent fluoroaliphatic radicals (Rf) and one or more polar moieties such as carbodiimido, carbonylimino, and/or ester moieties, such radicals and moieties bonded together by hetero atom-containing or organic linking ~5 groups; and (b) normally liquid or low melting solid, water soluble or dispersible, fluoroaliphatic radical-containing poly(oxyalkylenes), or compositions comprising or con-sisting essentially of mixtures of said oxyalkylenes, which poly(oxyalkylenes) have one or more monovalent fluoro-aliphatic radical (Rf) and one or more poly(oxyalkylene)moieties, such radicals and oxyalkylene moieties bonded together by hetero atom-containing groups or organic linking groups, or combinations of such groups. ~aid fluorochemical blends of components (a) and (b), some of 35 which blends are novel per se (viz., where the polar moiety is a N-containing polar moiety) are useful in the form of organic solutions or aqueous dispersions in the treatment J'~ ;3f. s ~

of fibrous substrates, such as textile fibers (or :Eilamen-ts) duriny their manufacture, and useful also in the treatment of finished or fabricated fibrous substra-tes such as carpe-ts, paper, and leather, to impart oil and water repellency -to the surface thereof.
According to one aspect of -the presen-t invention there is provided a composition comprising a blend of:
(a) 40 to 99 weight percent of a normally solid, water-insoluble, fluorochemical composition which is a fluoroaliphatic radical-containing compound, or composition comprising a mixture of 1~ such compounds, said compound having one or more monovalent fluoro aliphatic radicals having at least three fully fluorinated carbon atoms and one or more polar moieties selected from carbodiimido, carbonylimino, ester moieties and combinations thereof, said radi-cals and moieties being bonded together by hetero atom-containing or organic linking groups selected from polyvalent aliphatic, poly-valent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy, -N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof; and (b) 1 to 60 weight percent of a noramlly liquid or low ~1~ melting solid, water soluble or dispersible, fluoroaliphatic radi-cal-containing poly(oxyalkylene), or composition comprising a mix~
ture of such poly(oxyalkylenes), said poly(oxyalkylene) having one or more of said fluoroalipha-tic radicals and one or more poly(oxy-alkylene) moieties, said radicals and poly(oxyalky]ene) moieties bonded together by hetero atom-containing groups or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, oxyalkylene, ~3 -4a- 557-2680 iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamido-alkylene, carbonamidoalkylene, urethane, uxea, ester, and combina-tions thereof.
According to a fur-ther aspect of -the present invention there is provided a fi.ber finish comprising an organic solution or aqueous dispersion comprising a blend of:
(a) 40 to 99 weight percent of a normally solid, water-insoluble, fluorochemical composition which is a fluoroaliphatic radical-containing compound, or composition comprising a mixture of la such compounds, said compound having one or more monovalent fluoro-aliphatic radicals having at least three fully fluorinated carbon atoms and one or more polar moieties selected from carbodiimido, carbonylimino, ester moieties and combinations thereof, said radi-cals and moieties being bonded together by hetero atom-containing or organic linking groups selected from polyvalent aliphatic, poly-valent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy,-N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof; and (b) 1 to 60 weight percent of a normally liquid or low ~n melting solid, water soluble or dispersible, fluoroaliphatic radi-cal-containing poly(oxyalkylene), or composition comprising a mix-ture of such poly(oxyalkylenes), said poly(oxyalkylene) having one or more of said fluoroaliphatic radicals and one or more poly(oxy-alkylene) moieties, said radicals and poly(oxyalkylene) moieties bonded together by hetero atom-containing groups or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, oxyalkylene, -4a-.

-4b- 557-2680 iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamido-alkylene, carbonamidoalkylene, urethane, urea, ester, and combina-tions thereof.
A class of such fluorochemical carbodiimides (component (a) of said blends) can be represented by the general formula R ~QtXtN=c=N-AtnN=c=NtQtxR

which formula generically encompasses individual compounds or re-presents a mixture of such compounds as they are obtained from reac-tions used in their preparation.
Fluorochemical carbodiimides useful in this inven-tion and their preparation are described in United States Patent No.
4,024,178 (Landucci).
In formula I, "n" is a number (in the case where the for-mula is that of a mixture) or an integer (in the case where the formula is that of a compound) of 0 up to 20, preferably 0 to 10 and most preferably 0 to 5 t and "x" is 0 or 1. Each Q is the same or different divalent linking group. A is a divalent organic link-ing group which can contain a fluoroaliphatic radical, Rf, each A
being the same or different. Each Rl is the same or different and is selected from H, Rf, and terminal monovalent organic radicals such as alkyl, cycloalkyl, aryl, and combinations thereof, e.g.
aralkyl, which radicals can contain hetero moieties, e.g. -O-, -S-, -N-, -Si-, and -CO-, and is preferably free of active (or isocyanate-reactive~ hydrogen atoms (i.e., hydrogen atoms of yroups, such as mercapto, amino, carboxyl, and aliphatic hydroxyl groups, that can react readily with isocyanate under urethane bond-forming conditions, e.g., 20 to lOO"C). Generally, Rl will have no more than about 18 -4b--4c- 557-26gO
carbon atoms. Where Rl is said Rf, -the subscript x of the adjacent Q must be 1 and not O because R~ cannot be directly bonded to a N-atom of the ~3 -4c-~ ~f~

carbodiimide group. There is at least one Rf radical present in one or ~rore of the Rl and A groups for a given compound.
In the above general formula I, the divalent 5 organic linking group A connects successive carbodiimide moieties when n is 1 or more. Illustrative linking groups A are alkylene groups, such as ethylene, isobutylene, hexylene, and methylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as -CH2C6H~CH2_ 10 and -C6H4CH2C6H4~, having up to 20 carbon atoms} arylene groups, such as tolylene, -C6H3(CH3)-, poly(oxyalkylene) groups, such as -(C2H4O)yC2H4~ where y is 1 to about 5, and various combinations of these groups. Such groups can also include other hetero moieties (besides -O-), including -S-15 and -N- However, A is preferably free of groups with said active hydrogen atoms.
The A group can be a residue of an organic diisocyanate (from which the carbodiimido moiety can be derived, that is, A can be the divalent radical obtained by 20 removal of the isocyanate groups from an organic diisocyanate. Suitable diisocyanate precursors may be simple, e.~. tolylene-2,4-diisocyanate, methylene bis~4-phenyleneisocyanate), and mixtures thereof, or complex, as formed by the reaction of a simple diisocyanate 25 with an organic diol or polyol in appropriate proportions to yield an isocyanate-terminated polyurethane. Other isocyanates can also be used as starting materials. Some of these are described, for example, in U.S. Pat. No.
4,174,433. Representative A groups include 30 -CH2C6H4CH2C6H4CH2-, -C6~3(C~3)-, -C6H10CH2C6~l10-, -(CH2)6-, -C6l14CH2C6H4-, and CgF17SO2N[C2H4OCONHC6H3(CH3)~2. Although the fluoro-chemical carbodiimides used in this invention generally and preferably are derived from diisocyanates, the fluorochemical carbodiimides can be derived Erom triisocyanates, e.g. OcNc6H4cH2c6H3(Nco)c~l2c6H4Nco. A
mixture of di- and -tri-isocyanates can be used to provide fluorochemical carbodiimides which are branched but still retain ~he desired solubility and dispersibility characteristics of the linear fluorochemical carbodiimides depicted by formula I.
The Rl-Q groups are preferably radicals de~rived from isocyanate compounds and can be aliphatic, e.g.
C6H13-, aromatic, e.g. C6Hs-, aralkyl, e.g. C6HsC~l2-, fluoroaliphatic~ e.g. C6F13CH2-, C7FlscH2ocoNHc6H3(cH3~ ~ and C8~17SO2N(CH3)C2H~OCO~HC6H~CH2C6H~-. Ihe organic Rl-Q
radicals can have a variety of other structures, and can contain hetero atom-containing moieties, e ~. -O-, -S-, and -N-, but, as with the A group, it is preferably free of groups containing said active hydrogen atoms.
The fluoroaliphatic radical, Rf, is a fluorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, and, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals. The skeletal chain can include catenary oxygen, hexavalent sulfur, and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing st~ble linkages between fluorocarbon portions of Rf and not interferring with the inert character of the Rf radical.
25 While Rf can have a large number of carbon atoms, compounds where Rf is not more than 20 carbon atoms will be adequate and preferred since large radicals usually represent a less efficient utilization of fluorine than is possible with smaller Rf radicals. The large radicals also are generally less soluble in organic solvents. Generally, RE will have 3 to 20 carbon atoms, preferably 6 to about 12, and will contain 40 to 78 weight percent, preferably 50 to 78 weight percent, fluorine. The terminal uortion of the Rf group has at least three fully fluorinated carbon atoms, e.g.
35 CF3CF2CF2-, and the preferred compounds are those in which the Rf group is fully or substantially completely fluorinated, as in the case where Rf is perfluoroalkyl, CnF2n+1 -The function of the linking group Q in formula I
is to bond the Rl groups to the N atoms of the carbodiimide 5 units. Q can comprise a hetero atom-containing group or an organic group or a combination of such groups, examples of which are polyvalent aliphatic, e.g., -CH2-, -CH2CH2--, and -CH2CH(CH2-)2, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, -N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, e.g., -CH2CH2OCONH~, and urea, e.g., -NHCON~-.
The linkage Q for a specific fluorochemical carbodiimide useful in this invention will be dictated by the ease of preparation of such a compound and the availability of necessary precursors thereof. From the above description o~ Q, it is apparent that this linkage can have a wide variety of structures. However, as with the Rl and A
groups, Q is preferably free of moieties having said active hydrogen atoms.
The fluorochemical carbodiimides used in this invention are normally solid (i.e., solid at 20C) with melting points preferably in the range of 40 to 150C.
They are preferably soluble to the extent of at least 10 weight percent in ethyl acetate at ~0C.
?5 Representative reaction schemes for the prepara-tion o fluorochemical carbodiimides used in this invention are outlined below, where the products designated as I' are s~ecies of formula I supra.

_heme 1 30 2Rl-Q'-OH + 2A(NCO)2 > 2R Q NCO cat.,-(n+l)CO2 Rl-Q(N=C=N-A)nN=C-N-Q-R
I' -8- ~ o~ ,7 ~
Scheme 2 (n~2)A(Nc0)2 -(n~l)co2> OcNA-(N-c=N-A)nN=c=N-ANco _2~ Q OH>
R1-Q(N=C=N-A)nN=C=N-Q-R
I' Scheme 3 .

R-QI-OH + B(NCO)3 > R-Q(NC0)2 R-Q(NC)2 ~ B(NC0)3 ~ A(NC0)2 + R1-QNCO Cco2> ~ixed carbodiimide The mixtures of fluorochemical carbodiimid0s used in this invention may contain small amounts of -fluorochemical diurethane compounds (e.g., R-Q'-OCONH-A-NHCOO-Q'-R, a possible by-product in Scheme 1) free of carbodiimido groups due to the synthetic procedures generally followed.
The amount of this by-product depends on the mode of addition, molar ratio of reactants, and the relative reactivity of isocyanate functional groups.
A preferred class of carbonyli.mino compounds for use in this invention can be represented by the formula:

Al[NHCOY(Q)XR2]r II

where R2 is a group like Rl in formula I and at least one R2 group is a fluoroaliphatic group (Rf), Q and x are as defined for formula I, r is an inte~er of 1 to 10, preferably 2 or 3, Al is an organic linking group having 2 to 20 carbon atoms, which is a residue of an organic iso-cyanate and is free of isocyanate-reac~i.ve yrouL~s, such as aliphatic hydroxy, and Y is -N-, -O-, or -S-. Where there is a plurality of any R2, Ql Y and x in a given compound, they can be the same or different.

9 ~L, ~
Ihe fluoroaliphatic radical-containing carbonyl-imino compounds preferably have at least one major transi-tlon temperature greater than 25C, more preferably greater than that about 40C, and most preferably greater than about 45C. If desired, the compositions of the invention can contain mixtures of carbonylimino or imine compounds.
Carbonylimino compounds for use in this invention can be prepared by reacting organic isocyanates with fluoroaliphatic radical-containing compounds having an isocyanate-reactive hydrogen atom.
A preferred subclass of the carbonylimino com-pounds of formula II are those in which Y is -O-, viz., urethanes. Representative carbonylimino compounds of such preferred subclass are described in U.S. Patent No.
15 3 r 484,281. They are prepared by conventional urethane bond-forming reactions between fluoroaliphatic alcohols and organic isocyanates, preferably aromatic polyisocyanates.
If desired, fluorine-free aliphatic alcohols (e.g., fatty alcohols) can be incorporated into the reaction mixture used to form such carbonylimino compounds.
A representative reaction scheme for preparation of fluorochemical carbonylimino compounds used in this invention is outlined below.

Scheme 4 rR2(Q)xYH + A'(NCO)r ~>A~[NHCOY(Q)XR2]r II
Fluorochemical esters which are useful as compo-nent (a) of the fluorochemical blends of this invention include ~hos~ described in the aEorementioned prior ar~
publications.
A representative reaction scheme for the prepara-tion of fluorochemical ester compounds used in this invention is outlined below.

aRl-Q-OH + R(COOH)a CHato> R(COO-Q-Rl)a Representative Rf intermediates for the preparation o~ fluorochemical carbodiimide, carbonylimino, or esters used in this invention include:

C8Y17S02N(C2~15~C2H40H
C8F17c2H40H
C7F15cH20H
C7F15CON (C2H5)C2H40H

( CF3 ) 2CF ( CF2 ) 8C2H40H
( CF3 ) ~CFOC2F4C2H40H
C8E`17C2H4S02N (CH3 )C4H80H
C8F17SO2N ( CH3 ) C3H6NH2 C2F5{~3CH2NH2 /~
C3F7 (CFCF20)2 C~FCON~ NH
CF3 CE~3 C8F17s03-~-NH2 C8F17S03~1-NCO

C7F15CON ( CH3 ) C2H4SW

Representative organic isocyanates include:
tolylene-2,4-diisocyanate hexamethylene diisocyanate methylenebis(4-phenyleneisocy~nate) methylenebis(4-cyclohexyleneisocyanate) xylylene diisocyanate l-methoxy-2~4-phenylene diisocyanate l-chlorophenyl-2,4-diisocyanate, --.L 1--p-(l-isocyanatoethyl)phenyl isocyanate phenyl isocyanate m-tolyl isocyanate

2,5-dichlorophenyl isocyanate hexyl isocyanate Representative carboxylic acids or anhydrides which can be used to prepare Eluorochemical ester components by reaction with fluorochemical alcohols include adipic, citric, pyromellitic, and the like (such being disclosed in said WS. Patent Nos. 3,923,715 and 4,3~0,74~).
Generallyr the fluorochemical carbodiimide, carbonylimino compound, or esters will contain about 20 to 70 weight percent, preferably about 25 to 50 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 20 weight percent, impractically large amounts of the fluorochemical carbodiimide, carbonylimino compound, or esters will generally be required, while fluorine contents greater than about 70 weight percent are unnecessary to achieve the desired ~ surface properties and thus represent an uneconomical use of fluorine and may also present compatibility problems where it is desired to apply the fluorochemical blend as an organic solution.
A class of fluorochemical oxyalkylene, component ~5 (b) - the other essential component of the blends of this invention - are fluoroaliphatic polymers (or oligomers, the term polymer hereinafter including oligomer unless other-wise indicated) represented by the general formulas:

(Rf)s2[(K3)yZIB]t III
[(~f)SZ~(R3)yzlBl~t~w IV

where Rf is a fluoroaliphatic radical like that described for general formula I, Z is a linkage through which Rf and (R3)y moieties are covalently bonded together, -12~
(R3)y is a poly(oxyalkylene) moiety, R3 being an oxy-alkylene 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 mixtur~s) at least 5 generally 10 to 75 and can be as high as 100 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.
In formulas III and IV, where there are a plurality of Rf radicals, they are either the same or different. This also applies to a plurality of Z, Z', R3, B, B', and, in formula IV, a plurality of s, y and t.
Generally, the oxyalkylene polymers will contain about S to 10 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine. If the fluorine content is less than about 10 weight percent, impractically large amounts of the polymer will generally be required, 30 while fluorine contents greater than about 35 weight percent result in polymers which have too low a solubility to be efficient.
In said poly(oxyalkylene) radical, (R3)y, R3 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCH2CH2-, -OCH2C~l2cH2-~
-OCH(CH3)CH2-, and -OCH(CH3)CH(CH3)-, the oxyalkylene units in said poly(oxyalkylene) being the samer as in poly(oxypropylene), or present as a mixture, as in a heteric straight or branched chain or randomly distributed oxyethylene and oxypropylene units or as in a 5 straight or branched chain of blocks of oxyethylene units and blocks of oxypropylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more ca-tenary linkages. Where said catenary linkages have three or more valences, they provide a means for obtaining a branched 10 chain or oxyalkylene unitsO The poly(oxyalkylene) radicals in the polymers can be the same or different, and they can be pendent. The molecular weight of the poly(oxyalkylene) radical can be as low as 220 but preferably is about 500 to 2500 and higher, e.g~ 100,000 to 200,000 or higher.
The function of the linkages Z and Z' is to covalently bond the fluoroaliphatic radicals, Rf, the poly(oxyalkylene) moieties, (R3)y 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 fluoroaliphatic 20 radical is bonded or linked directly to a carbon atom or the poly~oxyalkylene) moiety. Z and Z' each can also comprise one or more linking groups such as polyvalent aliphatic and polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, and combinations 25 thereof, such as oxyalkylene, iminoalkylene, iminoarylene, sulfoamido, carbonamido, sulfonamidoalkylene, carbonamido-alkylene, ure-thane, urea, and ester. The linkages Z and Z' for a specific oxyalkylene polymer will be dictated by the ease of preparation of such an polymer and the availability 30 of necessary precursors thereof.
From the above description of Z and Z' it is apparent that these linkages can have a wide variety of structures, and in fact where either is a valence bond, it doesn't even exist as a structure. However large 2 or Z' is, the fluorine content (the locus of which is Rf) is in the aforementioned limits set forth in -the above descrip-tion, and in general the total Z and Z' content of the --14-- ~3 ~ ~
polymer is preferably less than 10 weight percent of the polymerO
The monovalent terminal organic radical, B, is one which is covalently bonded through Zl, to the poly(oxyalkylene) radical Thouyh the nature of B can vary, it preferably is such that it compliments 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 C6H5C(O)-, alkyl, preferably lower alkyl, such as methyl, 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 fluoroaliphatic radical-containing oxyalkylene used in this invention can be prepared by a variety of known methods, such as by condensation, free radical, or ionic homopolymerization or copolymerization using solution, suspension, or bulk polymerization techniques e.g., see "Preparative Methods of Polymer Chemistry," Sorenson and Campbell, 2nd ed., Interscience Publishers, (1968). Classes of representative oxyalkylenes useful in this invention include polyesters, polyurethanes, polyepoxides, polyamides and vinyl polymers such as poly--acrylates and substitute polystyrenes.
The polyacrylates are a particularly useful class of oxyalkylenes and they can be prepared, for example, by free radical initiated copolymerization of a fluoro-aliphatic radical-containing acrylate with a poly(oxyalkylene) acrylate, e.g. monoacrylate or diacrylate or mixtures thereof. As an example, a fluoroaliphatic acrylate, Rf-R"-O2C-CH=CH2 (where R" is, for example, sulfonamidoalkylene, carbonamidoalkylene, or alkylene), e-g-~ C8Fl7so2~(c4H9)cH2c~l2o2ccH=cH2~ can be copolymerized ~ i 3 60557-26~0 with a poly(oxyalkylene) monoacrylate, CH2=CHC(o)(R3) OCH3, to produce a polyacrylate oxyalkylenes.
Further description of fluorochemical oxyalkylenes useful in this invention will be omitted in the interest of brevity since such compounds and their preparation are known. See U.S. Patent No. 3,787,351 and U.S. Patent No.
4,289,892.
The amount of each component (a) and (b) can vary over a broad range, and will be selected to provide the desired balance of properties on the treated fiber of the finished article. Generally, component (a) will be the major amount of the blend and component (b~ will be the minor amount. The particular amount depends on the particular composition of the textile fiber or article to be treated and the particular chemical composition of (a) and (b~, as well as the application procedures used. Laboratory evaluation will often be a good indicator of appropriate relative amounts of compounds (a) and (b) to be used for obtaining the desired performance in commercial application.
~0 Generally, the relative amounts of components (a) and (b) fall within the following ranges:

Weight percent of fluorochemical solids in blend General Preferred Most Component Broad Ranqe Broad Range Preferred Ran~
(a)40-99 60-99 70-95 (b)1-60 1-40 5-30 The blends of this invention can be obtained by mixing (1) an organic solvent solution or aqueous dispersion of the fluorochemical component (a) with (2) the fluorochemical poly(oxyalkylene) which may be utilized in neat form or as an organic solvent solution or as an aqueous dispersion. If an aqueous emulsion is the desired form of ~ ~e!.~, ~he emulsification may be performed on the above organic solvent-containing blends, or individually emulsified components may be blended (by simple mixing techniques) as either solvent-containing or solvent-free emulsions. In the preparation of said emulsions it is gsnerally beneficial to ernploy cationic fluorochemical surfactants (e.g~, CgFl7S~2N(il)C~6~(C~3)Cl) a,ong with hydrocaïbon non-ionic surfactants (i.e., "Tween 80" polyoxyethylene sorbitan monooleate). Since the fluorochemical poly(oxyalkylenes) and mixtures thereof are themselves non-ionic surfactants, the hydrocarbon non-ionic co-surfactants may be totally or partially eliminated by the incorporation of the fluorochemical poly(oxyalkylene) into the solvent-containing blend prior to emulsification.
Substrates which can be treated in accordance with this invention are textile fibers (or filaments), and finished or fabricated fibrous articles such as textiles, e.g. carpet, paper, paperboard, leather, and the like. The ~0 textiles include those made from natural fibers, such as cotton and wool, and those made from synthetic organic fibers, such as nylon, polyolefin, acetate, rayon, acrylic, and polyester fibers. Especially good results are obtained on nylon and polyester fibers. The fibers or filaments as ~5 such or in an aggregated form, e.g. yarn, tow, web, or roving, or the fabricated textile, e.g., articles such as carpet and woven fabrics, can be treated with the fluoro-chemical blends. The treatment can be carried out by applying the fluorochemical blends as organic solutions or 30 aqueous or organic dispersions by known techniques cus-tomarily used in applying fluorochemicals, e.g. fluoro-chemical acrylate copolymers, to fibers and fibrous sub- ~
strates. (IE desired, such known fluorochemicals can be used in conjunction with the above-described fluorochemical 35 blends, such as fluoroaliphatic radical-containing polymers, e.g. acrylates and methacrylates). For exampls, the fluorochemical treatrnent can be by immersing the -17- ~ 2~
Eibrous substrates in a bath containing the fluorochemical blend, padding the substrate or spraying the same with the fluorochemical blend, or by foam, kiss-roll, or metering applications, e.g. spin finishing, and then drying the 5 treated substrates if solvent is present. If desired, the fluorochemical blend can be co-àpplied with conventional fiber treating agents (or adjuvants), e.g. antistatic agents or neat oils (non-aqueous fiber lub icants).
In the manufacture of synthetic oryanic fibers (see, for example, the review article in Kirk-Othmer, Encyclo~ a of Polymer Science and Technology, _, 374-404, 1968), the first step that normally takes place in the process, following initial formation of the filaments (e.g.
by melt spinning or solvent spinning), is coating the fiber surface with a small amount (generally less than 2~ active solids on fiber) of fiber finish comprising lubricating and antistatic agents. It is particularly advantageous to treat such textile fibers, e.g. nylon 6, with the fluoro-chemical blend of this invention in conjunction with the spin finish being applied to such textile fibers.
Fiber finishes are generally produced in the formof dilute aqueous emulsions or as an oil ("neat oil") which principally contains said lubricant and antistatic agent as well as emulsifier (surfactant) and may also contain ~5 materials such as bacteriocides and antioxidants.
Representative lubricants include mineral oils, waxes, veg0table oils (triglycerides) such as coconut oilr peanut oil, and castor oil, synthetic oils, such as esters, polyoxyethylene derivatives of alcohols and acids, and silicone oils.
The antistatic agents, emulsifiers, and sur-factants incorporated into the fiber finish are selected from similar chemical classes, which include:
(a) anionics, such as fatty acid soaps, sulfated vegetable oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as fatty amines, quaternary ammonium compounds, and quaternary phosphonium compounds;

(c) nonionics, such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acids, and ethoxylated fatty amides; and ~d) amphoterics, such as betaines, amino acids and their salts.
The preferred mode of applying the fluorochemical blend of this invention to synthetic organic fibers is to incorporate the blend into the above-described fiber finishes in an amount sufficient to achieve the desired 1~ properties, oil and water repellency and soil resistance.
Generally, the amount of fluorochemical blend to be used will be that sufficient to retain on the fiber of -the finished article, e.g., carpet, about 200 to ~600 ppm fluorine based on the weight of the fiber. Such additions 15 to the conventional fiber finish can be carried out without sacrificing or adversely affecting typical requirements that conventional fiber finishes must meet, namely lubrica-tion, thermal stability, low fuming at elevated tempera-ture, and wetting for fiber dyeability (color addition).
20 The conventional finish components of the fiber finishes containing the fluorochemical blends of this invention can be removed in a conventional manner after the fiber is manufactured in fabric form, e.g., carpets and upholstery fabrics. The fluorochemical blends withstand the typical 25 conditions encountered during fiber and yarn processing and also survive the more severe processing conditions which the greige goods encounter such as scouring and dyeing, and the finished goods encounter, such as washing, steam cleaning, and dry cleaning. The fluorochemical blends do 30 not interfere with, and are durable through, the normal fiber processing steps, e.g., drawing, texturizing, and heat setting, and provide oil and water repellency and anti-soiling properties to the finished article, e.g~, carpet made from the treated fibers.
The conventional application methods used to apply finishes to fibers (or filaments) can be used with the fluorochemical blend finishes of this invention. Such -19- ' methods include the use of either (a) a revolviny cera~i-~cylinder, i.e., kiss-roll, which is partially im~ersed in a pan containing the finish, over which the moving filaments pass and pick up a thin film of finish, (b) a metering pump supplying finish through a slot or hole in a fiber guide over which the moving filaments pass, (c) an immersion finish bath, or (d) spraying devices.
The fluorochemical blends of this invention are ~enerally compatible with (i.e., dispersible or suffi-ciently soluble in) commercial neat oil fiber finishes,yielding stable dispersions or solutions thereof, and thus the blends may be mixed with such finishes and coapplied ~or applied b~efore or after t~em). Solubilizing aids, such as "Carbitol" or "Cellosolve" solvents, can be added to the finish to enhance solubility of the fluorochemical blends in the neat oil finish.
Representative fluorochemical carbodiimides useful as component (a) in the fluorochemical blends of this invention havin~ the general formula V are shown in Table 1.

R-Q-A(N=C=N-A)n-Q-K V

Compound No.* R - - - -Q _ A
1 C8F17 -So2N(c2H5)c2~l4ocoNH C6H4CH2C6H4 2 C8F17 -so2N(c2Hs)c2H4ocoNH C6H3(CH3)

3 C8F17 -SO2N(C4Hg)C2H4OCONH C6H4C~2C6H4

4 C8F17 -C2H4OCONH C6H4CH2C6H4 S C8F17 -- - C2H40CONH C6H3(C~3) * For all compounds listed, n has an average value of 2, except for compound no. 2, where n has a value of about 1.8.

Representative fluorochemical oxyalkylenes useful as component (b) in the fluorochemical blends of this invention are shown in Table 2. Generally the preparation of the rluor~che~llical oxyalkylenes results in products which comprise mixtures of oxyalkylenes, the lengths of the fluoroaliphatic radical and the poly(oxyalky.lene) moiety

5 varying and the subscripts denoting the number of carbon atoms of the former and denoting the number of oxyalkylene units in a poly(oxyalkylene) segment beiny in both cases average numbers, and in this specification, e.g. Table 2, those subscripts should be understood as having such 10 average values, unless otherwise indicated.

1. C8F17S02N(C2H5)CH2C02(C2H40)15H
~- C8Fl7so2N(c2H5)c2El4o(c2H4o)l4H
3. CgF17c2H4O(c2H4o)lsH
~C2tl40)mH
15 4. C8F17S02N ~ (m~n = 25) (C2H40)nH
5. CgFl7so2N(c2H5)c2H4o(c3H6o)8H

6. C8F17C2H4SClHcO2(c3H6o)mH (m+n = 20) CH2C02 ( C3H6) nH

7- C8F17S02N(C2H5)C2H4O(C2H4O)7 5H

Representative Eluorochemical oxyalkylene 20 polyacrylates useful as component (b) in the blends oE this invention are those made by copolymerizing any of the fluorochemical acrylates of Table 3 with any of the fluorine-free poly(oxyalkylene) monomers of Table 4.

25 1. C8F17S02N(CH3)CH2CH200CCW=CH2, 2. C6F13C2H400CC(CH3)=c~2 3. C6F13C2H4SC2H4OOCcH=cH2 4c CgF17C2H4OOCC(CH3)=cH2 5- C8F17C2H4N(CE13)C2H4OOCC(CH3)=CH2, ~ 21 _ ~ r~
6 . C2F5C6FlocH2ooccH=cH2 r 7. C7FlscH20occH-cH2

8. C7Fl5co~(cH3)c2H4ooccH=cH2~

9. (CF3)2CF(CF2)6CH2C~l(OH)CH200CCH=CH2, S 10. (CF3)2CFOC2F4C2H400CCH=CH2, 11. C8Fl7c2H4so2N(c3H7)c2H4oocc~l=cH
12. C7FlsC2H4CONHC4HgOOCCH=CH2, 13. C3F7(CFCF20)2CFCH200CCH=CH2, 14- C7Fl5coocH2c(cH3)2cH2oocc~cH3)=cH2r 15. CgF17S02N(C2Hs)C4HgOOCCH=CH2, 16- (C3F7)2c6H3so2N(cH3)c2H4ooccH=cH
fCF2CF2~
17. C2FsCF\ ~NC2F4CON(CH3)C2H400CCH=CH2, 18- C6F17CF=CHCH2N(CH3)C2H400CCH=CH2, 19. C8F17S02N(C4Hg)C2H40COCH=CH2 20- C8Fl7so2N(c2H5)c2H4ococH(cH3)=cH2 1. CH2=cHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H4o2ccH=cH2 2. CH2=cHco2(c2H4o)l7cH3 3. CH2=c(cH3)CONH(c3H60)44H
4. CH2=C(CH3)C02(C2H40)90COC(CH3)=CH2 5. HS(C2H40)23(C3H60)35(c2H40)22c2H4sH

Specific fluorochemical oxyalkylene polymers are those of Table 5 described in terms of their monomers and the relative amounts thereoE.

-22- ~2~
TABLE S
~onomers Acrylate Oxyalkylene Weight Ratios, of Table 3 _f Table 4 acrylate/oxyalkylene 119 1 ~0/70 ~1 4 50/50 Other compatible optional comonomers t e.g. butyl

10 acrylate, acrylonitrile, etc., which need not contain fluoroaliphatic radicals, can be copolymerized with the fluorochemical acrylate and oxyalkylene comonomers, in amounts up to about 25 weight percent, to impro~e com-patibility or solubility of the fluorochemical oxyalkylene 15 component (b) in the fiber finish.
Weight ratios oE fluorochemical acrylate monomers (Table 3) and fluorochemical poly(oxyalkylene) monomers (Table 4) can vary but should be chosen along with said optional comonomers so that the carbon-bonded fluorine 20 content of the resulting copol~mer is in the desired range of 5 to 40 weight percent.
Representative fluorochemical urethane compounds useful in the practice of this invention as component (a~
are those of Table 5A.

Table 5A
1~ [c8Fl7so2N(c2H5)c2H4ocoNH]2c6H3(cH3) 2. RocoNHc6H4cH2c6H3(NHcooR)cH2c6H4N~cooR
where two of the R groups are C8F17SO2N(C2H5)C2H4- and one is C18H37 -Objects and advantages of this invention are illustrated in the following examples.

-23- ~ 7--~
Example 1 In a 2~1iter, 3-neclc flask, fitted with a mechanical stirrer, condenser, thermometer, addition funnel and electric heating mantle, was placed 375 g (1.5 moles) 5 methylenebis(4-phenyleneisocyanate) and 481 g methyl ethyl ketone (MEK). To this stirred heated solution (80-83C) was added 554 g (1.0 mole) N-ethyl(perfluorooctane)sulfon-amidoethyl alcohol over a 3 hour period and stirring and heating continued for an additional 3 hours.
To this stirred solution, containing fluoro-chemical urethane isocyanate and unreacted diisocyanate, was added 7.4 g camphene phenyl phosphine oxide, ClOHl6POC6H5. a carbodiimide-forming catalyst, and the reaction mixture was stirred and heated at about 80C for 15 about 8 hours, at which time essentially all of the isocyanate groups had been converted to carbodiimide groups as indicated by IR absorption analysis.
The solid fluorochemical carbodiimide product is represented by compound no. 1 in Table l.

Examples 2-5 Following the general procedure of Example l, except employing the reagents in Table ~ and molar concen-trations indicated in Table 7, the other fluorochemical carbodiimides of Table 1 were prepared. The reagents in 25 Table 6 are identified by symbols, e.g. A-l, etc., for later reference.

Alcohol Xea~ents A-l C~Fl7SO2N(C2tl5)c2~l4~ll A-2 CgFl7SO2N(C4Hg)C2H4OH

A-3 CgFl7c2H4oH

Jr~ 7 ~ 2 4--Isocy~nates ~IDI OCN-~CEl 2~NC 0 TD~: OCN~--~CNCO

Reactants (moles)**
Alcohol EX. No.* Reagent Isoc~anate 2 A--1 (2) TDI (2,.~) 3 A-2 ~IDI

* The numbers correspond to the ~ompound numbers of Table 1.
**All alcohol/isocyanate reagent molar ratios were 2t3 except as indicated for Example 2.

Examples 6-19 In each of -these examples, a gold-colored, plush, cut-pile, pre-wet nylon carpet (50 oz/yd2) was treated by top spray application ( 25% wet pickup) of a diluted mixture of an aqueous emulsion of the fluorochemical carbodiimide 20 o compound no. 1 of Table 1 and an a~ueous emulsion of a fluorochemical oxyalkylene, the dilution (with water) of the mixture of emulsions being done to obtain the desired concentration of fluorochemical components, (a) and (b), necessary to deposit the amounts (SOF) of fluorochemicals 25 on the carpet specified in Table 8. The treated carpet samples were dried for 30 minutes at 70C and heated further at 130C for 10 min. For purpose of comparison, control examples (C-l to C-9) were run in which the carpet treatment employed only one fluorochemical component (C-l -25- ~ ,f~
to C-8) or the example (C-9) did not include any treatmen'O
The oil repellency (OR), water repellency (',J~
and wal~-on soil resistance (WOS) were determined on the treated samples. The data is summari~ed in Table 8~
The water repellency test is one which is often used for this purpose. The aqueous stain or water repellency of treated samples is measured using a water/isopropyl alcohol test, and is expressed in terms of a water repellency rating of the treated carpet or fabric.
10 Treated carpets which are penetrated by or resistant only to a 100 percent waterJ0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 100/0, whereas treated fabrics resistant to a 0 percent water/100 percent isopropyl alcohol mixture (the 15 most penetrating of the test mixtures) are given a rating of 0/100. Other intermediate values are determined by use of other water/isopropyl alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10. The water repellency rating corresponds to the most penetrating mixture which does not penetrate or wet the fabric after 10 seconds contact. In general a water repellency rating of 90/10 or better, e.g, 80/20, is desirable for carpet~
The oil repellency test is also one which is 25 often used for this purpose. The oil repellenc~l of treated carpet and textile samples is measured by AATCC Standard Test 118-1978, which test is based on the resistance of j~, ~~~ treated fabric to penetration by oils of varying sur~ace tensions. Treated fabrics resistant only to "Nujol", a 30 brand of mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated Eabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not pene-trate or wet the fabric after 10 seconds contact rather than the 30 seconds contact of the Standard Test. ~igher numbers indicate better oil repellency. In general, an oil repellency of 2 or greater is desirable for carpet.
The soil resistance of treated and untreated (control) carpet was determined by exposure to pedestrian traffic according to AATCC Test method 122-1979, the exposure site being a heavily travelled industrial area for an exposure of about 15,000 "traffics". The samples are repositioned periodically to insure uniform exposure and 10 are vacuumed every 24 hours during the test and before visual evaluation. The evaluation employed the following "Walk-On-Soiling" tWOS) rating system:

WOS_Ratin~ Description 0 equal to control -l/2 slightly better (-~) or worse(-) than control +l impressive difference compared to control -l 1~2 very impressive difference compared to control -2 extremely impressive difference compared to ~ control ,k~2 .~ ~
Table 8 Fluorochemical Fluorochemical _ Oxyalk~lene Carbodiimide Compound Table Ex.No. %soFa No. No. ~ SOF OR WR WOS
-6 .09 2 5 .01 1.5 70/30 -1/2 to -1 7 .05 2 5 .05 1.5 70/30 +1 8 .09 c .01 1 70/30 +1/2 to 0 9 .05 c .05 2 60/40 0 .09 2 2 .01 2 70/30 0

11 .05 2 2 .05 2.5 70/30 0

12 .09 7 2 .01 2 60/40 -1/2

13 .05 7 2 .05 2 70/30 0

14 .09 d .01 1.5 70/30 0 .05 d .05 1.5 70/30 0 to +1/2 16 .09 e .01 1.5 70/30 -1/2 17 .05 e .05 3.5 50/50 -2 18 .09 5 2 .09 1.5 70/30 0 to +1/2 19 .05 5 2 .05 1.5 70/30 0 to +1/2 C-l none 2 5 .10 2 50/50 -1 1/2 C-2 none c .10 2.5 70/30 -1/2 C-3 none 5 2 .10 0 NWRb -2 C-4 none 6 2 .10 0 NWR -1 1/2 C-5 none d .10 0 NWR -2 C-6 none e .10 4O5 NWR -2 C-7 none 7 2 .10 0 NWR -1 1/2 C-8 .10 none none none 2 70/30 0 C-9 none none none none 0 NWR -2 ~ -27-a. % SOF means % fluorochemical solids on fabric b. NWR means no water resistance c. The c~npound used in this example was a terpol~ner of C8FL7so2N(cH3)cH2cH2ooccH CH2~
CH2=c(cH3)co2(c2H4o)9ococ(cH3) CH2, CH2=C(cH3)c02(c2H4o)9o d. The c~npound used in this example was a terpolymer of C8F17S2N(C4H9)C2H~CCH CH2' CH2=cHco2(c2H4Qlo)(c3H6o)22(c2H4o)9c2H4o2c 2 CH2=CHCO2(c2H40lo)(c3H6o)22(c2H4 )9 2 4 e. The compound used in this example was a terpolymer of 8Hl7so2N(c2H5)c2H4ococ(cH3)=cH2~
CH2=cHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H4o2cc 2' C 2 CHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H~oH

-27a-.
.J `

-2~ L~

The data oE Table 8 show that useful oil and water r~pell~ncv ~as obtained from all of the blends (Examples 6-19) and that the soil resistance of most of the blend examples were better than or equal to that of the 5 comparative example. Those properties obtained for Examples 6-19 as compared to the ExampLes C-l thru C-7, are particularly noteworthy.
The control Example C-8, which was carpet treated only with fluorochemical carbodiimide, had a particularly 10 harsh hand. However, where the blends were used (Ex. No.
6-19), the hand of the treated carpets was soft, which was considered to be equal to the untreated carpet, especially at the higher concentration of the fluorochemical oxyalkylene component.

Examples 20-22 These examples describe the treatment of nylon carpet fiber with aqueous emulsions of component (a) fluoro-chemical carbodiimide of compound no. 1 in Table 1 and component (b) various fluorochemical oxyalkylene blends of this invention in combination with an aqueous emulsion of a coconut oil based spin finish lubricant, and the results of testing of the dyed carpet prepared Erom the treated fibers.
The composition of the applied finish for these examples had fluorochemical solids to spin finish lubricant ?5 solids ratios in the range of 0.18:1 to 0.14:1.
The spin finish emulsion composition was applied by a metered slot applicator to melt extruded, undrawn yarn oE nylon 6 fibers. The yarn was made up of 118 Eilaments oE 18 denier (per filament). The resultant fiber imme-diately after application had Erom 1.0 to 1.5 weightpercent of the lubricant component on the fibers. The treated yarn was continuously drawn and texturized and made into level-loop carpet (28 oz/yd2), heat set at 196C for one minute, acid dyed, dried at 70C for 30 min~, heated at 130C for 10 min., and then evaluated for oil and water repellency, walk-on soil resistance, and retention of ~ 2~f~

fluorochemical treatment -through the dyeing process as determined by fluorine analysis. The testing results are shown in Table 9~ Comparison examples, C-10, C-ll, were run, one of them omitting any fluorochemical treatment, and the o-ther including a treatment with only one fluorochemical component, viz~, the carbodi-imide of compound no. 1 of Table 1.
Table 9 Relative amts., (in terms of wt Amount of Fluo-g fluorine) of rine on Carpet Fluorochemical Before After ~ Retention components Dyeing, Dyeing, of Fluoro-Ex. No. (a)/(b)* ppm ppmChemical OR WR WOS
80/20683 619 91 3 40/60 +1 21 80/20784 673 86 5 20/80 -~1/2 C-ll none 0 0 0 0 NWR -2 * The fluorochemical oxyalkylenes used in Ex. No. 22 was compound no. 2, of Table 5, that used in Example 21 was a terpolymer of C8F17SO2N(CH3)CH2CH2O0CCH=cH2, CH2=C(CH3)CO2(C2H4O)goCOC(CH3)=CH2/ and CH2=C(CH3)CO2(C2H4O)goH~ that used in Ex-ample 20 was a terpolymer of C8F17SO2N(C4Hg)C2H4OCOCH=CH2~ CH2=CHCO2(C2H4Olo)~
(C H6O)22(C2H4O)gC2H4O2CCH=CH2~ and CH2=CHCO2(c2H4Olo)(c3H6o)22(c2H4o)9c2H4oH~
The data of Table 9 show that improved oil and wa-ter repellency was ob-tained from most of the above blends (Ex. Nos. 20, 21, 22) and tha-t the soil re-sistance was generally better than the control (C-10). Particularly no-teworthy are the higher retention values of the blends as compared to the control C-10.

~V~ 3 Examples 23-26 In these examples, two difEeren-t rainwear fabrics were trea-ted wi-th an aqueous emulsion of a blend of (a) the fluorochemical carbodi.ir~lide of compound no. 1 of Table 1 and (b) a fluorochemical oxyalkylene in a padding -29a--30~ $~ ~ ~
operation, dried at 150C for 10 minutes~ and evaluated for initial o l repellency (OR) and resistance to a water spray (~R), then these properties evaluated again after 5 launderings (5L) and also after one dry cleaning ~DC).
The OR test used was the above-described AATCC
Standard Test 118-1978, the contact time before observation being the specified 30 sec., an O~ value o 3 or greater being particularly desirable for rainwear fabrics.
The water spray rating (~R) is measured by AATCC
10 Test Method 22-1979. The spray rating is measured using a 0 to 100 scale where 100 is the highest possible rating.
In general, a spray rating of 70 or greater is desirable, particularly for outerwear fabrics.
The treated fabrics were laundered using a mechanically agitated automatic washing machine capable of containing a 4 Kg. load, using water at 50C and a commercial detergent, and then the washed fabrics were tumble-dried in an automatic dryer for 40 minutes at 70C
and pressed in a flat-bed press (at 154C) before testing.
The treated fabrics were dry cleaned using perchloroethylene containing 1% of a dry cleaning detergent and tumbling in a motor driven tumble jar (AATCC Test Method 70-1975) for 20 minutes at 25C. After removing excess solvent in a wringer, samples were dried at 70,C for 10 minutes, then pressed on each side for 15 seconds on a flat-bed press maintained at 154C.
The data are summarized in Table 10 together with comparison examples C-12 through C-l9.

~ ?3~ ~3 Table 10 Relative a~ts.
(in terms of wt % fluorine) of fluorochemical components Total Initial SL DC
Ex. No. (a)/(b)* % SOF Fabric** OR SR OR SR OR SR
23 98/2 0.21 A 6 80 5 80 2.5 70 ~4 98/2 0.21 B 6 80 3 70 4 80 80/20 0.2 A 6 70 5.5 70 6 70 '>6 80/20 0.2 B 6 80 5 75 6 80 C-12 100/0 0.2 A 5 70 5 70 3 70 C-13 100/0 0.2 B 5.5 80 5 80 4.5 80 C-14 0/100 0.2 A O O O O
C-15 0/100 0.2 B O O O O O O
~-16 0/100 0.2 A 6.5 50 0 0 6 70 G-17 0/100 0.2 B 5 70 1 70 6 70 C-18 0/100 none A O O O O O O
C-19 -- none B O O O O O O

~0 * The fluorochemical oxyalkylene used in Ex. Nos. 23, 24 and C-14, C-15 was a terpolymer of C8F17S02N(C4Hg)C2H40COCH=CH2~ CH2=CHC02(C2H401o)(C3H60)22(C2H40)9-C H O CCH=CH , and CH2=CHC02(C2H4010)(C3H60)22(C2H4 )9 2 4 Ex. Nos. 25, 26 and C-16, C-17 was a terpolymer o:E C8F17S02N(CH3)CH2CH200CCH=CHCH2=C(CH3)C02(C2H40)90COC(CH3)=CH2, and CH2=C(CH3)C02(C2H40)goH.
** Fabric A is 100% nylon taEfeta; Fabric B is 100% woven polyester.
The data of Table 10 show that improved OR, SR, and durability -to laun-dering and dry cleaning properties were obtained with most of the blends as com- -31-pared to either component aloneO

Examples 27-40 In the following examples, aqueous emulsion blends of the fluorochemical urethane 1 of Table 5A and several dif~e:rent fluorochemical oxyalkylenes were used to treat nylon carpet, following the procedure of Ex. 6-19. The dried samples were evaluated for OR, WR
and ~S. The results are summarized in Table 11.

Table 11 Fluorochemical Fluorochemical Oxyalkylene Urethane Compound Table Ex.No. ~SOF No. No. ~ SOF OR WR ~S
27 .09 2 5 .01 2 70/30 -1/2 28 .05 2 5 .05 2.5 80/20 -1/2 to 0 29 .09 a .01 2 70/30 -1/2 to 0 .05 a .05 2 70/30 +1/2 31 .09 2 2 .01 2 70/30 +1/2 32 .05 2 2 .05 3 70/30 0 to +1/2 33 .09 7 2 .01 2 70/30 -1/2 34 .05 7 2 .05 4 90/10 0 to ~1/2 .09 b .01 1.5 70/30 0 to +1/2 36 .05 b ~05 2 NWR -1 37 .09 4 5 .01 2.5 70/30 -1/2 38 .05 4 5 .05 ~.5 NWR -1 39 .09 5 2 .01 2.5 70/30 0 to +1/2 .05 5 2 .05 3 70/30 0 to tl/2 C-20 .10 none none none 3 70/30 0 C-21 none none none none 0 MWR -2 '~

2~

a. The compound of this example was a terpolymer of c8E17so2N(CH3)cH2cH2ccH=
CH2=C(CH3)CO2(C2H4O)90COC(CH3)=CH2, and CH2=C(CH3)CO2(C2H4O)90H
b~ The compound of this example was a -terpolymer of C8F17SO2N(C4H9)C2H4OCOCH=CH2, 2 2( 2 4 1o)(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH2=cHco2(c2H O )-(C3H6O)22(C2H4O)9c2H4OH-The data of Table 11 show that all of the blend examples have better OR
and WOS than the untreated carpet, C-21, and most of the blend examples had bet-ter WR than the untreated carpet (C-21). Also, all of the blend examples had better WOS than the controls C-l to C-7 which used only the fluorochemical oxyal-1~ kylene component. It is particularly noteworthy that half of the blend exampleshad better WOS than the control Example C-20 where the urethane fluorochemical component was used alone.
Examples 41, 42 Following the procedure of previous Examples 23-26, two rainwear fab-rics were treated with an aqueous emulsion of a blend of (a) the fluorochemical urethane 2 of Table 5A and (b) the fluorochemical oxyalkylene 3 of Table 5 in a padding operation, dried at 150C for 10 minutes, and evaluated for initial OR
and SR, then these properties evaluated again after 5L and also after one DC. m e ~es~llts are given in Table 12.
Table 12 Relative amts. (in terms of wt % fluor-ine) of fluorochemicals Total Initial 5L DC
Ex. No.components (a)/(b) % SOF Fabric* OR SR OR SR OR SR
41 80/20 0.2 A 6.5 70 6 75 5 70 42 80/20 0.2 B 6 70 5.5 70 6 70 C-22 100/0 0.2 A 6 80 5.5 80 1 50 C-23 100/0 0.2 B 6 70 5 70 2 0 * Fabric A was nylon taffeta, and fabric B was woven polyester.
a. The compound of this example was a terpolymer of C8F17S02N(CH3)CH2CH200CCH=CH2, CH =C(CH )CO (C H O) COC(CH )=CH , and CH2=C(CH3)C02(C2H~O)goH.
The data of Table 12 show that the initial and 5L oil repellency obtai-ned with the blends (Ex. Nos. 41, 42) were bet-ter than resul-ts ob-tained with the fl~lorochemical urethane alone (Ex. C-22, C-23). The durability to dry cleaning obtained by use of the blend (Ex. Nos. 41, 42) is particularly notewor-thy when eompared to Examples C-22, C-23, using the fluorochemical urethane alone.
Various modifications and alterations of this invention will become l~ apparent to those skilled in the art without departing from the scope of this invention.

-33a-

Claims (18)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A composition comprising a blend of: (a) 40 to 99 weight percent of a normally solid, water-insoluble, fluorochemical composition which is a fluoroaliphatic radical-containing compound, or composition comprising a mixture of such compounds, said compound having one or more monovalent fluoroaliphatic radicals having at least three fully fluorinated carbon atoms and one or more polar moieties selected from carbodiimido, carbonylimino, ester moieties and combinations thereof, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy, -N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof; and (b) 1 to 60 weight percent of a normally liquid or low melting solid, water soluble or dispersible, fluoroaliphatic radical-containing poly(oxyalkylene), or composition comprising a mixture of such poly(oxyalkylenes), said poly(oxyalkylene) having one or more of said fluoroaliphatic radicals and one or more poly(oxyalkylene) moieties, said radicals and poly(oxyalkylene) moieties bonded together by hetero atom-containing groups or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfoner sulfoxy, phosphoxy, amine, oxyalkylene, iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, urea, ester, and combinations thereof.

2. A composition according to claim 1 wherein said fluorochemical composition (a) is a fluoroaliphatic radical-containing carbodiimide or carbonylimino compound.

3. A composition according to claim 1 wherein said fluorochemical composition (a) is represented by the general formula R1?Q?x?N=C=N-A??N=C=N?Q?xR1 where n is 0 to 20, x is 0 or 1, is a divalent organic linking group which can contain said fluoroaliphatic group, Rf, R1 is a hydrogen atom, said Rf, or an organic radical, Q
is a divalent hetero atom-containing group or organic linking group, or combination thereof.

4. A composition according to claim 1 wherein said fluorochemical composition (a) is represented by the formula R-Q-A(N=C=N-A)n-Q-R

where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4-and n is 2.

5. A composition according to claim 1 wherein said fluorochemical composition (a) is represented by the formula A'[NHCOY(Q)xR2]r where A' is a residue of an organic isocyanate Y is -N-, -O-, or -S-, Q is a divalent hetero atom-containing group or organic linking group, or a combination thereof, R2 is a hydrogen atom, fluoroaliphatic group, or an organic radical, at least one R2 being a fluoroaliphatic radical, x is 0 or 1, and r is an integer of 1 to 10.

6. A composition according to claim 1 wherein said fluoroaliphatic radical-containing poly(oxyalkylene) has the general formula (Rf)sZ[(R3)yZ'B]t or [(Rf)sZ[(R3)yZ'B']t]w where Rf is said fluoroaliphatic radical, Z is a linkage through which Rf and (R3)y are covalently bonded together, (R3)y is a poly(oxyalkylene) moiety, R3 being oxyalkylene with 2 to 4 carbon atoms, and y is an integer or number of at least 5 and can be as high as 100 or higher, B is 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)y radical to another Z, Z' is a linkage through which B or B' and (R3)y 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.

7. A composition according to claim 1 wherein said fluorochemical poly(oxyalkylene) is the copolymer of C8F17SO2N(CH3)C2H4O2CCH=CH2 and CH2=C(CH3)CO2(C2H4O)90COC(CH3)=CH2.

8. A composition according to claim 1 wherein said fluorochemical poly(oxyalkylene) is a terpolymer of C8F17SO2N(CH3)CH2CH2OOCCH=CH2, CH2=C(CH3)CO2(C2H4O)90COC(CH3)=CH2, and CH2=C(CH3)CO2(C2H4O)90H

9. A composition according to claim 1 wherein said fluorochemical poly(oxyalkylene) is a terpolymer of C8F17SO2N(C4H9)C2H4OCOCH=CH2, CH2=CHCO2(C2H4O10)(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH2=CHCO2(C2H4O10)(C3H6O)22(C2H4O)9C2H4OH.

10. A composition according to claim 1 wherein said fluorochemical poly(oxyalkylene) is a terpolymer of C8H17SO2N(C2H5)C2H4OCOC(CH3)=CH2, CH2=CHCO2(C2H4O)10(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH2=CHCO2(C2H4O)10(C3H6O)22(C2H4O)9C2H4OH.

11. A composition according to claim 1 wherein said fluorochemical composition (a) is represented by the formula R-Q-A(N=C=N-A)n-Q-R

where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4-, n is 2, and wherein said fluorochemical poly(oxyalkylene) is the copolymer of C8F17SO2N(CH3)C2H4O2CCH=CH2 and CH2=C(CH3)CO2(C2H4O)90COC(CH3)=CH2.

12. A fiber finish comprising an organic solution or aqueous dispersion comprising a blend of: (a) 40 to 99 weight percent of a normally solid, water-insoluble, fluorochemical composition which is a fluoroaliphatic radical-containing compound, or composition comprising a mixture of such compounds, said compound having one or more monovalent fluoroaliphatic radicals having at least three fully fluorinated carbon atoms and one or more polar moieties selected from carbodiimido, carbonylimino, ester moieties and combinations thereof, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy, -N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, urea, and combinations thereof; and (b) 1 to 60 weight percent of a normally liquid or low melting solid, water soluble or dispersible, fluoroaliphatic radical-containing poly(oxyalkylene), or composition comprising a mixture of such poly(oxyalkylenes), said poly(oxyalkylene) having one or more of said fluoroaliphatic radicals and one or more poly(oxyalkylene) moieties, said radicals and poly(oxyalkylene) moieties bonded together by hetero atom-containing groups or organic linking groups selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, oxyalkylene, iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, urea, ester, and combinations thereof.

13. The fiber finish according to claim 12 wherein said fluorochemical composition (a) is a fluoroaliphatic radical-containing carbodiimide, ester or carbonylimino compound.

14. The fiber finish according to claim 12 further comprising a fiber lubricant.

15. A method for imparting oil and water repellency to a fibrous substrate, which comprises treating the surface thereof with the fiber finish of claim 14.

16. In the manufacture of spun synthetic organic fibers wherein a fiber finish is applied to said fibers, the improvement comprising employing as said fiber finish the fiber finish of claim 14.

17. A fibrous substrate coated with the fluorochemical blend composition of claim 1.

18. A fibrous substrate according to claim 17 wherein said substrate is nylon carpet fiber.