CA1248274A - Blend of fluorochemical guanidines and poly (oxyalkylenes) - Google Patents

Abstract

ABSTRACT

Blends of fluoroaliphatic radical-containing, substituted guanidines 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

'1/1() ~ L / ('Al`l/WCI~:

BLEND OF FLUOROCHEMICAL
GUANIDINES AND POLY(OXYALKYLENES) This invention relates to the treatment of fibrous substrates, such as textile fibers, paper, and leather, with fluorochernical compositions to impart oil and water repellency, and to the resulting treated substrates.
In another aspect, it relates to the treatment of carpet fiber with a finish comprising a fluoroaliphatic radical-containin~ composition to impart oil and water repellency 10 and soil resistance to such fiber. In another aspect, it relates to fluoroaliphatic radical-containing compositions, and their preparation, which are useful in such treatment.
In the indu~trial production of textilss, such as carpet and apparel, and such other fibrous substrates as 15 paper and leather, it is common to treat such substrates with fluorochemicals containing fluoroaliphatic radicals ~often designated by the symbol "Rf") to impart oil and water repellency to the surace of such substrates. Fluoro-chemicals of this type and their application to fibrous ~0 substrates are described in various prior art publications, e.g., U.S. Patent Nos. 3,329,661 (Smith et al), 3,458,571 ~Tokoli), 3,574,791 (Sherman et al), 3,728,151 (Sherman et al), 3,916,053 (Sherman st al), 4,144,367 (Landucci), 3,896,251 (Landucci), 4,024,178 (Landucci), 4,165,338 25 (Katsushima et al), 4,215,205 (Landucci), 4,013,627 (Temple), 4,264,484 (Patel), and 4,325,857 (Champaneria et al), and Banks, R. E., Ed. "Organofluorine Chemicals and their Industrial Applications", Ellis Horwood, Ltd., West Sussex, England, 226-230 (1979).
Although some ~luorochemicals are useEul in many applications and many are commercial products, some are relatively expensive to prepare and apply, others are difficult to apply, and others are not durable or do not impart the required properties to the extent desired.

--2--~
Conventionally, fluorochemical compositions have been commercially 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 article. ~lowever, some of these fluorochemical compositions have had limited success for various reasons including incompatibility or reactivity of the fluorochemical with fiber finish co~po-nents such as lubricants, lack of durability of the fluorochemical on the treated ~iber to dyeing or otherfiber manufacturing operations, and insufficient water and oil repellency and soil resistance in the finished article.
It is an object of this invention to provide 1~ blends of fluoroaliphatic radical-containing, substituted ~uanidines (hereinafter often called fluorochemical guanidines for brevity) and fluoroaliphatic radical-con-taining poly(oxyalkylenes) (hereinafter often called fluorochemical oxyalkylenes for brevity), said blends being ~ useful ~or treating textile fibers and other Eibrous sub~trates to impart oil and water repellency thereto.
.~nother object of this invention is to provide blends of fluorochemical guanidines and fluorochemical oxyalkylenes which can be used to treat textile fibers in ~5 combination with or as a component of fiber finishes, e.g.
spin-finish lubricants, such blends being compatible with said Eiber finishes and not interfering with normal textile fiber processing steps.
A further object of this invention is to provide fluorochemical-treated textile fiber with a high percentage of the ~luorochemical retained on the Eiber through Eiber processing and dyeing steps, and with durable water and oil repellency and soil resistance properties.
It is yet another object of this invention to provide blends of fluorochemical guanidines and ~Eluro-chemical oxyalkylenes which can be used in the form of organic solutions or aqueous dispersions to treat fibrous 3 ~3,..~

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.
sriefly~ this invention provides, in one aspect, a compo-sition for imparting oil and water repellency to fibrous substrates comprising a blend of:
(a) 60-99 weight percent of a normally solid, water-insoluble, fluorochemical guanidine composition which is a fluoro-aliphatic radical-containing substituted (wholly or partially) la ~uanidine compound, or composi-tion comprising, or consisting es-sentially of, a mixture of such compounds, said compound having one or more monovalent fluoroaliphatic radicals (Rf) having at least three fully fluorinated carbon atoms and one or more substituted guanidino moieties, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups, preferably comprising carbameto (urethane) groups, with the provisos that when only one guanidino moiety is present, and only two organic substi-tuents are in said guanidino moiety, said substituents must be on different nitrogen atoms and that said fluorochemical guanidine ~a composition contains about 20 to 70 weight percent carbon-bonded fluorine; and (b) 1-40 weight percent of a normally liquid or low melt-ing solid, water soluble or dispersible, fluoroaliphatic radical-containing poly(oxyalkylene), or composition comprising, or consist-ing essentially of, a mixture of such poly(oxyalkylenes), said poly-(oxyalkylene) having one or more of said fluoroaliphatic radicals 7 ~r -3a- 557-2678 and one or more poly(oxyalkylene) moieties, said radicals and poly-(oxyalkylene) moieties bonded together by hetero atom-containing groups or organic linking groups or combinations of said groups, said fluoroaliphatic radical-containing poly(oxyalkylene) composi-tion contains about 5 to 40 weight percen-t carbon-bonded fluorine.
Said fluorochemical blends are useful in the form of organic solu-tions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers (or Eilaments~ during their manufacture, and useIul also in the treatment of finished or fabricat,ed fibrous sub-strates such as carpets, paper, and leather, to impart oil andwater repellency to the surface thereof.
A class of such fluorochemical guanidines (component (a) of said blends) can be represented by the general formula I

R tQtXtN=C-NH-AtnNH-C=NtQtXR
N N
/\ /\
(Q)x (Q)x (Q)x (Q)x -3a-` :

--4- ~ ~ 60557-2678 which formula generically encompasses individual compounds or represents a mixture of such compounds as they are obtained from reactions used in their preparation.
Guanidines are conveniently prepared by the reaction of carbodiimides and amino (-NH) compounds, e.g. amines, hydrazines, hydrazides, and amides, using yeneral routes fox ~uanidine synthesis as described, for example, by Kurzer, et al, Chemical Reviews, 67, 107, (1967), and in U.S. Patent No. 4,174,433 l~chafer, et al). In addition, carbodiimides can be prepared from ureas, thioureas, and other compounds as described by K. Wagner et al., Angewante Chemie Int. Ed., 20, 819 (1981). Many ~luorochemical guanidines used in this invention can be prepared in an analogous manner from fluorochemical carbodiimides and said imino compounds. Such fluorochemical carbodiimides and their preparation are described in U.S. Pat. No. 4,024,178 (Landucci).
In formula I, "n" is a number (in the case where the formula is that of a mixture) or an interger (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, and "x" is 0 or 1. Each Q is the ~0 same or different divalent linking group. A is a divalent organic linking ~roup which can contain a fluoroaliphatic radical, Rf, each 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 ~,.
,~

;?d ~
-4a- 60557-2678 ~or isocyanate-reactive) hydrogen atoms (i.e., hydrogen atoms or groups, such as mercapto, amino, carboxyl, and ali.phatic hydroxyl groups, that can react readily with isocyanate under urethane bond-forming conditions, e.g. 20 -to 100C). Generally, Rl will have no more than about 18 carbon atoms, Where Rl is said Rf, the subscript x of the adjacent Q must be 1 and not 0 because _5 ~_~d ~
RE cannot be directly bonded t~ a N-atom of the yuanic3ino group. Unless otherwise indicated, "R" means either Rl or R2. Each R2 is like R1 but in addition the two R2 groups of a guanidino group can be bonded together to form a 5 cyclic structure with the adjacent N atom of that guanidino group. There is at least one Rf radical present in one or more of the Rl, R2, and A groups for a given compound.
When only one guanidino moiety is present, and only two organic substituents are in said guanidino moiety, said substituents must be on different N atoms of the moiety.
In the above general formula I, the divalent organic linking group A connects successive guanidino 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 -CH2C6H4CH2-and -c6H4CH2C6H4-, having up to 20 carbon atoms, arylene groups, such as tolylene, -C6H3(CH3)-, poly(oxyal~ylene) groups, such as -(C2H4O)yC2H4~ where y is 1 to about 5, and ~0 various combinations of these groups. Such groups can also include other hetero moieties (besides -O-), including -S-and -N-~ However, A is preferably free of groups with said active hydrogen atoms.
The A group can be a residue of an organic ~5 diisocyanate (from which the carbodiimido and guanidino moieties can be derived by successive reactions), that is, A can be the divalent radical obtained by removal of the isocyanate groups ~rom an organic diisocyanate. Suitable diisocyanate precursors may be simple, e.g. tolylene-2,4-diisocyanate, methylene bis(4-phenyleneisocyanate), and mixtures thereof, or complex, as formed by the reaction oE
a simple diisocyanate 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 -CH2C6H4CH2C6~l4CH2 , C6H3(CH3) , C6~l10C~?C6H10~ CH2)6~, -C6H~CH2C6H~-, and CgF17SO2N[C2H4OCONHC6H3(CH3)~2. Although the fluoro-chemical guanidines used in this invention generally and preferably are derived from diisocyanates, the fluorochemical guanidines can be derived from triisocyanates, e.g. OCNC6H~CH2C6H3(NCO)CH2C6H4NcO. A
mixture of di- and tri-isocyanates can be used to provide fluorochemical guanidines which are branched but still retain the desired solubility and dispersibility characteristics of the linear fluorochemical guanidines depicted by formula I.
The R-Q groups are preferably radicals derived from isocyanate compounds and can be aliphatic, e.g.
C6~13-, aromatic, e.g. C6H5-, aralkyl, e.~. C6H5CH2-, fluoroaliphatic, e.g. C6F13CH2-, C7F15CH2OCONHC6H3(CH3)-, and C8F17SO2N~CH3)C2H4OcoNH~6H4c~2c6~-- The organic R-Q
radicals can have a variety of other structures, and can contain hetero atom-containing moieties, e.g. -O-, -S-, and -N-, but, as with the A groupr it is preferably free of groups containing said active hydrogen atoms.
The fluoroaliphatic radical, R~, is a fluorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, ~5 and, if sufficiently large, cyclic, or combinations thereoE, 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 stable linkages between fluorocarbon por~ions of Rf and not interferring with the inert character of the Rf radical~
While Rf can have a large number oE 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 RE radicals. The large radicals also are generally less soluble in organic solvents. Generally, Rf 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 portion of -the Rf yroup has a-t least three fully fluorinated carbon atoms, e.y. 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+l The fluorochemical guanidine contains 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 guanidine will generally be required, while fluorine contents greater than about 70 weight percent are un-necessary 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 fluoro-chemical blend as an organic solution.
The function of the linking group Q in formula I is to bond the R yroups to the N atoms of the guanidino units. Q can comprise a hetero atom-containing group or an organic group or a eombination of such groups, examples of which are polyvalent g , CH2 , CH2CH2-, and -CH2CH(CH2-)2, polyvalent aromatic, oxy, thio, carbonyl, sulfone, su]foxy, -N(CH3)-, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, earbonyloxy, urethane, e.g., -CH2CH2OCONH-, and urea, e.g., -NHCONH-. The linkage Q for a specific fluorochemical guanidine useful in this invention will be dictated by the ease of prepara-tion of such a compound and the availability of necessary precur-~l2 ~
-7a- 60557-2678 sors thereof. From the above description of Q, it is apparent that this linkage can have a wide variety of structures.
However, as with the R and A groups, Q is preferably free of moieties having said active hydrogen atoms. However large Q is, the fluorine content (the locus of which is Rf) of the fluoro-chemical guanidine is in the aforementioned limits~
It should be recognized that, in the above general formula I, isomeric or tautomeric forms may be present.
For example, for a given guanidino unit, the following tautomeric forms can exist:

-N=f-NH- -NH-I=N-R-Q-~-Q-R R-Q-N-Q-R

A B

When an R-Q iS H, then another isomeric structure can also be present:

-N=~-NH- -NH-~-NH-R-Q-NH R-Q-N

C D

All o~ the above tautomeric and isomeric forms, as well as mixed Rf groups and other organic moieties, can be present and are included in the fluorochemical guanidines used in this invention.
The fluorochemical guanidines used in this inven-tion are normally solid (i.e~, solid at 20C) with meltingpoints 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 20C.
The above-described fluorochemical guanidines can ~0 be prepared by successive substitutions on guanidine, or by conversion of precursor carbodiimides to guanidines via reaction with imino compounds (i.e., compounds containing ,NH), such as primary or secondary amines. The lmino compounds may contain a fluoroaliphatic radical in the instance where the carbodiimide precursor contains a fluoroaliphatic radical, and must contain a fluoroaliphatic radical in the instance where the carbodiimide precursor does not contain a fluoroaliphatic radical.
Fluoroaliphatic radical-containiny intermediates (R~ intermediates) generally are commercially made by electrochemical Eluorination of organic acids or halides thereof, or by telomerization of tetra~luoroethylene, followed by known reactions to form intermediates that contain a hydroxyl group that is capable of reaction with an isocyanate group to form a urethane linkage (-OCONH-).
Such urethane-forming reactions are generally carried out neat or in the presence of non-reactive solvents, such as ethyl acetate or methyl ethyl ketone, at moderate tempera-tures, such as 20 to 130C. Catalysts for the urethane ~ormation may be employed, but are unnecessary, and in some cases undesirable when aromatic diisocyanates are employed.
The mixture o~ ure-thane group-containing iso-cyanates and non-urethane-containing isocyanates are then converted to the carbodiimide precursors of the fluoro-chemical guanidines used in this invention after addition of low levels (e.g., 0.05 to 1.5 weight percent of ~ reactants) of a catalyst. There are many catalysts known to effect carbodiimide formation from isocyanates. Two of the most effective classes are phospholene oxides (described in U.S. Patent Nos. 2,853,473, 2,941,966, and ~,067,820) and phosphine oxides (described in U.S. Patent ~5 No. 3,862,989). The carbodiimide is then added neat or as an organic solvent solution to the imino compound. This mode of addition as well as moderate temperatures are generally employed to minimize the addition of a guanidino N-H moiety to a carbodiimide which generally leads to reaction mixtures that have considerably lower organic solvent solubility.
Representative reaction schemes for the prepara tion of fluorochemical guanidines ~Ised in this inventlon are outlined below, where the products designated as I' are species of formula I ~

Scheme l 1 _~nA(NCO)~
2Rl-Q'-OH ~ 2A(NCO)2 ~ 2R -Q~NCO cat.,-(n;l)CO2 R -Q(N=c=N-A)nN=c=N-Q-Rl ~R2-Q-NH- Q_R2 >

Rl-Q~HN-C=N-A)nHN-C=N-Q-Rl R2_Q_l N_Q_R2 I' Q Q
~2 ~2 Scheme ~

(n*2)A(NC)2 -(n~l)CO > OcNA-(N=c=N-A)nN=c=N-ANco +2R Q OH>
R -~(N=c=N-A)nN=c=N-Q-Rl +R2-Q-NH-Q-R2> I' Scheme 3 R-Q'-OH + B(NCO)3 ~ R-Q(NCO)2 R-Q~NCO)2 ~ B(NCO)3 + A(NCO)2 + Rl-QNCO CcO > Mixed carbodiimide The mixtures of fluorochemical guanidines used in this invention may contain small amounts of fluorochemical diurathane compounds (e.g., R-Q'-OCONH-A-N~COO-Q'-R, a possible by-product in Scheme 1) free of guanidino 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. The mixture of fluoro-chemical guanidines may contain small or minor amounts of compounds that arise from reaction of an initially formed guanidine with a carbodiimide group to give a higher molecular weight eluorochemical guanidine.

Fluorochemical guanidines in which some of the precursor carbodiimide moieties (in cases wher0 n is greater than 1) have not been reacted with an imino compound are also included as fluorochemical guanidines used in this invention.
Representative Rf intermediates for the preparation of fluorochernical guanidines used in this invention include:

C8F17S02N(C2H5)C2H40H
C8Fl7C2H40H
C7F15cH20H
C7Fl5coN(c2H5 )C2H40H

(CF3)2CF(CF2)gC2H40H
(CF3)2CFoC2F4C2H40H
C8F17C2H4s02N(cH3)c4H8oH
C8F17S02N(C~3)C3H6NH2 C2F5{~cH2NH2 C3F7(1CFCF20)2 CFCON\__~NH

C8F17s03--~ NH2 C8F17S03 ~ NCO

Representative organic isocyanates include:
tolylene-2~4-diisocyanate hexamethylene diisocyanate methylenebis(4-phenyleneisocyanate) methylenebis(4-cyclohexyleneisocyanate) -12- J ~

xylylene diisocyanate l-methoxy-2,4-phenylene diisocyanate l-chlorophenyl-2,4-diisocyanate, p-tl-isocyanatoethyl)phenyl isocyanate phenyl isocyanate m-tolyl isocyanate

2,5-dichlorophenyl isocyanate hexyl isocyanate Representative imino compounds include the ~ollowing: ammonia, methylamine, ethylamine, butylamine, diethylamine, diisopropylamine, dibutylamine, ethyleneimine, morpholine, piperidine, ~,N-dimethyl hydrazine, aniline, 3-aminopropyltrimethoxysilane, pyrrolidine, pyrrolidone, imidazole, ~uanidine, acetamidine, 2-methoxyethylamine, hexamethylenediamine, piperazine, formamide, acetyl hydrazide, sebacoyl dihydrazide.
In cases where certain imino compounds, e.g.
ethylene imine, guanidine, N,NI-dialkyl hydrazine, ethylene ~0 diamine, and hydrazides, are reacted with Eluorochemical carbodiimide precursors (Scheme 1, where the above imino com~ounds are used), adducts are formed which can rearrange to cyclic guanidino structures. These cyclic forms are also included as fluorochemical guanidine compounds used in ~5 this invention.
A class of fluorochemical oxyalkylene, component (b) - the other essential component of the blends of this invention - are fluoroaliphatic olic~omers (or polymers, the term oligomer hereinafter includinc~ polymer unless otherwise indicated) represented by the general formulas:

(Rf)sZ[(R3)yZI~lt II
[(Rf)sz[(R3)y~ t~w III

where Rf is a fluoroaliphatic radical like that described for general formula I, -13- ~ 7~ 60557-2678 Z is a linkage through which Rf and (R3)y moieties are covalently bonded together, (R3) is a poly(oxyalkylene) moiety, R beiny 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 mixtures) 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 1~ 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 R 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 II and III, 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 III, a plurality of s, y and t.
The oligomers contain about 5 to 40 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine.

-13a- 60557-2678 If the fluorine content is less than about 10 weight percent, impractically large amounts of the oligomer will generally be required, while fluorine contents greater than about 35 weight percent result in oligomers 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 L~

-ocH2cH2-~ -OCH2CH2Ctl2 ' -OCH(CH3)CH2-, and -OCH(CH3)CH(CH3)-, the oxyalkylene units in said polyloxyalkylene) being the same, as in poly(oxypropylene), or present as a mixture, as in a heteric straight or branched chain or randomly distributed oxye~hylene and oxypropylene units or as in a 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 catenary linkages. Where said catenary linkages have three or more valences, they provide a means for obtaining a branched chain or oxyalkylene units. The poly(oxyalkylene) radicals 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 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' ~0 together in the oligomer. Z and Z' can be a valence bond, for example, where a carbon atom of a fluoroaliphatic radical is bonded or linked directly to a carbon atom of the poly(oxyalkylene) moiety. Z and Z' each can also comprise one or more linking groups such as polyvalent ~5 aliphatic and polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, and combinations thereoE, such as oxyalkylene, iminoalkylene, iminoarylene, sulfoamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane~ urea, and ester. The linkages Z and Z' for a speci~ic oligomer will be dictated by the ease of preparation of such an oligomer and the availability of necessary precursors thereof.
From the above description oE Z ~nd 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 Z or Z' is, the fluorine content (the locus of which is Rf) is in the aforementioned limits set forth in the above description, and in general the total % and Z' content of the oligomer is preEerably less than 10 weight percent of the oligomer.
The monovalent terminal organic radical, s, is one which is covalently bonded through Z', to the poly~oxyalkylene) radical.
Though 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's 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 ~5 Chemistry," Sorenson and Campbell, 2nd ed., Interscience Publishers, (1968). rlasses oE representative oxyalkylene use~ul in this invention include polyesters, polyurethanes, polyepoxides, polyamides and vinyl polymers such as polyacrylates 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 ~iacrylate or mixtures thereof. As an example, a ~luoroaliphatic acrylate, Rf-R"-02C-CH=CH2 (where R" is, for example, sulfonamidoalkylene, carbonamidoalkylene, or alkylene), -16- "i~ fI 60557-2678 e-g-~ C8F17SO2N(C4Hg)CH2CH2O2CCH=CH2~ can be copolymerized with a poly(o~yalkylene) monoacrylate, CH2=CHC(o)(R3)XoCH3, to produce a polyacrylate oxyalkylene Further description of fluorochemical oxya]kylenes useful in this invention will be omitted in the interest of brevity since such compounds and their preparation are known, said U.S. Patent No. 3,787,351 and U.S. Patent No. 4,289,892.
The amoun-t of each component (a) and (b) can vary over a broad range, and will be selected to provide the desired 1~ balance of properties on the treated fiber of finished articleO
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 com-position of (a) and (b), as well as the application procedures used. Laboratory evaluation will often be a good indicator of appropriate relative amounts of components (a) and (b) to be used for obtaining the desired performance in commercial application-.
Generally, the relative amounts of components (a) and (b) fall within the following ranges:
Weight percent of fluorochemical solids in blend ComponentBroad Range Preferred Range (a) 60-99 70-95 (b) 1-40 5-30 -16a- ~ 60557-2678 The blends of this invention can be obtained by mi~ing (1) an organic solven-t solution or aqueous dispersion of the fluorochemical guanidine 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 the blend, the emulsification may be performed on -17~
the above organic solvent-containing blends, or individually emulsified comopnents may be blended (by simple mi~ing techniques) as either solvent-containing or solvent~free emulsions. In the preparation of said emulsions it is generally beneficial to employ cationic fluorochemical surfactants (i.e., C~F17SO2N(H)C3H6N(CH)3Cl) along ~ith hydrocarbon non-ionic surfactants (i.e., "Tween 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 textiles include those made Erom 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 such or in an aggregated form, e.g. yarn, tow, web, or roving, or the ~abricated 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 Eluorochemical blends as organic solutions or 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. (If desired, such known fluorochemicals can be used in conjunction with the -Eluorochemical blends, as will be shown below.) ~or example, the Eluorochemical treatment can be by immersing the fibrous 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 ~ ~rade ,nar~

t:$~

~inishing, and then drying the treated substrates if solvent is present. I~ desired, the fluorochemical blend can be co-applied with conventional fiber treating agents (or adjuvants), e.g. antistatic agents or neat oils (non-aqueous fiber lubricants).
In the manufacture of synthetic organic fibers (see, for example, the review article in Kirk-Othmer, Encyclopedia of Polymer Science and Technology, _, 374-404, 1968), the first step that normally ~akes 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 l; treat such textile Eibers, e.g. nylon 6, with the fluoro-chemical blend of this invention in conjunction with the spin finish being applied to such textile ibers.
Fiber finishes are generally produced in the form oE dilute aqueous emulsions or as an oil ("neat oil") which principally contains said lubricant and antistatic agant as well as emulsifier (surfactant) and may also contain materials such as bacteriocides and antioxidants.
Representative lubricants include mineral oils, waxes, vegetable oils (triglycerides) such as coconut oil, ~5 peanut oil, and castor oil, synthetic oils, such as esters, polyoxyethylene derivatives of alcohols and acids, and silicone oils.
The antistatic agents, emulsi~iers, and sur-factants incorporated into the fiber finish are selected from simllar chemical classes, which include:
(a) anionics, such as fatty acid soaps, sulfated ve~etable oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as Eatty amines, quaternary ammonium compoundsl and quaternary phosphonium compounds; 5 (c) nonionics, such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acids, and ethoxylated fatty amides; and f~

~d) amphoterics, such as ~etaines, amino acids and their salts.
The preferred mode oE 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 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 1600 ppm fluorine based on the weight of the fiber. Such additions to the con~entional fiber finish can be carried out without sacrificing or adversely affecting typical requirements ~hat conventional fiber finishes must meet, namely lS lubrication, thermal stability, low fuming at elevated temperature, and wet~ing for fiber dyeability (color addition). The conventional finish components of the fiber finishes containing the fluorochemical blends of this invention can be removed in a conventional manner after the ~0 ~iber is manufactured in Eabric form, e.g., carpets and upholstery fabrics. The fluorochemical blends withstand the typical conditions encountered during fiber and yarn processing and also survive the more severe processing conditions which the greige goods encounter such as ~5 scouring and dyeing, and the finished goods encounter, such as washing, steam cleaning, and dry cleaning. The Eluorochemical blends do 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 ~inished 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. ~uch methods include the use of either (a) a revolving ceramic cylinder, i.e., kiss-roll, which is partially immersed in a 7f~

pan containing ~he 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 generally 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~fore or after them). Solubilizing aids, such as "Carbitol" or "Cellosolve" solvents, can be added to the inish to enhance solubility of the fluorochamical blends in the neat oil finish.
Representative fluorochemical guanidines of this invention having the general formula IV are shown in Table 1.

R-Q-A(NH-I=N-A)n-Q-R IV
~2-N-R2 ~ ~~ i~

TABLE_ Canpound No . * R- Q A NR2X2 C8F17--~o2N(c2H5)c2H4ocol`lHC6~4CH2C6H4 N(C4~9)2 2 C8Fl7~so2~(c2Hs)c2H4ocoNH C6H~CH2C6H4 N(iC3H6)2

3 C8Fl7~so2N(c2H5)c2H4ocoNH C6H4cH2c6H~ N(C2Hs)2

4 C8Fl7-so2N(c2H5)c2H4o~oNH C6H3(CH3) NHCM(CH3)2 S C8F17 `SO2N(c2H5)c2H4Oco~l C6H3(CH3) NHCl2~25 6 C8Fl7~so2N(c2H5)c2H4ocoNH C6H4CH2C6H~ N O

7 C8Fl7-so2N(c2Hs)c2H4ocoNH C6H4CH2C6H4 ~ (CH3)2 C8F17 S02N(C2H5)C2H40cONH C6H3(CH3) NHC3H6Si(OMe)3 9 C8Fl7 ~so;~N(c2H5)c~H4ocoNH C6H4CH2C6H4 N~ J NS02C8F17 (CH3)2CHcH2 OCO~I C6~l4CH2c6H4N~ NsO2c8Fl7 11 C8F17 So2N(c2H5)c2H4ocoNH C6H4CH2C6H4 ~03SC8F17 12 C8F17 SO2N(C4H9)c2H4OcoNH C6H4CH2C6H4 N(C4Hg)2 13 C8F17 - C2H40CNH C6H4CH2C~H4N(C4H9)2 14 C8F17 ~C2H40CONH C6H3(CH3) N(C4H9)2 * For all compounds listed, n has an aver~e value o~ 2, except for cc~pound no. 4, where n has a value of about 1.8, Representative fluorochemical oxyalkylenes use:Eul as component (b) in the fluorochemical blends of this invention are shown in Table 2. Generally the preparation of the fluorochemical oxyalkylenes results in products which comprise mixtures thereo, the lengths oE the ~5 fluoroaliphatic radical, and the poly(oxyalkylene) moiety varying and the subc.cripts denotin~ the number of carbon atoms of the former and denoting the number of oxyalkylene units in a poly(oxyalkylene) segment being in both cases 3 ~" ~7 ~

avera~e numbers, and in this speci~ication, e.g. Table 2, those subscripts should be understood as having such average values, unless otherwise in-licated.

5 1. C8F17SO2N(c2Hs)cH2cO2(c2H4o)l5H
2. C~Fl7so2N(c2H5)c2H~lo(c2H4o)l4H
3. CgFl7c2H4o(c2H4o)l5H
~( C2H40 )mH
4, C8F17S2N ~ (m+n = 25) ( c 2H40 ) nH
5. C8Fl7so2N(c2H5)c2H4o(c3H6o)8H
.~ 6. C8~17C2H45lHcO2(c3H6O)mH (m~n = 20) CH2C02(C3H60)nH

Representative fluorochemical oxyalkylene polyacrylates useful as component (b) in this invention are those made by copolymeri~ing any of the fluorochemical acrylates of Table 3 with any of the fluorine-free lS poly(oxyalkylene) monomers of Table 4 1. C8F17S02N(CH3)CH2CE1200CCH=CH2, 2. C6F13c2H4Oocc(cH3)=cH2 3. C6F13C2H4SC2H4OOCcH=cH2 ~0 4. CgF17c2H4Oocc(cH3)=cH2 5- C8Fl7c2H4N(cH3)c2H4oocc(cH3)=cH2~

6. C2FsC6FlocH2ooccH=cH2

7- C7F15CH2CCH=CH2

8. C7Fl5coN(cH3)c2H4ooccH=cM2~

9. (CF3)2CF(CF2)6CH2CH(OH)CH2OOCCH-CH2-CH2,

10. (cF3)2cFoc2F4c2H4ooccH=cH2~

11- C8F17C2H4S02N(C3H7)C2H400CCH=CH2,

12. C7FlsC2H4CONHC4H~OOCCH=CH2, --23~

13- C3F7(fFcF2o)2cFcH2ooccH=c~l2r 1~. C7Fl5coocH2c~cH3)2cH2oocc(cH3)=cH2~
15- C8F17S02~(C2H5)C~HgOOCCH=CH2, 160 (C3F7)2c6H3s02N(cH3)c2H4ooccH=
CF2CF2~
5 17- C2F5C ~ ~ NC2F~CON(CH3)C2H400CCH=CH2, 1~, C6Fl7cF=cHcH~N(cH3)c2H4ooccH=cH
19- C8F17S02N(C4Hg)C2H40COCH=CH2 200 C8F17S02N(C2H5)C2H~OCOCH(CH3)=CH2 10 C 2 CHC02(C2H40)10(C3H~o)22(C2H~0)9C2H402CCH=CH2 2. CH2=CHc02(c2H4o)l7~
3. CH2=C~cH3)cONH(c3H6)44H
4' CH2=C(CH3)c02(c2H40)90Coc(cH3)-cH2 5, Hs(c2H4o)23(c3H6o)35(c2H4o)22c2H4sH

Other compatible optional comonomers, e.g. butyl acrylate, acrylonitrile, etc. which need not contain fluoroaliphatic radicals, can be copolymerized with the fluorochemical acrylate and oxyalkylene comonomers in amounts up to above 25 weight percent Weight ratios of 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 content of the resulting copolymer is in the desired range of 5 to 40 ~eight percent.
Objects and advantages of this invention are illustrated in the following examples.

2~

Example 1 In a 2-liter, 3-neck flask, fitted with a mechanical stirrer, condenser, thermometer, addition funnel and electric heating mantle, was placed 375 g (1.5 moles) 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 stirriny and heating continued for an additional 3 hours.
1~ To this s~irred solution, containing fluoro-chemical urethane isocyanate and unreacted diisocyanate, was added 7.4 g camphene phenyl phosphine oxide, ClOH16POC6H5r a carbodiimide-Eorming catalyst, and the reaction mixture was stirred and heated at about 80~C for 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 resulting solution of fluorochemical carbodi-imide was then allowed to cool to room temperature and added over a one hour period to a stirred solution of 129 g (l.Q mole) dibutylamine in 129 g MEK maintained at 30C.
The resulting reaction mixture was heated for one hour at 50C to complete the conversion of essentially all carbodiimide groups to guanidine groups as indicated by IR
~5 analysis. The solid fluorochemical guanidine product (represented by structure 1 in Table 1), isolated in quantitative yield by evaporation of the ~EK solvent under reduced pressure, was found to have a ~elting range o~
75-83C.

E~3~
Following the general procedure of Example 1, except employing the reagents in Table 5 and molar concen-trations indicated in Table 6, the other fluorochemical guanidines of Table 1 were prepared. The reagents in Table 5 are identified by symbols, e.g. A-l, etc., for later reference.

- 2 S ~

Alcohol Rea~nts A--l C 8 F l 7 SO 2 N ( C 2 H 5 ) C 2 H 4 0~

A-2 C8Fl7S02N(C4Hg)C2H40H

A-3 Cg~l7C2H40H

A--4 ( CH3 ~ 2CHCH20H

I socyanates MDI OCN- ~>--CH2- ~ -NCO

TDI ----~CH 3 OCN NCO

Imino Rea~ents I--l ~ C4Hg ) 2NH

I-2 ( iso-C3H7 ) 2NH

I--3 ( C2H5 ) 2NH

I -4 ( CH3 ) 2CHNH2 lS I--5 C12H25NH2 I-6 ~IH
\
I -7 ( CH3 ) 2NNH2 I-8 (CH30) 3siC3~16NH2 r~
I-9 C8F17S2N ~ NH

I-10 C8F17S3 ~ NH2 Con- Reactants (moles)**
pound Alcohol Imino Ex. No used* Rea~ent Isocyanate Reagent 2 2 A-l MDI I-2 3 3 A-l MDI I-3 4 4 A-l (2) TDI (2.8) I-4 (1.8) A-l TDI I-5 6 6 A-l MDI I-6 7 7 A-l MDI I-7 8 8 A-l TDI I-~
9 9 A-l MIM I-9 11 11 A-l M M I-10 12 12 A-2 MDI I-l 13 13 A-3 MDI I-l

14 14 A-3 TDI I-l ~0 * The numbers correspond to the fonmula numbers of Table 1.
**All alcohol/isocyanate/imino reagent molar ratios were 2/3/2, except as indicated for Example 4~

This example describes the treatment c~f a nylon 6 carpet fiber with a blend of fluorochemical guanidine and fluoroche~ical oxyalkylene of this invention dissolved in a spin finish lubricant and the testing of the dyed carpet prepared from the treated ~ibers.
The oil repellency (OR), water repellency ~WR) and walk-on soil resistance ~WOS) were determined on the treated samples.

-27-^
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~
Treated carpets which are penetrated by or resistant only to a 100 percent water/0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 100/0, whereas treated fabrics resistant to a 1~ 0 percent water/100 percent isopropyl alcohol mixture (the most penetra~ing 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 o~ 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.
~0 The oil repellency test is also one which is oeten used for this purpose. The oil repellency of treated carpet and textile samples is measured by AATCC Standard Test 118-1978, which test is based on the resistance o~
treated fabric to penetration by oils of varying sur~ace . 5 tensions. Treated fabrics resistant only to "Nujol", a brand o~ mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of a. Other intermediate values are determined by use of other pure oils or miY~tures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric after 10 seconds contact rather than the 30 seconds contact of the Standard Test. Higher numbers indicate better oil repellency. In general, an oil repellency of 2 or greater is desirable.
The soil resistance o~ treated and untreated (control) carpet was determined by exposure to pedestrian traffic according to AATCC Test Method 122-1979, the exposure site beiny a heavily travelled indus-trial area for an exposure of about 15,000 "traffics". The samples are reposi-tioned periodically to insure uniform exposure and are vacuumed every 24 hours during the test and before visual evaluation. The evaluation employed the fol-lowing "Walk-On-Soiling" (WOS) rating system:
WOS Rating Description O equal to control +1~2 slightly better (+) or worse (-) than control +1 impressive difference compared to control ~1-1/2 very impressive difference compared to control ~2 extremely impressive difference compared to control A neat oil spin finish consisting of 13.1% fluorochemical guanidine of formula 1 of Table 1, 5.0% fluorochemical poly(oxyalkylene)/acrylate copolymer (a 30~30/40 terpolymer prepared like Example 1 of United States Paten-t No. 3,787,351) composed of C8F17S2N(C4H9)C2H4CCH=CH2~ CH=CHCO2(C2H4O)lo(C3H6O)22(C2H4O)g~
C H O CCH=CH2, and CH=CHCO2(C2H4O)10(C3H6O)22(C2 4 )9 2 4 oil-based fiber lubricant, and 35.7% butoxyethoxyethanol was applied by a metered slot applicator to freshly melt-extruded, undrawn yarn of nylon 6 carpet denier fibers. The thus treated yarn was continuously drawn and texturized, plied to form a two-ply yarn, heat set at 190C for one minute, and then made into cut pile carpet. The carpet was acid dyed by three different processes, dried, and then evaluated for oil and water repellency, walk-on-soil resistance, and reten-tion of fluorochemical treatment (as measured by fluorine analysis) through the dyeing process. The runs are summarized and the testing results are in Table 7,Runs 1-3. Comparative Runs, Cl-C3, utilized a spin finish of the same composition except that the fluorochemical poly(oxyalkylene) component was omitted and 5.0%

additional butoxyethoxyethanol was added ins-tead.

Amount Fluorine on Carpet Before After Retention RunDyeing, ppmDyeing, ppmof Fluorine, % OR WR WOS
1 425 345a 81 3.550/50 +1-1/2 2 425 335b 79 3 50/50 +1 3 425 325 77 4 50/50 ~ 1/2 C-l 430 420a 98 2 70/30 0 C-2 430 400b 93 2.540/60 +1 C-3 ~30 350c 81 2.540/60 0 a. Continuous dye process was used for dyeing.
b. Bec~ dye (batch) process was used for dyeing.
. Continuous pad dye process was used for dyeing.
The test results show -that the fluorochemical blend of this invention, Runs 1-3, imparted desirable oil and water repellency and soil resistance to the nylon fiber and the fluorochemical was retained a-t high levels through dyeing.
The results also show significantly better OR and WOS values for Runs 1-3 compa-r~d to Runs C-l, C-2, C-3 (even at the lower fluorochemical retention level on ~0 fiber), den~onstrating the value of the fluorochemical poly(oxyalkylene) component in the finish of this invention.
Example 16 In this example, two different rainwear fabrics were treated by a padd-ing operation in Runs 1, 2 with an aqueous dispersion of a blend of 20 parts of the fluorochemical guanidine of formula 6 of Table 1 and 1 part of the 30/30/40 terpolymer of Example 15. An aqueous dispersion of said ~luorochemical quanidine was used in comparative Runs C-l and C-2. The treated fabrics were dried at 150C for 10 minutes. The treated rainwear fabrics were evaluated again aEter 5 launderings (5L) and dry cleaning (DC), The 0~ test used was the above-described AATCC Standard Test 118-1978, the contact ti~e before observation being the specified 30 sec., an OR value of 3 or greater being particularly desirable.
The water spray rating (SR) is measured by AATCC
1~ Test Method 22-1979. The spray rating is measured using a O 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 ~ 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 2SC. After removing excess solvent in a wringer/ samples were dried at 70C for ~5 10 minutes, then pressed on each side for 15 seconds on a flat-bed press maintained at 154C.
The runs are summarized and the test results are given in Table 80 Table 8 Fluorochemr Initial 5L DC _ Run ical Used Fabrica ~ SIsC % SOFb OR SR OR SR OR SR
1 Blend A 1.01 0.21 6 60 4 60 2 50 2 Blend B 0.23 0.21 5 70 4 70 2 70 C-1 FC-G 6* A 0.96 0.20 4.5 60 3.5 70 1.5 50 C-2 FC-G 6* B 0.22 0.20 5 75 3 70 1~570 C-3 None A 0 0 0 C-4 None B 0 0 0 0 * FC-G 6 is the fluorochemical guanidine having formula 6 of Table 1 a. Fabric A was 100% nylon taffeta.
Fabric B was 100% woven polyester.
b. ~ SOF means % fluorochemical solids on Eabric.
c. % SIB means % fluorochemical solids in bath.

The data of Table 8 show useful oil and water repellency was obtained Eor the rainwear, though laundering and dry cleaning decreased the oil repellency. Fur-thermore, the oil and water repellancy after laundering or dry cleaning of the fabrics treated with the blend (Runs 1, 2) is better than that of fabric treated with just the fluorochemical guanidine (Runs C-l, C-2).

Various modifications and alterations oE this invention will become apparent to those skilled in the art without departing from the scope of this invention.

Claims (14)

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

1. A composition for imparting oil and water repellency to fibrous substrates comprising a blend of: (a) 60-99 weight percent of a normally solid, water-insoluble, fluorochemical guanidine composition which is a fluoroaliphatic radical-containing substituted guanidine 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 substituted guanidino moieties, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups, with the provisos that when only one guanidino moiety is present, and only two organic substituents are in said guanidino moiety, said substituents must be on different nitrogen atoms and that said fluorochemical guanidine composition contains about 20 to 70 weight percent carbon-bonded fluorine; and (b) 1-40 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 or combinations of said groups, said fluoroaliphatic radical-containing poly(oxyalkylene) composition contains about 5 to 40 weight percent carbon-bonded fluorine.

2. A composition according to claim 1 wherein said fluorochemical guanidine compounds are represented by the general formula where n is 0 to 20, x is 0 or 1, A is a divalent organic linking group which can contain said fluoroaliphatic group, Rf, R1 and R2 are hydrogen atoms, said Rf, or an organic radical, the two R2 groups of a guanidino moiety can be bonded together to form a cyclic structure with the adjacent N-atom of said guanidine moiety, Q is a divalent hetero atom-containing or organic linking group, or combina-tion thereof.

3. A composition according to claim 1 wherein said fluorochemical guanidine is represented by the formula where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4-, R2-N-R2 is -N(C4H9)2, , or -N(iso-C3H7)2, and n is 2.

4. 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 anotehr 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.

5. A composition according to claim 1 wherein said fluorochemical poly-(oxyalkylene) is the copolymer of C8F17SO2N(C4H9)C2H4O2CCH=CH2 and CH2=CHCO2-(C2H4O)10(C3H6O)22(C2H4)9C2H4O2CCH=CH2.

6. A composition according to claim 1 wherein said fluorochemical guani-dine is represented by the formula where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4-, R2-N-R2 is -N(C4H9)2, , or -N(iso-C3H7)2, and n is 2, and wherein said fluorochemical poly(oxy-alkylene) is the copolymer of C8F17SO2N(C4H9)C2H4O2CCH=CH2 and CH2=CHCO2(C2H4O)10-(C3H6O)22(C2H4O)9C2H4O2CCH=CH2.

7. A composition according to claim 1 wherein said fluorochemical poly-(oxyalkylene) is the terpolymer of C8F17SO2N(C4H9)C2H4OCOCH=CH2, CH=CHCO-(C2H4O)10(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH=CHCO2(C2H4O)10(C3H6O)22(C2H4O)9-C2H4OH.

8. A composition according to claim 1 wherein said fluorochemical guani-dine is represented by the formula where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4-, R2-N-R2 is -N(C4H9)2, , or -N(iso-C3H7)2, and n is 2, and wherein said fluorochemical poly(oxy-alkylene) is the terpolymer of C8F17SO2N(C4H9)C2H4OCOCH=CH2, CH=CHCO2(C2H4O)10-(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH=CHCO2(C2H4O)10(C3H6O)22(C2H4O)9C2H4OH.

9. A fiber finish comprising an organic solution or aqueous dispersion comprising the composition of claim 1.

10. The fiber finish according to claim 9 further comprising a fiber lubri-cant.

11. A method for imparting oil and water repellency to a fibrous substrate, which comprises treating the surface thereof with the fiber finish of claim 9.

12. 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 10.

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

14. A fibrous substrate according to claim 13 wherein said substrate is nylon carpet fiber.