JPH0556385B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to the treatment of fibrous substrates such as textiles, paper and leather with fluorochemical compositions to impart oil and water repellency, and to the treated substrates. In another aspect, the present invention relates to treating carpet fibers with a finish comprising a composition containing a fluoroaliphatic group-containing compound to impart oil and water repellency and sludge resistance to the fibers. In another aspect, the present invention relates to compositions containing fluorochemical aliphatic groups that can be used in such treatments and their preparation. In the industrial manufacture of textiles such as carpets and apparel and other fibrous substrates such as paper and leather, fluoroaliphatic groups (referred to as ``R _f '') are used to impart oil and water repellency to the surface of the substrate. It is common practice to treat substrates with fluorochemicals containing fluorochemicals (often represented by the symbol). Fluorochemicals of this type and their application to fibrous substrates are described in various known publications, such as U.S. Pat. No. 3,329,661 (Smith et al., Smith et al.
al), Specification No. 3458571 (Tokoil),
Specification No. 3574791 (Sherman et al., Sherman
et al), Specification No. 3728151 (Shearman et al.,
Sherman et al), No. 3916053 (Sherman et al), No. 4144367 (Landucci), No. 3896251 (Landucci), No. 4024178 (Landucci), No. 4165338 (Katsushima et al.), No. 4190545
Specification (Marshall), same no.
Specification No. 4215205 (Landucci), same no.
Specification No. 4013627 (Temple), same no.
Specification No. 4264484 (Patel), No. 4029585
Specification No. 3462296 (Reynolds et al), Specification No. 3462296 (Reynolds et al), No.
Specification No. 4325857 (Cyanpaneria et al.
Fluorochemicals and their Industrial Applications, edited by Champaneria et al. and R.E. Banks.
Ellishoughts, West Sussex, England, pp. 226-230, 1979 (Banks, RE,
Ed. “Organo−fluorine Chemicals and their
Industrial Applications”, Ellis Horwood,
Ltd., Wes Sussex, England, 226−230 (1979))
It is described in. Although some fluorochemicals are versatile and many are commercially available, some are relatively expensive to prepare and apply, others are difficult to apply, and many are commercially available. Others are not permanent or do not adequately provide the desired properties. Traditionally, fluorochemical compositions have been applied commercially as a top coating to finished textile products such as carpets. Recently, several fluorochemical compositions have been commercially applied to textile fibers or yarns during their manufacture before being woven or processed into finished products. However, some of these fluorochemical compositions have limitations such as incompatibility or reactivity of the fluorochemical with fiber finishing components such as lubricants, and the durability of the fluorochemical on treated fibers to dyeing and other fiber manufacturing operations. Success has been limited for a variety of reasons, including lack of water, oil, and sludge resistance in the finished product. The object of the present invention is to provide (a) a fluoroaliphatic group-containing compound that imparts oil and water repellency, such as a fluoroaliphatic group-containing carbodiimide (hereinafter often abbreviated as fluorochemical carbodiimide); ester (hereinafter referred to as fluorochemical ester) or fluoroaliphatic group-containing carbonylimino compound (hereinafter often abbreviated as fluorochemical carbonylimino compound) and (b) aliphatic group-containing poly(oxyalkylene).
(hereinafter often abbreviated as fluorochemical oxyalkylene), which are useful for treating textile fibers and other fiber substrates to impart oil and water repellency. It is to provide. Another object of the invention is a blend of a fluorochemical carbodiimide, a fluorochemical carbonylimino or a fluorochemical ester compound with a fluorochemical oxyalkylene, in combination with, or as part of, a fiber finishing agent, such as a spin finishing lubricant. It is an object of the present invention to provide an ingredient that can be used to treat textile fibers, is compatible with its fiber finishing agents, and does not interfere with normal textile processing steps. Another object of the present invention is to provide a fluorochemical-treated textile fiber that retains a high percentage of fluorochemicals in the fibers during the fiber processing and dyeing process and has permanent water and oil repellency and sludge resistance. . Yet another object of the invention is a blend of a fluorochemical carbodiimide, a fluorochemical carbonylimino or a fluorochemical ester compound with a fluorochemical oxyalkylene, which can be applied to textile substrates such as textile fibres, filaments, yarns or finishes. such as those which can be used in the form of organic solvent solutions or aqueous dispersions to treat textile products such as carpets and other textile substrates such as paper and leather to impart oil and water repellency. There is a particular thing. In summary, the invention provides: (a) R ¹ (Q) _x (N=C=NA) _o -N=C=N(Q) _x R ¹ or A'[NHCOY(Q) _x R ² ] _r [In each formula, A is an alkylene group having 2 to 20 carbon atoms, an aralkylene group having up to 20 carbon atoms, an arylene group, a poly(oxyalkylene) group, and combinations thereof {these The group may include a hetero moiety and a fluoroaliphatic group R _f . }, R _f represents a fluorinated group having 3 to 20 carbon atoms and containing 40 to 78 wt. represents an aliphatic stable inert non-polar monovalent moiety, R ¹ is a hydrogen atom, R _f or selected from aliphatic groups, aromatic groups, aralkyl groups, fluoroaliphatic groups and combinations thereof. , and represents an organic group which may contain a heteroatom-containing moiety; at least one of A or R ¹ contains R _f and Q is a divalent heteroatom-containing group or an aliphatic group, an aromatic group, an aralkyl group; represents an organic linking group selected from groups, fluoroaliphatic groups and combinations thereof and which may contain a heteroatom-containing moiety, A' represents the residue of an organic isocyanate, and Y represents -N-, - represents O- or -S-, ^R2 is selected from a hydrogen atom, a fluoroaliphatic or aliphatic group, an aromatic group, an aralkyl group, a fluoroaliphatic group and combinations thereof, and a heteroatom-containing moiety at least one of R ² represents a fluoroaliphatic group, x represents 0 or 1, n represents 0 to 10, and r represents an integer of 2. ]; and ( _{b )} a _normally solid water-insoluble fluoroaliphatic group-containing compound _which can _be represented by ^the following _formula : Z [(R ³ ) _y Z′B′] _t } _w [In each formula, R _f is an oleophobic or hydrophobic compound having 3 to 20 carbon atoms and containing 40 to 78% by weight of fluorine atoms. Z represents a valent bond or polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphooxy and amine R _f and (R ³ ) _y represent a covalent linkage selected from one or more linking groups selected from the following, and (R ³ ) _y represents a poly(oxyalkylene) moiety; , R ³ represents oxyalkylene having 2 to 4 carbon atoms, y is 8 to 90
, B represents a hydrogen atom, acyl group, alkyl group, or aryl group that makes Z′B of the (R ³ ) _y Z′B moiety 50% by weight or less, and B′ represents B or a valence bond. , with the proviso that at least one B' represents a Z-bond (R ³ ) valence bond linking _{the y} group to another Z, and Z' represents a valence bond or a polyvalent aliphatic, polyvalent aromatic, oxy- , thio, carbonyl, sulfone, sulfoxy, phosphoxy and amine, B or B′ and (R ³ ) _y represent a covalent linkage together; s represents 1 to 27, t represents 1 to 1.4, and w represents 1 to 30. ] One or more normally liquid or low-melting solid water-soluble or dispersible fluoroaliphatic group-containing poly(oxyalkylene) compounds represented by: Some of them are new (i.e., when the polar part is a nitrogen-containing polar group)
Fluorochemical formulations of certain components (a) and (b) may be used in manufacturing textile substrates such as textile fibers (or filaments) or in finished or manufactured fibers such as carpets, paper and leather. It is useful to treat substrates in the form of organic solutions or aqueous dispersions to impart oil and water repellency to their surfaces. Such fluorochemical carbodiimides (component (a) of the above formulation) have the general formula: R ¹ (-Q) _x (-N=C=N-A-) _o -N=C =N(-Q -) _x R ¹ , the general formula encompassing individual compounds in the general formula or representing a mixture of compounds as resulting from the reaction used to prepare the compound. Fluorochemical carbodiimides useful in the present invention and methods for producing the same are disclosed in U.S. Pat. No. 4,024,178.
[Landucci], which is incorporated herein by reference. In the formula, "n" represents a number from 0 to 10 and most preferably from 0 to 5 (when the formula represents a mixture) or an integer (when the formula represents a single compound), and "x" represents 0 or 1. represent
Each Q represents the same or different divalent linking group. A represents a divalent organic linking group which can contain a fluoroaliphatic group R _f , and each A represents the same or different. R ¹ of each
represent the same or different groups, H, R _f and monovalent terminal organic groups, such as alkyl groups, cycloalkyl groups, aryl groups and combinations thereof, such as aralkyl groups, -O-, -S-,

【formula】

[Formula] and -CO- and preferably active (or isocyanurate-reactive) hydrogen atoms (e.g. with isocyanurate) under urethane bond forming conditions, i.e. Hydrogen atoms of groups such as mercapto groups, amino groups, carboxyl groups and aliphatic hydroxyl groups that can easily react)
selected from terminal organic groups with no Generally R ¹ contains up to 18 carbon atoms. When R ¹ represents R _f above, the adjacent sub-symbol x of Q is limited to 1 and cannot represent 0 because R _f cannot directly bond to the nitrogen atom of the carbodiimide group.
At least one R _f group is present in one or more of R ¹ and A in certain compounds. In the above general formula, when n represents 1 or a larger number, the divalent organic linking group A connects consecutive carbodiimide moieties. Linking group A
The implementation is an alkylene group having from 2 to about 20 carbon atoms, such as an ethylene group, an isobutylene group,
Hexylene and methylenedicyclohexylene groups, aralkylene groups having up to 20 carbon atoms, such as -CH ₂ C ₆ H ₄ CH ₂ - and -
_C6H4CH2C6H4- , _arylene group, _{e.g. tolylene group, -C6H3 ( CH3 )} -, _poly (oxyalkylene)
a group, for example y represents 1 to about 5 -
( _{C2H4O ) yC2H4-} and various combinations _of these groups _. Such groups also include -S- and

It can also contain other hetero moieties other than -O-, including [Formula]. However, it is preferable that A does not contain the group containing the active hydrogen atom. Group A can represent the residue of an organic diisocyanate which can lead to a carbodiimide moiety. That is, A can represent a divalent group obtained by removing an isocyanate group from an organic diisocyanate. Suitable diisocyanate precursors are, for example, single tolylene-2,4-diisocyanate, methylene bis(4-phenylene isocyanate) and mixtures thereof, or single diisocyanates and organic diols or It is a complex compound formed by reaction with an organic polyol. Other isocyanates can also be used as starting materials. Some of these are described, for example, in US Pat. No. 4,174,433. Typical A groups include -
CH ₂ C ₆ H ₄ CH ₂ C ₆ H ₄ CH ₂ −, −C ₆ H ₃ (CH ₃ )−,
C ₆ H ₁₀ CH ₂ C ₆ H ₁₀ −, −(CH ₂ ) ₆ −, −
C ₆ H ₄ CH ₂ C ₆ H ₄ − and C ₈ F ₁₇ SO ₂ N
[C ₂ H ₄ OCONHC ₆ H ₃ (CH ₃ )—] ₂ is included. The fluorochemical carbodiimides used in the present invention are generally and preferably derived from diisocyanates, but triisocyanates such as
It can also be derived from OCNC ₆ H ₄ CH ₂ C ₆ H ₂ (NCO) CH ₂ C ₆ H ₄ NCO. The mixture of di- and tri-isocyanates provides the desired solubility and dispersibility of the branched but still linear fluorochemical carbodiimide. The R ¹ -Q group is preferably a group derived from an isocyanate compound and is an aliphatic group such as C ₆ H ₁₃
-, aromatic groups e.g. _C6H5- , _aralkyl groups _{e.g. C6H5CH2-} , fluoroaliphatic _groups e.g.
C ₆ F ₁₃ CH ₂ −, C ₇ H ₁₅ CH ₂ OCONHC ₆ H ₃ (CH ₃ ) −
and _{C8F17SO2N ( CH3 )}
C ₂ H ₄ OCONHC ₆ H ₄ CH ₂ C ₆ H ₄ − can be represented. The organic R ¹ -Q group can have a variety of other structures, including moieties containing heteroatoms, such as -O-, -S-, and

It can contain [Formula]. However, like the A group, it is preferable that there is no group containing the above-mentioned active hydrogen. The fluoroaliphatic group R _f has the meaning defined above and can represent straight-chain, branched and, if sufficiently large, cyclic groups or combinations thereof, such as an alkylcycloaliphatic group. This backbone chain may contain heteroatoms bonded only to carbon atoms, such as catenary oxygen atoms, hexavalent sulfur atoms, and/or trivalent nitrogen atoms, such heteroatoms being of the fluorocarbon moiety of R _f and does not impair the inert nature of the R _f group. The reason that the number of carbon atoms in R _f should not exceed 20 is that larger groups usually have less efficient use of fluorine atoms than smaller R _f groups. Also, larger bases generally become less soluble in organic solvents. in general
R _f has 3 to 20, preferably 6 to about 12 carbon atoms and contains 40 to 78% by weight, preferably 50 to 78% by weight of fluorine atoms. the terminal R _f group has at least 3 fully fluorinated carbon atoms, e.g. CF ₃ CF ₂ CF ₂ −;
And preferred compounds are those in which the R _f group is completely or substantially completely fluorinated, such as when the R _f group represents a perfluoroalkyl group C _o F _2o+1 . The function of the linking group Q in the formula is to link the R ¹ group to the nitrogen atom of the carbodiimide unit.
Q consists of a heteroatom-containing group, an organic group, or a combination of these groups, examples of which are -CH ₂
-, _-CH2CH2- and _-CH2CH ( _CH2- ) ₂ , polyvalent aromatic group, oxy group, thio group, carbonyl group, sulfone group, sulfoxy group, -N( _H3 )- _, sulfone Amide group, carbonamide group, sulfonamide alkylene group, carbonamide alkylene group, carbonyloxy group, urethane group, such as -
CH ₂ CH ₂ OCONH− and urea, i.e.
NHCONH−. The linking group Q for certain fluorochemical carbodiimides useful in the present invention is determined by the ease of preparation of such compounds and the availability of necessary precursors of the compounds.
It is specified. From the above description of Q, it is clear that the structure of this linking group can vary widely. However, as in R ¹ and A, it is preferable that Q does not have a moiety having the active hydrogen atom. The fluorochemical carbodiimide used in the present invention is usually preferably heated at a temperature of 40 to 150°C.
a solid with a melting point in the range (e.g. solid at 20°C)
It is. They are stored in ethyl acetate at 20°C at least
Preferably, it dissolves 10% by weight. Representative reaction routes for the production of fluorochemical carbodiimides used in the present invention are summarized below. The product denoted by ' is one of the above formulas. Route 1 2R ¹ −Q′−OH+2A(NCO) ₂ ――→ 2R ¹ −Q′−NCO+nA(NCO) ₂ ――――――――――――――→ ―――――――― ――――――→ Catalyst, -(n+1)CO ₂ R ¹ -Q (N=C=N-A) _o N=
C=N-Q-R ¹ ' Path 2 (n+2)A(NCO) ₂ catalyst――――――――――→ (n+1)CO ₂ OCNA-(N=C=N-A) _o N= C=N-ANCO+2R ¹ -Q
′−OH ――――――――――――→ R ¹ −Q (N=C=N−A) _o N=C
=N-Q-R ¹ ' Route 3 R-Q'-OH+B(NCO) ₃ ---→R-Q(NCO) ₂ R-Q(NCO) ₂ +B(NCO) ₃ +A(NCO) ₂ +R ¹ - QNCO Catalyst ----→ -CO ₂ Mixed Carbodiimide The mixture of fluorochemical carbodiimides used in the present invention is generally prepared for subsequent synthetic operations by adding a small amount of fluorochemical diurethane compound free of carbodiimide groups (e.g. 1
By-product R-Q'-OCONH-A-
NHCOO-Q'-R).
The amount of this by-product will vary depending on the manner of addition, the molar ratio of the reactants, and the relative reactivity of the isocyanate functionality. Preferred carbonylimino compounds for use in the present invention have the following formula: A'[NHCOY(Q) _x ^R2 ] _r , where ^R2 represents a group similar to ^R1 in the formula, and at least one R ² groups represent a fluoroaliphatic group R _f , Q and x have the same meanings as defined in the formula, r represents an integer from 1 to 2, and A′ is a residue of an organic isocyanate and an aliphatic group. represents an organic linking group having from 2 to 20 carbon atoms without isocyanate-reactive groups such as hydroxyl groups, and Y represents

[Formula] represents -O- or -S-. ). ^R2 ,
If there are a plurality of any of Q, Y, and x, they may be the same or different. For carbonylimino compounds containing fluoroaliphatic groups, the temperature is preferably 25°C or higher, more preferably
One having at least one major transition temperature above 40°C, and most preferably above 45°C.
If desired, the compositions of the invention can contain a carbonylimino or a mixture of carbonylimino compounds. Carbonylimino compounds for use in the present invention can be prepared by reacting organic isocyanates with fluoroaliphatic group-containing compounds having isocyanate-reactive hydrogen atoms. A preferred subclass of carbonylimino compounds of the formula are those in which Y represents -O-, ie, urethanes. Representative carbonylimino compounds of this preferred subclass are described in US Pat. No. 3,484,281. They are prepared by conventional urethane bond-forming reactions between fluoroaliphatic alcohols and organic isocyanates, preferably aromatic polyisocyanates. If desired, fluorine-free aliphatic alcohols, such as fatty alcohols, can be added to the reaction mixture used to produce such carbonylimino compounds. Representative reaction routes for producing the fluorochemical carbonylimino compounds used in the present invention are summarized below. Route 4 _r R ² (Q) _x YH+A′(NCO _{) r} --→ A′ [NHCOY(Q) _x R ² ] This includes those described in the prior art publications mentioned in . Representative reaction routes for the production of fluorochemical ester compounds used in the present invention are summarized below. _a R ¹ -Q-OH+R (COOH) _a Catalyst ---→ -H ₂ OR (COO-Q-R ¹ ) _a Representative for producing fluorochemical carbodiimide-carbonylimino or -ester used in the present invention R _f intermediates include: C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₅ H ₄ OH C ₈ F ₁₇ C ₂ H ₄ OH C ₇ F ₁₅ CH ₂ OH C ₇ F ₁₅ CON (C ₂ H ₅ ) C ₂ H ₄ OH C ₈ F ₁₇ C ₂ H ₄ SC ₂ H ₄ OH (CF ₃ ) ₂ CF (CF ₂ ) ₈ C ₂ H ₄ OH (CF ₃ ) ₂ CFOC ₂ F ₄ C ₂ H ₄ OH C ₈ F ₁₇ C ₂ H ₄ SO ₂ N(CH ₃ )C ₄ H ₈ OH C ₈ F ₁₇ SO ₂ N(CH ₃ )C ₃ H ₆ NH ₂ C ₈ F ₁₇ C ₆ H ₄ NH ₂ C ₈ F ₁₇ C ₆ H ₄ NCO C ₇ F ₁₅ CH ₂ NCO C ₈ F ₁₇ C ₂ H ₄ SH C ₇ F ₁₅ CON(CH ₃ ) C ₂ H ₄ SH Representative Organic isocyanates include: Tolylene-2,4-diisocyanate Hexamethylene diisocyanate Methylene bis(4-cyclohexyl isocyanate) Methylene bis(4-phenyl isocyanate) Xylene diisocyanate 1-Methoxy-2,4-phenylene diisocyanate 1- Chlorophenyl-2,4-diisocyanate p-(1-isocyanatoethyl)phenyl isocyanate Phenyl isocyanate m-tolyl isocyanate 2,5-dichlorophenyl isocyanate Hexyl isocyanate For producing fluorochemical esters by reaction with fluorochemical alcohols Typical carboxylic acids or anhydrides that can be used are adipic acid, citric acid, pyromellitic acid or their anhydrides and the like (see U.S. Pat.
3923715 and 4340749). Generally a fluorochemical-carbodiimide,
-The carbonylimino compound or -ester is approximately
It contains 20 to 70% by weight, preferably about 25 to 50% by weight of carbon-bonded fluorine atoms. If the fluorine content is less than about 20% by weight, it will generally require an impractically large amount of the fluorochemical-carbodiimide, -carbonylimino compound or -ester, whereas a fluorine content greater than about 70% by weight is desirable. This results in an unnecessary and uneconomical use of fluorine to obtain a surface texture of 1.0 and can also pose compatibility problems where the fluorochemical formulation is used as an organic solution. Fluorochemical oxyalkylenes, which are the other essential component (b) of the formulations of the present invention, are fluoroaliphatic polymers or oligomers (hereinafter, unless otherwise specified, "polymer" shall include oligomers) as follows: Formula and: (R _f ) _s Z [(R ³ ) _y Z′B] _t [(R _f ) _s Z [(R ³ ) _y Z′B′] _t ] _w [where R _f is a general formula represents a fluoroaliphatic group similar to that described in , Z represents a valence bond or a 1 selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphooxy and amine
selected from one or more linking groups,
R _f and (R ³ ) _y together represent a covalent linkage, (R ³ ) _y represents a poly(oxyalkylene) moiety, and R ³ is an oxyalkylene group having 2 to 4 carbon atoms. and y is at least 5, generally from 10 to 75, and an integer (when the above formula represents a single compound) or a number (when the above formula represents a mixture) which may range from 100 to 100 or more. ), B represents a hydrogen atom or a monovalent terminal organic group, and B' represents a group or valence bond represented by B, provided that at least one B' is a bond of _R3 group. represents a valence bond connecting Z and another Z to each other, Z′ is a valence bond or selected from polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy and amine 1
B selected from one or more linking groups
or B' and (R ³ ) _y together represent a covalent linkage, s represents an integer or number that is at least 1 and can be 25 or more, and t is at least 1 and 60 or more represents an integer or number that can be greater than 1, and represents an integer or number that can be 30 or more. ]. When there are multiple R _f groups in formula and, they may be the same or different. This applies to Z, Z', R ³ , B, B' and also to s, y and t in the formula. Generally, oxyalkylene polymers are about 5 to
It contains 40% by weight, preferably about 10 to 30% by weight of carbon-bonded fluorine atoms. If the fluorine content is less than about 10% by weight, an impractically large amount of polymer is generally required, while a fluorine content of more than about 35% by weight results in a polymer with too low a solubility to be effective. In the above poly(oxyalkylene) group (R ³ ) _y ; R ³ is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCH ₂ CH ₂ -, -
OCH ₂ CH ₂ CH ₂ −, −OCH(CH ₃ )CH ₂ − and −
OCH(CH ₃ )CH(CH ₃ )-, and the oxyalkylene units in the above poly(oxyalkylene) may be the same, as in polyoxypropylene, or may be heterogeneous, linear or branched. or as a mixture, such as in randomly distributed oxyethylene units or oxypropylene units, or in linear or branched blocks of oxyethylene units or oxypropylene units. 1
One or more catenary linkages can interrupt or be included in the poly(oxyalkylene) chain. When the catenary bonds have a valency of three or more, they provide means for obtaining branched chains or oxyalkylene units. The poly(oxyalkylene) groups in the polymer may be the same or different, and they may be pendant. The molecular weight of the poly(oxyalkylene) group can be as low as 220, but is preferred from about 500 to 2500 and even higher, such as 100,000.
to 200,000 or higher. The function of the linking Z and Z' is to covalently bond the fluoroaliphatic group R _f , the poly(oxyalkylene) moiety (R ³ ) _y , and the groups B and B' together into the oligomer. For example, Z and Z' can represent valence bonds when a carbon atom of the fluoroaliphatic group is directly bonded or linked to a carbon atom of the poly(oxyalkylene) moiety. Z and Z' each have one or more linking groups, such as polyvalent aliphatic groups and polyvalent aromatic groups, oxy groups, thio groups, carbonyl groups, sulfone groups, phosphoxyl groups, amine groups, and Combinations thereof can also be included, such as oxyalkylene groups, iminoalkylene groups, iminoarylene groups, sulfamide groups, carboxamide groups, sulfamidealkylene groups, carbonamidoalkylene groups, urethane groups, ureas and esters. The bonds Z and Z' for a particular oxyalkylene polymer are dictated by the ease of making such polymer and the availability of the necessary precursors for the polymer. It is clear from the above description of Z and Z' that the structure of these linkages can vary within a wide range and, in fact, does not even exist as a structure in the case of either valence bond. However, if Z and Z' are large and the fluorine content (present in R _f ) is within the aforementioned ranges indicated in the discussion above, then generally the total Z and Z' content of the polymer will be less than 10% by weight of the polymer. Less is preferable. The monovalent terminal organic group represented by B is one that is covalently bonded to the poly(oxyalkylene) group via Z'. Although the nature of the B group may vary, it is desirable that it act on the poly(oxyalkylene) group in a manner that maintains and determines the desired solubility of the oxyalkylene. The group represented by B is a hydrogen atom, an acyl group such as _C6H5C (O)-, an _alkyl group, preferably a lower alkyl group such as a methyl group, a hydroxyethyl group, a hydroxypropyl group, a mercaptoethyl group, It may be an aminoethyl group or an aryl group such as phenyl, chlorophenyl, methoxyphenyl, nonylphenyl, hydroxyphenyl, aminophenyl. Generally, the group represented by Z′B is (R ³ ) _y
It will be less than 50% by weight of the Z′B portion. The oxyalkylene groups containing fluoroaliphatic groups used in the present invention can be prepared by condensation, free radical or ionic homopolymerization or copolymerization in a variety of known ways, such as using solution, suspension or bulk polymerization methods, such as Sorenson and “Preparative Methods of Polymer Chemistry” by Campbell, 2nd edition, Interscience Publishers, 1968 (“Preparative Methods of Polymer Chemistry”)
Methods of Polymer Chemistry”, Sorenson
and Campbell, 2nd ed., Interscience
Publishers, (1968)). Typical oxyalkylenes useful in this invention are polyesters, polyurethanes, polyepoxides, polyamides and vinyl polymers such as polyacrylates and substituted polystyrenes. Polyacrylates are a particularly useful group of oxyalkylenes, which include, for example, acrylates containing fluoroaliphatic groups and poly(oxyalkylenes).
It can be prepared by free radical initiated copolymerization with acrylates, such as monoacrylates or diacrylates or mixtures thereof. By way of example, fluoroaliphatic acrylates of R _f -R''- _O2C -CH= _{CH2 ( R} '' stands for example sulfonamidoalkylene, carbonamidoalkylene or alkylene) such as _C8F17SO2N
(C ₄ H ₉ )CH ₂ CH ₂ O ₂ CCH=CH _{2 CH 2 =} CHC(O)
Polyoxyalkylene acrylate can be prepared by copolymerizing with polyoxyalkylene monoacrylate represented by (R ³ ) _x OCH ₃ . A further description of the fluorochemical oxyalkylenes useful in the present invention may be found in the well-known U.S. Pat.
No. 3,787,351 and US Pat. No. 4,289,892 are described for this purpose and are omitted for brevity. The amounts of each component (a) and (b) may vary over a wide range and will be selected to impart the desired balanced properties to the treated fibers of the finished product. Generally, component (a) will represent the major amount of the blend and component (b) will represent the minor amount. The specific amount depends on the particular texture of the textile fiber or product to be treated, the particular chemical composition of (a) and (b), and the application method used. Ingredients that should be used to achieve the desired effect in commercial applications
To find out the appropriate relative amounts of (a) and (b), it is often best to conduct laboratory investigations. Generally the relative amounts of components (a) and (b) will be within the following ranges:

[Table] The formulations of the present invention consist of (1) an organic solvent solution or aqueous dispersion of a fluorochemical component; and (2) a fluorochemical poly(oxyalkylene) which may be used neat or as an organic solvent solution or an aqueous dispersion. ) can be obtained by mixing. If an aqueous emulsion is the desired form of the formulation, the emulsification may be carried out on a formulation containing an organic solvent as described above, or individually as a solvent-containing emulsion or a solvent-free emulsion, respectively. An emulsified component may be blended with. In the preparation of the above emulsions, cationic fluorochemical surfactants (e.g.
C ₈ F ₁₇ SO ₂ N(H)C ₃ H ₆ N(CH) ₃ Cl) with a hydrocarbon nonionic surfactant (i.e., Tween
Generally effective when used with Tween 80″ polyoxyethylene sorbitan monooleate). Fluorochemical poly(oxyalkylene)s and their mixtures are themselves nonionic surfactants; The fluorochemical poly(oxyalkylene) may be omitted in whole or in part by adding it to the solvent-containing formulation prior to emulsification. Substrates that can be treated in accordance with the present invention include textile fibers (or filaments), and textiles, such as finished or manufactured textile products such as carpet, paper, paperboard, and leather.Textiles include those made from natural fibers such as cotton and wool, and those made from nylon, polyolefin Particularly good results have been obtained with nylon and polyester fibers, including those made from synthetic organic fibers such as acetate, rayon, acrylic and polyester fibers, such as those mentioned above, or for example yarns, tows, webs or rovings. Fibers or filaments in aggregate form, such as fibers or filaments, or articles such as processed fabrics, such as carpets or folded fabrics, can be treated with fluorochemical formulations. fluorochemicals, such as fluorochemical acrylate copolymers, as aqueous solutions or aqueous or organic dispersions to fibers and fibrous substrates by known methods commonly used in applying fluorochemical substances, such as fluorochemical acrylate copolymers. (If desired, such known fluorochemicals may be used in conjunction with the fluorochemical formulations described above, e.g. fluoroaliphatic group-containing polymers such as acrylates and methacrylates. For example, the fluorochemical treatment , by dipping the fibrous substrate in a bath containing the fluorochemical formulation, by padding the substrate, by spraying the substrate with the fluorochemical formulation, or by foaming, kiss-rolling or metering processes such as spin finishing. If desired, the fluorochemical or formulation may be mixed with a conventional fiber treatment agent (or adjuvant) such as an antistatic agent or a neat It may be treated with oil (fiber lubricant). In the production of synthetic organic fibers (e.g.
Ozmer, Encyclopedia of Polymer Science and Technology Volume 8,
pp. 374-404, 1968, Kirk-Othmer,
Encyclopedia of polymer science and
Technology, 8 , 374-404, 1968), the first step (e.g. by melt-spinning or solvent-spinning) usually employed in the method, involving the initial formation of filaments, is The process involves applying a small amount of a fiber finish containing an agent (generally less than 2% active solids to the fiber) to the surface of the fiber. It is particularly advantageous to treat such textile fibers, such as nylon 6, with fluorochemical formulations in conjunction with spin finishes applied to such textile fibers. Textile finishes are dilute aqueous emulsions or oils ("neat oils") that primarily contain the above-mentioned lubricants and antistatic agents and emulsifiers (surfactants), and may also contain things such as antioxidants. It is generally manufactured in the shape of Typical lubricants include mineral oils, waxes, coconut oil, vegetable oils (triglycerides) such as peanut oil and castor oil, esters, polyoxyethylene derivatives of alcohols and acids, and synthetic oils such as silicone oils. Antistatic agents, emulsifiers and surfactants added to textile finishes are selected from a class of similar chemicals, including: (a) fatty acid soaps, sulfated vegetable oils, alkyl and ethoxylated alkyl phosphates; (b) cationic agents such as fatty acid amines, quaternary ammonium compounds and quaternary phosphonium compounds; (c) non-ionic agents such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acids and ethoxylated fatty amines; ionic agents, (d) amphoteric agents such as betaine, amino acids and their salts; A preferred method of applying the fluorochemical formulations of the present invention to synthetic organic fibers is to incorporate them into the fiber finishes described above in amounts sufficient to obtain the desired properties such as oil repellency, water repellency, and sludge resistance. . Generally, the amount of fluorochemical formulation to be used is sufficient to leave about 200 to 1600 ppm fluorine based on the weight of the fibers on the fibers of the finished product, such as carpet. Such additions to conventional textile finishes meet the typical requirements that conventional textile finishes must meet, namely lubrication, thermal stability, low smoke emission at high temperatures, and textile dyeability (pigmentation). This can be done without sacrificing or adversely affecting wettability. The conventional finish components of fiber finishes containing the fluorochemical formulations of the present invention can be removed in conventional manner after the fibers have been made into fabric form, such as carpet and upholstery fabrics. Fluorochemical formulations can withstand typical conditions during fiber and yarn processing processes, such as those encountered with raw fiber materials such as scouring and dyeing, as well as cleaning,
Survives even harsher conditions such as those encountered with finished products such as steam cleaning and dry cleaning. The fluorochemical formulation does not interfere with and withstand normal fiber processing steps, such as drawing, surface texturing and heat setting, and provides oil repellency to the finished product, such as carpets made from treated fibers. , imparts water repellency and sludge resistance. Conventional application methods used to apply finishes to fibers (or filaments) can also be used with the fluorochemical formulation-containing finishes of the present invention. Such methods include the use of any of the following: (a) A rotating ceramic cylinder, or kiss roll, which is partially immersed in a pan containing the finishing agent, over which the filament moves. (b) a metering pump that supplies the finish through a slot or hole in the fiber guide over which the filament passing passes, obtaining a thin film of finish; (c) an immersion finishing bath; or (d) Spray Equipment The fluorochemical formulations of the present invention are generally compatible with (i.e., dispersed in or sufficiently soluble in) commercially available neat oil fiber finishes;
They may therefore be mixed with them and applied at any time (or before or after). To increase the solubility of fluorochemical formulations in neat oil finishes, "Carbitol" or "Cellosolve" may be added to the finish.
A solubilization aid such as ``Cellosolve'' may be added. Representative fluorochemical carbodiimides having the following general formula that are useful as component (a) in the fluorochemical formulations of this invention are shown in Table 1. R-Q-A (N=C=N-A) _o -Q-R

Table 2 shows representative fluorochemical oxyalkylenes useful as component (b) in the fluorochemical formulations of the present invention. Generally, the production of fluorochemical oxyalkylenes results in products containing mixtures of oxyalkylenes, with varying lengths of fluoroaliphatic groups and poly(oxyalkylene) moieties. and the sub-symbols denoting the number of carbon atoms in the former and the number of oxyalkylene units in the poly(oxyalkylene) segment represent the average number in both cases and unless otherwise specified herein, e.g. in Table 2. It should be understood that it has such an average value. Table 2 1 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CO ₂ (C ₂ H ₄ O) ₁₅ H 2 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ O (C ₂ H ₄ O) ₁₄ H 3 C ₈ F ₁₇ C ₂ H ₄ O (C ₂ H ₄ O) ₁₅ H 4 (m+n=25) 5 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ O (C ₃ H ₆ O) ₈ H 6 C ₈ F ₁₇ C ₂ H ₄ S CHCO (C ₃ H ₆ O ) _n H | CH ₂ CO ₂ (C ₃ H ₆ O) _o H(m+n=20) 7 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ O (C ₂ H ₄ O) _7.5 H Representative fluorochemical oxyalkylene polyacrylates useful as component (b) in the formulations of this invention include any of the fluorochemical acrylates in Table 3 with any of the fluorine-free poly(oxyalkylene) monomers in Table 4. It is produced by copolymerization. Table 3 1 C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OOCCH=CH ₂ , 2 C ₆ F ₁₃ C ₂ H ₄ OOCC (CH ₃ )=CH ₂ , 3 C ₆ F ₁₃ C ₂ H ₄ SC ₂ H ₄ OOCCH = CH ₂ , 4 C ₈ F ₁₇ C ₂ H ₄ OOCC (CH ₃ ) = CH ₂ , 5 C ₈ F ₁₇ C ₂ H ₄ N (CH ₃ ) C ₂ H ₄ OOCC (CH ₃ ) =
CH ₂ , 6 C ₂ F ₅ C ₆ F ₁₀ CH ₂ OOCCH=CH ₂ , 7 C ₇ F ₁₅ CH ₂ OOCCH=CH ₂ , 8 C ₇ F ₁₅ CON(CH ₃ ) C ₂ H ₄ OOCCH=CH ₂ , 9 (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH)
CH ₂ OOCCH=CH ₂ , 10 (CF ₃ ) ₂ CFOC ₂ F ₄ C ₂ H ₄ OOCCH= CH ₂ , 11 C ₈ F ₁₇ C ₂ H ₄ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ OOCCH=
CH ₂ , 12 C ₇ F ₁₅ C ₂ H ₄ CONHC ₄ H ₈ OOCCH=CH ₂ , 13 14 C ₇ F ₁₅ COOCH ₂ C(CH ₃ ) ₂ CH ₂ OOCC(CH ₃ )=
CH ₂ , 15 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₄ H ₈ OOCCH=CH ₂ , 16 (C ₃ F ₇ ) ₂ C ₆ H ₃ SO ₂ N (CH ₃ ) C ₂ H ₄ OOCCH =
CH ₂ , 17 18 C ₆ F ₁₇ CF=CHCH ₂ N(CH ₃ )C ₂ H ₄ OOCCH=
CH ₂ , 19 C ₈ F ₁₇ SO ₂ N (C ₄ H ₉ ) C ₂ H ₄ OCOCH=CH ₂ , 20 C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₄ H ₄ OCOCH (CH ₃ )=
CH ₂ , Table 4 1 CH ₂ = CHCO ₂ (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₂₂
(C ₂ H ₄ O) ₉ C ₂ H ₄ O ₂ CCH=CH ₂ 2 CH ₂ = CHCO ₂ (C ₂ H ₄ O) ₁₇ CH ₃ 3 CH ₂ = C(CH ₃ )CONH(C ₃ H ₆ O ) ₄₄ H 4 CH ₂ = C (CH ₃ ) CO ₂ (C ₂ H ₄ O) ₉₀ COC (CH ₃ )
＝CH ₂ 5 HS (C ₂ H ₄ O) ₂₃ (C ₃ H ₆ O) ₃₅ (C ₂ H ₄ O) ₂₂ C ₂ H ₄ SH 6 CH ₂ ＝C (CH ₃ )CO ₂ (C ₂ H ₄ O) ₉₀ H 7 CH ₂ = CHCO ₂ (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₂₂
(C ₂ H ₄ O) ₉ C ₂ H ₄ OH Specific fluorochemical oxyalkylene polymers are those in Table 5 described by their monomers and the relative amounts of the monomers.

Table: Any other compatible comonomers, such as butyl acrylate, acrylonitrile, etc. that do not contain fluoroaliphatic groups, may be used to improve the compatibility or solubility of component (b), fluoroalkyleneoxyalkylene, in the textile finish. can be copolymerized with fluorochemical acrylates and oxyalkylene comonomers in amounts up to about 25% by weight. The weight ratio of fluorochemical acrylate monomer (Table 3) to fluorochemical polyoxyalkylene comonomer (Table 4) can be varied, but the fluorine content of the carbon bonds of the resulting copolymer is within the desired range of 5 to 40% by weight. The comonomer should be selected along with any of the above comonomers. Representative fluorochemical urethane compounds useful as component (a) in the practice of this invention are shown in Table 5A. Table 5A 1 [C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OCONH] ₂ C ₆ H ₃
(CH ₃ ) 2 ROCONHC ₆ H ₄ CH ₂ C ₆ H ₃ (NHCOOR)
CH ₂ C ₆ H ₄ NHCOOR In the table, two of the groups R are C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ )
One represents C ₂ H ₄ −, and one represents C ₁₈ H ₃₇ −. The objects and effects of the present invention will be explained in the following examples. Example 1 A 2-liter, 3-necked flask equipped with a mechanical stirrer, condenser, thermometer, addition funnel, and electric heating mantle was charged with 375 g (1.5 moles) of methylene bis(4-phenylene isocyanate) and 481 g of methyl ethyl ketone (MEK). This stirring and heating (80−83
554 g of N-ethyl (perfluorooctane) sulfonamide ethyl alcohol (1.0
mol) was added over 3 hours and stirring and heating continued for an additional 3 hours. Add camphenphenylphosphine oxide to a stirred solution containing this fluorochemical urethane isocyanate and unreacted diisocyanate.
7.4 g of C ₁₀ H ₁₆ POC ₆ H ₅ , carbodiimide forming catalyst were added and the reaction mixture was stirred and heated at about 80° C. for about 8 hours. At this time, virtually all the isocyanate groups had been converted to carbodiimide groups as shown by IR absorption analysis. This solid fluorochemical carbodiimide product is shown as Compound No. 1 in Table-1. Examples 2-5 Other fluorochemical carbodiimides of Table 1 were prepared following the general procedure of Example 1, except that the reagents in Table 6 were used at the molar concentrations shown in Table 7. Reagents in Table 6 are designated for later reference with symbols such as A-1.

【table】

[Table] Examples 6 to 19 In each of these examples, pre-moistened nylon carpet (50 oz/yd ² ) of golden yellow relatively long cut-pile fabric (plush, cut-pile) was used.
were treated by surface spray application (pickup at 25% moisture) of a diluted mixture of an aqueous emulsion of fluorochemical carbodiimide compound No. 1 of Table 1 and an aqueous emulsion of a fluorochemical oxyalkylene; ) dilution in the amounts listed in Table 8 (SOF)
This was done to obtain the desired concentrations of fluorochemical components (a) and (b) necessary to deposit fluorochemicals onto the carpet. The treated carpet samples were dried at 70°C for 30 minutes and then at 130°C for 10 minutes. For comparison, Comparative Examples C-1 to C-
9 tests were carried out in which only one type of fluorochemical component was used for carpet treatment (C
-1 to C-8) or Comparative Example C-9, no treatment was applied. Oil repellency (OR), water repellency (WR) and walk-on soil (Walk-
on soil) (WOS) was measured. The data are summarized in Table 8. Water repellency testing is a test method often used for this purpose. The aqueous stain or water repellency of the treated samples is determined using the water/isopropyl alcohol test and is expressed as a water repellency rating for the treated carpet or fabric. 100% water/0%
Treated carpets that are penetrated or resistant only to the isopropyl alcohol mixture (the least permeable of the test mixtures) receive a rating of 100/0.
A rating of 0/100 is given, while a treated fabric resistant to the 0%/water/100% isopropyl alcohol mixture (the most permeable of the test mixtures) is given a rating of 0/100. Other intermediate values are determined using other water/isopropyl alcohol mixtures in which the percentage amounts of water and isopropyl alcohol are each a multiple of 10. The water repellency rating corresponds to the most permeable mixture that does not penetrate the fabrics or wet them after 10 seconds of contact. Generally, a water repellency rating of 90/10 or higher, such as 80/20, is desirable for carpet. The oil repellency test is also a test method often used for this purpose. Technical manual for oil repellency of treated carpet and textile samples
and Annual Book of the American Association of Textile Chemists and Colorists (AATCC)
(Technical Manual and Yearbook of the
American Association of Textile Chemists
and Colorists) as measured by Standard Test Method 118-1978. This test is based on the resistance of treated fabrics to penetration of oils of various surface tensions. A rating of 1 is given to treated fabrics that are resistant only to Nujol, a mineral oil brand and the least penetrating of the tested oils, while it is resistant to heptane, which is the most penetrating. A value of 8 is given to a resistant treated fabric. Other intermediate values are determined using other pure oils or mixtures of oils. The rated oil repellency is 10 seconds per contact compared to the standard test of 30 seconds per contact.
It corresponds to the most penetrating oil or oil mixture that does not penetrate the fabric or wet it after seconds. Higher numbers indicate better oil repellency. Generally, an oil repellency of 2 or greater is desirable for carpets. The sludge resistance of treated carpet and untreated carpet (control) was determined by exposure to pedestrian traffic according to AATCC Test Method 122-1979. And the exposed site was a heavily trafficked industrial area with approximately 15,000 traffic exposures. Samples were replaced periodically to ensure uniform exposure and vacuumed every 24 hours during testing and prior to visual evaluation. The following "Walk-on-Soiling" (WOS) scoring system was used for the evaluation. WOS rating explanation 0 Equal to comparative example. ±1/2 Slightly better (+) slightly worse than the comparative example (-) ±1 Clear difference compared to the comparative example. ±1/2 A very obvious difference compared to the comparative example. ±2 Very noticeable difference compared to the comparative example.

【table】

[Table] The data in Table 8 is for all formulations (Example 6-
Useful oil and water repellency was obtained from 19) and the sludge resistance of most formulations was better than or equal to that of the comparative examples. The properties obtained in Examples 6 to 19 are particularly noteworthy compared to Comparative Examples C-1 to C-7. Examples 20-22 According to these examples, the fluorochemical carbodiimide of Compound No. 1 in Table 1 as component (a);
Treatment of nylon carpet fibers with a combination of an aqueous emulsion with the fluorochemical oxyalkylene blend of the present invention as component (b) and an aqueous emulsion of a coconut oil-based spinfinishing lubricant; The following describes the test results for dyed carpets. The finish compositions applied for these examples contained fluorochemical solids to spin finish lubricant solids in a ratio ranging from 0.18:1 to 0.14:1. The spun finish emulsion was applied to the melt spun, undrawn nylon 6 fiber yarn using a sized slot applicator. This yarn was made of 118 filaments of 18 denier (per filament). 1.0 or more on the fibers immediately after application.
1.5% by weight of oil component was attached. The treated yarn was continuously drawn and woven into a level-loop carpet (28 oz/yd ² )196
Heat treated for 1 minute at ℃, acid dyed, dried at 70℃ for 30 minutes, heated for 10 minutes at 130℃, and then determined by oil and water repellency, walk-on sludge resistance and fluorine analysis. The retention of fluorochemical treatments throughout the dyeing process was evaluated. The test results are shown in Table 9. Comparative example C-10,
C-11 were carried out, in one of them omitting either of the fluorochemical treatments and in the other incorporating treatment with only one fluorochemical component, namely the carbodiimide of compound No. 1 of Table 1.

[Table] The data in Table 9 is based on the above formulations (Example No. 20,
21, 22) and that the sludge resistance was generally better than Comparative Example C-10. Particularly noteworthy is the higher retention value of the formulation compared to Comparative Example C-10. Examples 23-26 Table 1 as component (a) in these examples
Two different rainwear fabrics were treated by padding method with an aqueous emulsion of a blend of fluorochemical carbodiimide of Compound No. 1 and fluorochemical oxyalkylene as component (b) and dried for 10 minutes at 150°C. and evaluated the initial oil repellency (OR) and resistance to water spray (SR), then again after 5 washes (5L) and again after 1
These properties were evaluated after dry cleaning (DC) twice. For the OR test, the AATCC standard test method 118-
1978 was used. Specifying a contact time of 30 seconds before measurement, an OR value of 3 or greater is particularly desirable for rainwear fabrics. The treated fabrics were washed using a mechanically agitated automatic washing machine capable of holding 4 kg of laundry, using water at 50°C and commercially available detergent. The washed fabrics were then spin-dried in an automatic dryer at 70°C for 4 hours and pressed in a flat-bed press at 154°C before measurement. The treated fabric was dry cleaned for 20 minutes at 25° C. using perchlorethylene containing 1% dry cleaning detergent and rotation in a motor-driven tumble jar (AATCC Test Method 70-1975). After removing excess solvent in a wringer, the samples were dried at 70°C for 10 minutes and then pressed for 15 seconds on each side on a flat-bed press maintained at 154°C. The data are shown together with Comparative Examples C-12 to C-19 in Table 10.

Table 10 The data in Table 10 show that most formulations provided improved OR, SR and wash resistance and dry cleaning properties compared to either component alone. Examples 27-40 In the following examples, aqueous emulsion formulations of the fluorochemical urethanes of Table 5A and several different fluorochemical oxyalkylenes 1 were used to treat nylon carpets.
−19 procedure was followed. OR for dry samples;
WR and WOS were evaluated and the results are summarized in Table 11.

【table】

[Table] The data in Table 11 shows that all of the example formulations have better OR and WOS than untreated carpet, C-21, and many of the example formulations have better OR and WOS than untreated carpet, C-21. Shows that he has a good WR. Furthermore, all formulation examples exhibited better WOS than Comparative Examples C-1 to C-7 using only the fluorochemical oxyalkylene component. It is noteworthy that half of the formulation examples showed better WOS than Comparative Example C-20, which used the urethane fluorochemical component alone. Examples 41, 42 Following the procedure of Examples 23-26 above, two rainwear fabrics were prepared with the fluorochemical urethane 2 of Table 5A as component (a) and the fluorochemical oxyalkylene of Table 5 as component (b). The initial OR and SR were evaluated by treating with an aqueous emulsion of a mixture of 3 and drying at 150° C. for 10 minutes, then again after 5 L and again after one DC.
The results are shown in Table 12.

[Table] The data in Table 12 shows that the oil repellency obtained from the formulations of Example Nos. 41 and 42 at the beginning and after 5L was that of Comparative Example C-22.
This shows that the results are better than those obtained with C-23 fluorochemical urethane alone. Comparative Example C using only fluorochemical urethane
The dry cleaning resistance obtained with the formulations of Example Nos. 41 and 42 compared to No. 22, C-23 is noteworthy. It will be apparent to those skilled in the art that various modifications and changes can be made without departing from the scope of the invention.

Claims (1)

[Claims] 1 (a) The following formula: R ¹ (Q) _x (N=C=N−A) _o −N=C=N(Q) _x R ¹ or A′[NHCOY(Q) _x R ² ] _r [In each formula, A is an alkylene group having 2 to 20 carbon atoms, an aralkylene group having up to 20 carbon atoms, an arylene group, a poly(oxyalkylene) group, and combinations thereof {these The group may include a hetero moiety and a fluoroaliphatic group R _f . }, R _f represents a fluorinated group having 3 to 20 carbon atoms and containing 40 to 78 wt. represents an aliphatic stable inert non-polar monovalent moiety, R ¹ is a hydrogen atom, R _f or selected from aliphatic groups, aromatic groups, aralkyl groups, fluoroaliphatic groups and combinations thereof. , and represents an organic group which may contain a heteroatom-containing moiety; at least one of A or R ¹ contains R _f and Q is a divalent heteroatom-containing group or an aliphatic group, an aromatic group, an aralkyl group; represents an organic linking group selected from groups, fluoroaliphatic groups and combinations thereof and which may contain a heteroatom-containing moiety, A' represents the residue of an organic isocyanate, and Y represents -N-, - represents O- or -S-, ^R2 is selected from a hydrogen atom, a fluoroaliphatic or aliphatic group, an aromatic group, an aralkyl group, a fluoroaliphatic group and combinations thereof, and a heteroatom-containing moiety at least one of R ² represents a fluoroaliphatic group, x represents 0 or 1, n represents 0 to 10, and r represents an integer of 2. ]; and ( _{b )} a _normally solid water-insoluble fluoroaliphatic group-containing compound _which can _be represented by ^the following _formula : Z [(R ³ ) _y Z′B′] _t } _w [In each formula, R _f is an oleophobic or hydrophobic compound having 3 to 20 carbon atoms and containing 40 to 78% by weight of fluorine atoms. Z represents a valent bond or polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphooxy and amine R _f and (R ³ ) _y represent a covalent linkage selected from one or more linking groups selected from the following, and (R ³ ) _y represents a poly(oxyalkylene) moiety; , R ³ represents oxyalkylene having 2 to 4 carbon atoms, y is 8 to 90
, B represents a hydrogen atom, acyl group, alkyl group, or aryl group that makes Z′B of the (R ³ ) _y Z′B moiety 50% by weight or less, and B′ represents B or a valence bond. , with the proviso that at least one B' represents a Z-bond (R ³ ) valence bond linking _{the y} group to another Z, and Z' represents a valence bond or a polyvalent aliphatic, polyvalent aromatic, oxy- , thio, carbonyl, sulfone, sulfoxy, phosphoxy and amine, B or B′ and (R ³ ) _y represent a covalent linkage together; s represents 1 to 27, t represents 1 to 1.4, and w represents 1 to 30. ] One or more normally liquid or low-melting solid water-soluble or dispersible fluoroaliphatic group-containing poly(oxyalkylene) compounds represented by the formula: A composition comprising: 2 (a) The following formula: R ¹ (Q) _x (N=C=NA) _o -N=C=N(Q) _x R ¹ or A' [NHCOY(Q) _x R ² ] _r where A is an alkylene group having 2 to 20 carbon atoms, an aralkylene group having up to 20 carbon atoms, an arylene group, a poly(oxyalkylene) group and combinations thereof {these groups include hetero moieties and It may contain a fluoroaliphatic group R _f . } represents a _divalent organic linking group selected from represents an aliphatic stable inert non-polar monovalent moiety, R ¹ is a hydrogen atom, R _f or selected from aliphatic groups, aromatic groups, aralkyl groups, fluoroaliphatic groups and combinations thereof. , and represents an organic group which may contain a heteroatom-containing moiety; at least one of A or R ¹ contains R _f and Q is a divalent heteroatom-containing group or an aliphatic group, an aromatic group, an aralkyl group; represents an organic linking group selected from groups, fluoroaliphatic groups and combinations thereof and which may contain a heteroatom-containing moiety, A' represents the residue of an organic isocyanate, and Y represents -N-, - represents O- or -S-, ^R2 is selected from a hydrogen atom, a fluoroaliphatic or aliphatic group, an aromatic group, an aralkyl group, a fluoroaliphatic group and combinations thereof, and a heteroatom-containing moiety at least one of R ² represents a fluoroaliphatic group, x represents 0 or 1, n represents 0 to 10, and r represents an integer of 2. ]; and ( _{b )} a _normally solid water-insoluble fluoroaliphatic group-containing compound _which can _be represented by ^the following _formula : Z [(R ³ ) _y Z′B′] _t } _w [In each formula, R _f is an oleophobic or hydrophobic compound having 3 to 20 carbon atoms and containing 40 to 78% by weight of fluorine atoms. Z represents a valent bond or polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphooxy and amine R _f and (R ³ ) _y represent a covalent linkage selected from one or more linking groups selected from the following, and (R ³ ) _y represents a poly(oxyalkylene) moiety; , R ³ represents oxyalkylene having 2 to 4 carbon atoms, y is 8 to 90
, B represents a hydrogen atom, acyl group, alkyl group, or aryl group that makes Z′B of the (R ³ ) _y Z′B moiety 50% by weight or less, and B′ represents B or a valence bond. , with the proviso that at least one B' represents a Z-bond (R ³ ) valence bond linking _{the y} group to another Z, and Z' represents a valence bond or a polyvalent aliphatic, polyvalent aromatic, oxy- , thio, carbonyl, sulfone, sulfoxy, phosphoxy and amine, B or B′ and (R ³ ) _y represent a covalent linkage together; s represents 1 to 27, t represents 1 to 1.4, and w represents 1 to 30. ] One or more normally liquid or low-melting solid water-soluble or dispersible fluoroaliphatic group-containing poly(oxyalkylene) compounds represented by A fiber finishing agent consisting of a dispersion. 3. The fiber finishing agent according to claim 2, wherein the fluoroaliphatic group-containing compound (a) is a fluoroaliphatic group-containing -carbodiimide compound, -ester compound, or -carbonylimino compound.