JPS59206479A - Fluorochemical blend composition and fibrous material treated therewith - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to treated substrates such as textile fibers, grains and leather. The present invention relates to finishing MIJ K having compositions containing fluorochemical aliphatic groups, and treating the fibers thereof to impart oil repellency, water repellency, and dirt resistance. The invention relates to compositions containing fluorochemical aliphatic groups and preparations thereof that can be used to treat such VC.

In the industrial manufacture of textiles such as carpets and apparel and other fibrous substrates such as paper and leather, fluorochemicals and aliphatic substances are used to impart oil repellency and low water content to the surface of the substrate. Fluorochemicals containing groups (fRfJ
It is common practice to treat substrates with Applications of this type to fluorochemical and fiber substrates are described in numerous well-known publications, such as U.S. Pat.
Specification No. 1 (Tokoli), No. 357479
1 '-5 bright ip pieces' (German et al., Sherma
Herman et al., No. 3728151 (Herman et al., No. 3).
91605,! No. 1 Specification 1: (German et al., Sher
maneL al ), Specification No. 4144367 (
lanthanum.

Landucci), Specification No. 5896251 (
Lantern, 1, anducci), No. 402-4:
17 amin a1%' (Lang 7, Landucci
), No. 4165338 (Kassima et al., Kat
Sushima et al), No. 4190545
Issue Specification 4i: (7-Si Jl, Le, Marshall
), No. 4215205 Minami 71flW (Lantern,
Landucci), Specification No. 4013S27 (
Temple), No. 4264484 @ (Patel, Patel), No. 4029585 Particulars - (Detre, ]) ettre I, No. 346229
Specification No. 6 (Reynolds et al. 5. Reynolds et al.
tal), Specification No. 4325857 (Champaneria et al.
, and R. Y. Baikes, eds., Fluorochemicals and Their Industrial Applications, Ellis Horwood, West Sussex, England, pp. '226-230, 1979.
Year (Banks.

) <, L, I'd, "Organo-
fluorine Chemicals and
theirIndustrial Application
ions”, Ellis Horwood,
Ltd.

WestSussex, England, 226
-230 (1979)).

Some fluorochemicals can be applied in many ways, and although many are commercially available, some are relatively inexpensive to apply and others are difficult to apply. Some are not seaworthy or do not adequately provide the required properties.

Traditionally, fluorochemical compositions have been applied as surface treatments to finished textile products such as carpets. Recently, some flurochemical compositions have been applied in commercial manufacturing to textile fibers or yarns during compression prior to being woven into a finished product. However, these fluorochemicals! Some of the concerns include the incompatibility and reactivity of fluorochemicals with fiber finishing ingredients such as lubricants, the lack of durability of fluorochemicals on treated fibers to dyeing and other textile manufacturing operations, and the lack of durability of fluorochemicals in finished products. Water repellency, oil repellency and
Results have been limited for various reasons, including insufficient water resistance and sewage resistance.

The object of the present invention is to provide a compound containing a fluoroaliphatic group that imparts oil repellency and water repellency, such as a full 10 aliphatic group-containing carbodiimide (hereinafter often abbreviated as fluorochemical carbodiimide), or a fluoroaliphatic group-containing compound that imparts oil repellency and water repellency. Containing esters (hereinafter referred to as fluorochemical esters) are carbonyliminated compounds containing fluoroaliphatic groups (
Hereinafter, it is often abbreviated as fluorochemical carbonylimino compound. ) and (bl aliphatic group-containing 7''-IJ oxyalkylene (hereinafter often abbreviated as fluorocarbon alkylene), which imparts oil repellency to textile fibers and other fibrous substrates. It is an object of the present invention to provide such formulations that are useful for treatment to impart water repellency.

Another object of the present invention is that the fluorochemical carbodiimide, fluoro)1 mycalcarbonyl imide, is a fluorochemical ester compound in combination with a fluorochemical oxyalkylene as a fiber finishing agent, e.g. 'Providing a lubricant that can be used in combination with or as an ingredient to treat FF5 fibers, is compatible with the fiber finishing agent, and does not interfere with normal textile processing processes. That's true.

Another object of the present invention is to provide a fluorochemical treated textile fiber which retains the fluorochemical in the fiber throughout the textile processing and dyeing process and has permanent water and oil repellency and stain resistance. There is a particular thing.

Yet another aspect of the present invention, B'XI, is a fluorochemical carbodiimide, a fluorochemical luponyliminomata, which is a compound with a fluorochemical ester compound, fluorochemical oxyalkylene, such as textile fibers, filaments, and yarns. Organic solvent solutions or aqueous solutions are used to treat textile substrates or finished textile products, such as carpets and other textile substrates such as paper and leather, to make them oil- and water-repellent. The object of the present invention is to provide a product that can be used in the form of a dispersion.

In summary, one aspect of the invention is (al), which imparts oil and water repellency to a fibrous substrate, and which contains a fluoroaliphatic group-containing compound, such as a carbodiimide, carbonylimino or ester compound, typically a solid , a water-insoluble fluorochemical composition, or a composition comprising/or consisting essentially of a mixture of said compounds, wherein said compound is one or more monovalent. fluoroaliphatic group (1#) and one or more polar moieties, such as carbodiimide, carbonylimino, and/or
or a composition containing an ester moiety, where the grafting and moieties are bonded together by a heteroatom-containing group or an organic linking group; or a water-dispersible polyoquine alkylene compound containing a fluoroaliphatic group, or a composition containing or consisting essentially of a mixture of these oxyalkylene compounds, in which one or more of the above compounds is present. It has more than one monovalent fluoroaliphatic group (Rf) and one or more polyoxyalkylene residues, and the oxyalkylene residues are heteroatom-containing groups or polyoxyalkylene groups. , or bonded to each other by a combination of these groups. The above-mentioned fluorochemical formulations (i.e., where the polar moieties are nitrogen-containing groups) are used in the manufacture of textile substrates such as textile fibers (or filaments), carpets, paper and leather. It is useful for treating the surface of finished or finished fibrous substrates, such as organic solutions or in the form of aqueous dispersions, to impart oil and water repellency to the surface of finished or finished fiber substrates.

This fluorochemical carbodiimide (component (a) of the above formulation) has the following general formula:
N=C==N −A+n−N=C=N+Q+xR”
I, the general formula generally encompassing individual compounds or representing mixtures of compounds as resulting from the reactions used to prepare the compounds.

Fluorochemical carbodiimides useful in the present invention and methods for their preparation are described in US Pat. No. 4,024,178 (Landucci 3), which is incorporated herein by reference.

In formula (2), "n" represents a number from 0 to 20, preferably from 1 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. Each Q represents the same or different divalent linking group. A represents a divalent organic linking group which can contain a fluoroaliphatic group R4, and each 1y AVi represents the same or different. Each Rii represents the same group or a different group, H, ]<4 and -valent terminal organic groups, such as alkyl groups, chloroalkyl groups, aryl groups and their mercapto which can readily react with active (inocyanurate-reactive) water atoms (e.g. inocyanurates under urethane bond forming conditions, i.e. from 20 to 100°C). General [R1 contains up to 18 carbon atoms. When <' represents the above Rf, the suffix X of the adjacent Q is limited to 1, and since J<f cannot directly bond to the nitrogen atom in the carbodiimide method, it cannot represent O.Specific compounds At least one Rf group is present in one or more R1 and A.

In the above general formula I, when n represents 1 or a larger number, a divalent chain linking group A connects consecutive carbodiimide moieties. Examples of the button group A are 2 to about 2
Alkylene radicals with 0 carbon atoms, such as ethylene radicals, imbutylene radicals, hexylene radicals and hexylene radicals, lohexylene radicals with 20 carbon atoms; groups, such as -('H2
c61(4('H2- and -〇6H4CH2C"tJ-
1,-, arylene group, e.g. λ-tolylene group, -C6H3(
CH3)-, polyoxyalkylene groups such as -(C2H,0)yC2)-14-, where y represents 1 to about 5, and various VC combinations of these groups. This radical can also contain a hetero moiety other than -S- and -P, including -S- and -P. However, it is preferable that A does not contain the group containing the active hydrogen atom.

The group A can represent the residue of an organic diincyanate which can lead to a carbodiimide moiety. That is, one can represent a divalent group obtained by removing an inocyanate group from organic diinocyane-1. A suitable diinozoanate precursor! Examples of the 1+17I substance include the single trileno-2,4-diynone atom, methylene bis(4-phenylene inzonate), and their intermediates.

Hardware, or a single item/association and an item.
It can represent a complex compound formed by reaction with an organic diol or organic polyol in a proportion suitable to obtain a polylanthanum-terminated polylanthanum. Other inocyanates can also be used as starting materials. Some of these are described in Japanese Patent No. 4,174,433. Representative A groups include -CH, (', I
-1. ("H2CdJ4(,'Hz,
C'61(:+(C', H3j,
C6H+oCH2C6H+o-.

-(cH2+6-, -C6H, CH2C6H4- and C8F', 7S02N[02H40C'(,)NHC
6H3(CH3) h is included. The fluorochemical carbodiimides used in the present invention are generally and preferably derived from diinocyanates, but triinocyanates such as 0CNC, H4C1 (2C6H2
(N('O)C'H2('', which can also be derived from 1-14NCO).A mixture of di- and tri-incyanates provides the desired dissolution of a branched but still linear fluorochemical carbosiimide of formula I. We are committed to both flexibility and decentralization.

The 1<I-Q group is preferably a group derived from an incyanate compound, and an aliphatic group such as ('6H, 3-5 aromatic group such as 06H5-, an aralkyl group such as C6H
3('', Hz-17/I/oro& aliphatic group, Example L HA'c'sF+, +cH2-.

('7H,,CH20CONHC6)13(CH3)-
and C3F17SO2N (CH3)C2H40C(J
NHC'61714t'1-t2C6H,- can be expressed as. Organic l<l-Q groups can have a variety of other structures and can be free of heteroatom-containing moieties, such as -0-, -S-, and -he-. However, like the A group, it is preferable that there is no group containing the above-mentioned active hydrogen.

The fluoroaliphatic group Rf is a fluorinated stable, inert,
It represents a non-polar group and preferably represents a monovalent moiety which is both saturated oleophobic and hydrophobic.

It can represent straight-chain, branched-chain and, to a large extent, cyclic groups or combinations thereof, such as alkylcycloaliphatic groups.

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 present between the fluorocarbon moieties of Rf. stably C-bonded,
And without impairing the inert nature of the R4 group, Rf can have a very large number of carbon atoms, but compounds in which -10,000 Rf does not exceed 20 carbon atoms are sufficient and preferred. The reason is that Fi in large groups and k < in small groups
This is because the effective utilization of fluorine atoms in the f group also decreases. Also, when it comes to large bases, it becomes difficult to dissolve in general Vc Ichitsuki solvents. Generally Hf has from 1 to 20 carbon atoms, preferably from 1 to about 12 carbon atoms, and from 4 to 78% by weight.
, preferably 50 to 78% by weight of fluorine atoms. The R4 group of the terminal part (is at least 6 fully fluorinated carbon atoms, e.g. CF3Cf!', CF2
-, and preferred compounds have i< f groups ・ζ-
As in the case of representing the fluoroalk group CnF2H+1,
A compound in which the Hf group is fully K or substantially fully fluorinated.

The function of the linking group Q in formula (2) is to bond the R1 group to the nitrogen atom of the carbodiimide unit.Q is a heteroatom-containing group, a heteroatom-containing organic group, or a combination of these groups Examples are -CH,-, -('')(2C[(2- and -CH2('
)I (CH2-)2, polyvalent aromatic group, oxy group, thio group, carbonyl group, sulfone group, sulfoxy group, -N
(R3)-, sulfonamide group, carbonamide group, sulfonamide alkylene group, carbonamide alkylene group, carbonyloxy7 group, urethane group, for example -(11
□('H20C'ONH- and urea, i.e. -NH(
,'0N)l-. The linking group Q for certain fluorochemical carbosiimides useful in the present invention is
Taking advantage of the ease of preparation of such compounds and the availability of necessary precursors of such compounds, the designated c, QVc
From the above description of , it is clear that the packaging of the linking group with can vary widely. However, as in R1 and AVc, QK preferably does not have the moiety σλ having the active hydrogen atom.

The fluorochemical carbosiimide used in the present invention is typically a solid (eg solid at 20°C), preferably with a melting point in the range of 40 to 150°C. It is preferable that they dissolve at least 10% by weight at 20° C. in n'F-F+2,000 l.

Representative reaction routes for the production of fluorochemical carbodiimides used in the present invention are summarized below. ■
The product designated ' is similar to formula I above.

Path-1 2R1-Q'-(JH+2A (NC(])2-)R1
-Q(N=C:N-A)nl'J=("=He Q,
1 (11' Path 2 +2R1-Q'-0H OCNA-(N=('=JJ-A)nN-C=I'1
-ARC)OR1-Q, (N-C-N-A l n
N = C,, -N -Q-RII'R-Q,' -OH+ B (NCO) a --R
-Q (NL'U )2R-Q (N(,'(J)2
+ B(NCO) 3 +A (N('(J 12 +
The mixture of fluorochemical carbodiimides used in the present invention is generally
Small amounts of fluorochemical diurethane compounds free of carbodiimide groups (e.g. by-products that can form in route 1 < -Q
'-QC(JN)l -A -Nl(eOtJ -Q'
-R).

The charge of this by-product depends on the manner of addition, the cell ratio of the reactants, and the relative reactivity of the incyanate functionality.

Preferred carbonylimino compounds for use in the present invention have the following formula II: A'(NHCO)', (Q, ) x R2]r
II (wherein i<2 is R in formula I
1, and at least one R2 group represents a fluoroaliphatic group Rf, Q and X have the same meaning as defined in formula represents an integer from 2 to 6, and A' represents an organic linking group having 2 to 20 carbon atoms, which is a residue of an organic inocyanate and has no incyanate-reactive group such as an aliphatic hydroxy group; , and Y represents -N-, -'O-m1ko represents -8-. ). R2
,Q.

When there are multiple numbers of Y and X, 1/j: They may be the same or different.

The carbonylimino compound containing a fluoroaliphatic group is preferably 25°C or higher, more preferably 40°C or higher,
And most preferably, it has at least one major transition temperature that is 45°C higher. If desired, the L9 compositions of the present invention can contain a carbonylimino or a mixture of carbonylimine compounds.

Carbonylimino compounds for use in the present invention can be prepared by reacting organic inocyanates with fluoroaliphatic group-containing compounds having ynonate-reactive hydrogen atoms.

A clever subclass of carbonylimino compounds represented by the formula II are those in which X represents 10-, ie, urethanes. Representative carbodiimino compounds of this preferred subclass of J:f) are described in US Pat. No. 3,484,281. They are prepared by a conventional urethane bond-forming reaction between a fluoroaliphatic alcohol and an aromatic inocyanate, preferably an aromatic polyinocyanate. The fluorochemical carbonyl used in the present invention can optionally be added to the reaction mixture containing a fluorine-free aliphatic alcohol, e.g. a fatty alcohol, to produce such a carbonylimino compound. Representative reaction routes for the production of imino compounds are summarized below.

Route 4 rRJQ)x'YH+A'(N('0)r-→A' C
NH, CUY (Q) x R2JrIngredients of the fluorochemical formulations of the present invention (al and useful fluorochemical esters (ti) including those described in the prior art publications mentioned above.

Typical reaction routes for the production of the fluorochemical heptanoester compounds used in the present invention are shown below. Representative R4
What is included in intermediates?

(,'s F 17802N (CtH5)02H4(
JHL"8F1□C'2H4 (JH C7F +50) 120H (','7F+s CON (c2H,)C2H40H
C81! ', □C2)[4SC2)14(JH(CF3
)2CF (CF2)sc2H40H(CFa)2
CF(JC,'2 F4 ('2H40HC8F1□C
2H4502N (C'H3) C4H3 (JHC8F
178()2N ([,'H3)03H6NH2('8
]”1. (”6)44 NH□Cs PI3 C,'
s I-LJ'J ('Ot゛7F,,CH,,NC'
.

("8Ji", 7(, '2H4S1-i(', F', 5
("ON ((n83)) C:2H,SH What is included in typical organic and inonate compounds?

[・Rylene-2,4-diisono-hexamylene di-inosyl-1-methylenepino (4-chlorohexyl-inocyanthate) Methylenebis(4-phenylinosy-yno-1-)quinrylenodiynon-a- 1. 1-meI-l-cy2,4-phenylenecyinoneanate 1-chlorophenyl-2,4-diino/anate p-(,1-1-cyano-toethyl)phenylincyan-tophenylino Typical carboxylic acids or anhydrides that can be used to prepare fluorochemical esters by reaction with cyanate m-)lylinocyanate 2,5-dichlorophenylinocyanatehexylinocyanate fluorochemical alcohols are adipic acid, citric acid, biromellitic acid or their anhydrides and chicken-like ones (
U.S. Patent Nos. 3,923,715 and 4,540,749
This includes the devices disclosed in this issue.

Generally, the fluorochemical-carbodiimide-carbonylimino compound monoester contains about 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 is generally impractical to use large amounts of fluorochemicals such as positive imides, -carbonylimino compounds, or monoesters, whereas fluorine content greater than about 70% by weight is generally impractical. ] Amount F: L (unnecessary to obtain the surface texture of F), which makes it easy to drink, and also has a fluorocarbon (as a liquid solution) compatibility when using the formulation. It is also possible that it raises the issue of capacity.

Other essential components of the formulations according to the invention are fluorochemical oxyalkylenes, hafluoroaliphatic polymers or oligomers (hereinafter, unless otherwise specified, "polymer" shall include oligomers) having the general formula: ■and■・(RflsZ E (R')yZ"' It
■[("Osl [(R')yZ'
B' 1t ]w ■ [In the formula, Rr represents the same fluoroaliphatic group as described in general formula I, 2 represents a linkage in which Rf and (RA)y moieties are covalently bonded together, and R3)y represents a holoxyalkylene moiety, R3 represents an oxyalkylene group having 2 to 4 carbon atoms, and y is at least 5, generally 1.
B represents an integer ranging from 0 to 75 and ranging from 100 to 100 or more (when the above formula represents a single compound) or a number (when the above formula represents a mixture);
represents a hydrogen atom or a monovalent lower organic group; B' represents a group represented by B or a valence bond, provided that at least one
B represents a valence bond connecting the R3 group attached to Z to the other 2, Z represents a linkage in which B or B and R3 are co-bonded together, S is at least 1, and The number 1 represents the U number, which can be 25 or more, t represents the number 1, and 0 or 0, which can be at least 1, and W is more dog than 1. Represents a firefly number numeral or number that can be 30-j or more. ].

When there are algebraic Rf groups in 2) and 2, they may be the same or different.

This applies to the 01 numbers Z, Z, R, B, B, and also to the s, y, and 1[ of 41F in equation (2).

Generally, the oxyalkylene polymer contains about 5 to 40 weight percent carbon Vc't, preferably about 1 to 3 weight percent carbon Vc't.
Contains combined fluorine atoms.

If the fluorine content is less than about 10% by weight, it generally requires impractically large amounts of polymer, while about 3%
If the polymer contains more than 5 parts by weight of fluorine, the solubility will be too low and the polymer will be ineffective.

The above polyoxyalkylene group (R”)yVCite:R
4 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OL:H2CH2-, -0CH,,C
H2-.

0CR(CH3)CH2- and -0CH(CH3)C1
((C stands for homogeneous and represents the same oxyalkylene unit in the above polyoxyalkylene, hapolyoxypropylene, or heterogeneous linear or branched oxyethylene randomly distributed. units or oxypropylene units, or as mixtures, such as in blocks of linear or branched oxyethylene units or blocks of oxypropylene units.One or more catenary bonds are present in the polyoxyalkylene chain. can be interrupted or included in the alkylene chain.

When the catenary bonds have six or more valences, they provide a means for branching or oxyalkylene groups. The polyoxyalkylene groups in the polymer may be the same or different, and they may be pendant.

The molecular weight of the polyoxyalkylene group may be as low as 220, but preferably about 500 to 2500 and even higher, such as 100,000 to 200.00.
It is higher than 0 reeds.

The function of Z and Z representing the linkage is the fluoroaliphatic group Rf5
The polyoxyalkylene moiety (RA) and the groups B and B are covalently bonded together into the oligomer. In other words, when the carbon atom of the fluoroaliphatic group is directly bonded (bonded or linked) to the carbon atom of the holoxyalkyne moiety, Z and Z can represent a single atomic bond.

In addition, 2 and Z each represent i″L1 or more linking groups, such as polyvalent aliphatic groups and polyvalent aromatic groups, oxy groups, thio groups, carbonyl groups, sulfone groups, sulfoxy Also includes groups, phosphoxyl groups, amine groups and combinations thereof, such as oxyalkylene groups, iminoalkylene groups, iminoallysine groups, sulfamide groups, carboamide groups, sulfamide alkylene groups, carbonamido alkylene groups, urethane groups, urea and esters. Bonds 2 and Z for particular oxyalkylene polymers are dictated by the ease of preparation of such polymers and the availability of essential precursors for the polymers.

It is clear from the above description of 2 and 2 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 any so valence bond. However, if 2 and 2 are large and the fluorine content (RfK present) is within the range indicated in the explanation above, then generally the total content of 2 and 2 in the polymer is less than 10% by weight of the polymer. preferable.

The monovalent terminal organic group represented by B is covalently bonded via Z to the poly(oxyalkylene) group.

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 bath solubility of the oxalkylene. The group represented by B is a hydrogen atom, an anol group such as C(O)-, an alkyl group, mtL< is a lower group such as a methyl group, a hydroxyethyl group, a hydroxyethyl group, a mercaptoethyl group, or an aminoethyl group. Alkyl group, spanning phenyl group, chlorophenyl group, methoxyphenyl group,
It may be an aryl group such as nonylphenyl group, hydroxyethyl group, aminophenyl group. Generally, the group represented by ZB is the residue represented by (gslyfu)
Probably lower than Shigeyuki.

The fluorochemical aliphatic group-containing oxyalkylene groups used in the present invention can be prepared by condensation, free radical cleavage or ionic homopolymerization or copolymerization, such as using solution, suspension or bulk polymerization techniques. Various known methods can be used, such as Sorenson and Campbell, "Preparative Methods of Polymer Chemistry," 2nd Edition, Interscience Publishers, 1968 ("Pre
Parative Methods of Poly
merChemistryn, 5orenson a
nd Campbell.

2nd edl, In1rsscience Pu
blishers.

(1968)) VC can be prepared by the method shown.

Representative oxy-alkylene compounds useful in the present invention.

Polyacrylates are a particularly useful group of oxyalkylenes, which include, for example, free radical-opening combinations of acrylates containing fluorochemical aliphatic groups and poly(oxyalkylene) azirylates, such as monoacrylates or diacrylates or mixtures thereof. Polymerization [thus can be prepared. - As an example, Mf-R-02C-cn=
A fluorochemical aliphatic acrylate represented by CH2 (the cage represents e.g. sulfonamidoalkylene, carbonamidoalkylene or alkylene) is
= CHCp)(RF) Y 0CHs can be copolymerized with poly(oxyalkylene) monoacrylate to produce polyacrylate oxyalkylene.

Further discussion of the fluorochemical oxyalgylenes useful in the iC of the present invention is not required since these compounds and their preparation are known and the aforementioned U.S. Pat. Nos. 5,787,551 and 4,289,892 are described for this purpose. , mM are omitted for brevity.

The amounts of each component (ta) and (bJO) may vary over a wide range and will be selected to achieve a desirable balance of properties in the treated fibers of the finished product. , components (al) account for the major amount of the blend and component (b) for the minor amount. It depends on the particular chemical composition of the compound and the application method used.

In commercial applications, it is often advisable to conduct laboratory investigations to determine the appropriate relative amounts of components ta) and (b) to be used to obtain the desired effect.

Generally the relative amounts of components (a) and Ib) will be within the following ranges: (a) 40-99 60-99 7O-95
(b) i -601-405-30 The formulations of the present invention are comprised of (1) an organic solvent solution or an aqueous dispersion of the fluorochemical component and (2) either neat or as an organic solvent bath or an aqueous dispersion. It can be obtained by mixing the fluorochemical poly(oxyalkylene) that may be used. If an aqueous emulsion is the desired form of the formulation, the emulsification may be carried out on formulations containing organic solvents as described above, or may be applied to emulsions containing solvents or emulsions without solvents. Each individual IJVc emulsified component may be blended as a suspension. In the above emulsion manufactured by Makoto, a cationic fluorochemical surfactant (i.e. Cal!; □5O2
N(E-1)C3N(CH),(J) is a hydrocarbon nonionic surfactant (i.e., Tween
Fluorochemical poly(oxyalkylene)s and their mixtures are themselves nonionic surfactants, so they are generally effective when used with 80" polyoxyalkylene (rubitan monooleate). The surfactant may be omitted in whole or in part by adding a fluorochemical poly(oxyalkylene) to the solvent-containing formulation prior to emulsification.

Substrates that are treated in accordance with the invention are textile fibers (or filaments) and finished or manufactured textile products such as textiles, such as carpet, paper, paperboard, and leather. Textiles include nylon and polyester fibers, including those made from natural fibers such as cotton and wool, and those made from synthetic organic fibers such as nylon, polyolefins, acetate, rayon, acrylic and polyester fibers. “About miscellaneous%
Good results are expected.

Treatment of fibers or filaments, such as those described above, in dimensional aggregates, such as yarns, tows, webs, rovings, or manufactured textiles, such as carpets or woven fabrics, with a fluorochemical formulation. I can do it.

This treatment is carried out using known methods commonly used in applying fluorochemical formulations, such as fluorochemical acrylate copolymers, as organic solutions or aqueous or organic dispersions. By,
This is done by applying to fibers and fibrous substrates. (If desired, such known fluorochemicals may be used in conjunction with the fluorochemical formulations described above, such as fluoroaliphatic group-containing polymers such as acrylates and methacrylates.

For example, the fluorochemical treatment may be performed by immersing the fibrous substrate in a bath containing a fluorochemical formulation, by padding the substrate, by spraying the base layer with a 570 fluorochemical formulation, or by sizing foam. , Ki71. This is done by rolling or metering, such as spin finishing, followed by drying the treated substrate if a solvent is present. If desired, the fluorochemicals or formulations may be treated with conventional fiber treating agents (or adjuvants) such as antistatic agents or neat oils (textile lubricants).

In the production of synthetic organic fibers (e.g. Kirku Ozmar, Encyclobetea of Polymer Science and Technology, Vol. 8, 374-404, 19
Kirk-Othrner, 1968.

Encyclopedia of polymer 5c
ience and Technology, 8. 3
74-404.1968+7), the first step that usually occurs in the process and involves the initial formation of filaments (e.g. by Nord spinning or solvent spinning) is
A small amount of textile finish containing lubricants and anti-static agents (
(generally less than 2% active solids based on the fiber) is applied 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 finishing agents applied to such textile fibers.

Textile finishes are mainly dilute aqueous emulsions or oils ("
It is generally produced in the form of "neat oil".

Typical lubricants include mineral oil, wax, coconut oil, vegetable oils (triglycerides) such as peanut oil and castor oil,
Includes esters, synthetic oils such as polyoxyethylene derivatives of alcohols and acids, and licone oils.

Antistatic agents, emulsifiers and surfactants added to the textile finishing agent are selected from similar chemical groups, including: fatty acid soaps, (IIF oxidized vegetable oils, alkyl and ethoxylated Anionic agents such as alkyl phosphates.

(b) Cationic agents such as fatty acid amines, quaternary ammonium compounds and quaternary phosphonium compounds.

(C) Chryceryl monooleate 1. Non-ionic agents such as ethoxylated alcohols, 4-ethoxylated fatty acids and ethoxylated fatty amines.

td) Amphoteric agents such as betaine, amino acids and their salts.

A method of applying the fluorochemical formulations of the present invention to synthetic fibres, is to apply a sufficient amount of the above-described fiber finishes to obtain the desired properties such as oil repellency, water repellency and dirt resistance. Melt by adding it inside. Generally, the amount of fluorochemical formulation to be used is sufficient to coat the fibers of the finished product, e.g., about 2 fluorochemicals by weight of the fibers in carpets.
00 to 1600 pprn of fluorine. These additions to traditional textile finishes meet the typical demands that textile finishes must meet: lubrication, thermal stability, low smoke at high temperatures, textile dyeability (pigmentation ) can be done without sacrificing or adversely affecting wettability. The conventional finish components of fiber finishes containing the fluorochemical formulations of the present invention are removed by conventional methods after the fibers have been made into textile form, such as carpets and upholstery. Fluorochemical formulations can withstand typical conditions during fiber and yarn processing processes such as scouring, scouring and dyeing, washing, steam cleaning and dry cleaning. Survives even in harsher conditions such as those encountered in finished products. Fluorochemical formulations do not interfere with normal fiber processing processes, such as drawing, surface texturing, and heat setting, and are capable of withstanding such processes in finished products, such as carpets made from treated fibers. Provides oil repellency, water repellency 2 and dirt water resistance.

Conventional application methods used to apply finishes to fibers (straddle filaments) can also be used with the fluorochemical formulation-containing finishes of the present invention. Such methods include the use of either: (a) a rotating ceramic cylinder 9 or kiss roll, which is partially immersed in a pan containing the finishing agent, over which the filament moves; (c) a metering pump which supplies the finishing agent through a slot or hole in the fiber guide, over which the filament passing passes to obtain an auxiliary film of finishing agent; (c) an immersion finishing bath, or (d) The spraying equipment uses the fluorochemical formulations of the present invention, which are generally compatible with commercially available neat oil textile finishes (i.e., dispersed therein or sufficiently bath-dissolved), and may therefore be mixed with and applied together with them. (It may be applied before and after kneading). A neat oil finish of the fluorochemical formulation is used to increase solubility in the agent;
A solubilization aid such as el 1osolveJ may be added.

Representative fluorochemical carbodiimides having the following general formula V 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)n-Q-RV compound
Rooster-” rot* R-□Q Ai
C8P',,-3OiN(C2Ha)CJ(,0CO
NHCACH, Q2CaF+ 7 802N (C2H
5) C, I (OCONH Hell (C 几) 3 C8F
', 7-30 (C crystal β le C) CM to CONH, (,
H4'eaFl? Q specialized ℃0NHC6
H4Cf (2α mountain 5 C8F, -C, tv (x) tJ(C4BB(CH,)*: For all listed compounds, n has an average value of 2 except for compound /I62. , for the compound/162, n has a value of approximately 1.8.

Table 2 lists representative fluorochemical oxyalkylenes useful as component (b) in the fluorochemical formulations of the present invention.
Shown below. In addition, in the production of fluorochemical oxyalkylenes, products containing mixtures of oxyalkylenes are desired, with varying lengths of fluoroaliphatic groups and polyoxyalkylene moieties. and the sub-symbols representing the number of carbon atoms in the former and the number of oxyalkylene units in the segment in polyoxyalkylene represent the average number in both cases;
In this specification, for example, in Table 2, unless otherwise specified, it should be understood that such an average value is assumed.

Table 2 1・08F+75O2N (CJ(p)CH2CO2
(C, crosspiece 0),, H”-Cat”17802N ((A)
C2H40((JItO)+4H" C8F+yc2
B40 (C+lJ, O) +sH5, Ca&5OzN
(c!a)C2J(,0(CsHaU)CH7C mountain, 5
O2N (C2H3) C2H40 (C21 circle 0)7.
58 Representative fluorochemical oxyalkylene polyacrylates useful as components (bJ) in the formulations of the present invention include:
Any of the fluorochemical acrylates in Table 6 in Table 4
It is produced by copolymerizing with any of the fluorine-free polyoxyalkylene monomers.

Table 6 1, CgF+ySO2N(CHa)CH2CH,,00
CCH=Cru.

2, ,C,F,3c2H400CC(Cle)=CH,
.

3, C,F,,C2H45C2H,00CCH=Cf
(2゜4, C8F, 7C2H4(J)OCC(CH,
), =CH.

5, C8F+7CJLN((J(a)c2&0(-)
CO(CHa)=CHz.

& C2F, C6F, oCH,,00CCH=CH2゜7, C7F,,CH,oOccH=cH2a C? F
15CON(C[)C2H400CCH=CH,.

9, (C11i', 1)20P'(CF2)acH2
CH (0 average C average 00 CCH=CH2゜1(L (CF3
)2CFOC2F, C2H400CCH=CH2゜11
,qF,,C,H4502N(C3H7)92B4
00CCH=CH2゜12, C7F,,C,[(,
C0NHC4H1IJOCCH=CH2゜1, c7
y, coocH2c(cn3)2cJ+pocc(cn
3)=cH215, C occupancy, 5qN(C,,H,,)C4
H80oCCf (=CH2゜16, (03F?)2
C6) 1,302N(CH3)C2)I400CCH=
CH2゜1a C, F, 7CF=CnCH2N(
cn,)C2J-J40gccu=CH2゜'”
Cf”tySOzN (C4”10) C! FI40
COCH=C1%20,, Cat! ”+7’:’0
zN(02B5)c2Il(40COCH(CH3)=
CH2 table 4 1, ca-cnco2 ((Ao)10(ciao)22
(c2ao)Qc2ao2ccn=CH2"C1(2-C"CO2'(C21(40L7CH
35C) 12=C(Cf(a)CONH(Cs”aO)
a+H4c5=c(Ckfs)C02(CAO)poc
oc(al(3)-ct-r, 2a H8(C2H4
0)23(CsaO)3s(CJ+0)t2c2f(,
SH Specific fluorochemical oxyalkylene polymers are the polymers in Table 5 described in terms of their monomers and relative amounts of the monomers.

Table 5 Monomers - Weight ratio of Table 4 in Table 5 1, 191 3.0/70 2 1 2 6 s/35 3 1 4 50/da 0 4 20 1 30/70 Any other suitable comonomer, For example, strong butyl acrylate containing fluoroaliphatic groups.

acrylonitrile) IJ, etc., can be used with fluorochemical acrylates and oxyalkylene comonomers at up to about 2°5% by weight to improve the compatibility or solubility of component (b), fluoroalkylene oxyalkylene, in the fiber finish. Can be copolymerized.

Fluorochemical acrylate monomers (Table 3) and fluorochemical polyoxyalkylene monomers (Table 4)
Although the weight ratio of fluorine to carbon can be changed, the fluorine content of carbon bonds in the resulting copolymer is within the desired range of 5 to 40% i%.
The above optional comonomers should be chosen as per the above.

Representative fluorochemical urethane compounds useful as component (a) in the practice of the invention are shown in Table 5A1711.

Table 5A 1, CC3F+7SOdN (CI5) C2840C
ONH: ] 2 (2H3 (CI too) 2, ROC (JN
l(C6)J, CH2C, H3(NHCOOR)CH4
In the J4NHCOOR table, two of the groups R are C, F, 5
o2N (C2 remaining) C2I (represents 4-, one is C, 8
Represents H, 7-.

The objects and effects of the present invention will be explained in the following examples.

Example 1 Methylene bis(4-phenylene isocyanate) 37517' was placed in a 2-liter 6-necked flask equipped with a mechanical stirrer, a condenser, 9 drops of hot sake, and an electric heating mantle.
(, 1,5 mol) and methyl ethyl ketone (MEK)
I put in 481 f. This stirring power g heat (80-83℃
) Sita solution K N -x 4- # (Herfluorooctane) sulfonamide ethyl alcohol 554 jF
(1.0 mol) was added over 3 hours and stirring and heating continued for a further [3 hours].

Camphenphenylphosphine oxide C,oH,, POC6H1,7
, 4f, the carbodiimide-forming catalyst was added and the reaction mixture was stirred and heated at about 80° C. for 8 hours. At this time, substantially all of the in-cyanto groups are ■R1]&
It had been converted to a carbodiimide group as shown by yield analysis.

This solid fluorochemical carbodiimide product is shown in Table 1 as Compound A1.

Practical IA8J Examples 2-5 Other fluorochemical carbodiimides of Table 1 were prepared following the general procedure of Practical IM IZll 1, except that the reagents in Table 6 were used at the molar concentrations shown in Table 7. Reagents in Table 6 are designated by symbols such as A-1 for later reference.

Table 6 Alcohol reagent A-10Jr+ -t 802N (Ct's) C2
j (4 (J HA -2C8F, 7SO2N (C4)
C21J, 40) JA -5C8F, -14 to 7C2
(Jl (Table 7 Reactant (mol) Material Alcohol 2 A-112J TDI (2
, 8) 3 A-21VN) 1 4 A-5MDI 5 A-3TDI Note 2 This number corresponds to the compound number in Table 1 **: All alcohol/inside reagent molar ratios are as in Example The scores other than 2 were 2/3.

Examples 6-19 In each of these examples, a golden yellow, 9 cut-pile pre-soaked nylon carpet (
Surface spray application (25% moisture pick-up) of a diluted mixture of an aqueous emulsion of the fluorochemical carbodiimide compound/i61 of Table 1 and an aqueous emulsion of a hyfluorochemical oxyalkylene (25% moisture pick-up) and treated by VC as specified in Table 8. The fluorochemical component (a) required for the amount of fluorochemical deposited on the carpet is
The emulsion mixture was diluted with water to obtain the desired concentrations of ) and (11).
It was dried at 130° C. for 30 minutes and further dried at 130° C. for 10 minutes. For comparison, Comparative Examples C-1 to C-Q were tested, in which one of the carpet treatments used a fluorochemical component of Taso God (C-1 to C-8), or Comparative Example C No treatment was applied that would give a score of -9.

Oil repellency (OR), water repellency (-WR) on treated samples
) and the play Walk-on Soil ('Waik-on
5 oil) (WOS) was measured. The data are summarized in Table 8.

Water repellency testing is a test method often used for this purpose. Aqueous stains of treated samples -t Aqueous stains are measured using the water/inopropyl alcohol test and expressed as a water repellency rating for the treated carpet or fabric. Treated carpets that are penetrable or resistant only to a mixture of 100% water and 10% Inglobil alcohol (the test mixture has low penetration) are 1001
A rating of 0 was given, while resistant to the 0% water/100% Inglobil alcohol mixture (the test mixture is also highly penetrating) 8! [Give a score of 0/100.] Other intermediate values are determined using other water/inpropyl alcohol mixtures in which the % amounts of water and inglovir alcohol are each 10 times the same. The water repellency rating is whether it penetrates into the fabric after 10 seconds of contact.
or correspond to the most penetrating mixtures that do not moisten them. 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. The oil repellency of treated carpet and textile samples was determined by the Technical Manual of the American Association of Textile Chemistry and Laboratories (AA).
TCC) (Technical Manual
and Year-book of the A
merican As5oiation ofTe
xtile Chemists and Co1
orists) as measured by Standard Test Method 118-1978. This test is based on the resistance of treated fabrics to oil penetration with the surface tension of cotton. Panugol (a mineral oil brand with the lowest penetrating power among the test oils)
A processed fabric with a pattern only for “Nujol)” [
A rating of 1 is given, while a value of 8 is given to the treated adjacent fabric with +it properties for the most penetrating heptane. Other intermediate values are determined using other pure oils or mixtures of oils. Ikuo oil was rated for 10 seconds of contact compared to the standard test of 30 seconds of contact.
'1. Corresponds to the most penetrating water or oil mixture that does not wet the water. The strawberry has better oil repellency than the strawberry. Oil repellency of 2F or greater is generally desirable for carpets.

Soil resistance of treated carpet and untreated Carbella l- (control) was determined by exposure to foot traffic according to AAT CC test method 122-1979. The exposed area was a heavily trafficked industrial area exposed to approximately 15,000 traffic. Periodically to ensure even exposure, the sample was replaced and tested. instep 2
Vacuum suction was applied every 4 hours and before visual assessment. The following ``Wo 1lc-On'' was used for evaluation.
-Soiling)” (Wo8) WOS rating using the rating system Description 0
Comparative example vc is equal.

±y2 Slightly 5 points (+) or slightly worse than the comparative example
-±1 Clear difference compared to the comparative example.

±14 Very obvious difference compared to the comparative example.

±2 Very noticeable difference compared to the comparative example.

a) 2% SO, F means fluorochemical solid precipitation amount (%) on the fabric b): Wo8 was treated with fluorochemical-carbodiimide only (Example/16C-8, 'VvO8 = 0) Means the water-on-oil value for carpets.

c): NWR means non-water resistant.

The data in Table 8 shows useful oil and water repellency from all formulations (Examples 6-19) and soil resistance for most formulations was better than or equal to that of the comparative examples. central 77i
Their %1 lives obtained with liIyυ6 to 19 are particularly noteworthy compared to comparative 1jc-1 to C-7.

Examples 20-22 According to these examples, the fluorochemical carbodiimide of Compound/161 in Table 1 as component taJ and the component (
Treatment of nylon carpet fibers as b) with an aqueous emulsion of the fluorochemical oxyalkylene formulation of the invention/in combination with an aqueous emulsion of a spinfinishing lubricant based on palm front and the dyeing produced from the treated fibers. Explain the test results for carpet.

The finish compositions used for these examples included fluorochemical solids to spin finish lubricant solids in a ratio ranging from 0.18:1 to Q, 14:1. It was done.

The spin finish emulsion was applied to the melt spun, undrawn nylon 6 fiber yarn using a dimensionally adjusted slot applicator. This yarn was made of 118 filaments of 18 denier (per filament). Immediately after application, 1.0 to 1.5% by weight of the oil component was deposited on the fibers.

The treated yarn is continuously drawn and woven to create a level-
Loop (1evel-1loop) carpet (28oz
/yd2), heat treated at 196°C for 1 minute, acid dyed, air dried at 70°C for 60 minutes, heated at 1,60°C for 10 minutes, and then oil and water repellent, water-on soil resistant and fluorinated. The retention of the fluorochemical treatment throughout the dyeing process, as determined by analysis, was evaluated. The test results are shown in Table 9. Comparative example C-10, 'C-
No. 11 was carried out, and in one of them, the fluorochemical treatment was omitted, and in the other, treatment with only the fluorochemical component of the Dassey building, that is, the carbodiimide of the compound of Table 1/I61 was introduced.

The data in Table 9 is based on the formulations described above (Example A20°21, 2
Comparative Example C-
This indicates that the score was better than 10. Especially Comparative Example C-1
Noteworthy is the higher retention value of the formulation compared to 0.

In these examples, in Example 23-2, two different raindrops were prepared by an aqueous emulsion of a blend of the compound of Table 1 as aJ/fluorochemical oxyalkylene of I61 and the fluorochemical oxyalkylene as component (b). The worn fabric was subjected to a padding process and heated at 150°C for 1
Dry for 0 minutes and evaluate initial oil repellency (OR) and resistance to water spray (SR), then wash again for 5 times (5
These properties were evaluated after L) and after one additional dry cleaning (DC).

The above AA T CC standard test method 118- is used for the OR test.
1978 was used. A pre-measurement contact time of 30 seconds is specified and an OR value of 5-J or better is preferred for rainwear fabrics.

The treated fabrics were washed using a mechanically agitated automatic washing machine with a capacity of 4 kf of laundry, using 50°C water and commercially available detergent. Next, the washed fabric is placed in an automatic dryer for 70 minutes.
It was spin-dried for 4 hours at 0.degree. C. and pressed in a flat-bed press at 154.degree. C. before measurement.

The treated fabric was washed in a dry cleaning detergent containing 1% chloroethylene and a motor-driven tumble jar (AA).
TCC test method 7O-1975) using rotation at 25°C.
Dry IJ-ning was carried out for 20 minutes. 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.

Table 10 shows the data together with Comparative Examples C-12 to C-19.

*: Example 26.2'4 and Comparative Examples C-14, C-1
The fluorochemical oxyalkylene 26 used in Example 5 and the fluorochemical oxyalkylene used in Example 42 C-16, C-17 are listed in Compound A63 in Table 5.

Material: Fabric A is 100% nylon taffeta (dense Δ
Fabric B is a 100% polyester woven fabric.

The data in Table 10 was revised to 01 (for most formulations compared to one or the other ingredient alone).

It is shown that resistance to S1ζ and washing baths and dry cleaning properties were obtained.

Examples 27-40 In the following examples, aqueous emulsion formulations of the fluorochemical urethanes of Table 5A and several different fluorochemical oxyalkylenes were used to treat nylon carpets, using the procedures of Examples 6-19. Followed the fox. The dried samples were evaluated for OR, WR, and WOS, and the results are summarized in Table 11.

The data in Table 11 shows that all formulation examples have better OR and WO8 than untreated carpet, C-21, and many of the formulation examples have better WR than untreated carpet (C-21). Indicates that it has. Additionally, all formulation examples exhibited better WO8 than Comparative Examples C-1 to C-7 using only the fluorochemical oxyalkylene component. WO8, which is better than Comparative Example C-20 in which half of Formulation Run 1 used only the urethane fluorochemical component.
It is worth noting that it was shown that

Example 41.42 Following the procedure of Examples 23-260 above, two rainwear fabrics were prepared with (a) fluorochemical urethane 2 of Table 5A as component and (b) fluorochemical oxyalkylene 3 of Table 5 as component. The initial OR and SR were evaluated by treating the mixture with an aqueous emulsion and drying at 150 °C for 10 min, then again after 5 L (/c1 further K and one DC
These properties were later evaluated. The results are shown in Table 12.

The data in Table 12 shows that the initial and 5 L oil repellency obtained with the formulations of Examples 917H41 and -42 was the same as that of Comparative Example C-22.
, C-23 showed better results than those obtained with the fluorochemical urethane alone. Comparative examples C-22 and C-23 using only fluorochemical urethane
The resistance to dry IJ-2ing obtained with the formulation of Example//'g41.42 compared to the formulation of Example //'g41.42 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.

Patent Applicant: Minnesota Mining and Manufacturing Corporation

Claims (1)

[Claims] fl) (a> one or more monovalent fluoroaliphatic groups having at least 3 fully fluorinated carbon atoms and one or more nitrogen-containing polar A fluorofatty group-containing compound having residues as described above and the residues linked together by a heteroatom-containing group or a linking group, usually a solid, water-insoluble fluorocarbon compound. Compositions consisting of chemical compounds, parabolites, or mixtures of compounds; oxyalkylene, also a mixture of 7-alkylenes, the polyoxylene having one or more of the above fluoroaliphatic groups and one or more polyoxylene residues; A composition comprising a composition in which the group is etherically linked to a heteroatom-containing group or an organic linking group or combinations of such groups. 2) The fluorochemical composition (a) has the following general formula: R1 + Q +
or 1, A' represents a divalent chain linking group that can contain a fluoroaliphatic group R, R1 represents a water atom, the above Rf or an organic group, and Q represents a divalent The composition according to claim 1, wherein the composition is a heteroatom-containing group or an organic linking group, or a combination thereof. (3) The fluorochemical composition (a) has the following formula: % formula % (wherein, H-Q is C3F17SU2N ('CzHs
) C. 0CONH-, A is -c6H4CH,C6)L
-, and n represents 2. ) The composition according to claim 1. (4) The fluorochemical composition (a) has the following formula ゛A'
CNH,CO,Y(QlxR2b (wherein A' represents a residue of an organic inocyanate, Y represents monoh, -0- or -S-, and Q represents a divalent heteroatom-containing group or an organic R2 represents a hydrogen atom, a fluoroaliphatic group or an organic group, and at least one R2 represents a fluoroaliphatic group; 8 represents 0 or 1; The composition according to claim 1, wherein r represents an integer from 1 to 10. (5) The fluoroaliphatic group-containing polyoxyalkylene has the following general formula: % formula % )) (wherein, Rf represents a fluoroaliphatic group, Z represents a covalent bond between R( and (l(3)y), (l(31y represents a polyoxyalkylene group, and and R3 represents an okylene alkylene group having 2 to 4 carbon atoms, y represents an integer of at least 5 and may be 100 or more, and B represents -(11fi of represents a terminal cleavage group, B' represents a group represented by B or a valence bond, provided that at least one 15' is a ZK bond and r: (R")y group 0-7!: , NoZ Vc bond L and 7L Vc II
III represents a covalent bond between the group represented by B or B' and the group represented by (R'')y, and S represents a small number (at least 1 and 25 or more). t represents an integer or number that is at least 1 and may be greater than or equal to 60; The composition according to claim 1, wherein the fluorochemical polyoxyalkylene is
CRF 17502N (CH3) C2H402CC
H"-CH2 and (:'H2=C(CH3) (,'O
z (C2H40)9o COC(CH31= CH2
and the fluorochemical composition (a) has the following formula: % formula % where R-Q (1'i C5Hty SO+N (
C2H5) C2H40CONH-, A represents -C6H, CH2C6H, -, and n represents 2. ) The composition according to claim 1. (7) , (al having one or more monovalent fluoroaliphatic groups with at least 6 fully fluorinated carbon atoms and one or more nitrogen-containing polar residues) , fluoroaliphatic group-containing compounds, usually solid, water-insoluble fluorochemical compositions, in which the groups and residues described above are linked together by a heteroatom-containing group or an organic linking group; or a composition consisting of a mixture of said compounds: and (b) a polyoxyalkylene, normally liquid or low-melting solid, water-soluble or water-dispersible, containing a fluoroaliphatic group; or Eri having many polyoxylene residues, the above groups and the polyoxylene residues are linked together to a heteroatom-containing group or a mechanically linked lJ group or the combination thereof (8) The fluorochemical composition (a) comprises a fluorochemical composition (a) containing a fluorochemical composition (a) containing a fluorochemical composition (a) containing a fluorochemical composition (a) containing a fluorochemical composition (a) of
The fiber finishing agent according to claim 7, which represents a -carbodiimide compound, -ester compound, or -carbonyl, imino compound containing a fatty acid radical. (9) Surface treatment of a fibrous base material (fiber finishing agent according to claim 8, which imparts oil and water repellency to the base material. α0(a) At least three completely fluorine one or more monovalent fluoroaliphatic groups having carbon atoms and one or more nitrogen-containing polar residues, and the above groups and residues are heteroatom-containing groups. or a composition comprising a normally solid, water-insoluble fluorochemical composition, or a mixture of compounds, such as a fluoroaliphatic group-containing compound linked together by an Atsuki linking group, and (+) ) normally liquid or low-melting solid, water-soluble or water-dispersible polyoxyalkylene containing fluoroaliphatic groups, or having boriogythia groups and one or more polyoxylene residues; The polyoxylene residues are combined with a heteroatom-containing group or an organic linking group or a composition comprising a mixture of polyoxolenes bonded together. fibrous base material.