Note: Descriptions are shown in the official language in which they were submitted.
BLENDS (~F FL~OROCHE~IC~LS
AND F~BXCUS S~lBSTR~TES TREATED T~EREWITH
,
This invention relates to the treatment of
fibrous substrates~ such as textile fibers, paper, and
leather, with fluorochemical compositions to impart oil and
water repellency, and to the resulting treated substrates.
In another aspect, it relates to the treatment of carpet
fiber ~ith a finish comprising a fluoroaliphatic radical-
containing composition to impart oil and water rspellency
and soil resistance to such fiberO In another aspect, i~
relates to fluoroaliphatic radical-containing compositions,
and their preparation, which are useful in such treatment.
In the industrial production of textiles, such as
carpet and apparel, and such other fibrous substrates as
paper and leather, it is common to treat such substrates
with fluorochemicals containing luoroaliphatic radicals
(often designated by the symbol "Rf") to impart oil and
water repellency to the surface of such substrates. ~luoro-
chemicals of this tyue and theix application to fibrous
substrates are described in various prior art publicdtiorls,
e.g., U.~. Patent Nos. 3,329,661 (Smith et al), 3/458j57
(Tokoli), 3,574,791 ~Sherman et al), 3,728,15i (Sherman et
al), 3,916,053 (Sherman et al), 4,144,367 (Lar,duccij,
3,896,251 (Landucci), 4~024,178 (Landucci), 4,165~33
(Katsushima et al), 4,190,545 (Marshall), 4,215,205
(~anducci), 4,013,627 (Temple), 4,264,484 (Patel),
4,029,585 (Dettre), 3,462,296 (Raynolds et al), and
4,325,857 (Champaneria et al), and Banks, R. E., Ed~
"Organofluorine Chemicals and their Industrial
Applications", Ellis Horwood, Ltd., West ~ussex, En~land,
226-230 (1979).
Althou~h some Eluorochemicals are useful in many
applications and many are commercial products, some ara
relatively expensive to prepare and apply, others are
difEicult to apply, and others are not durable or do not
impart the required properties to the extent desirad.
--2~ 3
Conventionally, fluorochemical compositions have
been coJ~mercially applied as a top coating to the finished
fibrous article, such as carpet~ Recently, several
fluorochemical compositions have been commercially applied
to textile fiber or yarn during its manufacture before it
is woven or fabricated into the finished art~cle. However,
some of these fluorochemical compositions have had limited
success for various reasons including incompatibility or
reactivity of the fluorochemical with fiber finish compo-
10 nents such as lubricants, lack of durability of thefluorochemical on the treated fiber to dyeing or other
fiber manufacturing operations, and insufficient water and
oil repellency and soil resistance in the finished article.
It is an object of this invention to provide
15 blends of (a) fluoroaliphatic radical-containing compounds
which impart oil and water repellency, such as fluoro-
aliphatic radical-containing carbodiimide (hereinafter
often called fluorochemical carbodiimides for brevity), or
fluoroaliphatic radical containing esters (hereinafter
~0 call~d fluorochemical esters), or fluoroaliphatic radical-
containing carbonylimino compounds (hereinafter often
called fluorochemical carbonylimino compounds for brevity),
and (b) fluoroaliphatic radical-containing
poly(oxyalkylenes) (hereinafter often called fluorochemical
25 oxyalkylenes for brevity), said blends being useful for
treating textile fibers and other fibrous substrates to
impart oil and water repellency thereto.
Another object of this invention is to provide
blends of fluorochemical carbodiimide, carbonylimino, or
30 ester compounds and fluorochemical oxyalkylenes, which
blends can be used to treat textile ibers in cornbination
with or as a component of fiber finishes, e.g. spin-finish
lubricants, such blends being compatible with said fiber
finishes and not interfering with normal textile fiber
35 processing steps.
A further object of this invention is to provide
fluorochemical-treated textile fiber with a high percentage
l.~f~
--3--
of the fluorochemical retained on the fiber through ~iber
processing and dye~ng steps, and with durable water and oil
repellency and soil resistance properties.
It is yet another object of this invention to
5 provide blends of fluorochemical carbodiimide, car-
bonylimino, or ester compounds and flurochemical oxy-
alkylenes which can be used in the form of organic
solutions or aqueous dispersions to treat fibrous
substrates such as textile fibers, filaments, yarns, or
finished fibrous articles, e.g. carpets, and other fibrous
substrates such as paper and leather, to impart oil and
water repellency thereto.
Briefly, this invention provides, in one aspect,
compositions comprising blends of: (a) normally solid,
15 water-insoluble, fluorochemical compositions which impart
oil and water repellency to fibrous substrates and are
fluoroaliphatic radical-containing compounds such as
carbodiimide, carbonylimino, or ester compounds, or
compositions comprising or consisting essentially of
20 mixtures of said compounds, which compounds have one or
more monovalent fluoroaliphatic radicals (Rf) and one or
more polar moieties such as carbodiimido, carbonylimino,
and/or ester moieties, such radicals and moieties bonded
together by hetero atom-containing or organic linking
~5 groups; and (b) normally liquid or low melting solid, water
soluble or dispersible, fluoroaliphatic radical-containing
poly(oxyalkylenes), or compositions comprising or con-
sisting essentially of mixtures of said oxyalkylenes, which
poly(oxyalkylenes) have one or more monovalent fluoro-
aliphatic radical (Rf) and one or more poly(oxyalkylene)moieties, such radicals and oxyalkylene moieties bonded
together by hetero atom-containing groups or organic
linking groups, or combinations of such groups. ~aid
fluorochemical blends of components (a) and (b), some of
35 which blends are novel per se (viz., where the polar moiety
is a N-containing polar moiety) are useful in the form of
organic solutions or aqueous dispersions in the treatment
J'~ ;3f. s ~
--4--
557-2680
of fibrous substrates, such as textile fibers (or :Eilamen-ts) duriny
their manufacture, and useful also in the treatment of finished or
fabricated fibrous substra-tes such as carpe-ts, paper, and leather,
to impart oil and water repellency -to the surface thereof.
According to one aspect of -the presen-t invention there is
provided a composition comprising a blend of:
(a) 40 to 99 weight percent of a normally solid, water-
insoluble, fluorochemical composition which is a fluoroaliphatic
radical-containing compound, or composition comprising a mixture of
1~ such compounds, said compound having one or more monovalent fluoro
aliphatic radicals having at least three fully fluorinated carbon
atoms and one or more polar moieties selected from carbodiimido,
carbonylimino, ester moieties and combinations thereof, said radi-
cals and moieties being bonded together by hetero atom-containing
or organic linking groups selected from polyvalent aliphatic, poly-
valent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy, -N(CH3)-,
sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene,
carbonyloxy, urethane, urea, and combinations thereof; and
(b) 1 to 60 weight percent of a noramlly liquid or low
~1~ melting solid, water soluble or dispersible, fluoroaliphatic radi-
cal-containing poly(oxyalkylene), or composition comprising a mix~
ture of such poly(oxyalkylenes), said poly(oxyalkylene) having one
or more of said fluoroalipha-tic radicals and one or more poly(oxy-
alkylene) moieties, said radicals and poly(oxyalky]ene) moieties
bonded together by hetero atom-containing groups or organic linking
groups selected from polyvalent aliphatic, polyvalent aromatic, oxy,
thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, oxyalkylene,
~3
-4a- 557-2680
iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamido-
alkylene, carbonamidoalkylene, urethane, uxea, ester, and combina-
tions thereof.
According to a fur-ther aspect of -the present invention
there is provided a fi.ber finish comprising an organic solution or
aqueous dispersion comprising a blend of:
(a) 40 to 99 weight percent of a normally solid, water-
insoluble, fluorochemical composition which is a fluoroaliphatic
radical-containing compound, or composition comprising a mixture of
la such compounds, said compound having one or more monovalent fluoro-
aliphatic radicals having at least three fully fluorinated carbon
atoms and one or more polar moieties selected from carbodiimido,
carbonylimino, ester moieties and combinations thereof, said radi-
cals and moieties being bonded together by hetero atom-containing
or organic linking groups selected from polyvalent aliphatic, poly-
valent aromatic, oxy, thio. carbonyl, sulfone, sulfoxy,-N(CH3)-,
sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene,
carbonyloxy, urethane, urea, and combinations thereof; and
(b) 1 to 60 weight percent of a normally liquid or low
~n melting solid, water soluble or dispersible, fluoroaliphatic radi-
cal-containing poly(oxyalkylene), or composition comprising a mix-
ture of such poly(oxyalkylenes), said poly(oxyalkylene) having one
or more of said fluoroaliphatic radicals and one or more poly(oxy-
alkylene) moieties, said radicals and poly(oxyalkylene) moieties
bonded together by hetero atom-containing groups or organic linking
groups selected from polyvalent aliphatic, polyvalent aromatic, oxy,
thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, oxyalkylene,
-4a-
.
-4b- 557-2680
iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamido-
alkylene, carbonamidoalkylene, urethane, urea, ester, and combina-
tions thereof.
A class of such fluorochemical carbodiimides (component (a)
of said blends) can be represented by the general formula
R ~QtXtN=c=N-AtnN=c=NtQtxR
which formula generically encompasses individual compounds or re-
presents a mixture of such compounds as they are obtained from reac-
tions used in their preparation.
Fluorochemical carbodiimides useful in this inven-tion and
their preparation are described in United States Patent No.
4,024,178 (Landucci).
In formula I, "n" is a number (in the case where the for-
mula is that of a mixture) or an integer (in the case where the
formula is that of a compound) of 0 up to 20, preferably 0 to 10
and most preferably 0 to 5 t and "x" is 0 or 1. Each Q is the same
or different divalent linking group. A is a divalent organic link-
ing group which can contain a fluoroaliphatic radical, Rf, each A
being the same or different. Each Rl is the same or different and
is selected from H, Rf, and terminal monovalent organic radicals
such as alkyl, cycloalkyl, aryl, and combinations thereof, e.g.
aralkyl, which radicals can contain hetero moieties, e.g. -O-, -S-,
-N-, -Si-, and -CO-, and is preferably free of active (or isocyanate-
reactive~ hydrogen atoms (i.e., hydrogen atoms of yroups, such as
mercapto, amino, carboxyl, and aliphatic hydroxyl groups, that can
react readily with isocyanate under urethane bond-forming conditions,
e.g., 20 to lOO"C). Generally, Rl will have no more than about 18
-4b-
-4c- 557-26gO
carbon atoms. Where Rl is said Rf, -the subscript x of the adjacent
Q must be 1 and not O because R~ cannot be directly bonded to a N-
atom of the
~3 -4c-
~ ~f~
carbodiimide group. There is at least one Rf radical
present in one or ~rore of the Rl and A groups for a given
compound.
In the above general formula I, the divalent
5 organic linking group A connects successive carbodiimide
moieties when n is 1 or more. Illustrative linking groups
A are alkylene groups, such as ethylene, isobutylene,
hexylene, and methylenedicyclohexylene, having 2 to about
20 carbon atoms, aralkylene groups, such as -CH2C6H~CH2_
10 and -C6H4CH2C6H4~, having up to 20 carbon atoms} arylene
groups, such as tolylene, -C6H3(CH3)-, poly(oxyalkylene)
groups, such as -(C2H4O)yC2H4~ where y is 1 to about 5, and
various combinations of these groups. Such groups can also
include other hetero moieties (besides -O-), including -S-
15 and -N- However, A is preferably free of groups with said
active hydrogen atoms.
The A group can be a residue of an organic
diisocyanate (from which the carbodiimido moiety can be
derived, that is, A can be the divalent radical obtained by
20 removal of the isocyanate groups from an organic
diisocyanate. Suitable diisocyanate precursors may be
simple, e.~. tolylene-2,4-diisocyanate, methylene
bis~4-phenyleneisocyanate), and mixtures thereof, or
complex, as formed by the reaction of a simple diisocyanate
25 with an organic diol or polyol in appropriate proportions
to yield an isocyanate-terminated polyurethane. Other
isocyanates can also be used as starting materials. Some
of these are described, for example, in U.S. Pat. No.
4,174,433. Representative A groups include
30 -CH2C6H4CH2C6H4CH2-, -C6~3(C~3)-, -C6H10CH2C6~l10-,
-(CH2)6-, -C6l14CH2C6H4-, and
CgF17SO2N[C2H4OCONHC6H3(CH3)~2. Although the fluoro-
chemical carbodiimides used in this invention generally and
preferably are derived from diisocyanates, the
fluorochemical carbodiimides can be derived Erom
triisocyanates, e.g. OcNc6H4cH2c6H3(Nco)c~l2c6H4Nco. A
mixture of di- and -tri-isocyanates can be used to provide
--6--
fluorochemical carbodiimides which are branched but still
retain ~he desired solubility and dispersibility
characteristics of the linear fluorochemical carbodiimides
depicted by formula I.
The Rl-Q groups are preferably radicals de~rived
from isocyanate compounds and can be aliphatic, e.g.
C6H13-, aromatic, e.g. C6Hs-, aralkyl, e.g. C6HsC~l2-,
fluoroaliphatic~ e.g. C6F13CH2-, C7FlscH2ocoNHc6H3(cH3~ ~ and
C8~17SO2N(CH3)C2H~OCO~HC6H~CH2C6H~-. Ihe organic Rl-Q
radicals can have a variety of other structures, and can
contain hetero atom-containing moieties, e ~. -O-, -S-, and
-N-, but, as with the A group, it is preferably free of
groups containing said active hydrogen atoms.
The fluoroaliphatic radical, Rf, is a
fluorinated, stable, inert, non-polar, preferably
saturated, monovalent moiety which is both oleophobic and
hydrophobic. It can be straight chain, branched chain,
and, if sufficiently large, cyclic, or combinations
thereof, such as alkylcycloaliphatic radicals. The
skeletal chain can include catenary oxygen, hexavalent
sulfur, and/or trivalent nitrogen hetero atoms bonded only
to carbon atoms, such hetero atoms providing st~ble
linkages between fluorocarbon portions of Rf and not
interferring with the inert character of the Rf radical.
25 While Rf can have a large number of carbon atoms, compounds
where Rf is not more than 20 carbon atoms will be adequate
and preferred since large radicals usually represent a less
efficient utilization of fluorine than is possible with
smaller Rf radicals. The large radicals also are generally
less soluble in organic solvents. Generally, RE will have
3 to 20 carbon atoms, preferably 6 to about 12, and will
contain 40 to 78 weight percent, preferably 50 to 78 weight
percent, fluorine. The terminal uortion of the Rf group
has at least three fully fluorinated carbon atoms, e.g.
35 CF3CF2CF2-, and the preferred compounds are those in which
the Rf group is fully or substantially completely
--7--
fluorinated, as in the case where Rf is perfluoroalkyl,
CnF2n+1 -
The function of the linking group Q in formula I
is to bond the Rl groups to the N atoms of the carbodiimide
5 units. Q can comprise a hetero atom-containing group or an
organic group or a combination of such groups, examples of
which are polyvalent aliphatic, e.g., -CH2-, -CH2CH2--, and
-CH2CH(CH2-)2, polyvalent aromatic, oxy, thio, carbonyl,
sulfone, sulfoxy, -N(CH3)-, sulfonamido, carbonamido,
sulfonamidoalkylene, carbonamidoalkylene, carbonyloxy,
urethane, e.g., -CH2CH2OCONH~, and urea, e.g., -NHCON~-.
The linkage Q for a specific fluorochemical carbodiimide
useful in this invention will be dictated by the ease of
preparation of such a compound and the availability of
necessary precursors thereof. From the above description
o~ Q, it is apparent that this linkage can have a wide
variety of structures. However, as with the Rl and A
groups, Q is preferably free of moieties having said active
hydrogen atoms.
The fluorochemical carbodiimides used in this
invention are normally solid (i.e., solid at 20C) with
melting points preferably in the range of 40 to 150C.
They are preferably soluble to the extent of at least 10
weight percent in ethyl acetate at ~0C.
?5 Representative reaction schemes for the prepara-
tion o fluorochemical carbodiimides used in this invention
are outlined below, where the products designated as I' are
s~ecies of formula I supra.
_heme 1
30 2Rl-Q'-OH + 2A(NCO)2 > 2R Q NCO cat.,-(n+l)CO2
Rl-Q(N=C=N-A)nN=C-N-Q-R
I'
-8- ~ o~ ,7 ~
Scheme 2
(n~2)A(Nc0)2 -(n~l)co2> OcNA-(N-c=N-A)nN=c=N-ANco _2~ Q OH>
R1-Q(N=C=N-A)nN=C=N-Q-R
I'
Scheme 3
.
R-QI-OH + B(NCO)3 > R-Q(NC0)2
R-Q(NC)2 ~ B(NC0)3 ~ A(NC0)2 + R1-QNCO Cco2> ~ixed carbodiimide
The mixtures of fluorochemical carbodiimid0s used
in this invention may contain small amounts of -fluorochemical
diurethane compounds (e.g., R-Q'-OCONH-A-NHCOO-Q'-R, a
possible by-product in Scheme 1) free of carbodiimido
groups due to the synthetic procedures generally followed.
The amount of this by-product depends on the mode of
addition, molar ratio of reactants, and the relative
reactivity of isocyanate functional groups.
A preferred class of carbonyli.mino compounds for
use in this invention can be represented by the formula:
Al[NHCOY(Q)XR2]r II
where R2 is a group like Rl in formula I and at least one
R2 group is a fluoroaliphatic group (Rf), Q and x are as
defined for formula I, r is an inte~er of 1 to 10,
preferably 2 or 3, Al is an organic linking group having 2
to 20 carbon atoms, which is a residue of an organic iso-
cyanate and is free of isocyanate-reac~i.ve yrouL~s, such as
aliphatic hydroxy, and Y is -N-, -O-, or -S-. Where there
is a plurality of any R2, Ql Y and x in a given compound,
they can be the same or different.
9 ~L, ~
Ihe fluoroaliphatic radical-containing carbonyl-
imino compounds preferably have at least one major transi-
tlon temperature greater than 25C, more preferably greater
than that about 40C, and most preferably greater than
about 45C. If desired, the compositions of the invention
can contain mixtures of carbonylimino or imine compounds.
Carbonylimino compounds for use in this invention
can be prepared by reacting organic isocyanates with
fluoroaliphatic radical-containing compounds having an
isocyanate-reactive hydrogen atom.
A preferred subclass of the carbonylimino com-
pounds of formula II are those in which Y is -O-, viz.,
urethanes. Representative carbonylimino compounds of such
preferred subclass are described in U.S. Patent No.
15 3 r 484,281. They are prepared by conventional urethane
bond-forming reactions between fluoroaliphatic alcohols and
organic isocyanates, preferably aromatic polyisocyanates.
If desired, fluorine-free aliphatic alcohols (e.g., fatty
alcohols) can be incorporated into the reaction mixture
used to form such carbonylimino compounds.
A representative reaction scheme for preparation
of fluorochemical carbonylimino compounds used in this
invention is outlined below.
Scheme 4
rR2(Q)xYH + A'(NCO)r ~>A~[NHCOY(Q)XR2]r
II
Fluorochemical esters which are useful as compo-
nent (a) of the fluorochemical blends of this invention
include ~hos~ described in the aEorementioned prior ar~
publications.
A representative reaction scheme for the prepara-
tion of fluorochemical ester compounds used in this
invention is outlined below.
aRl-Q-OH + R(COOH)a CHato> R(COO-Q-Rl)a
Representative Rf intermediates for the
preparation o~ fluorochemical carbodiimide, carbonylimino,
or esters used in this invention include:
C8Y17S02N(C2~15~C2H40H
C8F17c2H40H
C7F15cH20H
C7F15CON (C2H5)C2H40H
C8F17C2H4SC2H40H
( CF3 ) 2CF ( CF2 ) 8C2H40H
( CF3 ) ~CFOC2F4C2H40H
C8E`17C2H4S02N (CH3 )C4H80H
C8F17SO2N ( CH3 ) C3H6NH2
C2F5{~3CH2NH2
/~
C3F7 (CFCF20)2 C~FCON~ NH
CF3 CE~3
C8F17s03-~-NH2
C8F17S03~1-NCO
C8F17C6H4NH2
C8F17C6H4NC
C7F15CH2NCO
C8F17C2H4SH
C7F15CON ( CH3 ) C2H4SW
Representative organic isocyanates include:
tolylene-2,4-diisocyanate
hexamethylene diisocyanate
methylenebis(4-phenyleneisocy~nate)
methylenebis(4-cyclohexyleneisocyanate)
xylylene diisocyanate
l-methoxy-2~4-phenylene diisocyanate
l-chlorophenyl-2,4-diisocyanate,
--.L 1--
p-(l-isocyanatoethyl)phenyl isocyanate
phenyl isocyanate
m-tolyl isocyanate
2,5-dichlorophenyl isocyanate
hexyl isocyanate
Representative carboxylic acids or anhydrides
which can be used to prepare Eluorochemical ester
components by reaction with fluorochemical alcohols include
adipic, citric, pyromellitic, and the like (such being
disclosed in said WS. Patent Nos. 3,923,715 and 4,3~0,74~).
Generallyr the fluorochemical carbodiimide,
carbonylimino compound, or esters will contain about 20 to
70 weight percent, preferably about 25 to 50 weight
percent, of carbon-bonded fluorine. If the fluorine
content is less than about 20 weight percent, impractically
large amounts of the fluorochemical carbodiimide,
carbonylimino compound, or esters will generally be
required, while fluorine contents greater than about 70
weight percent are unnecessary to achieve the desired
~ surface properties and thus represent an uneconomical use
of fluorine and may also present compatibility problems
where it is desired to apply the fluorochemical blend as an
organic solution.
A class of fluorochemical oxyalkylene, component
~5 (b) - the other essential component of the blends of this
invention - are fluoroaliphatic polymers (or oligomers, the
term polymer hereinafter including oligomer unless other-
wise indicated) represented by the general formulas:
(Rf)s2[(K3)yZIB]t III
[(~f)SZ~(R3)yzlBl~t~w IV
where
Rf is a fluoroaliphatic radical like that described
for general formula I,
Z is a linkage through which Rf and (R3)y moieties
are covalently bonded together,
-12~
(R3)y is a poly(oxyalkylene) moiety, R3 being an
oxy-alkylene group with 2 to 4 carbon atoms and y
is an integer (where the above formulas are those
of individual compounds) or a number (where the
above formulas are those of mixtur~s) at least 5
generally 10 to 75 and can be as high as 100 or
higher,
B is a hydrogen atom or a monovalent terminal organic
radical,
B' is B or a valence bond, with the proviso that at
least one B' is a valence bond interconnecting a
Z-bonded R3 radical to another Z,
Z' is a linkage through which B, or B', and R3 are
covalently bonded together,
s is an integer or number of at least 1 and can be as
high as 25 or higher,
t is an integer or number of at least 1, and can be as
high as 60 or higher, and
w is an integer or number greater than 1, and can be
as high as 30 or higher.
In formulas III and IV, where there are a
plurality of Rf radicals, they are either the same or
different. This also applies to a plurality of Z, Z', R3,
B, B', and, in formula IV, a plurality of s, y and t.
Generally, the oxyalkylene polymers will contain
about S to 10 weight percent, preferably about 10 to 30
weight percent, of carbon-bonded fluorine. If the fluorine
content is less than about 10 weight percent, impractically
large amounts of the polymer will generally be required,
30 while fluorine contents greater than about 35 weight
percent result in polymers which have too low a solubility
to be efficient.
In said poly(oxyalkylene) radical, (R3)y, R3 is
an oxyalkylene group having 2 to 4 carbon atoms, such as
-OCH2CH2-, -OCH2C~l2cH2-~
-OCH(CH3)CH2-, and -OCH(CH3)CH(CH3)-,
the oxyalkylene units in said poly(oxyalkylene) being the
samer as in poly(oxypropylene), or present as a mixture, as
in a heteric straight or branched chain or randomly
distributed oxyethylene and oxypropylene units or as in a
5 straight or branched chain of blocks of oxyethylene units
and blocks of oxypropylene units. The poly(oxyalkylene)
chain can be interrupted by or include one or more ca-tenary
linkages. Where said catenary linkages have three or more
valences, they provide a means for obtaining a branched
10 chain or oxyalkylene unitsO The poly(oxyalkylene) radicals
in the polymers can be the same or different, and they can
be pendent. The molecular weight of the poly(oxyalkylene)
radical can be as low as 220 but preferably is about 500 to
2500 and higher, e.g~ 100,000 to 200,000 or higher.
The function of the linkages Z and Z' is to
covalently bond the fluoroaliphatic radicals, Rf, the
poly(oxyalkylene) moieties, (R3)y and radicals B and B'
together in the oligomer. Z and Z' can be a valence bond,
for example, where a carbon atom of a fluoroaliphatic
20 radical is bonded or linked directly to a carbon atom or
the poly~oxyalkylene) moiety. Z and Z' each can also
comprise one or more linking groups such as polyvalent
aliphatic and polyvalent aromatic, oxy, thio, carbonyl,
sulfone, sulfoxy, phosphoxy, amine, and combinations
25 thereof, such as oxyalkylene, iminoalkylene, iminoarylene,
sulfoamido, carbonamido, sulfonamidoalkylene, carbonamido-
alkylene, ure-thane, urea, and ester. The linkages Z and Z'
for a specific oxyalkylene polymer will be dictated by the
ease of preparation of such an polymer and the availability
30 of necessary precursors thereof.
From the above description of Z and Z' it is
apparent that these linkages can have a wide variety of
structures, and in fact where either is a valence bond, it
doesn't even exist as a structure. However large 2 or Z'
is, the fluorine content (the locus of which is Rf) is in
the aforementioned limits set forth in -the above descrip-
tion, and in general the total Z and Z' content of the
--14-- ~3 ~ ~
polymer is preferably less than 10 weight percent of the
polymerO
The monovalent terminal organic radical, B, is
one which is covalently bonded through Zl, to the
poly(oxyalkylene) radical
Thouyh the nature of B can vary, it preferably is
such that it compliments the poly(oxyalkylene) moiety in
maintaining or establishing the desired solubility of the
oxyalkylene. The radical B can be a hydrogen atom, acyl,
such as C6H5C(O)-, alkyl, preferably lower alkyl, such as
methyl, hydroxyethyl, hydroxypropyl, mercaptoethyl and
aminoethyl, or aryl, such as phenyl, chlorophenyl,
methoxyphenyl, nonylphenyl, hydroxyphenyl, and aminophenyl.
Generally, Z'B will be less than 50 weight percent of the
(R3)yZ'B moiety.
The fluoroaliphatic radical-containing
oxyalkylene used in this invention can be prepared by a
variety of known methods, such as by condensation, free
radical, or ionic homopolymerization or copolymerization
using solution, suspension, or bulk polymerization
techniques e.g., see "Preparative Methods of Polymer
Chemistry," Sorenson and Campbell, 2nd ed., Interscience
Publishers, (1968). Classes of representative oxyalkylenes
useful in this invention include polyesters, polyurethanes,
polyepoxides, polyamides and vinyl polymers such as poly--
acrylates and substitute polystyrenes.
The polyacrylates are a particularly useful class
of oxyalkylenes and they can be prepared, for example, by
free radical initiated copolymerization of a fluoro-
aliphatic radical-containing acrylate with a
poly(oxyalkylene) acrylate, e.g. monoacrylate or diacrylate
or mixtures thereof. As an example, a fluoroaliphatic
acrylate, Rf-R"-O2C-CH=CH2 (where R" is, for example,
sulfonamidoalkylene, carbonamidoalkylene, or alkylene),
e-g-~ C8Fl7so2~(c4H9)cH2c~l2o2ccH=cH2~ can be copolymerized
~ i 3 60557-26~0
with a poly(oxyalkylene) monoacrylate, CH2=CHC(o)(R3) OCH3,
to produce a polyacrylate oxyalkylenes.
Further description of fluorochemical oxyalkylenes
useful in this invention will be omitted in the interest of
brevity since such compounds and their preparation are
known. See U.S. Patent No. 3,787,351 and U.S. Patent No.
4,289,892.
The amount of each component (a) and (b) can vary
over a broad range, and will be selected to provide the
desired balance of properties on the treated fiber of the
finished article. Generally, component (a) will be the
major amount of the blend and component (b~ will be the
minor amount. The particular amount depends on the
particular composition of the textile fiber or article to be
treated and the particular chemical composition of (a) and
(b~, as well as the application procedures used. Laboratory
evaluation will often be a good indicator of appropriate
relative amounts of compounds (a) and (b) to be used for
obtaining the desired performance in commercial application.
~0 Generally, the relative amounts of components (a)
and (b) fall within the following ranges:
Weight percent of
fluorochemical solids in blend
General Preferred Most
Component Broad Ranqe Broad Range Preferred Ran~
(a)40-99 60-99 70-95
(b)1-60 1-40 5-30
The blends of this invention can be obtained by
mixing (1) an organic solvent solution or aqueous dispersion
of the fluorochemical component (a) with (2) the
fluorochemical poly(oxyalkylene) which may be utilized in
neat form or as an organic solvent solution or as an
-16-
aqueous dispersion. If an aqueous emulsion is the desired
form of ~ ~e!.~, ~he emulsification may be performed on
the above organic solvent-containing blends, or
individually emulsified components may be blended (by
simple mixing techniques) as either solvent-containing or
solvent-free emulsions. In the preparation of said
emulsions it is gsnerally beneficial to ernploy cationic
fluorochemical surfactants (e.g~, CgFl7S~2N(il)C~6~(C~3)Cl)
a,ong with hydrocaïbon non-ionic surfactants (i.e., "Tween
80" polyoxyethylene sorbitan monooleate). Since the
fluorochemical poly(oxyalkylenes) and mixtures thereof are
themselves non-ionic surfactants, the hydrocarbon non-ionic
co-surfactants may be totally or partially eliminated by
the incorporation of the fluorochemical poly(oxyalkylene)
into the solvent-containing blend prior to emulsification.
Substrates which can be treated in accordance
with this invention are textile fibers (or filaments), and
finished or fabricated fibrous articles such as textiles,
e.g. carpet, paper, paperboard, leather, and the like. The
~0 textiles include those made from natural fibers, such as
cotton and wool, and those made from synthetic organic
fibers, such as nylon, polyolefin, acetate, rayon, acrylic,
and polyester fibers. Especially good results are obtained
on nylon and polyester fibers. The fibers or filaments as
~5 such or in an aggregated form, e.g. yarn, tow, web, or
roving, or the fabricated textile, e.g., articles such as
carpet and woven fabrics, can be treated with the fluoro-
chemical blends. The treatment can be carried out by
applying the fluorochemical blends as organic solutions or
30 aqueous or organic dispersions by known techniques cus-
tomarily used in applying fluorochemicals, e.g. fluoro-
chemical acrylate copolymers, to fibers and fibrous sub- ~
strates. (IE desired, such known fluorochemicals can be
used in conjunction with the above-described fluorochemical
35 blends, such as fluoroaliphatic radical-containing
polymers, e.g. acrylates and methacrylates). For exampls,
the fluorochemical treatrnent can be by immersing the
-17- ~ 2~
Eibrous substrates in a bath containing the fluorochemical
blend, padding the substrate or spraying the same with the
fluorochemical blend, or by foam, kiss-roll, or metering
applications, e.g. spin finishing, and then drying the
5 treated substrates if solvent is present. If desired, the
fluorochemical blend can be co-àpplied with conventional
fiber treating agents (or adjuvants), e.g. antistatic
agents or neat oils (non-aqueous fiber lub icants).
In the manufacture of synthetic oryanic fibers
(see, for example, the review article in Kirk-Othmer,
Encyclo~ a of Polymer Science and Technology, _, 374-404,
1968), the first step that normally takes place in the
process, following initial formation of the filaments (e.g.
by melt spinning or solvent spinning), is coating the fiber
surface with a small amount (generally less than 2~ active
solids on fiber) of fiber finish comprising lubricating and
antistatic agents. It is particularly advantageous to
treat such textile fibers, e.g. nylon 6, with the fluoro-
chemical blend of this invention in conjunction with the
spin finish being applied to such textile fibers.
Fiber finishes are generally produced in the formof dilute aqueous emulsions or as an oil ("neat oil") which
principally contains said lubricant and antistatic agent as
well as emulsifier (surfactant) and may also contain
~5 materials such as bacteriocides and antioxidants.
Representative lubricants include mineral oils,
waxes, veg0table oils (triglycerides) such as coconut oilr
peanut oil, and castor oil, synthetic oils, such as esters,
polyoxyethylene derivatives of alcohols and acids, and
silicone oils.
The antistatic agents, emulsifiers, and sur-
factants incorporated into the fiber finish are selected
from similar chemical classes, which include:
(a) anionics, such as fatty acid soaps, sulfated vegetable
oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as fatty amines, quaternary ammonium
compounds, and quaternary phosphonium compounds;
-18-
(c) nonionics, such as glyceryl monooleate, ethoxylated
alcohols, ethoxylated fatty acids, and ethoxylated
fatty amides; and
~d) amphoterics, such as betaines, amino acids and their
salts.
The preferred mode of applying the fluorochemical
blend of this invention to synthetic organic fibers is to
incorporate the blend into the above-described fiber
finishes in an amount sufficient to achieve the desired
1~ properties, oil and water repellency and soil resistance.
Generally, the amount of fluorochemical blend to be used
will be that sufficient to retain on the fiber of -the
finished article, e.g., carpet, about 200 to ~600 ppm
fluorine based on the weight of the fiber. Such additions
15 to the conventional fiber finish can be carried out without
sacrificing or adversely affecting typical requirements
that conventional fiber finishes must meet, namely lubrica-
tion, thermal stability, low fuming at elevated tempera-
ture, and wetting for fiber dyeability (color addition).
20 The conventional finish components of the fiber finishes
containing the fluorochemical blends of this invention can
be removed in a conventional manner after the fiber is
manufactured in fabric form, e.g., carpets and upholstery
fabrics. The fluorochemical blends withstand the typical
25 conditions encountered during fiber and yarn processing and
also survive the more severe processing conditions which
the greige goods encounter such as scouring and dyeing, and
the finished goods encounter, such as washing, steam
cleaning, and dry cleaning. The fluorochemical blends do
30 not interfere with, and are durable through, the normal
fiber processing steps, e.g., drawing, texturizing, and
heat setting, and provide oil and water repellency and
anti-soiling properties to the finished article, e.g~,
carpet made from the treated fibers.
The conventional application methods used to
apply finishes to fibers (or filaments) can be used with
the fluorochemical blend finishes of this invention. Such
-19- '
methods include the use of either (a) a revolviny cera~i-
~cylinder, i.e., kiss-roll, which is partially im~ersed in a
pan containing the finish, over which the moving filaments
pass and pick up a thin film of finish, (b) a metering pump
supplying finish through a slot or hole in a fiber guide
over which the moving filaments pass, (c) an immersion
finish bath, or (d) spraying devices.
The fluorochemical blends of this invention are
~enerally compatible with (i.e., dispersible or suffi-
ciently soluble in) commercial neat oil fiber finishes,yielding stable dispersions or solutions thereof, and thus
the blends may be mixed with such finishes and coapplied
~or applied b~efore or after t~em). Solubilizing aids, such
as "Carbitol" or "Cellosolve" solvents, can be added to the
finish to enhance solubility of the fluorochemical blends
in the neat oil finish.
Representative fluorochemical carbodiimides
useful as component (a) in the fluorochemical blends of
this invention havin~ the general formula V are shown in
Table 1.
R-Q-A(N=C=N-A)n-Q-K V
TABLE 1
Compound
No.* R - - - -Q _ A
1 C8F17 -So2N(c2H5)c2~l4ocoNH C6H4CH2C6H4
2 C8F17 -so2N(c2Hs)c2H4ocoNH C6H3(CH3)
3 C8F17 -SO2N(C4Hg)C2H4OCONH C6H4C~2C6H4
4 C8F17 -C2H4OCONH C6H4CH2C6H4
S C8F17 -- - C2H40CONH C6H3(C~3)
* For all compounds listed, n has an average value of 2,
except for compound no. 2, where n has a value of about 1.8.
Representative fluorochemical oxyalkylenes useful
as component (b) in the fluorochemical blends of this
-20
invention are shown in Table 2. Generally the preparation
of the rluor~che~llical oxyalkylenes results in products
which comprise mixtures of oxyalkylenes, the lengths of the
fluoroaliphatic radical and the poly(oxyalky.lene) moiety
5 varying and the subscripts denoting the number of carbon
atoms of the former and denoting the number of oxyalkylene
units in a poly(oxyalkylene) segment beiny in both cases
average numbers, and in this specification, e.g. Table 2,
those subscripts should be understood as having such
10 average values, unless otherwise indicated.
TABLE 2
1. C8F17S02N(C2H5)CH2C02(C2H40)15H
~- C8Fl7so2N(c2H5)c2El4o(c2H4o)l4H
3. CgF17c2H4O(c2H4o)lsH
~C2tl40)mH
15 4. C8F17S02N ~ (m~n = 25)
(C2H40)nH
5. CgFl7so2N(c2H5)c2H4o(c3H6o)8H
6. C8F17C2H4SClHcO2(c3H6o)mH (m+n = 20)
CH2C02 ( C3H6) nH
7- C8F17S02N(C2H5)C2H4O(C2H4O)7 5H
Representative Eluorochemical oxyalkylene
20 polyacrylates useful as component (b) in the blends oE this
invention are those made by copolymerizing any of the
fluorochemical acrylates of Table 3 with any of the
fluorine-free poly(oxyalkylene) monomers of Table 4.
TABLE 3
25 1. C8F17S02N(CH3)CH2CH200CCW=CH2,
2. C6F13C2H400CC(CH3)=c~2
3. C6F13C2H4SC2H4OOCcH=cH2
4c CgF17C2H4OOCC(CH3)=cH2
5- C8F17C2H4N(CE13)C2H4OOCC(CH3)=CH2,
~ 21 _ ~ r~
6 . C2F5C6FlocH2ooccH=cH2 r
7. C7FlscH20occH-cH2
8. C7Fl5co~(cH3)c2H4ooccH=cH2~
9. (CF3)2CF(CF2)6CH2C~l(OH)CH200CCH=CH2,
S 10. (CF3)2CFOC2F4C2H400CCH=CH2,
11. C8Fl7c2H4so2N(c3H7)c2H4oocc~l=cH
12. C7FlsC2H4CONHC4HgOOCCH=CH2,
13. C3F7(CFCF20)2CFCH200CCH=CH2,
CF3 CF3
14- C7Fl5coocH2c(cH3)2cH2oocc~cH3)=cH2r
15. CgF17S02N(C2Hs)C4HgOOCCH=CH2,
16- (C3F7)2c6H3so2N(cH3)c2H4ooccH=cH
fCF2CF2~
17. C2FsCF\ ~NC2F4CON(CH3)C2H400CCH=CH2,
CF2CF2
18- C6F17CF=CHCH2N(CH3)C2H400CCH=CH2,
19. C8F17S02N(C4Hg)C2H40COCH=CH2
20- C8Fl7so2N(c2H5)c2H4ococH(cH3)=cH2
TABLE 4
1. CH2=cHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H4o2ccH=cH2
2. CH2=cHco2(c2H4o)l7cH3
3. CH2=c(cH3)CONH(c3H60)44H
4. CH2=C(CH3)C02(C2H40)90COC(CH3)=CH2
5. HS(C2H40)23(C3H60)35(c2H40)22c2H4sH
Specific fluorochemical oxyalkylene polymers are
those of Table 5 described in terms of their monomers and
the relative amounts thereoE.
-22- ~2~
TABLE S
~onomers
Acrylate Oxyalkylene Weight Ratios,
of Table 3 _f Table 4 acrylate/oxyalkylene
119 1 ~0/70
21 2 65/35
~1 4 50/50
420 1 30/70
Other compatible optional comonomers t e.g. butyl
10 acrylate, acrylonitrile, etc., which need not contain
fluoroaliphatic radicals, can be copolymerized with the
fluorochemical acrylate and oxyalkylene comonomers, in
amounts up to about 25 weight percent, to impro~e com-
patibility or solubility of the fluorochemical oxyalkylene
15 component (b) in the fiber finish.
Weight ratios oE fluorochemical acrylate monomers
(Table 3) and fluorochemical poly(oxyalkylene) monomers
(Table 4) can vary but should be chosen along with said
optional comonomers so that the carbon-bonded fluorine
20 content of the resulting copol~mer is in the desired range
of 5 to 40 weight percent.
Representative fluorochemical urethane compounds
useful in the practice of this invention as component (a~
are those of Table 5A.
Table 5A
1~ [c8Fl7so2N(c2H5)c2H4ocoNH]2c6H3(cH3)
2. RocoNHc6H4cH2c6H3(NHcooR)cH2c6H4N~cooR
where two of the R groups are C8F17SO2N(C2H5)C2H4- and one
is C18H37 -
Objects and advantages of this invention are
illustrated in the following examples.
-23- ~ 7--~
Example 1
In a 2~1iter, 3-neclc flask, fitted with a
mechanical stirrer, condenser, thermometer, addition funnel
and electric heating mantle, was placed 375 g (1.5 moles)
5 methylenebis(4-phenyleneisocyanate) and 481 g methyl ethyl
ketone (MEK). To this stirred heated solution (80-83C)
was added 554 g (1.0 mole) N-ethyl(perfluorooctane)sulfon-
amidoethyl alcohol over a 3 hour period and stirring and
heating continued for an additional 3 hours.
To this stirred solution, containing fluoro-
chemical urethane isocyanate and unreacted diisocyanate,
was added 7.4 g camphene phenyl phosphine oxide,
ClOHl6POC6H5. a carbodiimide-forming catalyst, and the
reaction mixture was stirred and heated at about 80C for
15 about 8 hours, at which time essentially all of the
isocyanate groups had been converted to carbodiimide groups
as indicated by IR absorption analysis.
The solid fluorochemical carbodiimide product is
represented by compound no. 1 in Table l.
Examples 2-5
Following the general procedure of Example l,
except employing the reagents in Table ~ and molar concen-
trations indicated in Table 7, the other fluorochemical
carbodiimides of Table 1 were prepared. The reagents in
25 Table 6 are identified by symbols, e.g. A-l, etc., for
later reference.
TABLE 6
Alcohol Xea~ents
A-l C~Fl7SO2N(C2tl5)c2~l4~ll
A-2 CgFl7SO2N(C4Hg)C2H4OH
A-3 CgFl7c2H4oH
Jr~ 7
~ 2 4--
Isocy~nates
~IDI OCN-~CEl 2~NC 0
TD~: OCN~--~CNCO
TABLE 7
Reactants (moles)**
Alcohol
EX. No.* Reagent Isoc~anate
2 A--1 (2) TDI (2,.~)
3 A-2 ~IDI
4 A--3 MDI
A-3 TDI
* The numbers correspond to the ~ompound numbers of Table 1.
**All alcohol/isocyanate reagent molar ratios were 2t3
except as indicated for Example 2.
Examples 6-19
In each of -these examples, a gold-colored, plush,
cut-pile, pre-wet nylon carpet (50 oz/yd2) was treated by
top spray application ( 25% wet pickup) of a diluted mixture
of an aqueous emulsion of the fluorochemical carbodiimide
20 o compound no. 1 of Table 1 and an a~ueous emulsion of a
fluorochemical oxyalkylene, the dilution (with water) of
the mixture of emulsions being done to obtain the desired
concentration of fluorochemical components, (a) and (b),
necessary to deposit the amounts (SOF) of fluorochemicals
25 on the carpet specified in Table 8. The treated carpet
samples were dried for 30 minutes at 70C and heated
further at 130C for 10 min. For purpose of comparison,
control examples (C-l to C-9) were run in which the carpet
treatment employed only one fluorochemical component (C-l
-25- ~ ,f~
to C-8) or the example (C-9) did not include any treatmen'O
The oil repellency (OR), water repellency (',J~
and wal~-on soil resistance (WOS) were determined on the
treated samples. The data is summari~ed in Table 8~
The water repellency test is one which is often
used for this purpose. The aqueous stain or water
repellency of treated samples is measured using a
water/isopropyl alcohol test, and is expressed in terms of
a water repellency rating of the treated carpet or fabric.
10 Treated carpets which are penetrated by or resistant only
to a 100 percent waterJ0 percent isopropyl alcohol mixture
(the least penetrating of the test mixtures) are given a
rating of 100/0, whereas treated fabrics resistant to a
0 percent water/100 percent isopropyl alcohol mixture (the
15 most penetrating of the test mixtures) are given a rating
of 0/100. Other intermediate values are determined by use
of other water/isopropyl alcohol mixtures, in which the
percentage amounts of water and isopropyl alcohol are each
multiples of 10. The water repellency rating corresponds
to the most penetrating mixture which does not penetrate or
wet the fabric after 10 seconds contact. In general a
water repellency rating of 90/10 or better, e.g, 80/20, is
desirable for carpet~
The oil repellency test is also one which is
25 often used for this purpose. The oil repellenc~l of treated
carpet and textile samples is measured by AATCC Standard
Test 118-1978, which test is based on the resistance of
j~,
~~~ treated fabric to penetration by oils of varying sur~ace
tensions. Treated fabrics resistant only to "Nujol", a
30 brand of mineral oil and the least penetrating of the test
oils, are given a rating of 1, whereas treated Eabrics
resistant to heptane (the most penetrating of the test
oils) are given a value of 8. Other intermediate values
are determined by use of other pure oils or mixtures of
oils. The rated oil repellency corresponds to the most
penetrating oil (or mixture of oils) which does not pene-
trate or wet the fabric after 10 seconds contact rather
-26-
than the 30 seconds contact of the Standard Test. ~igher
numbers indicate better oil repellency. In general, an oil
repellency of 2 or greater is desirable for carpet.
The soil resistance of treated and untreated
(control) carpet was determined by exposure to pedestrian
traffic according to AATCC Test method 122-1979, the
exposure site being a heavily travelled industrial area for
an exposure of about 15,000 "traffics". The samples are
repositioned periodically to insure uniform exposure and
10 are vacuumed every 24 hours during the test and before
visual evaluation. The evaluation employed the following
"Walk-On-Soiling" tWOS) rating system:
WOS_Ratin~ Description
0 equal to control
-l/2 slightly better (-~) or worse(-) than control
+l impressive difference compared to control
-l 1~2 very impressive difference compared to
control
-2 extremely impressive difference compared to
~ control
,k~2 .~ ~
Table 8
Fluorochemical
Fluorochemical _ Oxyalk~lene
Carbodiimide Compound Table
Ex.No. %soFa No. No. ~ SOF OR WR WOS
-
6 .09 2 5 .01 1.5 70/30 -1/2 to -1
7 .05 2 5 .05 1.5 70/30 +1
8 .09 c .01 1 70/30 +1/2 to 0
9 .05 c .05 2 60/40 0
.09 2 2 .01 2 70/30 0
11 .05 2 2 .05 2.5 70/30 0
12 .09 7 2 .01 2 60/40 -1/2
13 .05 7 2 .05 2 70/30 0
14 .09 d .01 1.5 70/30 0
.05 d .05 1.5 70/30 0 to +1/2
16 .09 e .01 1.5 70/30 -1/2
17 .05 e .05 3.5 50/50 -2
18 .09 5 2 .09 1.5 70/30 0 to +1/2
19 .05 5 2 .05 1.5 70/30 0 to +1/2
C-l none 2 5 .10 2 50/50 -1 1/2
C-2 none c .10 2.5 70/30 -1/2
C-3 none 5 2 .10 0 NWRb -2
C-4 none 6 2 .10 0 NWR -1 1/2
C-5 none d .10 0 NWR -2
C-6 none e .10 4O5 NWR -2
C-7 none 7 2 .10 0 NWR -1 1/2
C-8 .10 none none none 2 70/30 0
C-9 none none none none 0 NWR -2
~ -27-
a. % SOF means % fluorochemical solids on fabric
b. NWR means no water resistance
c. The c~npound used in this example was a terpol~ner of
C8FL7so2N(cH3)cH2cH2ooccH CH2~
CH2=c(cH3)co2(c2H4o)9ococ(cH3) CH2,
CH2=C(cH3)c02(c2H4o)9o
d. The c~npound used in this example was a terpolymer of
C8F17S2N(C4H9)C2H~CCH CH2'
CH2=cHco2(c2H4Qlo)(c3H6o)22(c2H4o)9c2H4o2c 2
CH2=CHCO2(c2H40lo)(c3H6o)22(c2H4 )9 2 4
e. The compound used in this example was a terpolymer of
8Hl7so2N(c2H5)c2H4ococ(cH3)=cH2~
CH2=cHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H4o2cc 2'
C 2 CHco2(c2H4o)lo(c3H6o)22(c2H4o)9c2H~oH
-27a-
.
.J `
-2~ L~
The data oE Table 8 show that useful oil and
water r~pell~ncv ~as obtained from all of the blends
(Examples 6-19) and that the soil resistance of most of the
blend examples were better than or equal to that of the
5 comparative example. Those properties obtained for
Examples 6-19 as compared to the ExampLes C-l thru C-7, are
particularly noteworthy.
The control Example C-8, which was carpet treated
only with fluorochemical carbodiimide, had a particularly
10 harsh hand. However, where the blends were used (Ex. No.
6-19), the hand of the treated carpets was soft, which was
considered to be equal to the untreated carpet, especially
at the higher concentration of the fluorochemical
oxyalkylene component.
Examples 20-22
These examples describe the treatment of nylon
carpet fiber with aqueous emulsions of component (a) fluoro-
chemical carbodiimide of compound no. 1 in Table 1 and
component (b) various fluorochemical oxyalkylene blends of
this invention in combination with an aqueous emulsion of a
coconut oil based spin finish lubricant, and the results of
testing of the dyed carpet prepared Erom the treated fibers.
The composition of the applied finish for these
examples had fluorochemical solids to spin finish lubricant
?5 solids ratios in the range of 0.18:1 to 0.14:1.
The spin finish emulsion composition was applied
by a metered slot applicator to melt extruded, undrawn yarn
oE nylon 6 fibers. The yarn was made up of 118 Eilaments
oE 18 denier (per filament). The resultant fiber imme-
diately after application had Erom 1.0 to 1.5 weightpercent of the lubricant component on the fibers. The
treated yarn was continuously drawn and texturized and made
into level-loop carpet (28 oz/yd2), heat set at 196C for
one minute, acid dyed, dried at 70C for 30 min~, heated at
130C for 10 min., and then evaluated for oil and water
repellency, walk-on soil resistance, and retention of
~ 2~f~
fluorochemical treatment -through the dyeing process as determined by fluorine
analysis. The testing results are shown in Table 9~ Comparison examples, C-10,
C-ll, were run, one of them omitting any fluorochemical treatment, and the o-ther
including a treatment with only one fluorochemical component, viz~, the carbodi-
imide of compound no. 1 of Table 1.
Table 9
Relative amts.,
(in terms of wt Amount of Fluo-
g fluorine) of rine on Carpet
Fluorochemical Before After ~ Retention
components Dyeing, Dyeing, of Fluoro-
Ex. No. (a)/(b)* ppm ppmChemical OR WR WOS
80/20683 619 91 3 40/60 +1
21 80/20784 673 86 5 20/80 -~1/2
22 70/30607 570 94 5 10/90 0
C-10 100/0709 545 77 3 40/60 0
C-ll none 0 0 0 0 NWR -2
* The fluorochemical oxyalkylenes used in Ex. No. 22 was compound no. 2, of Table
5, that used in Example 21 was a terpolymer of C8F17SO2N(CH3)CH2CH2O0CCH=cH2,
CH2=C(CH3)CO2(C2H4O)goCOC(CH3)=CH2/ and CH2=C(CH3)CO2(C2H4O)goH~ that used in Ex-
ample 20 was a terpolymer of C8F17SO2N(C4Hg)C2H4OCOCH=CH2~ CH2=CHCO2(C2H4Olo)~
(C H6O)22(C2H4O)gC2H4O2CCH=CH2~ and CH2=CHCO2(c2H4Olo)(c3H6o)22(c2H4o)9c2H4oH~
The data of Table 9 show that improved oil and wa-ter repellency was ob-
tained from most of the above blends (Ex. Nos. 20, 21, 22) and tha-t the soil re-
sistance was generally better than the control (C-10). Particularly no-teworthy
are the higher retention values of the blends as compared to the control C-10.
~V~ 3
Examples 23-26
In these examples, two difEeren-t rainwear fabrics were trea-ted wi-th an
aqueous emulsion of a blend of (a) the fluorochemical carbodi.ir~lide of compound
no. 1 of Table 1 and (b) a fluorochemical oxyalkylene in a padding
-29a-
-30~ $~ ~ ~
operation, dried at 150C for 10 minutes~ and evaluated for
initial o l repellency (OR) and resistance to a water spray
(~R), then these properties evaluated again after 5
launderings (5L) and also after one dry cleaning ~DC).
The OR test used was the above-described AATCC
Standard Test 118-1978, the contact time before observation
being the specified 30 sec., an O~ value o 3 or greater
being particularly desirable for rainwear fabrics.
The water spray rating (~R) is measured by AATCC
10 Test Method 22-1979. The spray rating is measured using a
0 to 100 scale where 100 is the highest possible rating.
In general, a spray rating of 70 or greater is desirable,
particularly for outerwear fabrics.
The treated fabrics were laundered using a
mechanically agitated automatic washing machine capable of
containing a 4 Kg. load, using water at 50C and a
commercial detergent, and then the washed fabrics were
tumble-dried in an automatic dryer for 40 minutes at 70C
and pressed in a flat-bed press (at 154C) before testing.
The treated fabrics were dry cleaned using
perchloroethylene containing 1% of a dry cleaning detergent
and tumbling in a motor driven tumble jar (AATCC Test
Method 70-1975) for 20 minutes at 25C. After removing
excess solvent in a wringer, samples were dried at 70,C for
10 minutes, then pressed on each side for 15 seconds on a
flat-bed press maintained at 154C.
The data are summarized in Table 10 together with
comparison examples C-12 through C-l9.
~ ?3~ ~3
Table 10
Relative a~ts.
(in terms of wt
% fluorine) of
fluorochemical
components Total Initial SL DC
Ex. No. (a)/(b)* % SOF Fabric** OR SR OR SR OR SR
23 98/2 0.21 A 6 80 5 80 2.5 70
~4 98/2 0.21 B 6 80 3 70 4 80
80/20 0.2 A 6 70 5.5 70 6 70
'>6 80/20 0.2 B 6 80 5 75 6 80
C-12 100/0 0.2 A 5 70 5 70 3 70
C-13 100/0 0.2 B 5.5 80 5 80 4.5 80
C-14 0/100 0.2 A O O O O
C-15 0/100 0.2 B O O O O O O
~-16 0/100 0.2 A 6.5 50 0 0 6 70
G-17 0/100 0.2 B 5 70 1 70 6 70
C-18 0/100 none A O O O O O O
C-19 -- none B O O O O O O
~0 * The fluorochemical oxyalkylene used in Ex. Nos. 23, 24 and C-14, C-15 was a
terpolymer of C8F17S02N(C4Hg)C2H40COCH=CH2~ CH2=CHC02(C2H401o)(C3H60)22(C2H40)9-C H O CCH=CH , and CH2=CHC02(C2H4010)(C3H60)22(C2H4 )9 2 4
Ex. Nos. 25, 26 and C-16, C-17 was a terpolymer o:E C8F17S02N(CH3)CH2CH200CCH=CHCH2=C(CH3)C02(C2H40)90COC(CH3)=CH2, and CH2=C(CH3)C02(C2H40)goH.
** Fabric A is 100% nylon taEfeta; Fabric B is 100% woven polyester.
The data of Table 10 show that improved OR, SR, and durability -to laun-
dering and dry cleaning properties were obtained with most of the blends as com- -31-
pared to either component aloneO
Examples 27-40
In the following examples, aqueous emulsion blends of the
fluorochemical urethane 1 of Table 5A and several dif~e:rent
fluorochemical oxyalkylenes were used to treat nylon carpet, following
the procedure of Ex. 6-19. The dried samples were evaluated for OR, WR
and ~S. The results are summarized in Table 11.
Table 11
Fluorochemical
Fluorochemical Oxyalkylene
Urethane Compound Table
Ex.No. ~SOF No. No. ~ SOF OR WR ~S
27 .09 2 5 .01 2 70/30 -1/2
28 .05 2 5 .05 2.5 80/20 -1/2 to 0
29 .09 a .01 2 70/30 -1/2 to 0
.05 a .05 2 70/30 +1/2
31 .09 2 2 .01 2 70/30 +1/2
32 .05 2 2 .05 3 70/30 0 to +1/2
33 .09 7 2 .01 2 70/30 -1/2
34 .05 7 2 .05 4 90/10 0 to ~1/2
.09 b .01 1.5 70/30 0 to +1/2
36 .05 b ~05 2 NWR -1
37 .09 4 5 .01 2.5 70/30 -1/2
38 .05 4 5 .05 ~.5 NWR -1
39 .09 5 2 .01 2.5 70/30 0 to +1/2
.05 5 2 .05 3 70/30 0 to tl/2
C-20 .10 none none none 3 70/30 0
C-21 none none none none 0 MWR -2
-32-
'~
2~
a. The compound of this example was a terpolymer of c8E17so2N(CH3)cH2cH2ccH=
CH2=C(CH3)CO2(C2H4O)90COC(CH3)=CH2, and CH2=C(CH3)CO2(C2H4O)90H
b~ The compound of this example was a -terpolymer of C8F17SO2N(C4H9)C2H4OCOCH=CH2,
2 2( 2 4 1o)(C3H6O)22(C2H4O)9C2H4O2CCH=CH2, and CH2=cHco2(c2H O )-
(C3H6O)22(C2H4O)9c2H4OH-
The data of Table 11 show that all of the blend examples have better OR
and WOS than the untreated carpet, C-21, and most of the blend examples had bet-
ter WR than the untreated carpet (C-21). Also, all of the blend examples had
better WOS than the controls C-l to C-7 which used only the fluorochemical oxyal-
1~ kylene component. It is particularly noteworthy that half of the blend exampleshad better WOS than the control Example C-20 where the urethane fluorochemical
component was used alone.
Examples 41, 42
Following the procedure of previous Examples 23-26, two rainwear fab-
rics were treated with an aqueous emulsion of a blend of (a) the fluorochemical
urethane 2 of Table 5A and (b) the fluorochemical oxyalkylene 3 of Table 5 in a
padding operation, dried at 150C for 10 minutes, and evaluated for initial OR
and SR, then these properties evaluated again after 5L and also after one DC. m e
~es~llts are given in Table 12.
Table 12
Relative amts. (in
terms of wt % fluor-
ine) of fluorochemicals Total Initial 5L DC
Ex. No.components (a)/(b) % SOF Fabric* OR SR OR SR OR SR
41 80/20 0.2 A 6.5 70 6 75 5 70
42 80/20 0.2 B 6 70 5.5 70 6 70
C-22 100/0 0.2 A 6 80 5.5 80 1 50
C-23 100/0 0.2 B 6 70 5 70 2 0
-33-
* Fabric A was nylon taffeta, and fabric B was woven polyester.
a. The compound of this example was a terpolymer of C8F17S02N(CH3)CH2CH200CCH=CH2,
CH =C(CH )CO (C H O) COC(CH )=CH , and CH2=C(CH3)C02(C2H~O)goH.
The data of Table 12 show that the initial and 5L oil repellency obtai-
ned with the blends (Ex. Nos. 41, 42) were bet-ter than resul-ts ob-tained with the
fl~lorochemical urethane alone (Ex. C-22, C-23). The durability to dry cleaning
obtained by use of the blend (Ex. Nos. 41, 42) is particularly notewor-thy when
eompared to Examples C-22, C-23, using the fluorochemical urethane alone.
Various modifications and alterations of this invention will become
l~ apparent to those skilled in the art without departing from the scope of this
invention.
-33a-
