 |
Claims  |
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We claim:
1. A composition consisting essentially of:
from about 0.25% to about 55% by weight of an essentially nonhalogenated
polymer having a glass transition temperature above room temperature;
from about 0.05 to about 50% by weight of polymer of an ionic,
non-polymeric fluoro surfactant with from 5 to 30 carbons per hydrophilic
end; and
at least about 40 percent by weight of composition of a carrier in which
said polymer is dissolved or suspended.
2. A composition as claimed in claim 1 wherein said polymer is suspended in
said carrier and said composition further comprises an emulsifier in
amounts sufficient to suspend said polymer in said carrier.
3. A composition as claimed in claim 2 wherein said emulsifier is cationic.
4. A composition as claimed in claim 2 wherein said emulsifier is
cetyltrimethyl ammonium bromide.
5. A composition as claimed in claim 2 wherein said emulsifier is a
quaternary ammonium halide.
6. A composition as claimed in claim 1 wherein said ionic, non-polymeric
fluoro surfactant is from about 1% to about 10% by weight of polymer.
7. A composition as claimed in claim 1 wherein said polymer includes
monomeric units derived from alkyl methacrylates, styrenes,, alkyl
acrylates, olefins and copolymers thereof.
8. A composition as claimed in claim 7 wherein said polymer is
predominantly derived from alkyl methacrylate.
9. A composition as claimed in claim 8 wherein said copolymer contains at
least about 90% monomeric units derived from lower alkyl methacrylate.
10. A composition as claimed in claim 9 wherein said polymer is a copolymer
with from about 0.5 to about 10 percent by monomeric unit derived from
N-methylol acrylamide.
11. A composition as claimed in claim 10 wherein said copolymer contains
from about 95 to about 99.5 percent methyl methacrylate and from about 0.5
to about 5.0 percent N-methylol acrylamide by monomeric unit.
12. A composition as claimed in claim 7 wherein said polymer includes as
the predominant monomer a monomer derived from a compound soluted from the
group consisting of 3-3-dimethyl-1-butene, 3-methyl-1-butene,
isobornylacrylate, 5-tert-butyl-2-methylstyrene, styrene,
N-vinylpyrralidone, diacetone acrylanide and 3-vinyl pyridine.
13. A composition as claimed in claim 1 wherein said ionic, non-polymeric
fluoro surfactant has 6-20 carbons.
14. A composition as claimed in claim 13 wherein said ionic, non-polymeric
fluoro surfactant has 6-12 carbons.
15. A composition as claimed in claim 1 wherein said ionic, non-polymeric
fluoro surfactant includes a radical of the formula (CF.sub.3).sub.2
CFOCF.sub.2 CF.sub.2 -- or C.sub.n F.sub.2n+1 where n = 6-12.
16. A composition as claimed in claim 15 wherein said ionic, non-polymeric
surfactant is (CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CF.sub.2).sub.n
(CH.sub.2).sub.m COOM where n is 2-12, m is 0-10, M is H or alkali metal.
17. A composition as claimed in claim 15 wherein said surfactant is
##STR21##
where m = 0-8, M is H or alkali metal and R is either (CF.sub.3).sub.2
CFOCF.sub.2 CF.sub.2 (CF.sub.2 CF.sub.2).sub.n with n = 0-5 or R is
C.sub.n F.sub.2n+1 with n = 6-12.
18. A composition as claimed in claim 15 wherein said ionic, non-polymeric
fluoro surfactant is R(CH.sub.2).sub.m SO.sub.3 M where m is 0-10, M is
alkali or alkali earth metal and R is
(CF.sub.3).sub.2 CFOCF.sub.2 (CF.sub.2 CF.sub.2).sub.n -- with n = 0-5 or R
is C.sub.n F.sub.2m+1 with n = 6-12.
19. A composition as claimed in claim 15 wherein said ionic, non-polymeric
fluoro surfactant is
R(CH.sub.2).sub.m OCOCH.sub.2 N.sup.+ (CH.sub.2 CH.sub.2 O).sub.3 Cl.sup.-
wherein m is 0-5 and R is (CF.sub.3).sub.2 CFOCF.sub.2 (CF.sub.2
CF.sub.2).sub.n with n = 0-5 or R is C.sub.n F.sub.2n+1 with n = 6-12.
20. A composition as claimed in claim 15 wherein said ionic, non-polymeric
surfactant is
##STR22##
where R is (CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.n with n = 1-5 or R
is C.sub.n F.sub.2n+1 where n = 6-12.
21. A composition as claimed in claim 15 wherein said ionic, non-polymeric
surfactant is [RCH.sub.2 CH.sub.2 SC(NH.sub.2).sub.2 ].sup.+ I.sup.- where
R is (CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.n with n = 1-5 or R is
C.sub.n F.sub.2n+1 with n = 6-12.
22. A composition as claimed in claim 15 wherein said ionic, non-polymeric
fluoro surfactant is selected from the group consisting of:
(a) (CF.sub.3).sub.2 CFO(CF.sub.2).sub.2 (CH.sub.2).sub.m COOM,
(b) C.sub.n F.sub.2n+1 (CH.sub.2).sub.m COOM,
(c) (CF.sub.3).sub.2 CFO(CF.sub.2).sub.b (CH.sub.2).sub.d
CH(CH.sub.2).sub.m COOM
(cf.sub.3).sub.2 cfo(cf.sub.2).sub.b (CH.sub.2).sub.d CH(CH.sub.2).sub.m
COOM,
(d) C.sub.n F.sub.2n+1 (CH.sub.2).sub.d CH(CH.sub.2).sub.m COOM
C.sub.n F.sub.2n+1 (CH.sub.2).sub.d CH(CH.sub.2).sub.m COOM,
(e) (CF.sub.3).sub.2 CFO(CF.sub.2).sub.b (CH.sub.2).sub.m SO.sub.3 M, and
(f) C.sub.n F.sub.2n+1 (CH.sub.2).sub.m SO.sub.3 M
wherein n is 6 to 12, M is H or alkali metal, m is 0 to 10, a is 4 to 14, b
is 2 to 7 and d is 1 to 4.
23. A textile fabric including a fiber to which the composition of claim 1
has been applied.
24. A textile fabric as claimed in claim 23 wherein said ionic,
non-polymeric fluoro surfactant has a radical (CF.sub.3).sub.2 CFOCF.sub.2
CF.sub.2 -- or C.sub.n F.sub.2n+1 where n = 6-12.
25. A textile fabric as claimed in claim 23 wherein the fabric has
remaining from the composition, exclusive of carrier, a solids content of
about 0.25% to about 10% by weight of fabric.
26. A textile fabric as claimed in claim 25 wherein the fabric has
remaining from the composition, exclusive of carrier, a solids content of
about 1% to about 4% by weight of fabric.
27. A textile fabric as claimed in claim 23 wherein said fiber is nylon.
28. The textile fabric of claim 23 wherein said polymer includes
predominantly methyl methacrylate monomeric units.
29. The textile fabric of claim 23 wherein said ionic, nonpolymeric fluoro
surfactant is a carboxylic acid, an alkali metal salt of a carboxylic
acid, a sulfonic acid, an alkali metal salt of a sulfonic acid, a
quaternized N-halomethyl amide or a quaternized haloalkyl ester.
30. The textile fabric of claim 23 wherein the percent of said polymer is
from about 1 to about 4 percent by weight of said fabric.
31. A process for treating a textile fabric comprising applying to the
fabric a composition as claimed in claim 1.
32. A process as claimed in claim 31 wherein said process includes
preparing the polymer as a suspension using an emulsifier and adding the
ionic, nonpolymeric fluoro surfactant to the suspension.
33. A process as claimed in claim 32 wherein said fluoro surfactant is
compatible with said ionic, non-polymeric emulsifier.
34. A process as claimed in claim 31 wherein said fiber is nylon.
35. A process as claimed in claim 31 including diluting said composition
with carrier until the composition is at least 70% carrier and then
applying the composition to the fiber.
36. A process as claimed in claim 31 wherein the composition is applied in
quantities sufficient to deposit from about 0.25% to about 9% polymer by
weight of fabric.
37. A process as claimed in claim 36 wherein the composition is applied in
quantities sufficient to deposit from about 1% to about 4% polymer by
weight of fiber. |
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Claims |
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Description |
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BACKGROUND OF THE INVENTION
This invention relates to a process for rendering fabrics, particularly
pile fabrics such as carpeting, resistant to soiling.
"Fabrics" as used herein means textile fabrics manufactured from natural or
synthetic textile fibers. Synthetic fibers are those fibers manufactured
from organic polymeric materials such as polyamides, including nylon,
polynitriles such as polyacrylonitriles and polyacrylates such as
polymethylmethacrylate and copolymers of polynitriles and polyacrylates.
Natural fibers include cotton, wool, silk and regenerated cellulose fibers
such as rayon. Fabrics which are treated in accordance with the process of
the invention include both woven and pile fabrics but pile fabrics are of
particular interest in that they have a particular tendency to pick up
soils. Of particular interest are carpets having a pile composed of
natural or synthetic fibers since such carpets tend to soil particularly
rapidly.
Carpets which are resistant to soiling in the sense that they soil to a
lesser degree or less rapidly are therefore particularly advantageous.
Pile fabrics, and in particular upholstery fabrics, which are composed of
natural or synthetic fibers, are similarly prone to rapid soiling in use
and such fabrics which are resistant to soiling are likewise advantageous.
In the prior art, fabrics, particularly carpets and pile upholstery
fabrics, were treated to improve soil resistance. Prior art compositions
for treating fabrics such as carpets, were not generally acceptable in
that soil resistance and particularly dry soil resistance was not
sufficiently enhanced and since wear resistance of the compositions was
poor. Some of the better compositions for improving soil resistance
contained fluorine containing polymers. Such compositions, while being an
improvement over compositions which contained no fluorine, generally still
do not provide as much soil resistance as was desired, and wear
characteristics of the compositions were generally poor.
For simplicity, the fabric with all additives except the present
composition will be referred to as "fiber". Polymer treated fabrics are
known. For example, fabrics treated with methyl methacrylates are
disclosed in U.S. Pat. No. 3,433,666.
Fluorinated, nonpolymeric surfactants are also known. Fluorinated sulfonic
acids and salts are disclosed in British Pat. No. 1,261,767 and German
Pat. No. 1,935,991. U.S. Pat. No. 3,821,290 discloses
perfluoroisoalkoxyalkyl sulfonic acids. Perfluoro substituted diphatic
acids are disclosed in U.S. Pat. No. 2,951,051. French Pat. No. 1,463,275
discloses methacrylate polymer in conjunction with surface active agents
to provide dry soil resistance to carpets. British Pat. No. 1,155,552
discloses polystyrene emulsions in conjunction with surface active agents.
BRIEF DESCRIPTION OF THE INVENTION
The dry soil resistant fabric finish of the invention includes a polymer
with a glass transition transmission above room temperature, a fluoro
surfactant having 5 to 30 carbons per hydrophilic end and a carrier. The
polymer is preferably a cationic latex produced with an emulsifier. The
emulsifier itself is preferably cationic. The nonpolymeric, fluoro
surfactant preferably has either a (CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2
-- radical or a C.sub.n F.sub.2n+1 -- radical, where n is 6 to 12. The
polymer is preferably essentially non-halogenated.
The preferred finish composition is from about 0.25 to about 45 percent (by
weight of composition) polymer, from about 0.5 to about 50 percent (by
weight of polymer) fluoro surfactant and the remainder (at least 40% by
weight of composition) carrier, preferably water. More preferably, the
fluoro surfactant is about 1-10% by weight of polymer.
The preferred method of the invention includes applying the above
composition to a textile fabric.
The preferred fabric includes from about 0.25 to about 10 percent by weight
polymer, about 2 to about 10 percent (by weight of polymer) ionic
emulsifier and from about 0.5 to about 50 percent (by weight of polymer)
fluoro surfactant, with the remainder fiber (including all additives
except the present composition).
DETAILED DESCRIPTION OF THE INVENTION
The compositions of the invention include a polymer component, a
fluorinated surfactant component and a carrier component. Preferably, the
polymer is a latex, with sufficient amounts of an ionic, and preferably
cationic emulsifier to suspend the polymer. About 0.5 to about 50% by
weight of polymer is the ionic fluorinated surfactant with from 5 to 30
carbons per hydrophilic end. The balance of the composition, which would
be at least 45% by weight of the entire composition, is a liquid carrier.
A wide variety of polymers, both homopolymers and copolymers, are suitable
for the present compositions. Nonhalogenated polymers are preferred. Any
significant halogen content produces glass transition temperature below
room temperature and thus a sticky polymer. Exemplary monomeric units are
derived from alkyl methacrylates, styrenes, alkyl acrylates, olefins and
mixtures thereof. The criteria for suitable polymers is a glass transition
temperature above room temperature (about 25.degree. C). A list of
polymers with their glass transition temperatures may be found at pages
III-64 and through III-84 of "Polymer Handbook" by J. Brandrup and E. H.
Immergut (N.Y., 1966).
Other exemplary polymers include poly(hexadecyl acrylate), poly(isobornyl
acrylate), poly(tetradecyl acrylate), poly(isobornyl methacrylate). It
should be appreciated that glass transition temperature is somewhat
additive with many copolymers such that a copolymer may have a
sufficiently high glass transition temperature even though, considering
its predominant monomeric unit, the homopolymer would not have a glass
transition temperature above room temperature.
The monomeric units for such polymers include lower alkyl methacrylate and
especially methyl methacrylate. Other monomeric units include, by way of
example, 3-3-dimethyl-1-butene; 3-methyl-1-butene; isobornylacrylate;
cyclohexylmethacrylate; isobutylmethacrylate;
5-tert-butyl-2-methylstyrene; styrene; N-vinylpyrralidone; diacetone
acrylanide; and 3-vinyl pyridine. Copolymers may be used with more than
one of the above exemplary monomeric units, such as:
methylmethacrylate/N-vinylpyrrolidone 80/20 copolymer, ethyl
methacrylate-diacetone acrylamide 80/20 copolymer, styrene/acrylonitrile
50/50 copolymer, and styrene/maleic anhydride 50/50 copolymer.
Other monomeric units may also be incorporated into copolymers. Among the
preferred copolymers is that of methyl methacrylate with N-methylol
acrylamide, with the methyl methacrylate being more than 90%, and
preferably about 98.5%, of the monomeric units.
A broad range of known polymers can be used in the present invention so
long as the temperature of glass formation is above room temperature.
Typically, such polymers have molecular weight from about 20,000 to about
2,000,000 although this range is not critical.
The composition of the present invention may, in some forms, be prepared
with the polymer dissolved in carrier. However, many preferred polymers
are prepared as a latex or emulsion in the carrier with the use of an
emulsifier in amounts sufficient to suspend the monomer sources in the
carrier during polymerization, and to hold the polymer suspended as a
latex. It will be appreciated that such amounts can be determined by
routine experimentation. Such latexes are well known in the art, and as
can be appreciated, many polymers can be prepared with cationic, anionic
or nonionic emulsifiers. As will also be appreciated, cationic emulsifiers
produce a cationic environment for the polymer or a "cationic latex" and
anionic emulsifiers produce an anionic environment for the polymer or an
"anionic latex". Nonionic emulsifiers give no charge to the polymer, and
therefore in spite of any small charge on the polymer itself, such latexes
are regarded as nonionic.
The emulsifiers of the composition may be selected from a broad range of
materials. While, in general, cationic primary emulsifiers are preferred,
it will be understood that the emulsifier chosen must usually be
compatible with the fluoro surfactant. Noncompatible emulsifiers (an
anionic emulsifier with a cationic fluoro surfactant or vice versa) may be
used, but must be prepared carefully to avoid destabilization of the latex
when fluoro surfactant is added. Exemplary primary emulsifiers include
cetyltrimethyl ammonium bromide, which is preferred with methyl
methacrylate polymers.
Other exemplary cationic emulsifiers include: Barquat MX50
[alkyldimethylbenzyl ammonium chloride], Hyamine 2389 [methyldodecylbenzyl
trimethyl ammonium chloride 80%/methyldodecylxylylene bis (trimethyl
ammonium chloride) 20%] and Hyamine 10X [diisobutylcresoxyethoxyethyl
dimethyl ammonium chloride].
In general, such cationic emulsifiers are preferred to nonionic and anionic
emulsifiers. Preferrably, the cationic emulsifier is sufficiently charged
to cause the latex of polymer and emulsifier to be cationic. In some
forms, and with certain polymers, anionic or nonionic emulsifiers could
still be used in the composition.
For example, anionic surfactants such as sodium laurel sulfate may be used
as emulsifiers in compositions with certain polymers. However, with the
preferred lower alkyl methacrylate polymers suspended in sodium laurel
sulfate, dry soil resistance is not materially improved.
The fluorinated surfactant of the composition can be anionic or cationic
with, respectively, negative and positive hydrophilic groups. These
compounds should have 5-30, and preferably 6-20 and most preferably 6-12
carbons per hydrophilic group. Thus the exemplary dimer acids below could
have up to 60 carbons. Preferably, the surfactant and emulsifier are
compatible as discussed above. Exemplary anionic groups include carboxylic
groups, bisulfate and sulfate groups. Exemplary cationic groups include
tertiary ammonium halides. Many such compounds are disclosed in U.S. Pat.
No. 3,899,366, incorporated herein by reference. Exemplary structures
include the following:
(a) Segmented Carboxylic Acid
C.sub.n F.sub.2n+1 (CH.sub.2).sub.m COOM
where:
n = 6-12 and m is 0-11
M = h or alkali metal
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CF.sub.2).sub.n (CH.sub.2).sub.m
COOM
where:
n = 2-12, m is 0-10, M = H or alkali metal
(b) Dimer Acids
##STR1##
where: n = 0-5, m=0-8, M = H or alkali metal
(c) As in (b) above where the fluoroalkyl segment is C.sub.n F.sub.2n+1
where:
n = 6-12
(d) Segmented Sulfonic Acids
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CF.sub.2 CF.sub.2).sub.n
(CH.sub.2).sub.m SO.sub.3 M
where:
n = 0-5, m = 0-10, M = akali or alkaline earth metal
(e) As in (d) above where the fluoroalkyl segment is C.sub.n F.sub.2n+1
where:
n = 0-5
(f) Quaternized Haloalkyl Esters of Perfluoroalkoxy Alkanols
##STR2##
where: n = 0-5, m = 0-5, Et is ethoxy
(g) As in (f) above where the fluoroalkyl segment is C.sub.n F.sub.2n+1
where:
n = 6-12
(h) Quaternized N-Halomethyl Amides of Fluoro Acids
##STR3##
where: n =1-5
(i) As in (h) above where the fluoroalkyl segment is C.sub.n F.sub.2n+1
where:
n = 6-12
(j) Isothiouronium Halides
[(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.n CH.sub.2 CH.sub.2
SC(NH.sub.2).sub.2 ].sup.+ I.sup.-
where:
n = 1-5
(k) As in (j) above where the fluoroalkyl segment is C.sub.n F.sub.2n+1
where:
n = 6-12
Preferred fluorinated surfactants include one of the following radicals:
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CF.sub.2 CF.sub.2).sub.n -- with n =
0 to 5
C.sub.n F.sub.2n+1 -- with n= 6 to 12.
Such preferred radicals include (CF.sub.3).sub.2 CFO(CF.sub.2).sub.12 --;
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 --; C.sub.6 F.sub.13 --; C.sub.9
F.sub.19 -- and C.sub.12 F.sub.25 --.
Thus, preferred fluoro surfactants include such compounds and salts as:
(C.sub.6 F.sub.13)COOH; (C.sub.8 F.sub.17)(C.sub.5 H.sub.10)COO.sup.-
Li.sup.+ ; (C.sub.12 F.sub.25)COO.sup.- Na.sup.+ ;
(C.sub.6 F.sub.13)(C.sub.11 H.sub.22)COO.sup.- K.sup.+ ; (CF.sub.3).sub.2
CFOCF.sub.2 CF.sub.2 (CF.sub.2).sub.2 COOH;
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (cf.sub.2).sub.12 (ch.sub.2).sub.5
coo.sup.- k.sup.+ ;
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (cf.sub.2).sub.4 (ch.sub.2).sub.10
coo.sup.- li.sup.+ ;
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2 CH(CH.sub.2).sub.8 COO.sup.-
Na.sup.+
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 CH.sub.2 CH(CH.sub.2).sub.8 COO.sup.-
Na.sup.+ ;
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CF.sub.2 CF.sub.2).sub.5 CHCOOH
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (cf.sub.2 cf.sub.2).sub.5 chcooh;
(c.sub.6 f.sub.13)ch.sub.2 ch(ch.sub.2).sub.2 cooh
(c.sub.6 f.sub.13)ch.sub.2 ch(ch.sub.2).sub.2 cooh;
(c.sub.12 f.sub.25)ch.sub.2 ch(ch.sub.2).sub.4 coo.sup.- na.sup.+
(C.sub.12 F.sub.25)CH.sub.2 CH(CH.sub.2).sub.4 COO.sup.-Na.sup.+ ;
(C.sub.8 F.sub.17)CH.sub.2 CH(CH.sub.2).sub.8 COO.sup.- K.sup.+
(c.sub.8 f.sub.17)ch.sub.2 ch(ch.sub.2).sub.8 coo.sup.- k.sup.+ ;
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (ch.sub.2).sub.10 so.sub.3.sup.-
k.sup.+ ;
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (cf.sub.2 cf.sub.2).sub.5
(ch.sub.2).sub.4 co.sub.3 h;
(cf.sub.3).sub.2 cfocf.sub.2 cf.sub.2 (cf.sub.2 cf.sub.2).sub.10
(ch.sub.2).sub.2 so.sub.3.sup.- .sub.2 ca.sup.++ ;
(C.sub.6 F.sub.13)(CH.sub.2).sub.2 SO.sub.3 .sup.-.sub.2 Mg .sup.++ ;
(C.sub.12 F.sub.25)(CH.sub.2).sub.10 SO.sub.3.sup.- Na.sup.+ ;
(CF.sub.3).sub.2 CFOCF.sub.2 CF.sub.2 (CH.sub.2).sub.5 OCOCH.sub.2 N.sup.+
(Et).sub.3 Cl.sup.- ;
(C.sub.6 F.sub.13)(CH.sub.2).sub.3 OCOCH.sub.2 N.sup.+ (Et).sub.3 Cl.sup.-
;
##STR4##
[(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2)CH.sub.2 CH.sub.2
SC(NH.sub.2).sub.2 ].sup.+ I.sup.- ;
[(cf.sub.3).sub.2 cfo(cf.sub.2 cf.sub.2).sub.2 ch.sub.2 ch.sub.2
sc(nh.sub.2).sub.2 ].sup.+ i.sup.- ;
[(c.sub.6 f.sub.13)ch.sub.2 ch.sub.2 sc(nh.sub.2).sub.2 ].sup.+ i.sup.- ;
and
[(C.sub.12 F.sub.25)CH.sub.2 CH.sub.2 SC(NH.sub.2).sub.2 ].sup.+ I.sup.-.
a broad range of carrier solvents may be used according to the present
invention. With appropriate polymer, surfactant and emulsifier, water may
be used as the preferred carrier. If necessary, more expensive organic
solvents may be used.
The preferred dry soil resistant compositions of this invention consists of
a mixture of poly(lower alkyl methacrylate) and a fluorosurfactant
described above in the ratio of from about 99.5 parts poly(lower alkyl
methacrylate) to 0.5 parts fluorosurfactant, to about 50 parts
methacrylate to 50 parts fluorosurfactant. The preferred composition
consists of about 94 parts methacrylate to 6 parts fluorosurfactant all on
a dry solids basis. The dry soil resistant formulation may have a solids
content ranging between 0.5% to 50% with the preferred concentration at
the time of application being about 0.5-20% solids.
The preferred formulations are mixed by polymerizing the polymer or
copolymer in the presence of some carrier and of the primary emulsifier,
adding the fluoro surfactant, and diluting with carrier before use.
Alternatively, fluoro surfactant may be added to the dissolved polymer.
Fluorochemical quaternary ammonium surfactants may also be used as the
primary emulsifier. However, the hydrocarbon emulsifiers are generally
preferred because they generally give a more stable latex and a higher
solids content emulsion. The use of a fluorochemical primary emulsifier in
the polymerization is expensive and gives a product with no better dry
soil resistance than provided by polymers made with hydrocarbon
emulsifiers to which the fluoro surfactant has been added after the
completion of the polymerization.
In actual operation, the carpet finisher would dilute the composition so as
to provide a pad or spray composition containing about 0.25-10% solids.
The fabric would thus be about 0.25-10% polymer and about 0.05 to 50%
fluoro surfactant (by weight of polymer). If the composition was a latex,
some emulsifier would also be included. The remainder of the fabric would
be fiber (including other additives). The actual bath concentration will
depend on the pick-up which is in turn a function of line speed, mode of
application, etc. In general, deposition of between 1 and 4% solids gives
optimum dry soil resistance. As a general rule, application sufficient to
deposit about 0.25-9% preferably about 1-4% polymer by weight of fiber
gives sufficient dry soil resistance.
After spraying or padding, the carpet is generally passed through a drying
device to remove solvent or moisture. Temperature or residence in the
drying device is not critical to performance nor is a cure necessary for
satisfactory performance.
The fluoro surfactants of the invention have been found neither to
interfere with the dye in fabrics nor to block dyeing of pretreated fibers
or fabrics.
The various groups of fluoro surfactants may be synthesized by known
techniques. For example, some mechanisms are shown in Table I:
__________________________________________________________________________
Intermediate or
Group of Fluoro
Surfactant Method of Synthesis Reference(s)
__________________________________________________________________________
R.sub.f I=C.sub.m F.sub.2m+1 I or U.S. Pat. Nos.
(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2)I
3,641,083
3,651,105
3,678,068
a) Segmented Carboxylic Acids
##STR5## U.S. Pat. Nos. 2,951,051 3,231,604
3,697,564
& c)
Dimer Acids
##STR6## [from synthesis of a] U.S. Pat.
No. 3,899,366
d
& e)
Segmented Sulfonic Acids
##STR7## U.S. Pat. No. 3,821,290
f
& g)
Quaternized Haloalkyl Esters
##STR8## 3,563,999
h
& i)
Quaternized N-Halomethyl Amides
##STR9## U.S. Pat. No. 3,674,800 see
3,681,413 2,764,602 2,764,602
2,764,603
##STR10##
j
& k)
Isothiouronium Halides
##STR11## see Roberts & Caserio PRINCIPLES
OF ORGANIC CHEMISTRY 750
__________________________________________________________________________
(1964)
EXAMPLE 1--Techniques for Dry Soil Resist Tests and Evaluation
VACUUM CLEANER SOIL
Vacuum cleaner disposable bags were collected from several residential
homes and the soil removed from them. It was then sterilized in a
circulating oven at 125.degree. C for one hour. The sterilized soil was
then freed from hairs, lint, larger solid particles, etc., and sifted
through a 40 mesh screen. Finally, the soil was sifted through a 100 mesh
screen and stored in jars. The jars were rotated on a ball mill for one
hour to homogenize the soil.
ACCELERATED SOILING METHOD
The accelerated soiling method used was essentially the same as American
Association of Textile Chemists and Colorists (AATCC) Test Method 123-
1970. It consisted of placing two specimens of the carpet (one treated and
one untreated) in a porcelain ball mill jar with the back of each specimen
against the inside cylindrical surface. The two specimens had been,
initially, cut from the same piece of carpet in the same direction of
construction. Ten grams of the soil were placed as uniformly as possible
and 50 flint pebbles were added in the jar. The cover was now fastened and
the jar rotated for 15 minutes on the ball mill at about 75-80 RPM. A
large number of experiments had shown, earlier, that under these
conditions the carpet specimens were always evenly soiled.
At the end of 15 minutes, the ball mill was stopped, the specimens removed
and shaken free of excess dirt. Now the specimens were individually
cleaned by using a tank type vacuum cleaner. Cleaning was continued till
no further improvement could be seen in the appearance of the specimen.
RATING OF DRY SOIL RELEASE PERFORMANCE
The two soiled specimens (treated and untreated) were compared, under
uniformly diffused good lighting conditions, against each other. In most
of the cases, ratings were given as under.
0 = Worse dry soiling than the untreated soiled specimen.
50 = Dry soiling equal to the untreated soiled specimen.
70 = Dry soiling slightly less than the untreated soiled specimen
80 = Dry soiling noticeably less than the untreated soiled specimen
90 = Dry soiling considerably less than the untreated soiled specimen
95 = Dry soiling significantly less than the untreated soiled specimen
100 = Dry soiling produces no visible effects versus unsoiled fabric
samples
In many cases, it becomes difficult to assign number ratings to treated
samples when their dry soil release performance was between 95 and 100. In
such cases, a ranking method can be used with advantage. Such methods have
been described by various authors. Essentially, the procedure consists of
the following. An operator is asked to arrange (coded) soiled and vacuumed
samples in order of their increasingly better appearance. The sample with
least soiling gets #1 and the one with heaviest soiling is assigned the
last number in a given batch of samples. This procedure is then repeated
by another operator. There is no limit to the number of operators that can
be employed. Usually, three or five operators are considered satisfactory.
Average ratings then can be used to assign relative measure of goodness of
different treatments. This method also lends itself excellently to
statistical analysis and is a popular tool in the hands of statisticians.
This ranking method has been used in assessing relative goodness of
various treatments described in this disclosure.
APPLICATION
During this study, all aqueous based formulations were applied by soaking
the carpet pieces in the pad bath for 30 seconds and then squeezing
through a Butterworth padder. Pressure on the rolls of the Butterworth
padder was adjusted to give about 100% wet pick up. The wet samples of the
carpet were pin framed and dried in an air circulating oven at 125.degree.
C.
When a dry soil release finish was applied from solvent solutions, an
electrically driven Atlas laboratory wringer was used. Solution
concentration and wet pick up were adjusted to deposit the desired amount
of the finish on the carpet fibers. The wrung samples were pin framed, air
dried and further dried in an air circulating oven at 125.degree. C for
about 15 minutes.
In all these evaluations, nylon-6 carpet dyed brilliant gold, was used. The
color of this carpet was chosen specifically to show better differences in
degree of soiling. This carpet had jute primary backing. No secondary
backing was applied.
EXAMPLE 2
DRY SOIL RELEASE OF POLYMER OR COPOLYMER, FLUOROSURFACTANT, AND COMBINATION
Cationic latices of polymethyl methacrylate or copolymethyl methacrylate --
N-methylol acrylamide 98.5/1.5 (both prepared by emulsion polymerization
with the help of cationic emulsifier cetyl trimethyl ammonium bromide)
were applied to nylon carpet. Also, in this series of investigations,
several fluorinated surface active agents were applied to identical carpet
by techniques described in Example 1. In addition to the above two types
of finishes, identical nylon pieces were treated with formulations
containing the hydrocarbon cationic latex (polymethyl methacrylate or
copolymethyl methacrylate -- N-methylol acrylamide) and one of the
hydrocarbon surface active agents described above under this example.
The treated pieces were soiled and evaluated by methods described in
Example 1. The results are summarized in Table II.
TABLE II
__________________________________________________________________________
LEVEL
APPLIED
DRY SOIL
TREATMENT (% OWF)
RELEASE
__________________________________________________________________________
Copoly MMA/NMA (Cationic; prepared
by using cetyl trimethyl ammonium
bromide) 2.0 (Solids)
95
Poly MMA (Cationic; prepared by
using cetyl trimethyl ammonium
bromide) 2.0 (Solids)
95
CF.sub.3 (CF.sub.2).sub.6 COOH
0.06 (F)
70
C.sub.3 F.sub.7 OC.sub.2 F.sub.4 (CH.sub.2).sub.10 COOH
0.06 (F)
85
C.sub.3 F.sub.7 OC.sub.8 F.sub.16 (CH.sub.2).sub.10 COOH
0.06 (F)
95
##STR12## 0.06 (F)
60
(C.sub.3 F.sub.7 OC.sub.2 F.sub.4 C.sub.2 H.sub.4 SC(NH.sub.2).sub.2).su
p.+ I.sup.- 0.06 (F)
90
C.sub.3 F.sub.7 OC.sub.4 F.sub.8 (CH.sub.2).sub.11 OCOCH.sub.2 N.sup.+
(C.sub.2 H.sub.5).sub.3 Cl.sup.-
0.06 (F)
> 90 but < 95
C.sub.3 F.sub.7 OC.sub.6 F.sub.12 CH.sub.2 CH.sub.2 SO.sub.3 H
0.06 (F)
Better than
#1 or #2 above
10.
Copoly MMA/NMA (as in #1 above)
2.0 (Solids)
Better than
+ +
C.sub.3 F.sub.7 (CF.sub.2).sub.6 COOH
0.06 (F)
#1 or #3 above
Copoly MMA/NMA (as in #1 above)
2.0 (Solids)
Better than
+ +
C.sub.3 F.sub.7 OC.sub.2 H.sub.4 (CH.sub.2).sub.10 COOH
0.06 (F)
#1 or #4 above
Copoly MMA/NMA (as in #1 above
2.0 (Solids)
Better than
+ +
C.sub.3 F.sub.7 OC.sub.8 F.sub.16 (CH.sub.2).sub.10 COOH
0.06 (F)
#1 or #5 above
Copoly MMA/NMA (as in #1 above
2.0 (Solids)
Better than
+
C.sub.3 F.sub.7 OC.sub.8 F.sub.16CH.sub.2CH(CH.sub.2).sub.8 CO.sub.2
+ #1 or #6 above
C.sub.3 F.sub. 7 OC.sub.8 F.sub.16CH.sub.2CH(CH.sub.2).sub.8 CO.sub.2
0.06 (F)
Poly MMA (as in #2 above)
2.0 (Solids)
Better than
+
C.sub.3 F.sub.7 OC.sub.8 F.sub.16CH.sub.2CH(CH.sub.2).sub.8 CO.sub.2
+ #2 or #6 above
C.sub.3 F.sub.7 OCH.sub.8 F.sub.16CH.sub.2CH(CH.sub.2).sub.8 CO.sub.2
0.06 (F)
Copoly MMA/NMA (as in #1 above)
2.0 (Solids)
Better than
++ - +
(C.sub.3 F.sub.7 OC.sub.2 F.sub.4 C.sub.2 H.sub.4 SC(NH.sub.2).sub.2)
0.06 (F)
#1 or #7 above
Copoly MMA/NMA (as in #1 above)
2.0 (Solids)
Better than
++- +
C.sub.3 F.sub.7 OC.sub.2 F.sub.4 (CH.sub.2).sub.11 OCOCH.sub.2 N(C.sub.2
H.sub.5).sub.3 Cl 0.06 (F)
#1 or #8 above
Copoly MMA/NMA (as in #1 above)
2.0 (Solids)
Better than
+ +
C.sub.3 F.sub.7 OC.sub.6 F.sub.12 CH.sub.2 CH.sub.2 SO.sub.3 H
0.06 (F)
#1 or #9 above
__________________________________________________________________________
Unexpected results were seen (Table II) when the dry soil performance of
the formulations, containing the hydrocarbon cationic latex and a
fluorochemical surface active agent, was compared with that of the
hydrocarbon or the fluorochemical surface active agent applied
individually. The performance of a given formulation was dramatically
superior fo that of either of the component treating agents applied alone.
Although no explanation is advanced for such an unexpected behavior, it is
clear that a definite synergism exists between the cationic polymeric or
copolymeric latex and the fluorochemical surface active agent. Such
synergism is exhibited irrespective of the ionic charge on the surface
active fluorochemical moiety. Formulations of the sulfonic acid C.sub.3
F.sub.7 O(CF.sub.2).sub.n CH.sub.2 SO.sub.3 H, where n = 6, 8 or 10, with
cationic latices were particularly effective in dramatically improving the
soil release performance.
EXAMPLE 3
A test was run according to the procedure described in Example 1 using some
of the polymers and fluoro surfactants of the present invention, some of
the compositions of the present invention and some commercial products.
The results, set forth in Table III, demonstrate the effectiveness of the
compositions of the present invention in resisting soiling.
TABLE III
__________________________________________________________________________
PERFORMANCE COMPARISON OF SOME SOIL RESISTANCE PRODUCTS FOR CARPETS
LEVEL
APPLIED
FINISH APPLIED (% OWF) SOIL RESISTANCE PERFORMANCE
__________________________________________________________________________
MMA/NMA (98.5:1.5) 4.0% (Solids)
After accelerated soiling for 15
minutes 96
C.sub.3 F.sub.7 OC.sub.6 F.sub.12 C.sub.2 H.sub.4 SO.sub.3 H
0.06% (Fluorine)
After accelerated soiling for 15
96nutes
C.sub.3 F.sub.7 OC.sub.6 F.sub.12 C.sub.2 H.sub.4 SO.sub.3 H
0.06% (Fluorine)
After accelerated soiling for 15
98nutes
MMA/NMA (98.5:1.5) 2.0% (Solids)
C.sub.3 F.sub.7 OC.sub.4 F.sub.8 . C.sub.10 H.sub.20 COOH
0.06% (Fluorine)
After accelerated soiling for 15
96nutes
C.sub.3 F.sub.7 OC.sub.4 | | |
