U.S. patent number RE30,337 [Application Number 05/964,063] was granted by the patent office on 1980-07-15 for textile treatment composition.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Basil L. Loudas.
United States Patent |
RE30,337 |
Loudas |
July 15, 1980 |
Textile treatment composition
Abstract
Textiles, particularly carpets, are endowed with oil and water
repellency and soil resistance by treatment thereof with certain
detergent-compatible fluorochemical compounds which can also be
used in conjunction with anionic or nonionic detergents to provide
cleaning/treating compositions for cleaning such textiles
simultaneously with the treatment. The textile treating
compositions of the invention comprise certain detergent-compatible
fluorochemical compounds which are dissolved and/or dispersed in a
suitable liquid vehicle. The textile treating/cleaning compositions
of the invention also contain an anionic and/or a nonionic
detergent.
Inventors: |
Loudas; Basil L. (Stillwater,
MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (Saint Paul, MN)
|
Family
ID: |
25508081 |
Appl.
No.: |
05/964,063 |
Filed: |
November 27, 1978 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
446003 |
Feb 26, 1974 |
04043923 |
Aug 23, 1977 |
|
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Current U.S.
Class: |
252/8.62;
510/278; 510/280; 510/299; 558/54; 558/56; 562/556 |
Current CPC
Class: |
D06M
13/428 (20130101); D06M 15/277 (20130101) |
Current International
Class: |
D06M
15/21 (20060101); D06M 15/277 (20060101); D06M
13/00 (20060101); D06M 13/428 (20060101); C08K
005/02 (); C08K 005/05 (); D06M 013/00 () |
Field of
Search: |
;252/8.6,8.75,8.8,351
;8/142 ;260/456A,456F ;562/556 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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995411 |
|
Aug 1976 |
|
CA |
|
2044508 |
|
Feb 1971 |
|
FR |
|
6606734 |
|
Nov 1966 |
|
NL |
|
857336 |
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Dec 1960 |
|
GB |
|
Primary Examiner: Lieberman; Allan
Attorney, Agent or Firm: Alexander; Cruzan Sell; Donald M.
Francis; Richard
Claims
What is claimed is:
1. A composition comprising a liquid vehicle containing from about
1% to about 25% by weight of a detergent-compatible organic
fluorochemical compound containing about 10 to 60 weight percent
carbon-bonded fluorine and having the formula (R.sub.f Q).sub.e
(XCO).sub.m A(COOM).sub.p where R.sub.f is fluorinated aliphatic
radical of at least three carbon atoms, "Q" is a divalent linking
group, "M" is a cation selected from NH.sub.4.sup.+, Na.sup.+,
K.sup.+, Li.sup.+, H.sup.+ or is a protonated alkyl amine having
from 1-6 carbon atoms in the alkyl group "A" is a polyvalent
organic radical having a valency of m+p and is the residue of a
polybasic organic acid or an organic anhydride, "X" is NR (wherein
R is hydrogen or an alkyl group of from 1 to 14 carbon atoms),
.Iadd.or .Iaddend.N .[.or O.]. and e, p and m are integers of 1 or
2.
2. The composition of claim 1 wherein said liquid vehicle is a
mixture of water and sufficient compatible water-soluble organic
solvent to dissolve and/or disperse said fluorochemical
compound.
3. The composition of claim 2 wherein said organic solvent is
selected from the group consisting of 2-butoxy ethanol, isopropyl
alcohol and ethyl alcohol.
4. The composition of claim 1 wherein "A" is the residue of
chlorendic anhydride.
5. The composition of claim 1 wherein said fluorochemical compound
is ##STR22##
6. The composition of claim 1 wherein R.sub.f is C.sub.8 F.sub.17
and M is K.sup.+, Na.sup.+ or NH.sub.4.sup.+.
7. A composition comprised of a liquid vehicle containing (1) from
about 1% to about 25% of a detergent-compatible fluorochemical
compound containing from about 10 to about 60 percent carbon-bonded
fluorine and having the formula (R.sub.f Q).sub.e (XCO).sub.m
A(COOM).sub.p where R.sub.f is fluorinated aliphatic radical of at
least three carbon atoms, "Q" is a divalent linking group, "M" is a
cation selected from NH.sub.4.sup.+, Na.sup.+, K.sup.+, Li.sup.+,
H.sup.+ or is a protonated alkyl amine having from 1-6 carbon atoms
in the alkyl group, "A" is a polyvalent organic radical having a
valency of M+p and is the residue of a polybasic organic acid or an
organic anhydride, "X" is NR (wherein R is hydrogen or an alkyl
group of from 1 to 14 carbon atoms), .Iadd.or .Iaddend.N .[.or O.].
and e, p and m are integers of 1 or 2, and (2) compatible non-ionic
or anionic detergent, said detergent being water dispersible at
concentrations of at least 1% by weight and being capable of drying
to a non-oily, non-tacky residue, the weight ratio of said
detergent to said fluorochemical compound being on the order of 1:1
to 2:1.
8. The composition of claim 7 wherein said liquid vehicle comprises
water and sufficient compatible water-soluble organic solvent to
dissolve and/or disperse said fluorochemical compound.
9. The composition of claim 8 wherein said liquid vehicle is a
mixture of water and an alcohol selected from the group consisting
of 2-butoxy ethanol, isopropyl alcohol and ethanol.
10. The composition of claim 7 wherein said fluorochemical compound
is ##STR23##
11. The composition of claim 10 wherein R.sub.f is C.sub.8 f.sub.17
and M is K.sup.+, Na.sup.+ or NH.sub.4.sup.+.
12. The composition of claim 7 wherein said detergent is a salt of
lauryl sulfate or lauryl ether sulfate.
13. The composition of claim 7 wherein the weight ratio of said
detergent to said organic fluorochemical compound is on the order
of 2:1.
14. The composition of claim 1 wherein "Q" is selected from the
group consisting of alkylene [--(CH.sub.2).sub.n --], sulfonamido
alkylene [--SO.sub.2 NR(CH.sub.2).sub.n --], alkylene carboxyloxy
alkylene [--(CH.sub.2).sub.n COOCH.sub.2 CH.sub.2 --], and
sulfonamido alkyleneoxy alkylene [--SO.sub.2 NR(CH.sub.2 CH.sub.2
O).sub.n CH.sub.2 CH.sub.2 --] wherein "R" is hydrogen or a lower
alkyl group having from about 1 to 14 carbon atoms and n is an
integer from about 1 to 15.
Description
BACKGROUND OF THE INVENTION
This invention relates to textile treatment with novel compositions
to impart water and oil repellency and soil resistance. In another
aspect, the invention relates to cleaning/treating compositions for
cleaning such textiles simultaneously with such treatment.
DESCRIPTION OF THE PRIOR ART
The treatment of textiles with fluorochemicals to impart water and
oil repellency has been known for some time. As disclosed in U.S.
Pat. Nos. 3,068,187; 3,256,230; 3,256,231; 3,277,039; and
3,503,915, fluorinated polymers have been mixed with
non-fluorinated polymers to obtain a treating composition which
will impart water and oil repellency to textiles, paper and
leather. Such prior art compositions, however, are generally
designed for initial factory treatment of the textile and are not
suited for use after the textile article has been soiled in
use.
U.S. Pat. No. 3,377,197 discloses treating previously cleaned
textile fabric, leather, rugs, etc., with fluorine-containing
organometallic compounds to impart resistance against soiling,
staining and wetting. U.S. Pat. No. 3,382,097 discloses a treatment
for imparting oil and soil repellency to textile fabric, leather,
rugs, etc., by treating with a solution of certain fluorinated
organic carboxylic acids. This reference also suggests combining a
detergent with a fluorochemical acid in an aqueous medium for a
one-step cleaning and treating operation, but it does not impart
water repellency. And, although Netherlands patent application No.
6,606,734 suggests dispersing an insoluble fluorocarbon compound in
a laundering composition useful for a two-step cleaning operation,
such disclosure does not provide a one-part treating/cleaning
composition.
Other prior art cleaning compositions, such as carpet shampoos, do
not impart water and oil repellency. Rather, many such conventional
cleaning compositions leave hydrophilic or oleophilic residues on
the cleaned substrate which actually attract and hold dirt.
Although some cleaning compositions contain ingredients designed to
impart soiling resistance, such compositions do not impart water
and oil repellency.
SUMMARY OF THE INVENTION
The present invention provides novel compositions for the
fluorochemical treatment of textiles such as carpets, upholstery
and the like, to impart water and oil repellency and stain
resistance thereto. Quite surprisingly, these novel compositions
can also contain detergent and thereby clean and impart repellent
properties in one operation.
In accordance with the invention, a textile treatment is provided
by certain detergent-compatible organic fluorochemical compounds.
The textile treating compositions of the invention comprise certain
detergent-compatible fluorochemical compounds which are dissolved
and/or dispersed in a suitable liquid vehicle. The textile
treating/cleaning compositions of the invention also contain an
anionic and/or a nonionic detergent. The term "detergent
compatible" is used herein to denote that the organic
fluorochemical compounds are physically and chemically unaffected
by anionic and non-ionic detergents at concentrations thereof
typically encountered in textile cleaning solutions, and thus
capable of being applied during a cleaning operation. Additionally,
the organic fluorochemical compound treatment, applied to a
substrate such as a carpet, can be cleaned with conventional
carpet-cleaning detergent-containing solutions without removing or
rendering ineffective the organic fluorochemical, provided that
excessive detergent residue does not remain.
DETAILED DESCRIPTION
The detergent-compatible organic fluorochemical compounds that are
useful in the invention are those in which a fluorinated,
preferably saturated, aliphatic radical is linked to a
non-fluorinated organic radical which bears at least one carboxylic
acid group which may be neutralized. The non-fluorinated organic
radical has at least 6 members (e.g., carbon atoms) in a skeletal
backbone structure which links the fluoroaliphatic radical to the
carboxylic acid group. This skeletal structure can include catenary
oxygen and/or trivalent nitrogen hetero atoms, providing a stable
linkage between the fluoroaliphatic radical and the carboxylic acid
group. These fluorochemical compounds are capable of dissolving in
an organic solvent, preferably in a water-soluble or
water-dispersible organic solvent.
The fluoroaliphatic radicals, hereinafter called "R.sub.f
radicals", are saturated, and generally monovalent aliphatic
moieties. They can be straight chain, branched chain, and, if
sufficiently large, cyclic, or combinations thereof, such as
alkylcycloaliphatic radicals. The fluoroaliphatic skeletal chain
can include catenary oxygen and/or trivalent nitrogen hetero atoms
bonded only to carbon atoms, such hetero atoms providing stable
linkages between fluorcarbon groups and not interfering with the
inert character of the R.sub.f radical. While R.sub.f can have a
large number of carbon atoms, R.sub.f radicals having no more than
20 carbon atoms will be adequate and preferred since larger
radicals usually represent a less efficient utilization of fluorine
than is possible with smaller R.sub.f radicals. Generally, R.sub.f
will have 3 to 20 carbon atoms, preferably 6 to about 12, and will
contain 40-78 weight percent, preferably 50-77 weight percent,
carbon-bonded fluorine. The terminal portion of the R.sub.f radical
has preferably at least one fully fluorinated carbon atom, e.g.,
CF.sub.3, and the preferred R.sub.f radical is substantially
completely, or fully fluorinated, as in the case where R.sub.f is
perfluoroalkyl, C.sub.n F.sub.2n+1.
Generally, the detergent-compatible organic fluorochemical
compounds will contain about 10 to 60 weight percent, preferably
about 15 to 45 weight percent, of carbon-bonded fluorine. If the
fluorine content is less than about 10 weight percent, these
compounds may no longer be detergent compatible, while fluorine
contents greater than about 60 weight percent will require
compounds which are uneconomical to use.
Suitable liquid vehicles for the compositions of the invention will
dissolve or disperse the detergent-compatible fluorochemical. The
preferred liquid vehicles are organic solvents or organic
solvent/water mixtures. The organic solvents for this purpose are
volatile at room temperature and will preferably be capable of
dissolving and/or dispersing 1 part detergent-compatible
fluorochemical compound per 10 parts organic solvent and preferably
will dissolve and/or disperse in water at least 1 part organic
solvent per 10 parts water. The organic solvents are non-toxic, do
not have an odor which is objectionable to the normal person and do
not harm carpet fibers or structure.
Organic fluorochemical compounds which are detergent compatible and
preferred in the present invention have the structure: (R.sub.f
Q).sub.e (XCO).sub.m A(COOM).sub.p wherein R.sub.f is fluorinated
aliphatic radical as described above, "Q" is a divalent linking
group, "M" is a cation selected from NH.sub.4.sup.+, Na.sup.+,
K.sup.+, Li.sup.+, H.sup.+, or a protonated alkyl amine having from
1-6 carbon atoms in the alkyl group, "A" is a polyvalent organic
radical having a valency of m+p and is preferably derived from a
polybasic organic acid or an organic anhydride, "X" is NR (wherein
"R" is hydrogen or a lower alkyl group of from 1 to 14 carbon
atoms),
.Iadd.or .Iaddend.N .[.or O.]. "e", "p" and "m" are integers of 1
or 2.
It should be noted that because of the polyvalent nature of the "A"
group, the fluorochemical compounds may be a polyanhydride polymer
structure having repeating structure ##STR1## wherein "R" is alkyl
of from 1-6 carbon atoms or alkoxy alkyl such as butoxyethyl,
ethoxyethyl, etc, z is from zero to 1, b is from zero to 10 times a
and a plus b is an integer representing the number of repeating
units in the polymer.
The divalent linking group "Q" has a valency of 2 and may include
one or more groups such as alkylene [--(CH.sub.2).sub.n --],
sulfonamido alkylene [--SO.sub.2 NR(CH.sub.2)--], alkylene
carboxyloxy alkylene [--(CH.sub.2).sub.n COOCH.sub.2 CH.sub.2 --],
and sulfonamido alkylenoxy alkylene [--SO.sub.2 NR(CH.sub.2
CH.sub.2 O).sub.n CH.sub.2 CH.sub.2 --]wherein "R" is hydrogen or a
lower alkyl group having from about 1 to 14 carbon atoms and n is
an integer from about 1 to 15.
The polyvalent organic radical "A" has, as previously mentioned, a
valency of m to p and may be aromatic, araliphatic, cycloaliphatic
or heteroaromatic and is preferably the residue of a polybasic acid
or an anhydride from which the carboxyl groups have been deleted.
Such anhydrides and acids include maleic, succinic, phthalic,
tetrachlorophthalic, chlorendic, tetrabromophthalic,
3-nitrophthalic, 4-nitrophthalic, cis 1,2-cyclohexane dicarboxylic,
5-norbornene-2, 3-dicarboxylic, 1,8-naphthalene dicarboxylic and
benzophenone tetracarboxylic and others.
The detergent-compatible organic fluorochemical compounds described
above and useful in the present invention may be prepared in any of
a variety of ways. Most conveniently, the compounds which are
preferred in the invention are prepared by reacting a precursor
fluorochemical amine .[.or alcohol.]. with a suitable anhydride.
Precursor amines .[.and alcohols.]. will have the structure R.sub.f
QXH where "R.sub.f ", "Q" and "X" are as described above. Useful
illustrative examples of such precursor amines .[.and alcohols.].
include:
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2
OH.].
.[.CF.sub.3 (CF.sub.2).sub.3 SO.sub.2
N(CH.sub.3)CH(CH.sub.3)CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.3 SO.sub.2 N(CH.sub.2 CH.sub.3)CH.sub.2
CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.3 SO.sub.2 N(CH.sub.3)CH.sub.2
CH(CH.sub.3)OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.2 CH.sub.3)CH.sub.2
CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.9 SO.sub.2 N(CH.sub.2 CH.sub.2
CH.sub.3)CH.sub.2 CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.2 CH.sub.2
CH.sub.3)CH.sub.2 CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(C.sub.2
H.sub.5)(CH.sub.2).sub.6 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(C.sub.2
H.sub.5)(CH.sub.2).sub.11 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(C.sub.4
H.sub.9)(CH.sub.2).sub.4 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.3)(CH.sub.2).sub.4
OH.].
CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.2 CH.sub.3)CH.sub.2
CH.sub.2 NH.sub.2
[CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.2 CH.sub.3)CH.sub.2
CH.sub.2 ].sub.2 NH
CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(CH.sub.2 CH.sub.3)CH.sub.2
CH.sub.2 N(CH.sub.3)H
.[.CF.sub.3 C.sub.6 F.sub.10 C.sub.2 F.sub.4 SO.sub.2
N(CH.sub.3)CH.sub.2 CH.sub.2 OH.].
.[.C.sub.2 F.sub.5 O(C.sub.2 F.sub.4 O).sub.3 CF.sub.2 CONHC.sub.2
H.sub.4 OH.].
.[.CF.sub.3 (CF.sub.2).sub.7 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2
OCH.sub.2 CH.sub.2 CH.sub.2 OH.]. ##STR2## .[.CF.sub.3
(CF.sub.2).sub.6 SO.sub.2 CH.sub.2 CH.sub.2 OH.].
.[.CF.sub.3 (CF.sub.2).sub.6 COCH.sub.2 CH.sub.2 OH.].
.[.C.sub.7 F.sub.15 CON(C.sub.2 H.sub.5)C.sub.2 H.sub.4 OH.].
.[.C.sub.8 F.sub.17 SO.sub.2 N(C.sub.4 H.sub.9)CH.sub.2 CH.sub.2
OH.].
.[.C.sub.7 F.sub.15 CON(CH.sub.3)CH.sub.2 CH.sub.2 OH.].
.[.C.sub.8 F.sub.17 SO.sub.2 NH(CH.sub.3)(CH.sub.2).sub.4 OH.].
.[.C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)(CH.sub.2).sub.11 OH.].
.[.C.sub.6 F.sub.13 SO.sub.2 NCH.sub.3 (CH.sub.2).sub.4 OH.].
##STR3## C.sub.7 F.sub.15 CH.sub.2 NH.sub.2 C.sub.8 F.sub.17
SO.sub.2 N(C.sub.4 H.sub.9)CH.sub.2 CH.sub.2 NH.sub.2 ##STR4##
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CONHCH.sub.2
CH.sub.2 NH.sub.2
C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2
NHCH.sub.2 CH.sub.2 NH.sub.2
Many of the precursor fluorochemical amines .[.and alcohols.]. are
well known and/or commercially available. U.S. Pat. No. 3,346,612
discloses a method of preparing the fluorochemical amines while
U.S. Pat. No. 3,398,182 discloses some useful amines .[.and
alcohols.]..
In the reaction which produces the preferred detergent-compatible
organic fluorochemical compound, the precursor fluorochemical amine
.[.or alcohol.]. is reacted usually with about an equivalent amount
of the anhydride. In certain instances, e.g., the polyanhydride
polymers previously mentioned, the ratio (by equivalents) of amine
.[.or alcohol.]. to anhydride may vary between 1:10 and 1:1. This
reaction is most conveniently accomplished in a solvent for both
the reactants and the reaction product. Typical solvents for the
precursor fluorochemical amine are water miscible and include
dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone,
ketones such as acetone or methyl ethyl ketone, ethers such as
tetrahydrofuran, and alkoxy ethanols, such as 2-ethoxy ethanol or
2-butoxy ethanol (e.g."Butyl Cellosolve"). .[.Preferred solvents
for the precursor alcohols are aprotic and include dimethyl
formamide dimethyl formamide, dimethyl acetamide, N-methyl
pyrrolidone, pyridine and triethylamine..].
When the precursor .[.alcohol or.]. amine is dissolved in an
aprotic solvent, a minimum amount thereof to dissolve the reactants
is used, since these solvents are generally removed before using
the reaction product in a textile treatment.
The dissolved precursor fluorochemical amine is typically reacted
with the anhydride by slowly adding the latter to a solution of the
former with sufficient agitation to obtain uniform dispersal.
Reaction times are relatively short and the reactions are typically
carried out at temperatures in the range of about
20.degree.-80.degree. C. and at atmospheric pressures. An ambient
(air) reaction atmosphere may be used but dry nitrogen is
preferred.
It has been found that if the reaction temperatures are maintained
between about room temperature (20.degree. C.) and 80.degree. C., a
high yield of the desired organic fluorochemical compound is
produced with minimal side products from secondary reaction. If the
temperature is elevated about 85.degree. C., some reaction of the
anhydride and solvent may occur or the amide may partly cyclize,
reducing the water solubility of the resultant compounds which may
be undesirable in some instances.
.[.Fluorochemical alcohols may be reacted with the anhydride by
direct melt esterification or in the presence of aprotic solvents,
preferably with esterification promoting catalysts such as
perfluoromethane sulfonic acid or a tertiary amine..].
Once the reaction has been completed to produce the desired
detergent-compatible fluorochemical compound, if the solvent used
is undesirable for the final water dilution (because of being slow
drying, having a bad odor, etc.), the product may be removed from
the reaction solvent for example by precipitating it therefrom with
an aqueous acid solution. The precipitate is then dissolved and/or
dispersed in the liquid vehicle.
The resultant fluorochemical compound product, which has a free
carboxylic acid group, may be neutralized with a slight excess of a
base to make it water-soluble or water-dispersible. Suitable bases
for this purpose are at least moderately water-soluble and include
ammonia, potassium hydroxide, sodium hydroxide, morpholine or an
alkylamine such as triethylamine, propylamine, ethylamine,
isopropylamine, isobutylamine, butylamine, ethanolamine,
diethanolamine, diethylaminoethanol, 2-amino-2-ethyl propanol,
etc.
The term "dispersible" as used herein means that the ingredients of
the mixture either are mutually soluble, or otherwise stably
dispersible, e.g., forming a colloidal suspension in water at the
desired concentration.
The organic solvent either dissolves the acidic fluorochemical
compounds or aids in the water-dispersibility of the neutralized
fluorochemical compound, providing aqueous treating or
treating/cleaning compositions which are preferred. The preferred
ratio of organic fluorochemical compound to organic solvent is on
the order of 1:1 to 1:5, by weight. Organic solvents which may be
utilized include ethanol, alkoxyethanols such as 2-ethoxy or
2-butoxy ethanol, tetrahydrofuran, methyl ethyl ketone, acetone,
dimethyl formamide etc, and mixtures thereof. Organic solvents
having no or limited water-solubility, e.g., hexoxy ethanol, may be
used in minor proportions with organic solvents which are more
water-soluble.
The solutions of fluorochemical compound, water and solvent
described above, when applied to clean or previously cleaned
textile materials and dried, provide a high degree of water and oil
repellency and soil resistance. Not only is such repellency
provided, but the treated textile may be subsequently cleaned with
common detergent-containing textile cleaing solutions and still
thereafter retain these repellency properties if most of the
detergent is removed (e.g., by means of wet-vacuuming).
Typical concentrations of the organic fluorochemical compound will
be on the order of about 10 to 25 weight percent by weight
fluorochemical compound per total weight of a concentrated
solution, depending upon its solubility. For use, the concentration
of organic fluorochemical compound will be on the order of 1 to 2%
by weight. Excellent water and oil repellency and stain resistance
are obtained on carpeting having an add-on weight of at least 1 g
per sq. meter of fluorochemical compound, preferably 2-5 grams per
sq. meter.
It should be noted that certain of the detergent-compatible
fluorochemical compounds of the invention, i.e., where "X" in the
general formula noted above is nitrogen, will be endowed with
improved repellency properties upon being heated at an elevated
temperature, e.g., over 100.degree. C., preferably at about
125.degree. C. One example is the fluorochemical compound produced
as described above by reacting a dicarboxylic anhydride and a
primary fluorochemical amine, as the acid or neutralized with base
such as ammonia or morpholine. Heating times sufficient to note
this improvement will typically be between 10 minutes and 5 hours.
This further treatment may be accomplished on the textile surface
during its production, by treating the textile with the treating
compositions described above and by heating the treated
textile.
As previously mentioned, the solution may be a cleaning/treating
composition containing a detergent. The detergents should be
water-dispersible at concentrations of at least 1% by weight.
Detergents which are useful in such compositions are nonionic or
anionic detergents which dry to a non-oily, non-tacky residue from
an aqueous medium. Solid detergents which leave a dry residue are
desirable. Cationic detergents are not useful because they are not
generally compatible with the other ingredients in the
compositions.
Useful anionic detergents include alkali metal or ammonium salts of
fatty acids (e.g., 12 carbons or more), alcohol sulfates (or
sulfonates), alcohol phosphates (or phosphontes), alkyl sulfonates,
alkyl phosphates (or phosphonates), polyoxyalkylene alcohol
sulfates (or sulfonates), polyoxyalkylene alkyl carboxylates, and
polyoxyalkylene alcohol phosphates (or phosphonates).
Examples of commercial anionic detergents that are useful in the
invention include sodium lauryl sulfate (commercially available
under the trade designation "Avirol" 101), potassium lauryl sulfate
(commercially available under the trade designation "Culverol"
KLS), magnesium lauryl sulfate (commercially available under the
trade designation "Culverol" MgLS), sodium myristyl sulfate
(commercially available under the trade designation "Maprofix"
MSP90), sodium cetyl sulfate (commercially available under the
trade designation "Conco" Sulfate A), sodium tridecyl sulfate
(commercially available under the trade designation "Sipex" TDS),
sodium 7-ethyl-2-methyl-4-undecyl sulfate (commercially available
under the trade designation "Tergitol" 4). Of these, sodium lauryl
sulfate is the preferred detergent.
Nonionic detergents, either by themselves or in conjunction with
anionic detergents, can also be used in the cleaning/treating
compositions. When nonionic detergents are used, it is preferred
that they be normally solid materials, or if not solid, that they
be used in amounts less than about 20% by weight of the total
solids in the cleaing/treating solution. Useful commercial nonionic
surfactants include "Igepal DM-970" and "Pluronic F 68".
The weight ratio of detergent to organic fluorochemical compound is
on the order of 1:1 to 2:1, by weight. At more than 2:1 detergent
to organic fluorochemical compound, some reduction in the water
repellency properties of carpet treated with the organic
fluorochemical compound may be noted.
The treating or cleaning/treating composition of the invention may
contain other ingredients which increase effectiveness or improve
physical appearance. For example these compositions may contain an
additional known anti-redeposition agent. A typical example of such
an anti-redeposition agent is the ammonium salt of the hydrolyzed
copolymer of styrene and maleic anhydride. Other useful
anti-redeposition agents include polyvinyl pyrolidone and water
dispersible acrylate copolymers. Other optional additives include
germicidal materials, perfumes and the like.
In use, the diluted cleaning/treating compositions are typically
applied to the surface being cleaned and treated using conventional
equipment. For example, for carpet cleaning, a conventional
scrubbing device, which may be fitted with a liquid dispenser, is
used, the cleaning/treating solution being dispensed from such a
dispenser. The cleaning/treating and the treating solutions of this
invention may be sprayed upon the surface to be cleaned and/or
treated by conventional spraying devices or as an aerosol. The
aerosol dispensing container will contain the desired solution and
sufficient aerosol propellent to dispense the solution. Such
propellents are typically low boiling chloro-, fluoro-substituted
alkanes (e.g., "Freon 12") or low boiling alkanes or mixtures
thereof such as a mixture of isobutane and propane.
Compositions according to the invention are applied to various
textile substrates, typically carpeting of synthetic fibers, and
the treated substrates were evaluated for oil and water repellency,
as follows:
OIL REPELLENCY TEST
The test for oil repellency (which is similar to the method
described in AATCC Test No. 118-1966T) involves wetting the fabric
by a selected series of liquid hydrocarbons of different surface
tensions. The test liquids are as follows:
______________________________________ Oil Repellency Rating Number
Test Liquid ______________________________________ 1 "Nujol" 2 65
35 "Nujol" n-hexadecane by volume 3 n-hexadecane 4 n-tetradecane 5
n-dodecane 6 n-decane 7 n-octane 8 n-heptane
______________________________________
"Nujol" is the trademark of Plough, Inc., for a mineral oil having
a Saybolt viscosity 360/390 at 38.degree. C. and a specific gravity
0.880/0.900 at 15.degree. C.
In the test, one test specimen, approximately 20.times.20 cm, is
conditioned for a minimum of four hours at 21.+-.1.degree. C. and
65.+-.2% relative humidity prior to testing. The test specimen is
then placed on a smooth, horizontal surface and, beginning with the
lowest-numbered test liquid, a small drop--approximately 5 mm in
diameter (0.05 ml. volume)--is placed with a dropping bottle
pipette on the test specimen in several locations. The dropping
bottle pipette is a 60 ml. dropping bottle with a ground-in pipette
and "neoprene" rubber bulb. (Prior to use, the bulb should be
soaked in heptane for several hours and rinsed in fresh heptane to
remove soluble substances). The drop is observed for 30 seconds at
an angle of approximately 45.degree..
If no penetration or wetting of the fabric at the liquid-fabric
interface and no wicking around the drop occurs, a drop of the next
higher-numbered test liquid is placed at a side adjacent on the
fabric to the first drop, again observing the drop for 30 seconds.
This procedure is continued until one of the test liquids shows
obvious wetting of the fabric under or around the drop within 30
seconds. An untreated nylon tufted pile carpet has an oil
repellency of zero. The same carpeting treated with the treatment
of the invention has an oil repellency up to 6.
WATER REPELLENCY TEST
The treated carpet is tested for water repellency, after it is
dried for at least 4 hours at room temperature (about 20.degree.
C.) and under ambient laboratory humidity conditions (about 55%
relative humidity).
One drop of room temperature tap water (about 2-3 mm in diameter)
is then carefully applied utilizing an eye dropper held about 1 cm
from the fiber surface which will receive it. The test is repeated
on an adjacent area with a drop of an isopropyl alcohol/water
solution (10/90% by weight). The drop is observed and one of the
following ratings given, depending upon the observations:
______________________________________ Rating Observations
______________________________________ excellent The water drop
does not wet the surface and remains almost spherical in shape for
at least 2 hours. The isopropyl alcohol/water solution drop remains
on the fiber surface for at least 1 hour good The water drop
remains on the fiber surface for at least 1 hour with practically
no wetting although the shape may not be spherical. The isopropyl
alcohol/water solution remains at least 10 minutes before
penetrating the fiber fair The water drop may wet the upper surface
of the fiber but does not substantially penetrate the bulk of the
carpeting for at least 1 hour The isopropyl alcohol/water solution
penetrates the bulk of the carpeting almost immediately poor Both
the water and the alcohol solution immediately penetrate the bulk
of the carpet ______________________________________
Untreated nylon carpeting samples generally have a poor to fair
water repellency while the same carpet treated with compositions
according to the invention have a water repellency of fair to
excellent. The fair rating of an untreated carpet, typically
temporary, is usually caused by oily residues which are usually on
a new carpet surface. A permanent fair water repellency is
acceptable for a carpet treatment.
The invention is illustrated by the following examples, wherein all
parts are by weight unless otherwise specified.
EXAMPLE 1
The organic fluorochemical compound ##STR5## was prepared by
reacting tetrachlorophthalic anhydrice (hereinafter called "TCPA"
and sold under the trade designation "Tetrathal") with the
fluorochemical amine, m-aminophenol-perfluorooctane sulfonate,
##STR6## and neutralizing with ammonia. Twenty-five parts of TCPA
was suspended in 75 parts of dimethyl formamide, the suspension
heated to about 50.degree. C. and 5 parts of triethylamine added,
producing a reddish-brown color. Next, 50 parts of the
fluorochemical amine was added with mixing and continued heating at
50.degree. C. producing a clear solution which was cooled to room
temperature. The slightly soluble monocarboxylic acid derivative
was produced and isolated by diluting the clear solution with about
6 volumes of dilute acetic acid solution, causing this derivative
to precipitate as a white solid. The precipitate was filtered,
washed with distilled water and air dried at room temperature.
The desired organic fluorochemical compound treatment concentrate
was prepared by dissolving and neutralizing the acid derivative
(about 1.0 part) in a solution consisting of 0.5 parts ammonia, 3.0
parts "Butyl Cellosolve" and 5.5 parts water.
This treatment concentrate was dilued with about nine volumes of
water and the resultant solution was applied to a previously
cleaned, rinsed and dried 2 foot square tufted looped pile nylon
carpet test sample and permitted to dry overnight, producing a
dried add-on weight of 5.4 grams/m.sup.2. The treated carpet, when
tested for oil and water repellency as described above, had an oil
repellency of 5 and a water repellency rating of "excellent".
EXAMPLE 2
18 parts of TCPA was reacted with 50 parts of fluorochemical amine,
m-aminophenol-perfluorooctane sulfonate. The fluorochemical amine
was mixed with 130 parts of "Butyl Cellosolve" in the reaction
flask and the mixture heated to about 60.degree. C. until clear.
Then the TCPA was added in one lot and the mixture heated to about
70.degree. C. with continued stirring. When the reaction mixture
became clear, heat was discontinued and 20 parts of ammonium
hydroxide solution (28% NH.sub.3) was added followed immediately by
a mixture of 330 parts of deionized water and 10 parts of chelating
agent solution ("Versenol-120") with stirring ("Versenol 120" is
water solution containing 41.0% trisodium salt of N-hydroxy-ethyl
ethylene diamine triacetic acid). Then, 300 parts of a 10% by
weight aqueous solution of styrene/maleic anhydride copolymer
("SMA-3000"), hydrolyzed with ammonia, anti-redeposition agent was
added followed by 130 parts of detergent solution ("Richonol A",
30% sodium lauryl sulfate), 5 parts of fluorochemical surfactant
("FC 128") with heating to about 95.degree., giving a clear
cleaning/treating concentrate to which was added 0.5 part IFF
5009-S fragrance.
The concentrate was diluted 16 times with water to make a
cleaning/treating composition. Soiled tufted loop pile nylon
carpeting cleaned with this composition shows oil repellency of 3,
a "good" water repellency and excellent soiling resistance. A
carpet sample as cleaned and treated with the composition of this
example and an identical carpet sample was cleaned and treated with
a control composition which lacked the fluorochemical amine adduct.
When both test samples were placed in a heavy pedestrian traffic
situation, examination after one week showed the carpet treated
according to the invention to be cleaner.
EXAMPLE 3
The fluorochemical amine, m-aminophenol-perfluorooctane sulfonate,
(50 parts) was dissolved with stirring in 140 parts "Butyl
Cellosolve" at 60.degree. C., producing a clear solution. Then 25
parts TCPA was added with stirring and heating to 80.degree. C.
until reaction was complete. The reaction mixture was reduced in
temperature to 60.degree.-65.degree. C. and 20 parts concentrated
ammonium hydroxide (28% NH.sub.3) was added followed immediately by
430 parts of deionized water and 4 parts of "Versenol 120"
chelating agent solution. A clear solution was obtained, to which
was added 150 parts "Richonol A" detergent, 657 parts of 10%
styrene maleic acid copolymer ("SMA 3000") ammonium salt solution
in water, 6 parts fluorochemical surfactant "FC-128", 1.5 part
fragrance, and water sufficient to bring the total to 1500
parts.
One part of the resultant composition was diluted with two parts
distilled water to give a solution which was placed in a
conventional 12 ounce aerosol can with about 10% by weight of
isobutane aerosol propellent. The aerosol shampoo was sprayed upon
the surface of a 2.times.2 ft. soiled test sample of nylon
carpeting, and the carpet cleaned by utilizing a sponge mop
applicator to work the carpet surface. Another soiled carpet
sample, the same type and size, was cleaned in the same manner with
a prior art composition known as "New Johnson's Glory". Both
cleaned samples were dried, and placed in a heavy pedestrian
traffic situation. After one week, the sample treated with the
composition according to the invention was considerably cleaner
than that treated with the "New Johnson's Glory". Upon subsequent
cleanings, the carpet treated according to the invention cleaned
much easier than the carpet treated with the "New Johnson's
Glory".
EXAMPLE 4
50 parts of m-aminophenol-perfluorooctane sulfonate was first
dissolved in 140 parts of "Butyl Cellosolve" at 60.degree. C. and
18 parts TCPA was added with continued stirring and heating to
about 80.degree. C. until the reaction was complete. The reaction
mixture was cooled to about 60.degree.-65.degree. and 20 parts
concentrated ammonium hydroxide solution (28% NH.sub.3) was added
followed immediately by 218 parts deionized water, 337.5 parts 10%
solution of styrene/maleic anhydride copolymer ("SMA 3000")
hydrolyzed with ammonia, 135 parts "Richonol" A detergent, 4.5
parts fluorochemical surfactant ("FC 128") and 18.0 parts organic
solvent ("Super Hiflash Naphtha"), producing a cleaning/treating
concentrate.
Two 30 cm by 65 cm new nylon carpet test samples from the same
carpet lot were cleaned, one sample with 100 ml of "CHEMSPEC 161"
soil retardant carpet shampoo at the recommended dilution of 16:1
and the other sample with a solution consisting of 1 part of the
concentrate described above and 8 parts water. After drying, the
two samples were used in a heavy pedestrian traffic situation for
over 2 weeks. The sample cleaned with composition of the invention
described above had a "good" water repellency, and an oil
repellency of 4 and appeared cleaner both before and after
vacuuming than the sample cleaned with the "CHEMSPEC No. 161" rug
shampoo.
After vacuuming, equal amounts of the following common household
items which cause stains were applied over each treated carpet
sample in the order shown:
red dyed vegetable oil
salad dressing
mustard
ketchup
These household items were allowed to stand on the carpet samples
for over one hour, and then the excess was carefully removed with a
spatula and the carpet surface blotted with an absorbent cloth. The
remaining residue was removed by shampooing one test sample with
100 ml of a solution consisting of 1 part "CHEMSPEC 161" shampoo
concentrate and 16 parts water. Immediately after cleaning both
carpet samples appeared to be free of stains, but after drying at
room temperature for about 12 hours, the sample shampooed with the
composition of the invention appeared cleaner than the sample
shampooed with the "CHEMSPEC 161" shampoo.
When the dried samples were placed in a heavy pedestrian traffic
situation for 24 hours, severe soiling was noticed on the "CHEMSPEC
161" cleaned sample, especially in the areas stained as described
above. The sample treated with the composition of this example
looked clean over its entire surface with the exception of a very
small portion of the area where the salad dressing stain had been
placed. Fifteen days later the sample treated with the composition
of this example was dramatically cleaner than the other sample.
EXAMPLE 5
"Butyl Cellosolve" (140 parts) and 50 parts of m-aminophenol
perfluorooctane sulfonate were charged in a 3 neck flask fitted
with a mechanical stirrer, thermometer and heating mantle, the
contents raised to 60.degree. C. with stirring until they became
clear. Then, 25 parts TCPA was added with continued stirring and
heating to about 80.degree. C., maintaining this temperature until
the solution became clear. The temperature of the flask contents
was then lowered to about 60.degree.-65.degree. and 20 parts
concentrated ammonium hydroxide solution (28% NH.sub.3) was added,
followed immediately by 521 parts deionized water, 4 grams of
"Versenol 120" chelating agent solution and 0.5 part fragrance,
producing a treatment concentrate.
EXAMPLE 6
Four 12.times.12 inch samples of new nylon tufted loop pile carpet
(identified as A-D herein) were sprayed with a test solution
consisting of 50 grams of the solutions diluted as shown below. The
solutions consisted of 1 part of the concentrate of Example 5
diluted with the amount of water shown in the following table.
______________________________________ Carpet Sample Volumes of
Water ______________________________________ A 4 B 10 C 20 D 40
______________________________________
After drying at room temperature, each of the treated carpet
samples had an oil repellency of 6 and "good" to "excellent" water
repellency.
EXAMPLE 7
The concentrate of Example 5 was diluted with 4 volumes of water
and the resultant solution was applied by means of an electric
motor driven sprayer onto the surface of nylon loop pile carpet
which had been used for some time as an entryway floor covering for
the employee entrance of a large office building, at about 320
g/m.sup.2 solution, producing an add-on weight of about 6.4
g/m.sup.2. The next day the carpet showed "excellent" water
repellency and an oil repellency of 5-6. One month later (after an
estimated pedestrian traffic of 60,000 pedestrian passes) water
repellency was still "excellent" and oil repellency was 6 at the
edge and 4 in the main traffic lane.
EXAMPLE 8
The concentrate described in Example 5 was diluted 4 times with
water and the resultant solution was sprayed at 215 g/m.sup.2 with
a mechanical sprayer over the surface of wool carpet which had been
used for some time in an executive office area, resulting, after
overnight drying, in a dried add-on weight of 4.3 g/m.sup.2.
Initially, the carpet showed "excellent" water repellency and an
oil repellency of 6. After two months of use the repellency results
were unchanged.
EXAMPLE 9
The concentrate described in Example 5 was diluted 4 times with
water and the resultant solution was sprayed at 215 g/m.sup.2 over
the surface of a nylon carpet which had been used for some time in
a men's rest room in a large office building, resulting in a dried
add-on weight of 3.2 g/m.sup.2. For up to 2 months later, the
carpet showed "excellent" water repellency and an oil repellency of
5. The more heavily used area of the carpet (near the entrance)
showed an oil repellency of 2 and "good" water repellency.
EXAMPLE 10
150 parts "Butyl Cellosolve" was mixed with 50 parts of the
fluorochemical amine, m-amino-phenol perfluorooctane sulfonate, at
50.degree. C., until a clear solution developed. Then, 18 parts
TCPA was added with continued mixing and heating to 70.degree. C.
until the resultant solution cleared. Heating was discontinued and
26 parts concentrated ammonium hydroxide (28% NH.sub.3) was added
with stirring, followed by a mixture of 200 parts distilled water,
4 parts "Versenol-120", 340 parts 10% styrene/maleic anhydride
copolymer "SMA-3000", ammonia neutralized, aqueous solution, 200
parts "Richonol A" detergent solution, 18 parts "Super Hi-flash
Naphtha" organic solvent, 500 parts distilled water and 4 parts
fluorochemical surfactant ("FC-128"), giving a clear
cleaning/treating solution.
One half of a 30 cm.times.60 cm sample of new nylon loop pile
carpeting was shampooed with 50 ml of Johnson's "Rugbee" shampoo at
the recommended dilution. The remaining half was shampooed with 50
ml of the solution described above. The carpet samples were allowed
to dry overnight at room temperature, then soiled artificially.
The artificial soiling involved securing carpet samples to the
inside walls of a cylinder which contains 100 small ceramic
cylinders and a soiling formulation, and rotating the cylinder at
42 revolutions per minute for 20 minutes. The cylinder was 33.3 cm
high and has an inside diameter of 24.9 cm. The carpet samples were
ordinarily secured to the inside walls of the cylinder with
double-coated pressure-sensitive adhesive. The small ceramic
cylinders were 1.9 cm by 1.9 cm in size and weighed about 23 grams
each.
The soiling formulation used in the soiling test comprised:
______________________________________ Parts
______________________________________ Peat Moss 70 Gray Portland
Cement (Type 1) 30 Silica gel (200 mesh) 30 Clay 30 Sodium chloride
(about 80 mesh) 7 Gelatin 7 Carbon black 23 Red iron oxide 1
Stearic acid 3.2 Oleic acid 3.2 Peanut oil 6 Lanolin 2
______________________________________
The half treated according to the invention looked cleaner than the
untreated half both before and after vacuuming. Then each half
again was shampooed with 60 ml of the shampoos previously used and
observations made. The half treated according to the invention
cleaned easier and cleaner than "Rugbee"-treated half using the
same technique and effort. When dried, the carpet half treated with
the composition according to the invention had a "good" water
repellency and had an oil repellency of 2-3. The remaining half
cleaned with the Johnson's "Rugbee" had a "poor" water repellency
and a zero oil repellency.
EXAMPLE 11
In this example isopropyl alcohol was used as the organic solvent
and sodium hydroxide as the neutralizing base 200 parts of
isopropyl alcohol and 50 parts of the fluorochemical amine
described in Example 1 were heated with stirring to about
60.degree. C., and 25 TCPA were added with additional stirring
heating to 75.degree. C. Within 30 minutes the mixture became
clear, indicating completion of the reaction. After cooling the
resultant solution to 50.degree. C., 3.6 parts of sodium hydroxide
in 50 parts water were added, followed by a mixture of 4 parts
"Versenol 120", 0.5 parts of fragrance and 283 parts of deionized
water. The resultant solution was heated to 75.degree.-80.degree.
C. until a clear shampoo concentrate was formed.
The concentrate was diluted with 10 volumes of water and the
diluted solution sprayed on nylon carpet at about 540 g of
spray/m.sup.2 and the treated carpet allowed to dry at room
temperature. Repellency testing showed water repellency to be
"excellent" and an oil repellency of 6.
.[.EXAMPLE 12.].
.[.The fluorochemical compound active material in the carpet
treatment described below was the ammonium salt of a half ester
derived from chlorendic anhydride and fluorochemical alcohol. Sixty
parts of the fluorochemical alcohol, C.sub.8 F.sub.17 SO.sub.2
N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OH, (0.1 mole), and 50 parts of
chlorendic anhydride (0.13 mole) were melted together at
140.degree.-150.degree. C. for 30 minutes, producing a homogeneous
glassy melt. "Butyl Cellosolve" (55 parts) was added to the melt
and the mixture heated at 140.degree. C. for an additional 10
minutes with mixing. The mixture was cooled to
60.degree.-65.degree. and 30 parts concentrated ammonium hydroxide
(28% NH.sub.3) was added followed by 355 parts deionized water,
producing a clear treatment concentrate which was diluted with 10
volumes of water for use..].
.[.The diluted treatment solution was applied to test samples of
nylon and acrylic carpet (both looped pile construction), producing
on each a dried add-on weight of 5.4 g/m.sup.2. After drying both
test carpet samples showed "good" water repellency and an oil
repellency of 4. Side by side artificial soiling tests with control
untreated carpet samples showed the antisoiling ability of the
treated carpet samples to be much superior to that of the untreated
controls..].
.[.EXAMPLE 13.].
.[.A carpet treatment based on the reaction product of a
fluorochemical amine and a fluorochemical alcohol with chlorendic
anhydride in a one step process. Thirty parts of the fluorochemical
alcohol, C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2
CH.sub.2 OH, (0.05 mole) was placed in a 1,000 ml "Pyrex" glass
flask equipped with a thermometer and stirrer and a heating mantle
and heated to 100.degree. C. with stirring. Fifty parts chlorendic
anhydride (0.13 mole) was added with continued stirring and heating
to about 140.degree. C. for 30 minutes. Thereafter, the flask
contents were cooled to 90.degree. C. and a solution of 30
parts..]. ##STR7## .[.in 150 parts "Butyl Cellosolve" added,
resulting in a reduction in temperature to 80.degree. C. After
maintaining an 80.degree. C. temperature about 10 minutes, the
flask contents were cooled to about 65.degree. C. and 25 parts
concentrated ammonium hydroxide (28% NH.sub.3) added followed
immediately by 315 parts of distilled water, producing a clear
treatment concentrate which was diluted with 10 volumes of water
for use..].
.[.The diluted treatment was applied over the surface of an
"Antron" nylon looped pile carpet sample, after drying providing a
dried add-on weight of 5.4 g/m.sup.2. The treated carpet had a
"good" to "excellent" water repellency and an oil repellency of 4.
Artificial soiling of the treated carpet sample and an untreated
control revealed that the treated sample had excellent antisoiling
properties..].
EXAMPLES .Badd..[.14-56.]..Baddend. .Iadd.12-45 .Iaddend.
Textile treating compositions Examples 14-56 were prepared of
materials shown in the following table and tested for repellency on
new tufted nylon carpeting which had been exhaustively cleaned.
Shampooing was with "Triple S" rug and upholstery shampoo
manufactured by Standardized Sanitation Systems, Inc. The shampooed
carpet samples were dried at room temperature for at least 12
hours, cut into 7 to 10 cm wide strips, placed in a household
automatic washing machine for full cycle utilizing water only to
rinse, and dried in a household dryer.
Before repellency testing, the stripped test samples had a zero oil
repellency and a "poor" water repellency. The treatments of
Examples 14-56, after being dried at room temperature for about 12
hours produced a dry add-on weight on the order of 3 to 6.5 grams
per sq. m.
__________________________________________________________________________
Neutral- Reactants (moles) Reaction izing Organic Repellency Ex.
Fluorochemical Acid or anhydride solvent base solvent Water Oil
__________________________________________________________________________
.[.14.]..Iadd.12.Iaddend. ##STR8## 1.0 tetrachlorophthalic
anhydride 1.0 IPA.sup.1 NaOH BC.sup.2 IPA excellent 5
.[.15.]..Iadd.13.Iaddend. " " tetrachlorophthalic BC NH.sub.3 BC "
6 anhydride .[.16.]..Iadd.14.Iaddend. " " tetrachlorophthalic IPA
dieth- IPA fair 4 anhydride anol amine .[.17.]..Iadd.15.Iaddend. "
" tetrachlorophthalic ethanol NaOH ethanol excellent 5 anhydride
.[.18.]. .Iadd.16.Iaddend. " " tetrachlorophthalic IPA KOH IPA
anhydride BC " 6 .[.19.]..Iadd.17.Iaddend. " " tetrabromophthalic
anhydride 1.0 BC NH.sub.3 BC " 4 .[.20.]..Iadd.18.Iaddend. " "
chorendic anhydride 1.0 IPA NH.sub.3 IPA " 5
.[.21.]..Iadd.19.Iaddend. " " chorendic BC NH.sub.3 BC " 5
anhydride .[.22.]..Iadd.20.Iaddend. " 1.0 3-nitrophthalic
good.sup.4 anhydride 1.0 DMF.sup.3 NH.sub.3 BC.sup.2 fair 4
.[.23.]..Iadd.21.Iaddend. " 1.0 4-nitrophthalic BC good.sup.4 2
anhydride 1.0 BC NH.sub.3 acetone fair 5 .[.24.]..Iadd.22.Iaddend.
" 0.9 1,2-cyclohexane dicarboxylic acid good.sup.4 anhydride 1.0 BC
NH.sub.3 BC fair 4 .[.25.]..Iadd.23.Iaddend. " 2.0 benzophenone
tetra- dietha- carboxylic acid nol dianhydride 1.0 BC amine BC
excellent 5 .[.26.]..Iadd.24.Iaddend. " 1.0 norbornene dicarbox-
ylic acid anhydride 1.0 BC NH.sub.3 BC good 5
.[.27.]..Iadd.25.Iaddend. " 1.0 phthalic fair.sup.4 3 anhydride 1.0
DMF NH.sub.3 IPA.sup.1 poor 4 .[.28.]..Iadd.26.Iaddend. " 1.0
naphthalic 1,8-dicar- boxylic acid good.sup.4 anhydride 1.0 DMF
NH.sub.3 BC poor 5 .[.29.]..Iadd.27.Iaddend. " 2.0 pyrromellitic
dianhydride (PMDA) 1.0 DMF.sup.3 NH.sub.3 BC.sup.2 good 4
.[.30.]..Iadd.28.Iaddend. " 1.0 maleic anhydride 1.0 DMF NH.sub.3
IPA.sup.1 good.sup.4 poor 5 .[.31.]..Iadd.29.Iaddend. " 1.0 "SMA
1000".sup.5 2.0 BC NH.sub.3 BC good 3 .[.32.]..Iadd.30.Iaddend. "
1.0 "SMA 2000".sup.6 1.0 BC NH.sub.3 BC good 3 31 .Iadd." 1.0 "SMA
2000" 2.0 BC NH.sub.3 BC excellent.sup.4 2 good.Iaddend.
.[.34.]..Iadd.32.Iaddend. " 1.0 "SMA 3000".sup.7 1.0 BC NH.sub.3 BC
excellent.sup.4 2 good .[.35.]..Iadd.33.Iaddend. ##STR9## 1.0
"Gantrez AN 139".sup.8 1.0 DMF NH.sub.3 BC good.sup.4 1 2
.[.36.]..Iadd.34.Iaddend. " 1.0 TCPA 0.7 DMF NH.sub.3 BC excellent
5 .[. 37.]..Iadd.35.Iaddend. ##STR10## 1.0 chlorendic anhydride 1.0
BC.sup.2 NH.sub.3 BC good 5 .[.38.]..Iadd.36.Iaddend. " 1.0
tetrachloro- phthalic BC/ anhydride 1.0 BC NH.sub.3 acetone good 4
.[.39.]..Iadd.37.Iaddend. C.sub.8 F.sub.17 SO.sub.2 NHCH.sub.2
CH.sub.2 NH.sub.2 1.0 tetrachloro- 1.0 N-methyl triethyl phthalic
pyroli- amine BC good 4 anhydride done .[.40.]..Iadd.38.Iaddend. "
1.0 chlorendic anhydride 1.0 DMF.sup.3 NH.sub.3 BC good 4
.[.41.]..Iadd.39.Iaddend. ##STR11## 1.0 chlorendic anhydride 1.0 BC
NH.sub.3 BC good 1 .[.42.]..Iadd.40.Iaddend. " 1.0 tetrachloro-
phthalic anhydride 1.0 BC NH.sub.3 BC good.sup.4 1 fair
.[.43.]..Iadd.41.Iaddend. " 2.0 tetrachloro- 1.0 BC NH.sub.2 BC
good.sup.4 3 phthalic anhydride fair 3 .[.44.]..Iadd.42.Iaddend.
##STR12## 1.0 chlorendic anhydride 1.0 BC.sup.2 NH.sub.3 BC
excellent 4 .[.45.]..Iadd.43.Iaddend. ##STR13## 1.0 "SMA
3000".sup.7 2.0 BC NH.sub.3 BC good 2 .[.46.]..Iadd.44.Iaddend.
##STR14## 0.8 tetrachloro- phthalic anhydride 1.0 BC NH.sub.3 BC
excellent 5 .[.47.]..Iadd.45.Iaddend. ##STR15## 1.0
"SMA 1000".sup.5 3.0 BC NH.sub.3 BC excellent .sup.4 good 2 .[.48
##STR16## 1.0 chlorendic anhydride 1.25 none NH.sub.3 BC good 2 49
##STR17## 1.0 chlorendic anhydride 1.25 N-methyl pyroli- done
triethyl- amine NH.sub.3 BC fair 4 50 ##STR18## 1.0 cyclohexane
1,2- dicarboxylic acid anhydride 1.3 none NH.sub.3 BC.sup.2 fair 4
51 " 1.0 chlorendic anhydride 1.25 N-methyl NH.sub.3 BC good pyroli
done triethyl- amine 52 ##STR19## 1.0 chlorendic anhydride 1.25
N-methyl NH.sub.3 IPA.sup.1 good 2 pyroli- Done triethyl- amine 53
##STR20## 1.0 cyclohexane 1,2- dicarboxylic acid anhydride 1.3
N-methyl pyroli- triethyl- NH.sub.3 BC fair 5 54 " 1.0 tetrachloro-
phthalic anhydride 1.0 DMF.sup.1 NH.sub.3 BC good 4 55 ##STR21##
1.0 "SMA 1000".sup.5 2.0 DMF NH.sub.3 BC excellent.sup.4 fair 1 3
56 " 1.0 "SMA 1000".sup.5 4.5 DMF NH.sub.3 BC fair 2.].
__________________________________________________________________________
.sup.1 isopropyl alcohol .sup.2 "Butyl Cellosolve"- .sup.3 dimethyl
formamide .sup.4 dried in oven at 120.degree. C. .sup.5
styrene/maleic anhydride (1:1) copolymer .sup.6 styrene/maleic
anhydride (2:1) copolymer .sup.7 styrene/maleic anhydride (3:1)
copolymer .sup.8 copolymer of maleic anhydride and methyl vinyl
ether
* * * * *