Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
'~ 2~98~ 20
WO92/10605 PCT/US91/09155
TITLE
MALEIC ANHYDRIDE/OLEFIN POLYMER STAIN-RESISTS
FIELD OF THE INVENTION
The present invention relates to polyamide
textile substrates treated with stain-resistant
compositions comprising water-soluble or
water-dispersible maleic anhydride/ alpha-olefin
polymers, and processes for their synthesis. The
substrates of this invention possess stain-resistance
but do not suffer from yellowing to the extent that
some previously known materials do.
BACKGROUND OF THE INVENTION
Polyamide substrates, such as nylon carpeting,
upholstery fabric and the like, are subject to staining
by a variety of agents, e.g., foods and beverages. An
especially troublesome staining agent is FD&C Red Dye
No. 40, commonly found in soft drink preparations.
Different types of treatments have been proposed to
deal with staining problems. One approach is to apply
a highly fluorinated polymer to the substrate. Another
is to use a composition containing a sulfonated
phenol-formaldehyde condensation product.
For example, Liss et al., in U.S. Patent No.
4,963,409, disclose stain-resistant synthetic polyamide
textile substrates having deposited on them sulfonated
phenol-formaldehyde polymeric condensation products.
However, sulfonated phenol-formaldehyde condenation
products are themselves subject to discoloration;
commonly they turn yellow. Yellowing problems are
described by W. H. Hemmpel in a March 19, 1982 article
in America's Textiles, entitled Reversible Yellowing
Not Finisher's Fault. Hemmpel attributes yellowing to
exposure of a phenol-based finish to nitrogen oxides
`.
.
~UY~
WO92/10605 PCT/US91/09155
and/or ultraviolet radiation. To deal with the
yellowing problem, the condensation products were
modified by Liss et al. by acylation or etherification
of some of the phenolic hydroxyls. In a preferred
embodiment disclosed by Liss et al., the modified
condensation products were dissolved in a hydroxy-
containing solvent, such as ethylene glycol prior to
there being applied to the textile substrate.
Allen et al., in U.S. Patent 3,83S,071,
disclose rug shampoo compositions which upon drying
leave very brittle, non-tacky residues which are easily
removed when dry. The compositions comprise water-
soluble metal, ammonium or amine salt of a styrene-
maleic anhydride copolymer, or its half ester, and a
detergent. Water-soluble metal salts of Group II and
the alkali metals (particularly magnesium and sodium)
are preferred and ammonium salts are most preferred by
Allen et al.
On the other hand, Fitzgerald et al., in
U.S. Patent Application Serial No. 07/502819, filed
2 April 1990, disclose the usefulness of agueous
solutions of hydrolyzed vinylaromatic/maleic anhydride
copolymers in the treatment of textiles to render them
resistant to staining. The preferred copolymer of
Fitzgerald et al. is a hydrolyzed styrene/maleic
anhydride copolymer. Fitz~erald et al. disclose that
- the monoalkyl ester of their maleic anhydride/vinyl
aromatic polymer was ineffective as a stain-resist.
Maleic anhydride/alpha-olefin polymers are
known. U.S. Reissue Patent No. 28,475 discloses
copolymerization of maleic anhydride and l-olefins,
such as, l-hexene, l-tetradecene and l-octadecene.
European Patent Application No. 306,992 published
15 March 1989 discloses maleic anhydride/-l-alkene
(C4_30) polymers. Florjanczyk et al. in
:;
~9~2~
(-` WO92/10605 PCT/US91/09155
Terpolymerization of Maleic Anhydride With Vinyl
Monomers, J. Polymer SCI.. Part A: Polym. Chem.
27 ~12). 4099-108, disclose terpolymers of maleic
anhydride with (i) l-hexene, propylene, isobutylene,
styrene, isoprene or l,3-butadiene, and (ii) methyl
methacrylate, methyl acrylate or acrylonitrile.
BRIEF SUMMARY OF THE INVENTION
The present invention provides polyamide
fibrous substrates treated with water-soluble or
water-dispersible maleic anhydride/alpha-olefin
polymers so as to impart stain-resistance to the
substrates, and methods for preparing the same.
Commonly, prior art materials known to be useful as
stain-blockers were sulfonated phenol-formaldehyde
condensates (excepting those of Fitzgerald et al.,
supra). Finding a non-sulfonated material, such as the
water-soluble or water-dispersible alpha-olefin/maleic
anhydride polymers of this invention, to be useful for
this purpose was unexpected.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the use of
water-soluble or water-dispersible maleic
anhydride/alpha-olefin polymers, or mixtures of the
same, as stain-resists for fibrous polyamides. A
variety of linear and branched chain alpha-olefins can
be used for the purposes of this invention.
Particularly useful alpha-olefins are dienes containing
4 to 18 carbon atoms, such as butadiene, chloroprene,
isoprene, and 2-methyl-l,5-hexadiene; l-alkenes
containing 4 to 8 carbon atoms, preferably C4_l0, such
as isobutylene, l-butene, l-hexene, l-octene, and the
like, with isobutylene being most preferred. A part of
the alpha-olefins can be replaced by other monomers,
: .
. .
.
.
2a~
W092/10605 PCT/US91/09155 ~ `
e.g. up to 50 wt% of alkyl(Cl_4) acrylates, alkyl(Cl_4)
methacrylates, vinyl acetate, vinyl chloride,
vinylidine chloride, vinyl sulfides, N-vinyl
pyrrolidone, acrylonitrile, acrylamide, as well as
mixtures of the same.
A part (1-75%) of the maleic anhydride can be
replaced by maleimide, N-alkyl(Cl_4) maleimides,
N-phenyl-maleimide, fumaric acid, itaconic acid,
citraconic acid, aconitic acid, crotonic acid, cinnamic
acid, alkyl(Cl_lg) esters of the foregoing acids,
cycloalkyl(C3_8) esters of the foregoing acids,
sulfated castor oil, or the like.
At least 95 wt% of the maleic anhydride co- or
terpolymers have a number average molecular weight of
in the range between about 700 and 200,000, preferrably
between about lO00 and lO0,000.
In accordance with the present invention, it
has been unexpectedly found that water-soluble or
water-dispersible interpolymers (i.e. copolymers,
terpolymers, and the like) of maleic anhydride and one
or more l-alkenes having 4 to 8 carbon atoms,
particularly isobutylene, l-hexene and l-octene, impart
excellent stain-resistance to polyamide substrates
(e.g. carpeting) at low pH. Copolymers of maleic
anhydride with butadiene or propylene were found by the
inventor to be less effective as stain-resists on such
substrates than were interpolymers of maleic anhydride
and l-alkenes containing 4 to 8 carbon atoms.
Surprisingly, he found also that copolymers of maleic
anhydride and at least one olefin selected from
ethyleen and l-alkenes having lO to 24 carbon atoms
impart no detectable stain-resistance to such
substrates.
The maleic anhydride polymers useful in the
present invention can be prepared according to methods
. . .: , , ,
2~S(~12~'
WO92/10605 PCT/US91/091~5
well-known in the art. The maleic anhydride polymers
thus obtained can be hydrolyzed to the free acid or
their salts by reaction with water or alkali, or they
can also be reacted with Cl_4 alkyl alcohol to provide
polymeric alpha-olefin/maleic acid monoesters, which
have stainblocking properties. Generally, the
hydrolyzed maleic anhydride polymer, or the monoester
polymer, should be sufficiently water-soluble that
uniform application to a fibrous polyamide surface can
be achieved at an appropriate acidity. However,
applications using water dispersions of the polymer
mixed with a suitable surfactant may be used to impart
stain-resistance.
one can blend the stain-resists of the present
invention with other known stain-resists, such as
phenol-formaldehyde condensation products as disclosed
in U.S. Patents 4,833,009 and 4,965,325; methacrylic
acid polymers disclosed in U.S. Patent No. 4,937,123;
or hydrolized polymers of maleic anhydride and one or
more ethylenically unsaturated aromatic compounds
described by Fitzgerald et al., supra.
The polymers suitable for the purposes of this
invention contain between about 0.7 and 1.3 polymer
units derived from one or more alpha-olefin monomers
per polymer unit derived from maleic anhydride. The
alpha-olefin content of the polymers of this invention
comprise between (a) 100 and 80 mol% of at least one
1-alkene containing 4 to 8 carbon atoms or terminally
unsaturated diene containing 4 to 18 carbon atoms and
(b) 0 to 20 mol% of at least one 1-alkene containing 3,
or 10 to 18, carbon atoms. Polymers containing about
one polymer unit derived from one or more olefin
monomers per polymer unit derived from maleic anhydride
are most effective in imparting stain resistance to
textile substrates. The molecular weight of the
WO92/10605 2 ~ ~ ù 12 ~ PCT/US91/09155
polymers useful in the invention does not appear to be
a limitation so long as the polymers are water-soluble
or water-dispersible. Thus, for example, hydrolyzed
isobutylene/maleic anhydride copolymers having number
average molecular weights between about 6000 and
lOo,oO0 impart good stain-resistance to polyamide
substrates. Even at a pH as low as l.5, water-soluble
isobutylene/maleic anhydride copolymers having number
average molecular weights between about 6000 and
lO0,000 remained in solution in water at 60OC.
The polymers suitable for the purposes of this
invention can be prepared by hydrolyzing the maleic
anhydridetolefin polymers according to methods
well-known in the art. For example, they can be
lS hydrolyzed to the free acid or their salts by reaction
with water or alkali. Generally, the maleic anhydride
polymer should be sufficiently water-soluble that
uniform application to a fiber surface can be achieved
at an appropiate acidity. ~owever, applications using
dispersions of the polymers with suitable surfactants
may be used to impart stain-resistance.
The olefin/maleic anhydride polymers of
this invention can be used as such in treating
polyamide textile substrates. They can be effectively
applied to polyamide fibrous substrates by a wide
variety of methods known to those skilled in the art,
such as:
padding,
spraying,
foaming in conjunction with foaming agents,
batch exhaust in beck dyeing equipment, or
continuous exhaust during a continuous
dyeing operation.
They can be applied by such methods to dyed or undyed
polyamide textile substrates. In addition, they can be
-
.
,
.
~ ~W092/1 ~ 5 2 0 9 ~ ~ 2 ~ PCT/US91/09155
applied to such substrates in the absence or presence
of a polyfluoroorganic oil-, water-, and/or soil-
repellent materials. In the alternative, such a
polyfluoroorganic material can be applied to the
textile substrate before or after application of the
polymers of this invention thereto.
The quantities of the polymers of this
invention which are applied to the textile substrate
are amounts ef~ective in imparting stain-resistance to
the substrate. Those amounts can be varied widely; in
general, one can use between l and 5% by weight of them
based on the weight of the textile substrate, usually
2.5% by weight or less. The polymers can be applied,
as is common in the art, at pHs ranging between about 2
lS and 7. However, more effective exhaust deposition can
be obtained at a pH as low as l.5. When the latter low
pH is used, the preferred level of application to the
textile substrate is about 2.5% by weight, based on the
weight of the textile substrate. In an embodiment, a
pH between about 2 and 3 is used. Nore effective
stainblocking is obtained if the polymers
are applied to the textile substrate at either 20C
followed by heat treatment at a temperature in the
range between about 50 and 150C for about l to 60
minutes, or applied at temperatures in the range
between about 40 and 95C for about l to 60 minutes.
For example, at a pH between about 2 and 3, a
temperature between about 70 and 90C is preferred.
However, stain-blocking can be obtained when
application is effected even at that of cold tap water
(10-15C).
The polymers of this invention can also be
applied in-place to polyamide carpeting which has
already been installed in a dwelling place, office or
other locale. They can be applied as a simple aqueous
`:
''
.
WO92~10605 2 ~ ~3 g ~ r~ PCr/US91/Ogl55 ~
preparation or in the form of aqueous shampoo
preparation, with or without one or more polyfluoro-
organic oil-, water-, and/or soil-repellent materials.
They may be applied at the levels described above, at
s temperatures described, and at a pH between about 1 and
12, preferably between about 2 and 9.
~he following Examples are given to illustrate
the invention not limit it. Unless otherwise
indicated, all parts and percentages are by weight and
temperatures in the Examples and Tests are in degrees
Celsius. In the examples that follow, stain resistance
was measured by the technique described below.
EXAMPLE 1
A butadiene/maleic anhydride copolymer having
a number average molecular weight of about 5,000 to
10,000 and commercially available as a hydrolyzed
product, ~Lindron~ 10 (Lindau Chemical), was diluted
with water to a 10 wt% active ingredient solution.
A 1 wt% aqueous solution of the copolymer at 600C
became cloudy at a pH of about 2Ø
EXAMPLE 2
A 500 ml autoclave was charged with 40 g of
maleic anhydride (0.408 mole), 300 ml of ethylbenzene
and 4.3 g of 70 wt% of benzoyl peroxide. It was
closed, vented twice with propylene and heated under
stirring to 70 deg.C. The autoclave was then
pressurized with propylene to 200 psi. After agitation
for 3 hours at 70C, a solution of 2.7 g of 70 wt%
benzoyl peroxide in 10 ml of ethylbenzene was blown
into the reactor and the reaction was continued at 70C
for another 14 hours. The vessel was then cooled and
vented. The maleic anhydride/propylene copolymer
product, in form of a dispersion, was discharged and
.
,
~3~2~
~, ~
W092/1~05 PCT/US91/09155
filtered giving 46.7 g of a white powder having a
number average molecular weight, by gel permeation
chromatography (GPC), of 2150. A portion of the solid
copolymer (lO g) was hydrolyzed at 80-95C in the
presence of 82.5 g deionized water, 6.7 g 30 wt% sodium
hydroxide and 2 drops of a 1% solution of benzyl-
triethylammonium chloride resulting after about l to 2
hours in a clear solution containing lO wt% of a
water-soluble maleic anhydride/propylene copolymer.
EXAMPLE 3
An isobutylene/maleic anhydride copolymer
(lOg) having a number average molecular weight (GPC) of
32,600 and an MW/Mn of 2.96, commercially available
from Kuraray Co.(Japan) as nIsobam~-04, was hydrolyzed
to a lO wt% solution in accordance with the method
described in Example 2. A l~ aqueous solution of the
resulting isobutylene/maleic acid copolymer remained
clear down to pH l.5 at 60C.
EXAMPLE 4
An isobutylene/maleic anhydride copolymer
(lOg) having a number average molecular weight ~GPC) of
91,400 and an MW/Mn of 2.86, commercially available
25 from Kuraray Co.(Japan) as ~Isobam~-lO, was hydrolyzed
to a lO wt% solution by the method described in
Example 2. A l~ aqueous solution of the resulting
water-soluble maleic anhydride/isobutylene copolymer at
60~C became cloudy at pH l.6.
EXAMPLE 5
An isobutylene/maleic anhydride/ N-phenyl-
maleimide terpolymer (lOg) having a molecular weight of
about 40,GOO (GPC), commercially available from Kuraray
3S Co. (Japan) as BM-30 polymer, was hydrolyzed to a lO
.
-
, . .
2 ~ 9 ~ 2 -~
WO92/10605 PCT/US91/09155
wt% solution by the method described in Example 2.
A 1% aqueous solution of the resulting water-soluble
maleic anhydride/isobutylene/maleimide terpolymer at
60C became cloudy at pH 2.5.
EXAMPLE 6
A solution of maleic anhydride (9.8g - 0.1
mol) and 1-hexene (8.4g - 0.1 mole) in propylene glycol
methyl ether acetate ~30G) was heated under agitation
and nitrogen to 60 deg.C. A solution of 2.5 g of 75 wt%
t-butyl peroxyneodecanoate in 6 g of propylene glycol
methyl ether acetate was then injected into the
reaction vessel within half hour via a syringe pump.
The reactants were agitated for another 2 hours at 60C
lS before being cooled to room temperature. The product
was the poured into methanol which caused precipitation
of a white solid which was filtered and air dried to
give 10.5 g of a maleic anhydride/1-hexene copolymer.
Hydrolysis was carried out by a procedure similar to
that described in Example 2.
EXAMP~E 7
A solution of 9.8 g of maleic anhydride (o.l
mole) and 11.2 g of 1-octene ~0.1 mole) in 30 g of
propylene glycol methyl ether acetate was heated under
agitation and nitrogen to 95C. A solution of 2 g of
t-butyl peroxy-2-ethylhexanoate in 6 g of propylene
glycol methyl ether acetate was then injected into the
reaction vessel within half hour via a syringe pump.
The reactants were agitated for another 2 hours at 95C
before being cooled to room temperature. The product
was then poured into methanol which caused
precipitation of a white solid which was filtered and
air-dried to give 12.7 g of a maleic acid/1-octene
copolymer having a number average molecular weight by
:
2~ 0 ~ ~ :L h ~
f -
W092/10605 PCT/US91/09155
vapor phase osmometry (VPO) of 2800. The approximate
composition of the copolymer by 13C NMR:
l-octene/maleic anhydride = 0.72/1.00
Hydrolysis was carried out by a procedure similar to
that of Example 2. A 1% aqueous solution of the
resulting maleic acid/1-octene copolymer at 60C became
cloudy at about pH 2.7.
EXAMPLE 8
An isobutylene/maleic anhydride copolymer (50
parts) having a number average molecular weight (GPC)
of 32,000, commercially available from Kuraray
Co.(Japan) as ~Isobamn-04, was reacted under agitation
with methanol (SO parts) at reflux temperature (about
65C) for 23 hours. Excess methanol was then removed
at reduced pressure (20 mm ~g) at 70-90C to give the
isobutylene/maleic acid monomethyl ester which was then
dissolved at room temperature in dilute ammonium
hydroxide ( 2.5 parts of ammonia in 356 parts of water~
to give a 14.5 wt % solution.
EVALUATION METHOD
Nylon fiber was treated with 1.2 wt% or 2.4
wt% stain resist at a goods-to-liquor ratio of 1:32 at
a pH of 2.0 or 2.35 for 45 minutes at 80 or 95C. The
fiber was then washed, air-dried and exposed at room
temperature to a dye solution consisting of 0.2 g of
FD&C Red Dye No.40 and 3.2 g of citric acid in 1 liter
of deionized water at a goods-to-liquor ratio of 1:40.
After approximately 65 hours, the dye adsorbed onto the
fiber was determined at a wavelength of 498-502 nm by
comparing the absorbance with that of the Control. Thus
a number of 90 means 90% of the dye is adsorbed,
indicating little stain resistance to the dye. The
lower the number, the better is the resistance to
.
~: .
~ 'J . ~
W O 92/10605 PC~r/US91/09155
12
stain. The results of the evaluation are set forth in
TABLE 1.
TABLE 1
s
% Dye Adsorbed
At 80C At 95C
EXAMPLE~H 2 . O DH2 . 3 5 ~H2 . 3 5 e~_Z 3
24 16 17
2 48 36 19
3 2 3 3
4 2
2 3
6 3 30
lS 7 4 2
8 14 22
9 6 39 12
CONTROL** 8 9 8 9
_______________
* Fiber treated with 2 . 4 wt% stain resist
** No stainblocker
. . - ~
