Note: Descriptions are shown in the official language in which they were submitted.
6~ii5~ 4 3 0 5 0 CAI~ 9A
--1-- .
PROCESS FOR PROVIDING POL~YAMIDE MATERIALS
WITH STAIN RESISTANCE
S This invention relates to a process for providing
fibrous polyamide materials such as nylon carpet with stain
resistance and to fibrous polyamide materials so treated.
Fibrous polyamide articles such as nylon carpets
are particularly susceptible to staining by natural and
artificial acid colorants such as are commonly found in many
foods and beverages. A need has long been felt for
processes for economically providing such fibrous polyamide
articles with resistance to staining by acid colorants.
Particularly desirable are processes by which durable stain
lS resistance can be imparted to fibrous polyamide articles
during conventional processing and treating operations.
U.S. Patent No. 3,961,881 (Sumner et al.)
discloses a process for coloring synthetic polyamid~ textile
materials which comprises applying to the textile materials
by a dyeing, padding or printing process, an aqueous
dispersion of pH less than 7 of a disperse dyestuff
containing at least one carboxylic acid group and in the
~-~ presence of a tanning agent, whereby level colorations are
obtained which have excellent wet fastness properties. As
set forth by Sumner et al.~ examples of natural agents
include tannic acid and the vegetable tannins, while
synthetic agents include condensation products of naphthols,
naphthalene sulphonic acids and formaldehyde, condensation
products of phenol, naphthalene, formaldehyde and sulphuric
acid, condensation products of dihydroxydiphenylsulphone and
; formaldehyde, condensation products of
dihydroxydiphenylsulphone sulphonic and aliphatic,aldehydes,
condensation products of sulphurized phenols, naphtha]ene
and ormaldehyde.
U.S. Patent No. 2,205,883 ~Graves) discloses
tanning agents which are the acidic polymerization products
of the polymerization of methacrylic acid with itself as
well as interpolymerization of methacrylic acid with other
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materials.
U.S. Patent No. 3,408,319 (Rau) discloses tanning
compositions which are made by copolymerization of a mixture
of (A~ methacrylic acid, acrylic acid or mixtures of such
acids with (B) a sulfated unsaturated oil. The unsaturated
acid used is preferably 75 to 100% methacrylic acid and 25
to 0% respectively of acrylic acid, and generally the use of
methacrylic acid exclusively is most practical from the
standpoint of cost and effectiveness. The amount of
sulfonated oil is from 10 to 25% by weight of the acid
monomer.
U S. Patent No. 3,994,744 (Anderle et al.)
discloses aqueous cleaning compositions having a minimum
film-forming ternperature o~ at least 30C and comprising a
polymer having a glass transition temperature of at least
35C and a metal salt, form a tacky film after being applied
to a soiled substrate. Soil adheres to the tacky film
which, as a result of the drying of said composition,
fractures to form a removable residue. The compositions
contain polymers preferably derived from a carboxylic acid
monomer and a soft monomer and/or a hard monomer. Preferred
soft monomers are vinyl acetate and the alkyl esters of
acrylic acid wherein the alkyl group contains from 1-12
carbon atoms. Suitable hard monomers include lower alky
methacrylates wherein the lower alkyl group contains 1-3
carbon atoms, cycloalkyl acrylates and methacrylates wherein
the cycloalkyl group contains 5-7 carbon atoms, and hard
vinyl monomers. examples of acid monomer include acrylic,
methacrylic, itaconic, maleic and crotonic acids and
monoalkyl esters of itaconic and maleic acids wherein the
alkyl group contains 1-8 carbon atoms.
U.S. Patent No. 4,081,383 (Warburton, Jr. et al.)
discloses an anti-soiling treatment for carpets and carpet
yarns. The carpets or carpet yarns prior to carpec
manufacture are coated with a polymeric material containing
either (A) a blend o~ a methacrylic acid emulsion copolymer
and an epoxy resin or (B) a methacrylic acid emulsion
copolymer having epoxy monomer units therein. The copolymer
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in either case contains 40-75% by weight methacrylic acid
and the glass transition temperature of cured coatings of
the polymeric material is at least 50C.
U.S. Patent No. 4,334,~76 (seier et al.) discloses
a process for producing leather wherein leather stock is
subjected to a multiple-stage tanning process involving a
first treatment with an aqueous dispersion or solution of a
synthetic polymeric composition made by polymerizing at
least one member selected from the group consisting of
acrylic acid and methacrylic acid and, optionally, one or
more polymerizable compounds selected from the group of
alkyl esters of acryllc acid, alkyl esters of methacrylic
acid and sulfated unsaturated drying oils, followed by a
second treatment with a zirconium tanning compound having a
0-45~ basicity by the Schorlemmer scale.
U.S. Patent No. 4,388,372 ~Champaneria et al.)
discloses a durable antisoiling coating composition for
textile filaments comprising a perfluoroalkyl ester of a
citric acid urethane and fluorinated alcohols in combination
with a modified epoxy resin which is the reaction product of
a carboxyl-functional vinyl polymer, an epoxy resin and a
tertiary amine. Preferred vinyl resins for use in making
the modified epoxy resin reaction product are the
terpolymers of styrene/ethyl acrylate/methacrylic acid, and
particularly such terpolymers wherein the monomers are in a
mol ratio to one another respectively of about 1:1:2.
U.S. Patent No. 4,526,581 (Prentiss et al.)
discloses a process for producing leather whic~ employs a
copolymer tanning agent comprising at least 60 mole percent
residues of methacrylic acid and at least about 5 m~le
percent of residues of at least one alkyl acrylate selected
from methyl, ethyl, propyl, and butyl acrylates, the
copolymer having a weight average molecular weight from
about 3,500 to 9,000.
U.S. Patent No. 4,699,812 (Munk et al.) discloses
a method Eor imparting stain resistance to fibers containing
free amino groups, and especially polyamide fibers, by
contacting the fiber with a solution of an aliphatic
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~ 60557-3573(S)
sulfonic acid containing 8 to 24 carbon atoms under acidic
conditions.
The present invention, in one aspect, provides a method
~or imparting to fibrous polyamide materials stain resistance to
acid colorants comprising contacting the fibrous polyamide
materials with an aqueous treating solutlon comprising
polymethacrylic acid, copolymers of methacrylic acid, or
combinations thereof, and drying said substrate, said copolymers
of methaarylic acid comprise at least about 30 weight percent
methacrylic acid and said polymethacryllc acid, copolymers of
methacrylic acid, or combinations thereof having the lower 90
weight percent having a weight average molecular weight in the
range of abou~ 2500 to 250,000 and a number average molecular
weight in the range of about 500 to 20,000 and being provided in
a sufficient amount and having a solubility such that said
,
fibrous polyamide substrate has an acid colorant stain resistance
of at least 5. Generally, a rating of at least 5 is
satiæfactory, a rating of 7 is good, and a rating of 8 is
excellent when the treated substrate is tested according to the
test method set forth hereinafter, which test method challenyes
the substrate with an aqueous solution of FD&C Red Dye No. 40, a
common stain test solution.
~he present lnvention, in another aspect, provldes
fibrous polyamide ~ubstrate~ treated with an aqueous treating
solution comprlsing polymethacrylic aaid, copolymers of
methacrylic acid, or combinations thereof, said copolymers of
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methacrylic acid comprise at least about 30 weight percent
methacrylic acid and said polymethacrylic acid, copolymers of
methacrylic acid, or combinations khereof having the lower 90
weight percent having a weight averaye molecular weight in the
range of about 2500 to 250,000 and a numbe:r average molecular
weight in the range of about 500 to 20,000 and being provided in
a sufficient amount and having a solubility such that said
fibrous polyamide substrate has an acid colorant stain resistance
of at least 5. Generally, a rating of at least 5 is
satisfactory, a rating of 7 is good, and a rating of 8 is
excellent.
The present lnvention, in a further aspect, provides an
aqueous solution useful in imparting stain resistance to acid
colorants to fibrous polyamide materials, the solution comprising
polymethacrylic acid, copolymers of methacrylic acid, or
combinations thereof, said polymethacrylic acid, copolymers o~
methacrylic acid, or combinations thereof being provided in a
sufficient amount and having a solubility and molecular weight
such that sald
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solution is capable of providing said fibrous polyamide
substrate with an improved acid colorant stain resistance.
Generally, a rating of at least 5 is satisfactory, a rating
of 7 is good, and a rating of 8 is excellent.
The FIG. shows a photograph of carpet samples
tested for stain resistance according to the test method set
forth hereinafter.
The polymethacrylic acid, copolymers of meth-
acrylic acid, or combinations thereof useful in the present
invention are preferably hydrophilic. As used herein, th~
term "methacrylic polymer", is intended to include the
polymethacrylic acid homopolymer as well as polymers formed
from methacrylic acid and one or more other monomers. The
monomers useful for copolymerization with the methacrylic
acid are monomers having ethylenic unsaturation. Such
monomers include, for example, monocarboxylic acids,
polycarbox~lic acids, and anhydrides; substituted and
unsubstituted esters and amides of carboxylic acids and
anhydrides; nitriles; vinyl monomers; vinylidene monomers;
~onoolefinic and polyolefinic monomers; and heterocyclic
monomers.
Representative monomers include, for example,
acrylic acid, itaconic acid, citraconic acid, aconitic acid,
maleic acid, maleic anhydride, fumaric acid, crotonic acid,
cinnamic acid, oleic acid, palmitic acid, vinyl sulfonic
acid, vinyl phosphonic acid, alkyl or cycloalkyl esters of
the foregoing acids, the alkyl or cycloalkyl groups having 1
to 18 carbon atoms such as, for example, ethyl, butyl,
- 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl,
cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and
methacrylates, and amides of the foregoing acids, such as,
for example, acrylamide, methacrylamide, methylolacrylamide,
and 1,1-dimethylsulEoethylacrylamide, acrylonitrile,
methacrylonitrile, styrene, -methylstyrene,
p-hydroxystyrene, chlorostyrene, sulfostyrene, vinyl
; alcohol, N-vinyl pyrrolidone, vinyl acetate, vinyl chloride,
vinyl ethers, vinyl sulfides, vinyl toluene, butadiene,
isoprene, chloroprene, ethylene, isobutylene, vinylidene
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chloride, sulfated castor oil, sulfated sperm oil, sulfated
soybean oil, and sulfonated dehydrated castor oil.
Particularly useful monomers include, for example, alkyl
acrylates having 1-4 carbon atoms, itaconic acid, sodium
sulfostyrene, and sulfated castor oil. Of course, mixtures
of the monomers, such as, for example, sodium sulfostyrene
and styrene, and sulfated castor oil and acrylic acid, can
be copolymerized with the methacrylic acid.
The methacrylic polymers useful in the present
invention can be prepared using methods well-known in the
art for polymerization of ethylenically unsaturated
monomers.
Preferably, the methacrylic acid comprises about
30 to 100 weight percent, more preferably 60 to 90 weight
percent, o~ the methacrylic polymer. The optimum proportion
of methacrylic acid in the polymer is dependent on the
comonomer used, the molecular weight of the pol~mer, and the
pH at which the ~aterial is applied. Wh~n water-insoluble
comonomers, such as ethyl acrylate are copolymerized with
~he methacrylic acid, they may comprise up to about 40
weight percent of the methacrylic polymers. When
water-soluble monomers, such as acrylic acid or sulfoethyl
acrylate are copolymerized with the methacrylic acid, the
water-soluble comonomers preferably comprise no more than 30
weight percent of the methacrylic polymer and preferably the
methacrylic polymer also comprises up to about 50 weight
percent water-insoluble monomer.
Generally, the methacrylic polymer should be
sufficiently water-soluble that uniform application and
penetration of the polymer into the fiber surface can be
achieved. However, when the polymer is excessively water
soluble, acid colorant stain resistance and durabiLity to
cleaning ~ay be reduced.
The g~ass transition temperature of the polymer
can be as low as about 35C, although higher glass
transition temperatures are preferred. When polymer having
high glass transition temperatures, i.e., as high as 230C
or higher, are used, an additional benefit of improved soil
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resistance of the fibrous polyamide substrate can be
obtained.
The weight average molecular weight and the number
average molecular weight of the methacrylic polymer should
be such that satisfactory stain resistance is provided by
the polymer. Generally, the lower 90 weight percent of the
polymer material preferably has a weight average molecular
weight in the range of about 2500 to 250,000, more
preferably in the range of about 3000 to 100,000~
Generally, the lower 90 weight percent of the polymer
material preferably has a number average molecular weight in
the range of about 500 to 20,000, more preferably in the
range of about 800 to lO,000. Generally, more water-soluble
comonomers are preferred when the molecular weight. of the
polymer is high and less water-soluble or water-insoluble
comonomers are preferred when the molecular weight of the
- polymer is low.
Commercially available methacrylic polymers ~-
generally useful in the present invention include LeukotanTM
20 970, Leukotan~M 1027, LeukotanTM 1028, and Leukot~nTM QR
lG83, available from Rohm and Haas Co.
The amount of the methacrylic polymer used should
` be sufficient to provide the desired degree of stain
resistance to the polyamide substrate. Generally, when the
substrate is nylon 66, lower application levels can be used
than when the substrate is nylon 6 or wool. When the
polyamide material is heat-set carpet yarn, yarn heat-set
under moist conditions, e.g., in an autoclave, generally
requires higher application levels than yarn heat-set under
substantially dry conditions. Preferably, the amount of
methacrylic polymer used is at least about 0.1 weight
percent, more preferably at least about 0.5 weight percent,
most preferably at least about 1 weight percent, based on
the weight of the fiber when the fibe~ is nylon 66 carpet
fiber. Preferably, the amount of methacrylic polymer used
is at least about 0.5, more preEerably at least about 1
weight percent, based on the weight of the fiber when
treating nylon 6 carpet fib~r.
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Generally, the methacrylic polymer is applied from
an aqueous solution. The pH of the solution is preferably
below about 7, more preferably below about 5. Generally,
amounts of methacrylic polymer in excess of 3 weight percent
owf provide little added benefit and may cause the fiber to
have a harsh hand.
The methacrylic polymer can-be applied from an
aqueous exhaust bath such as is used in beck dyeing of
carpet. The methacrylic polymer can be added to the aqueous
dye bath solution and exhausted concurrently with the dye.
Generally, the dye bath is maintained at a temperature at or
near the boiling point for a period of 10 to 90 minutes or
more to effect exhaustion of the dye and the methacrylic
polymer.
~lternatively, the methacrylic polymer can be
added to the aqueous dye bath after exhaustion of the dye or
the dye bath can be drained and fresh water added prior to
the addition of the methacryli~ polymer. Generally, the
bath is maintained at a temperature at or nehr boiling for a
period of time sufficient to exhaust the methacrylic
;~ polymer, usually 10 to 90 minutes.
The methacrylic polymer can be applied during
continuous dyeing, such as with ~usterTM or OttingTM carpet
; dyeing equipment. The methacrylic polymer can be added
directly to the aqueous dye solution and the solution is
conventionally applied to the polyamide carpet.
Alternatively, the methacrylic polymer can be applied during
a wetting out step prior to application of the dye.
The methacrylic polymer can also be applied to
polyamide material by a padding operation. This can be done
as a separate step or in conjunction with the appl:ication of
various convention finishes such as wetting agents,
softeners, and leveling agents. After application of the
solution, the polyamide material ls co.lventionally dried.
The methacrylic polymer can also be applied by
foam techniques which are well-known in the art. Generally,
the methacrylic polymer is applied from an aqueous solution
which may further contain a foaming agent. The foaming
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agents us2d are those typically used in foam dyeing.
The methacrylic polymer can also be applied to
polyamide fabrics by other methods well known to those
skilled in the art. Other suitable methods include
S application by paddi~g, low-pressure padding such as can be
accomplished with Kuster FlexnipT~ equipment, spray
applicators such as those available from Otting
International, or dip boxes which need not be equipped with
moisture reduction apparatus such as squeeze rolls. The
methacrylic polymer is generally applied in these methods
from an aqueous solution at ambient conditions followed by
steaming for from 15 to 180 seconds, then drying or from an
aqueous solution at elevated temperatures, e.g., 60C to
90C, followed by skying for lS to 180 seconds, then drying.
lS The meth~crylic polymer can also be applied to
- nylon carpet during carpet shampooing. Useful techniques
- include the use of scrubbing machines and steam or hot water
cleaning machines.
Fluorochemical compositions for providing oil and
water repellency can also be applied in conjunction with the
methacrylic polymer. The fluorochemical composition can be
added in an appropriate amount to the treating solution.
The following non-limiting examples serve to
illustrate the invention. In the following examples, all
ratios are by weight and percentages are welght percent
unless otherwise indicated.
In the examples, the following staining test was
used: A 6.5 g test sample of carpet, which has been dyed
usin~ a blue disperse dye with a 45 minute beck dyeing
cycle, is immersed in 40 g of an aqueous solution containing
0.00~ weight percent F'D&C Red Dye No. 40 and 0.04 weight
percent citric acid. The solution ls allowed to remain on
the test sample for e ght hours at room temperature, i.e.,
about 22C. The sample is rinsed under running tap water,
dried and then evaluated for staining using a graduated
rating scale which ranges from 1 to 8, as shown in the
drawing where 1 represents no discernible removal of the red
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dye stain and 8 represents complete removal of the red dye
stain. In general, an eight-hour stain resistance of at
least 5 is satisfactory, at least 7 is good, and 8 is
excellent.
Preparation of methacrylic polymer (Polymer A):
To a reaction vessel equipped with a reflux
condenser, a mechanical stirrer, and a thermometer, were
charged 14 g sulfated castor oil (75% solids) and 95 g
deionized water. This solution was heated to 90C and 1.2 g
ammonium persulfate were added. To this solution were added
simultaneously dropwise 47.6 g methacrylic acid, 11.9 g
acrylic acid, and 5 g ammonium persulfate in 55 g water over
a period of about 1 hour. The reaction mixture was further
15 stirred for 90 minutes at 90C and then cooled to 50C. The
resultant copolymer solution was partially neutralized to pH
4.3 by the addition of 9.7 g 50% aqueous sodium hydroxide.
The resultant product contained 39.3% copolymer solids D
:.
Polymers B through X were prepared using a
procedure similar to that used in the preparation of
Polymer A using the monomers and reactant ratios set forth
in Table 1.
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Table 1
Reactant
Polymer ~eactant(sJ ratio
A methacrylic acid 68
sulfonated castor oil 15
acrylic acid 17
B methacrylic acid 100
C methacrylic acid 80
ethyl acrylate 20
D methacrylic acid 65
ethyl acrylate 35
E methacrylic acid 80
ethyl acrylate 20
F methacrylic acid 84
sulfated castor oil 16
G methacrylic acid 80
sodium sulfostyrene 10
styrene 10
H methacrylic acid 21
sulfated castor oil 10
ethyl acrylate 9
I methacrylic acid 68
sulfated castor oil 15
acrylic acid 17
J acrylic acid 100
R acrylic acid 70
ethyl acrylate 30
;
Polymer L was prepared by placing in a ~ottle 46 g
water, 8 g methacrylic acid, 2 g sodium sulfostyrene, 0.3 g
mercapto propionic acid, without regard to order, and
finally 0.3 g potassium persulfate. The bottle was
evacuated and purged three times with nitrogen. The bottle
cap ~as tightened and the bottle placed in a water bath
having a temperature of 72C under agitation for a period of
16 hours. The resulting polymer solution was clear and
fluid with a polymer solids content of 19 weight percent.
Polymers M through Q were prepared using a
procedure similar to that used in the preparation of Polymer
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L using the monomers and reactant ratios set forth in Table
2.
Table 2
Methacrylic Reactant
Polymer Reactants ratio
L methacrylic acid80
sodium sulfostyrene 20
10 M methacrylic acid50
so*ium sulfostyrene S0
N methacrylic acid80
itaconic acid 20
0 methacrylic acid80
vinyl acetate 20
P methacrylic acid80
1,1-dimethylsulfoethyl-
acrylamide 20
Q methacrylic acid80
- 20 hydroxyethyl acrylate 20
Polymer R was prepared using th~ procedure used to
prepare Polymer M except that the following ingredients were
used: 92 g water, 16 g methacrylic acid, 2 g sodium
sulfostyrene, 2 g styrene, 0.6 g mercapto propionic acid,
0.6 g sodium dodecyl benzene sulfonate, without regard to
order, and finally 0.6 g ammonium persulfate. Polymer S was
prepared according to the procedure set forth in Example 1
of U.S. Patent No. 4,081,383 -~
The weight average molecular weight (Mw) and the
number average molecular weight (Mn) of the lower 90 weight
percent of various of the thus-prepared polymers were
~etermined using a column hank having four Ultrahydrogel
columns, i.e., linear, 1000, 500, and 250, available frol~
Waters Assoc. and polyacrylic acid standards available from
; American Polymer Standards Company. The results are set
forth in Table 3.
Table 3
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Polymer Mw Mn
B 8,100 2,680
C 85,S00 3,380
1:) 58, oao 3, 430
E2, 920, 000414, 000
F5,820 2,460
H8,470 3,410
J5,830 1,331
K36,1;11 5,490
S532,000 47,63q
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The weight average moleculac weight and the number
lS average ~olecular weight of the lower 90 weight percent of
several commercially available methacrylic acid-based
: polymers, LeukotanT~ 970, LeukotanTM 1027, LeukotanTH 1028,
and LeukotanTM QR 1083, all available from ~ohm and Haas C~.
-and an acrylic acid-based polymer, LeukotanTM LP 1042, also
available from Rohm and Haas Co., were also deter~inedO The
results are set forth in Table 4.
. Table 4
:: 25 Polymer Mw Mn
Leukotan 970 6,360 2,320
Leukotan~M 1027 9,020 2,910
Leukotan 102~ 9,460 5,592
:: LeukotanTM QR 1083 5,280 1,410
Leukotan LP 1092 2, 560 1, 400
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Examples 1-14 and Comparative Examples C1-C4
In Example 1, a treating solution was prepared
containing 0.35 g Polymer A solids in 92 g water with the pH
S adjusted to 4.0 using 20% aqueous formic acid. To simulate
a continuous treatment process, the treating solution was
- poured into a dye press and heated to 80C. A 23 g sample
of dyed carpet prepared using nylon 6 fiber, available fro~
BASF, which had been heat set under moist conditions was
steamed for 2 minutes and then immersed in the treating
solution for 1 minute with pressure being applied to ensure
thorough penetration of the treating solution. The treated
sample was put through squeeze rollers at 30 psi to remove
excess liquid and then dried at 70C for 45 minutes and
130~C ~or 10 minutes.
n Examples 2-14 and Comparative Examples C1-C4,
nylon 6 carpet samples were prepared and treated as in
Example 1 except the polymers used were as set forth in
Table 5.
Each sample was evaluated for stain resistance,
the results being set forth in Table 5.
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Table 5
Stain
. xample Polymerresistance
1 A 7
2 B 6
3 C 7
4 D 7
F 7
6 G 7
7 H 8
8 I 7
9 L 6
N 6
11 0 5
1 2 Q
13 R 7
. 14 p 5
` Cl E 3
C2 . J 2
: C3 R 2
C 4 M
~: As can be seen from the data in Table 5, the
polymers of the invention (Exampl2s 1-14) provide
satisfactory to excellent stain resistance to the moist
heat-set nylon 6 carpet samples. Of the Comparative `
Examples, Comparative Example. Cl which was treated with a ~ :
high molecular weight methacrylic acid-based copolymer and
`~ 30 Comparative Examples C2 and C3 which were treated with :
polyacrylic acid and an acrylic acid copolymer, respectively
exhibit particularly poor stain resistance.
E~ample 15_and Comparative Examples C5 and C6
: 35
Carpet samples were prepared as in Example 1 using
carpet prepared from the moist heat-set nylon 6 fiber except
that the samples were treated with the following
commercially available polymers: r,xample 15 - LeukotanT
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970, a methacryli~ acid-based polymer, available from Rohm
and Haas Co.; Comparative Example CS - ~eukotan~M LP 1042 ,
an acrylic acid-based polymer, available from Rohm and ~aas
Co.; and Comparative Example C6 - AcrysolTM RM-5t an acrylic
acid-based monomer, available from Rohm and Haas Company.
Each sample was tested for stain resistance. The results are
set forth i~ Table 6.
Table 6
',
Stain
Example resistance
C5 3
C6 2
As can be seen from the data in Ta~le 6, the
methacrylic acid-based LeukotanTM 970 provided good stain
`~ resistance, while the acrylic acid-based LeukotanTM LP 1042
and AcrysolTN RM-5 provided very little stain re6istance.
Comparative Exa~ples C7 and C8
In Comparative Example C7, a polymer of
methacrylic acid, styrene, and methyl methacrylate was
prepared substantially fo11Owing the teachings of U.S.
Patent Mo. 4,081,383 ~Warburton, Jr. et al.), Example 1.
:
; A mixture of 69 parts methacrylic acid, 27 parts
~ styrene and 5 parts methyl methacrylate was added to 80
- 30 parts of water containing 0.07 parts o~ 80~ active
isopropylbenzenehydroperoxide, 1.13 parts sodium
dodecylbenzenesolfonate, 0.0375 parts of the sodium salt of
ethylene diamine tetraacetic acid, and 0.0135 parts iE
FeSO~.7H20. The resu'ting elnulsion was degassed by sti ring
under nitrogen for 30 minutes. Then, 0.0104 parts of sodium
sulfoxylate formaldehyde in 1.15 parts of water was added.
The temperature rose from 24C to 50C over 18 minutes.
~ ~ Then 0.08 parts of 80% active isopropylbenzenehydroperoxide
`~ and 0.0104 parts of sodium sulfoxylate formaldehyde in 1.15
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parts water were added. The lower 90 weight percent of the
resulting polymer had a weight average m~lecular weight of
532,000 and a number average molecular weight of 47,600.
A carpet sample was prepared as in Example 1 using
carpet prepared from the moist heat-set nylon 6 fiber except
that the sample was treated with the above-prepared
Warburton, Jr. et al. polymer. The sample was tested for
stain resistance and received a rating of only 2, showing
poor stain resistance.
In Comparative Example C8, 200 parts of the
above-prepared polymer as a 20~ solids aqueous ~olution were
added to a WaringTM blender and agitated. Epoxy resin
(DERT~ 736, available from Dow Chemical Company) was then
added (8 parts) slowly over several minutes. The blend was
diluted to 23% solids.
A carpet sample was prepared as in Example 1 using
carpet prepared from the moist heat-set nylon 6 fiber except
that the sample was treated with the above-prepared
copolymer/epoxy resin. The sample was tested for stain
~0 resistance and received a rating of only 2, showing poor
stain resistanceO
:
Examples 16-18
: '
In Example 16, a solution containing 75 g/l
LeukotanTM 970, and 10 g/l Alkafoam D, a foaming a~ent
available from Alkaril Chemicals, Inc., was prepared and
~oamed onto a sample of carpet prepared from nylon 66 yarn
heat set under moist conditions using a Gaston County
laboratory FF~ model foam ~inishing machine, available from
Gaston County Dyeing Machine Company, using a 60:1 blow
ratlo and a wet pickup rate of 20~ to provide an application
rate oE 0.5% LeukotanTM 970 based on the weight of the
carpet. The sample was clried at 120C for 2~ minutes.
In Examples 17 and 18, carpet samples were treated
as in Example 15 except Polymer H and Polymer C,
respectively were substituted for the LeukotanTM 970.
The treated samples were tested for stain
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resistance. The results are set forth in Table 7.
Table 7
Stain
Example resistance
16 6.5
17 7
18 5
As can ~e seen from the data ~n Table 7, the
polymers of the invention provide adequate to good stain
resi~tance to nylon carpet prepared from moist heat-set
nylon 66 carpet fiber.
Examples 19-22 and Comparative Examples C9-C11
:.
~-~ In Example 19, a treating bath was prepared
containing 0.69 g Polymer B solids in 690 g water with the
`~ 2Q pH adjusted to 3.5 using 20% aqueous formic acid. A 23 g
sample of dyed carpet prepared using nylon 6 fiber,
- available from BASF, which had ~een heat s~t under moi~t
conditions was steamed for 2 minutes and then placed in the
treating bath. Under agitation, the temperature was raised
to 70C over 30 minut~s and held at 70C for 15 minutes.
The sample was removed from the bath, put through squeeze
rolls at 30 psi, and then dried at 70C for 45 minutes and
130C for 10 minutes.
In Examples 20-22 and Comparative Examples
C9-C11, samples of carpet were treated as in Example 19
except the polymer set forth in Table 8 were substituted for
Polymer ~.
The treated samples were tested for stain
resistance. The results are set forth in Table 8.
Table 8
Stain
Example Polymer resistance
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19 B 7O5
H 8
21 Leukotan 970 7
22 C 7.5
C9 Epoxy resin blend
of Example ~la 2
C10 K 2.5
Cll Acr~solTM RM-5 2
As can be seen from the data in Table 8, the
methacrylic polymers provide excelle~t stain resistance.
The pol~mer/epoxy resin blend of Warburton, Jr. et al. and
the acrylic acid-based polymers provide little stain
resistance.
Examples 23-25
n Examples 23-25, carpet samples were treated as
in Example 1 except that LeukotanT~ 1027, Leukotan~M 1028,
and LeukotanTM Q~ 1083, respectively, each a methacrylic
acid-ba~ed polymer available from Rhom and Haas Co., were
substituted for Polymer A. The treated ~amples were tested
for stain resistance. The results are set ~orth in Table 9.
Table 9
Example SR
23 7
24 7
As can be seen rom the data in Table 9, the
LeukotanTM QR 1083 provided better than satisfactory stain
resistance, while the Leuk~tanTM 1027 and the Leukotan
1028 provided good stain resistance.
Examples 26-28 and Comparative Examples C12-C14
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In Example 26, a treating bath was prepared
containing a. 2 9 Polymer B in 80 g water with p~ adjusted to
3.5 using 20% aqueous formic acid. ~ 20 g sample of dyed
carpet prepared using nylon 66 fiber which had been heat set
under dry conditions was steamed for 2 minutes and then
placed in the treating bath. Under agitation, the
temperature was raised to 70C over 30 minutes and held at
70C for 15 minutes. The sample was removed from the bath,
rinsed, put through squeeze rolls at 30 psi, and then dried
10 at 70C for 45 minutes and 130C for 10 minutes.
In Examples 27-28 and Comparative Examples
Cl2-C14, samples of carpet were treated as in Example 26
except the polymers set forth in Table 10 were substituted
for Polymer B.
The treated samples were tested for stain
resistance. The results are set forth in Table 10.
Table 10
- Stain
ExamplePolymer _~istance
26 B 8
27 C 8
28 H 8
C12 Polymer o~ Example C8 4
C13 J 2
C14 R 3
As can be seen from the data in Table 10,
methacrylic polymers of the invention provide greater stain
resistance than do acrylic acid-based polymers (Comparative
~xamples C13 and C14) when applied on nylon 66 carpet fiber.
Further, the methacrylic acid copolymer used in Comparative
Example C12 performs unsat~sfactorily due to its high
molecular weight.
The various modifications and alterations of this
invention will be apparent to those skilled in the art
without departing from the scope and spirit of this
invention and this invention should not be restricted to
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that set forth herein for illustrative purposes.
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