Note: Descriptions are shown in the official language in which they were submitted.
CA 02202215 1997-04-09
- 2 -
BACKGROUND OF THE INVENTION
a) Field of the Invention
This invention relates to a fibrous
polyamide substrate having durable resistance to
staining by acid colorants and to a method of
rendering a fibrous polyamide substrate durably
resistant to staining by acid colorants.
b) Description of Prior Art
Fibrous polyamide substrates, such as nylon
carpeting are susceptible to staining by both
naturally occurring and commercial acid colorants
found in many common foods and beverages. The demand
for reduced staining from such acid colorants has by
and large been met by treatment with compositions
comprising sulfonated naphthol and/or sulfonated
phenol-formaldehyde condensation products as
disclosed, for example, in the following Patents:
United States Patent No. 4,501,591 (Ucci and Blyth);
No. 4,592,940 (Blyth and Ucci); No. 4,680,212 (Blyth
and Ucci); and No. 4,780,099 (Greschler, Malone and
Zinnato); or by treatment with compositions comprising
sulfonated novolak resins together with
polymethacrylic acid as disclosed in United States
Patent No. 4,822,373 (Olson, Chang and Muggli). The
use of polymers or copolymers of methacrylic acid of
low weight average molecular weight and low number
average molecular weight is described in U.S. Patent
4,937,123 (Chang, Olson and Muggli).
The initial stain resistant properties
imparted to polyamide substrates, such as carpeting,
that have been treated using the above mentioned
compositions degenerates significantly with each wet
cleaning the substrate receives. Improved stain
resistance after wet cleaning can be achieved by
increasing the amount of stain-resist product
initially applied to the substrate. However, this
CA 02202215 1997-04-09
- 3 -
generally leads to discoloration caused by yellowing
of the substrate initially, and further discoloration
results following exposure to oxides of nitrogen
and/or light. This discoloration in most cases is
attributed to dihydroxydiphenyl sulfone and its
associated S02 group.
Stain-resist products currently available in
the market place are generally novolak-type resins
based on dihydroxydiphenyl sulfone condensed with
phenol sulfonic acid or naphthalene sulfonic acid and
an aldehyde in various proportions. The chemical
structure of these resins may generally be depicted as
follows:
(a) Condensation product of naphthalene
sulfonic acid and dihydroxydiphenyl sulfone with
formaldehyde
OH
S03H
~ CHZ_
- CH2
/
S02
OH
(b) Condensation product of phenolsulfonic
acid and dihydroxydiphenol sulfone with formaldehyde
CA 02202215 1997-04-09
- 4 -
OH OH
CH2 CH2 -
S03H
S02
OH
It is generally known that increasing the
ratio of dihydroxydiphenol sulfone to phenol sulfonic
acid or naphthalene sulfonic acid will increase the
stain resist properties of the resin and subsequently
cause a higher degree of yellowing or discoloration
initially and further discoloration upon exposure to
oxides of nitrogen and/or light. It is also evident
that when the ratio of phenol sulfonic acid or
naphthalene sulfonic acid to dihydroxydiphenyl sulfone
is increased, the result is lowered stain-resist
properties and less discoloration.
The addition of acrylic polymers and/or
copolymers to the previously mentioned condensation
products, as disclosed in United States Patent No.
4,822,373 (Olson, Chang and Muggli), allows the use of
a novolak resin condensate containing a high ratio of
dihydroxydiphenol sulfone without adverse
discoloration. This is achieved due to the
dramatically reduced percentage of novolak resin in
the product which is adjusted to obtain a desired
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- 5 -
maximum level of discoloration while maintaining a
minimum level of durable stain resistance. The high
level of initial stain resistance is supplied
primarily by the acrylic polymers and/or copolymers
and, after wet cleaning stain resistance is maintained
by the novolak resin condensate, the acrylics having
largely been removed during the wet cleaning process.
SUMMARY OF THE INVENTION
This invention seeks to provide fibrous
polyamide substrates having durable resistance to
staining by acid colorants.
This invention further seeks to provide a
method of rendering a fibrous polyamide substrate
durably resistant to staining by acid colorants.
Still further, in a particular embodiment,
the invention seeks to provide such a substrate or
method in which a treating solution is employed which
contains a polymer or copolymer of methacrylic acid of
high weight average and number average molecular
weight.
In accordance with one aspect of the
invention there is provided a fibrous polyamide
substrate having durable resistance to staining by
acid colorants, the substrate having applied thereto a
treating solution comprising a sulfonated, phosphated
resol resin and a methacrylic polymer or copolymer
having a number average molecular weight in the range
of 20,000 to 40,000.
In accordance with another aspect of the
invention there is provided the method of treating a
fibrous polyamide substrate, to render it durably
resistant to staining by acid colorants comprising:
applying to the substrate material a solution
comprising sulfonated, phosphates resol resin together
with a methacrylic polymer or copolymer having a
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number average molecular weight in the range of 20,000
to 40,000.
DESCRIPTION OF PREFERRED EMBODIMENTS
The novel compositions developed according
. 5 to the present invention, that is to say, the
phosphated, sulfonated resol resins supplemented by a
methacrylic polymer or copolymer and, optionally, a
fluorochemical, when applied to fibrous polyamide
substrates provide substrates that exhibit superlative
resistance to staining by acid colorants, stain-
resistant qualities that are not significantly
impaired following repeated washing. It is to be
noted too that the novel compositions according to the
invention tend to minimize discoloration of the
fibrous polyamide substrates both during manufacture
and subsequently following exposure either to oxides
of nitrogen or light.
The novel stain-blocking resin compositions
according to the invention differ materially from
.20 stain-blockers of the prior art, many of which, as has
been mentioned, rely on use of partially sulfonated
novolak resins. The new resins are in fact resol
resins heretofore unknown in the art, and are lighter
in color than prior art novolak resins.
The series of reactions terminating in the
preparation of the partially sulfonated and phosphated
resins according to the invention runs as follows:
condense phenol and sulfonated naphthalene in the
presence of an aldehyde, preferably formaldehyde, in
an alkaline medium, pH 9 to 10. Following the
formaldehyde condensation the pH of the medium is
adjusted to between 4 to 5, and a sulfonating agent
such as sodium metabisulfite (Na2S205) is added. The
reaction leading to partial sulfonation of the phenol
-35 is continued for I to 2 hours at 105°C. The reaction
mixture is then cooled to 50°C, phosphoric acid
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_ 7 _
(H3P04) is added, the temperature is raised to 90 to
105°C and the phosphating reaction is continued for 1
to 2 hours.
The ratio of sulfonated naphthalene to
phenol initially is between 0 and 40 percent,
preferably 10 to 25 percent, by weight, sulfonated
naphthalene to 75 to 90 percent phenol, by weight,
while the ratio of formaldehyde should be at least one
mole of phenol to one mole HCHO, and may be 1.3:1.
The sulfonated naphthalene employed at. the
initial stage of the reaction may be any one of three
naphthalene derivatives, namely, either the 1-, 2- or
3-monosulfonic acid derivatives with the 2-
monosulfonic derivative being preferred.
Sufficient H3P04 is employed to assure
between 1 and 15 percent, preferably 5 to 150, more
preferably 5 to 10~ and especially loo by weight
phosphation. Following phosphation an alkaline
solution is added to adjust the pH to between 5 and 6
and the solids content to between 30 and 40 percent,
by weight, the alkali used being either sodium or
potassium hydroxide.
The product is yellow to light brown in
color, the color tending to darken on exposure to
light or air, or to oxides of nitrogen, but color may
be stabilized by the addition of a small amount of
sodium formaldehyde-H-sulfoxylate, NaHS02.HCH0.2H20,
at a pH below 7 and a temperature below 90°C for 20 to
60 minutes, preferably 30 minutes, the quantity of the
sulfoxylate being 0.1 to 4.0 percent, preferably 0.5
to 2.0 percent. The sulfoxylate treatment reduces
color by 20 to 50 percent and prevents further
discoloration.
The reaction scheme according to the
invention may generally but without undue restriction
be graphically illustrated as follows:
CA 02202215 1997-04-09
(1)
OH
S03H
HCHO
alk
OH
S03H
CH2
(2)
OH
S03H
Na2S205
CH2 105°C
OH
S03H
CH2
S03H
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_ g _
(3)
OH
S03H
~ ~ H3P04
CH2 90°-105
03H
15 ,OH
0 - P = C
OOH
S03H
CH2
RESOL B S03H
In the foregoing reaction the ratio of
naphthalene sulfonic acid to phenol is, in weight
percent, 1 to 40 percent naphthalene sulfonic acid to
60 to 99 percent phenol.
Where phenol alone is used without
naphthalene sulfonic acid the phosphated structure
should be
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,OH OH OH
5 OH O - P = O
~ OH
CH2 H2 CH2
10 S03H S03H
15 Additional structures that may be obtained
during the reactions are as follows:
S03H
20
H2
25
/OH
0 - P = O OH
3 0 ~ OH
CH2 CH2 CH2
CH20S03
35
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or
~Oi~ OH OH
OH O - P = O
~ r)Ii
~ CH2 CH2 CH2 H2
CH20S03H
The present invention provides fibrous
polyamide substrates, which exhibit improved
resistance to stain by acid colorants after washing
with detergent, that have had applied thereto a
composition comprising a partially phosphated,
partially sulfonated resol resin and a methacrylic
polymer or copolymer or combinations thereof including
polymethacrylic acid and polymethylmethacrylate, as
well as copolymers based on methacrylic acid and a
comonomer, and methylmethacrylate and a comonomer.
The combination may also include fluorochemical.
Methacrylate monomers include methacrylic
acid and its esters, for example, methylmethacrylate.
Thus the polymer may be, for example, polymethacrylic
acid or polymethylmethacrylate. Suitable comonomers
for the methacrylate copolymers include monocarboxylic
acids, polycarboxylic acids, carboxylic acid
anhydrides, esters or amides of carboxylic acids,
nitriles, vinylidene monomers and olefinic monomers.
By way of example there may be mentioned alkyl
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acrylates wherein the alkyl moiety has 1 to 4 carbon atoms,
itaconic acid, sodium sulfostyrene and sulfated castor oil.
An especially preferred comonomer is acrylic acid.
Suitably the polymer or copolymer contains 30 to 100
weight percent of methacrylic acid or methylmethacrylate and
preferably more than 60%, by weight, of methacrylic acid.
It has been found that especially good results are
achieved employing a treating solution consisting essentially
of the sulfonated, phosphated resol resin and a methacrylic
acid polymer or copolymer of high weight average molecular
weight and high number average molecular weight.
The methacrylic acid polymer or copolymer may
suitably have a weight average molecular weight of 2,000 to
500,000, but preferably has a high weight average molecular
weight above 100,000, more preferably above 140,000, and still
more preferably above 150,000 and up to 170,000. The
methacrylic acid polymer or copolymer has a high number
average molecular weight of 20,000 to 40,000, preferably
25,000 to 35,000, more preferably 30,000 to 35,000; and a
molecular size M.Z. suitably of 200,000 to 600,000.
It was surprising that polymers of high weight
average (M. W.) and number average (M. N.) molecular weight
would provide good results, especially in the light of the
teachings of U.S. Patent 4,937,123 and the commercial products
based on methacrylic polymers and copolymers described in U.S.
Patent 4,937,123. In the latter U.S. Patent the polymers and
copolymers of methacrylic acid which gave acceptable results
all had relatively low weight average and number average
molecular weights; furthermore, the commercial Leukotan (Trade
Mark of Rohm & Haas) metacrylic acid-based polymer described
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in the U.S. Patent also had low weight average and
number average molecular weights. In the methacrylic
acid-based polymers in the Examples of the U.S.
Patent, polymer D in Table 3 of the patent, with a
number average molecular weight of 3,430, and polymer
C with a weight average molecular weight of 85,500
represent the highest values for polymers considered
to provide satisfactory results.
The present invention employs methacrylic
polymers or copolymers of significantly higher M..N.,
and preferably significantly higher M.W. than those
methacrylic polymers and copolymers particularly
taught to be useful in U.S. Patent 4,937,123.
Generally the resol products of this
invention are applied to the polyamide substrate from
an aqueous solution at a pH below 5 after the dyeing
process. The resol products may be applied from an
aqueous exhaust bath or by continuous application
methods such as padding, foam, flooding or spray; all
of which are well known to those skilled in the art.
Fluorochemical compositions provide oil,
water and soil repellency and thus can be applied in
conjunction with the resol products of this invention.
Methacrylic polymers including polymeth
acrylic acid and polymethylmethacrylates may also be
applied in conjunction with the resol resins of this
invention to further reduce or eliminate any
likelihood of initial yellowing or of discoloration
upon exposure to light or discoloration upon exposure
to oxides of nitrogen.
The resole resin is applied in an amount of
at least 0.1 to 5.0 percent based on the weight of the
substrate; and the methacrylic polymer or copolymer is
applied in an amount of at least 0.1 to 5.0 percent
based on the weight of the substitute.
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The treating solution suitably contains at
least 0.01 percent, by weight of the resole and at
least 0.1 percent, by weight, of the methacrylic
polymer or copolymer, based on the weight of the
treating solution.
TEST METHODS
In the test procedures and examples
described below all percentages are by weight unless
otherwise indicated, the molecular weight (M.W.) is
the weight average molecular weight, and the molecular
weight (M. N.) is the number average molecular weight.
INITIAL STAIN RESISTANCE ("IS")
A 5" x 5" sample of the substrate to be
tested is placed on a flat, non-absorbent surface. A
two inch ring is placed on the sample and 20 ml of
staining solution is poured into the ring and worked
into the substrate. The ring is removed and the
sample is left undisturbed for 24 hours at ambient
temperature. The staining solution is prepared by
dissolving 45 grams of cherry flavoured KOOL AID
(Trade Mark), which contains Acid Red Dye No. 40
sugar-sweetened in 500 ml of water at 20°C. After 24
hours the sample is rinsed with cool tap water and
dried.
Thestain resistance of the sample is
visually rated of color
by
assessing
the
amount
remaining in the stained area by comparison
with the
unstained portion. on a scale
The
sample
is
rated
from 1 to 8 wherein 8 is excellent stain resistance
and 1 is p oorstain resistance categorized
as follows:
8 excelent stain resistance,
=
7 good stain resistance,
=
6 poor stain resistance,
=
5 unacceptable staining,
=
4 unacceptable staining,
=
3 unacceptable staining,
-
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- 15 -
2 = unacceptable staining,
1 = unacceptable staining.
AFTER WET CLEANING STAIN RESISTANCE ("W.S.")
The sample to be tested is first immersed in
a detergent solution containing 15 grams of DUPONOL
WAQE (Trade Mark of E. I. DuPont de Nemours for a
surface active agent based on lauryl sulfate) per
litre of water at a pH of 10 and at 20°C for 15
minutes. The sample is removed from the detergent
solution and rinsed thoroughly with cool tap water. and
dried. The staining solution is then applied and
evaluated as set out in the initial stain resistance
procedure.
INITIAL YELLOWING (DISCOLORATION) EVALUATION ("ID")
In the examples a graduated scale from 1 to
5 was used to evaluate yellowing where 5 represents no
yellowing, 4 represents acceptable yellowing and 3 or
less represents unacceptable yellowing.
DISCOLORATION UPON EXPOSURE TO LIGHT ("LD")
In the examples a graduated scale from 1 to
5 was used to evaluate discoloration upon exposure to
light where 5 represents no discoloration, 4
represents acceptable discoloration and 3 or less
represents unacceptable discoloration. Exposure to
light was carried out according to AATCC test methods
with an exposure time of 40 standard hours.
The following resol resins A and B where
prepared according to the preceding general disclosure
for use in examples of this invention:
RESOL A:
To a clean tank was added 3 parts by weight
of water followed by 1.3 parts by weight of a 45~
solution of potassium hydroxide to establish a pH of
9. Molten phenol was added in 18 parts, by weight,
the mixture was heated to raise the temperature to
CA 02202215 1997-04-09
. - 16 -
80°C and a 37~ solution of formaldehyde was added
slowly in small portions in a total of 15.5 parts by
weight.
After the addition of the final portion of
the formaldehyde solution, the mixture was heated to
raise the temperature slowly to 105-110°C, and was
maintained at this temperature for 60 minutes, then
cooled to 70°C. The pH of the thus cooled mixture was
adjusted to 6-7 with 1.5 parts by weight of a 56$
solution of acetic acid. Sodium metabisulfite .was
added in an amount of 7.14 parts by weight and the
mixture was heated to raise the temperature slowly to
105-110°C and was maintained at this temperature for
90 minutes. The mixture was cooled to 70°C and 2.6
parts by weight of an 85~ solution of phosphoric acid
was added and the mixture was heated to raise the
temperature to 105-110°C and was maintained at this
temperature for 60 minutes. The mixture was allowed
to cool and there was added 46.46 parts by weight of
water and 4.5 parts by weight of 45g caustic potash
solution to establish a pH of 4-5 and the resole resin
was recovered from the aqueous mix. The above parts
by weight are to a total of 100 parts.
RESOL B:
The same procedure was followed as for Resol
A but employing the following amounts by weight,
sequentially, to a total of 100 parts and employing
molten phenol and naphthalene monosulfonate in place
of the molten phenol of Resole A.
3~ water
1.4~ 45~ potassium hydroxide solution
16$ molten phenol
2~ naphthalene monosulfonate
14.6 37$ formaldehyde solution
1.5~ acetic acid
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- 17 -
6.3$ sodium metabisulfite
2.38$ phosphoric
acid
48.32 water
4.50 45$ caustic potash solution.
Resol resi ns A and B combined with
methacryl ic polymers used in examples of this
invention are of the following composition, in which
the molecular
weight (M.
W.) are weight
average
molecular weights.
Resol 'A' /Acrylic "A" - 55o by weight Resol A com-
bined with 45o by weight
methacrylic, polymer of
250,000 to 5000,00 M.W.
Resol 'A' /Acrylic "B" - 55o by weight Resol A com-
-15 bined with 45~ by weight
methacrylic polymer of
40,000 to 80,000 M.W.
Resol 'A' /Acrylic "C" - 55$ by weight Resol A com-
bined with 45~ by weight
methacrylic polymer of
2,000 to 10,000 M.W.
Resol 'A' /Acrylic "D" - 55~ by weight Resol A com-
bined with 15~ by weight
methacrylic polymer of
250,000 to 500,000 M.W.
30$ by weight methacrylic
polymer of 2,000 to 10,000
M.W.
15o by weight methacrylic
'30 polymer of 2,000 to 10,000
M.W.
Resol 'B' /Acrylic "A" - 55o by weight Resol B com-
bined with 45o by weight
methacrylic polymer of
250,000 to 500,000 M.W.
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- 18 -
Resol 'B'/Acrylic "B" - 55$ by weight Resol B com-
bined with 45g by weight
methacrylic polymer of
40,000 to 80,000 M.W.
Resol 'B'/Acrylic "C" - 55~ by weight Resol B com-
bined with 45$ by weight
methacrylic polymer of
2,000 to 10,000 M.W.
Resol 'B'/Acrylic "D" - 55~ by weight Resol B com-
bined with 15o by weight
methacrylic polymer of
250,000 to 500,000 M.W.
30o by weight methacrylic
polymer of 2,000 to 10,000
M.W.
Commercially available stain
resist products
used for comparison with the
products of the present
invention are designated as follows:
Comparative stain resist A - FX661: a novolak,
acrylic blend available
from 3M Co.
Comparative stain resist B - FX369: a novolak resin
available from 3M.
Comparative stain resist C - Algard DP3 4694: a
novolak resin available
from Allied Colloids
Inc.
The nylon 6 and 66 substrates used in
examples of this invention were in cut pile carpet
form that was processed through a dyeing cycle without
dyestuffs being present so as to yield an uncolored
substrate free of fibre lubricating oils. These
substrates are designated as follows:
Nylon 66 - Monsanto fibre type 1837; moist
heat set
Nylon 6 - BASF fibre, moist heat set.
CA 02202215 1997-04-09
- 19 -
c~vwwrtnr r i
A treating solution was prepared containing
2.Og resol A based on the nylon 66 sample weight of 15
grams and exhausted onto the fibre at a liquor ratio
of 15:1, at a pH of 2.5 and at 75°C for a period of 20
minutes. The sample was then rinsed and dried.
EXAMPLE 2
A treating solution was prepared containing
4.Og resol A based on the nylon 6 sample weight of 15
grams and exhausted onto the fibre at a liquor ratio
of 15:1 at a pH of 2.5 and at 75°C for a period of 20
minutes. The sample was rinsed and dried.
EXAMPLE 3
A nylon 66 sample was prepared as in Example
1 except that 2.Oo of resol B replaced resol A.
EXAMPLE 4
A nylon 6 sample was prepared as in Example
2 except that 40 of resol B replaced resol A.
EXAMPLE 5
A nylon 66 sample was prepared as in Example
1 except that 2$ comparative stain resist B replaced
resol A.
EXAMPLE 6
A nylon 6 sample was prepared as in Example
2 except 4 % comparative stain resist B replaced resol
A.
EXAMPLE 7
A nylon 66 sample was prepared as in Example
1 except that 2~ comparative stain resist C replaced
resol A.
EXAMPLE 8
A nylon 6 sample was prepared as in Example
2 except that 4~ comparative sample C replaced resol
A.
Examples 1 through 8 were evaluated for
initial stain resistance (IS) after wet cleaning stain
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- 20 -
resistance (WS), initial discoloration (ID) and
discoloration upon exposure to light (LD), the results
being set forth in Table I.
TABLE 1
Example I.S. W.S. I.D. L.D.
1 8 7 3-4 3
2 8 7 3 3
3 8 7 3-4 3-4
4 8 6 3-4 3
5 8 6 3-4 3
6 8 5 3 2-3
7 7 5 4-5 4-5
8 6 4 4 4
As can be seen from the data in Table 1, the
polyamide substrates treated with resol resins of this
invention (Examples 1 to 4) generally demonstrate a
higher initial stain resistance and stain resistance
after wet cleaning than comparative novolak resins
(Examples 5 to 8). It is also apparent that certain
novolak resins, although demonstrating inferior to
unacceptable stain resistance, do exhibit less
discoloration initially and upon exposure to light
(Examples 7 and 8).
EXAMPLE 9
A treating solution was prepared containing
4.0~ resol A/Acrylic A blend based on a nylon 6 sample
weight of 15 grams and exhausted onto the fibre at a
liquor ratio of 15:1 at a pH of 2.5 and at a
temperature of 75°C for a period of 20 minutes. The
sample was rinsed and dried.
In Examples 10 through 17, nylon 6 samples
were prepared and treated as in Example 9 except the
stain resist compounds used were as set forth in Table
2.
CA 02202215 1997-04-09
- 21 -
TABLE 2
Example Stain Resist Comp ound
Resol 'A'/Acrylic 'B'
5 11 Resol 'A'/Acrylic 'C'
12 Resol 'A'/Acrylic 'D'
13 Resol 'B'/Acrylic 'A'
14 Resol 'B'/Acrylic 'B'
Resol 'B'/Acrylic 'C'
10 16 Resol 'B'/Acrylic 'D'
17 Comparative resist
stain A.
Examples 9 through 17 were evaluated for
initial stain resistance, after wet cleaning stain
15 resistance, initial discoloration, discoloration upon
exposure to light and oxides of nitrogen, the results
being set forth in Table 3.
TABLE 3
Examt~le I.S. w.S. I.D. L.D.
9 8 5 5 5
10 8 5 5 5
11 8 5-6 5 4-5
12 8 5 5 5
13 8 4 5 5
14 8 5 5 5
15 8 5 5 4-5
16 8 5 5 5
17 8 4 5 4-5
As can be seen from the data in Table 3, the
polyamide substrate treated with resol resins of this
invention combined with methacrylic polymers (Examples
9 to 16) demonstrate significant improvements in
initial discoloration and discoloration upon exposure
to light when compared to the uncombined resol resins
CA 02202215 1997-04-09
- 22 -
of Examples 1 to 4. It is also apparent that resol
resins combined with methacrylic polymers of this
invention (Examples 9 to 16) exhibit lower stain
resistance ratings after wet cleaning as compared to
the uncombined resol resins of Examples 1 to 4. Resol
resins of this invention combined with methacrylic
polymers in Examples 9 through 16 in all examples
demonstrate superior or equal properties to
comparative sample #17 which is a novolak resin
combined with acrylic polymer.
Examples 18 and 19 resol resin A was
combined with methacrylic polymer blends as follows:
EXAMPLE 18
Resol 'A'/Acrylic "E" - 25~ by weight resol
"A" combined with
25g by weight methacrylic
polymer of 250,000 to 500,000
M.W.;
25o by weight methacrylic
polymer of 40,000 to 80,000
M.W.; and
25~ by weight methacrylic
polymer of 2,000 to 10,000
M.W.
EXAMPLE 19
Resol 'A'/Acrylic "F" - 70$ by weight resol
"A" combined with
loo by weight methacrylic
polymer of 250,000 to 500,000
M.W.;
10$ by weight methacrylic
polymer of 40,000 to 80,000
M.W.; and
loo by weight methacrylic
polymer of 2,000 to 10,000
M.W.
CA 02202215 1997-04-09
- 23 -
In Example 18, a treating solution was
prepared containing 4.0$ resol 'A'/acrylic "E" blend,
as previously described, based on a nylon 6 sample
weight of 15 grams and exhausted onto the fibre at a
liquor ratio of 15:1 at a pH of 2.5 and at a
temperature of 75°C for a period of 20 minutes, the
sample was rinsed and dried.
Example 19 was prepared and treated as in
Example 18 except the stain resistant Resol
'A'/acrylic "F" blend as previously described was used
to replace stain resistant Resol 'A'/acrylic "E"
blend.
Examples 18 and 19 were tested and reported
in Table 4 along with data from Examples 2, 12 and 17
for comparative purposes.
TABLE 4
Example I.S. W.S. I.D. L.D.
18 8 4-5 5 5
19 8 6-7 5 4-5
.20 2 8 7 3 3
12 8 5 5 5
17 8 4 5 4-5
As can be seen from the data in Table 4, the
polyamide substrates of Examples 18, 19 and 12 treated
with Resol resin containing various proportions of
methacrylic polymers of blended molecular weights
exhibited superior stain resistance after wet cleaning
when compared to the novolak/acrylic of comparative
Example 17 and inferior stain resistance after wet
cleaning when compared to 100 Resol "A" of Example 2.
Furthermore the blended resol/acrylics of Examples 12
and 18 exhibited superior performance upon exposure to
nitrous oxides when compared with the comparative
novolak/acrylic blend of Example 17. It is also noted
that when the proportion of methacrylic polymer
CA 02202215 1997-04-09
- 24 -
present in the resol resin is approximately a ratio of
1:1 as in Example 12 optimum results are obtained with
respect to stain resistance after wet cleaning,
initial discoloration and discoloration upon exposure
to light and oxides when compared to comparative
Example 17.
Comparisons of Examples 2, 12, 18 and 19
demonstrate that as the concentration of resol resin
to methacrylic polymer is reduced a) the stain
resistance after wet cleaning is reduced and b) the
propensity for discoloration from tested sources is
also reduced.
EXAMPLE 20
A treating solution containing 75g/L. Resol
'A'/Acrylic 'D' blend and 50g/L Milease F15N (Trade
Mark), a non ionic fluorochemical available from
I.C.I., U.S.A. plus 20g/L. Alkafoam D (Trade Mark), a
foaming agent available from Alkaril Chemicals, Inc.,
and having a pH of 4 using acetic acid was prepared
and foamed onto a sample of nylon 66 carpet using a
blow ratio of 60:1 and a wet pick up of 20~ to provide
an application rate of 1.5~ Resol 'A'/Acrylic 'D' plus
1$ fluorochemical based on the weight of the sample.
The sample was dried at 120°C for 20 minutes. The
treated sample was tested with results as set forth in
Table 5 along with results from Example 12 Resol
'A'/Acrylic 'D' without fluorochemical.
TABLE 5
Example I.S. W.S. I.D. L.D.
18 8 6 5 5
12 8 5 5 5
Example 18 containing Resol 'A'/Acrylic 'D'
and a fluorochemical demonstrated no adverse affects
- due to the presence of fluorochemical when compared
CA 02202215 1997-04-09
- 25 -
with Example 12 which did not contain a
fluorochemical. It should be noted that less stain
resistant chemical is required when directly applied
to the substrate via foam methods, when compared to
indirect application via exhaust methods.
EXAMPLE 21
A treating solution containing 75g/L Resol
resin B and 50g/1 of Milease F15N (Trade Mark) a non
ionic fluorochemical available from I.C.I., U.S.A.
plus 20g/L Alkafoam D (Trade Mark), a foaming agent
available from Alkaril Chemicals and having a pH of 4
using acetic acid was prepared and foamed onto a
sample of nylon 66 carpet using a blow ratio of 60:1
and a wet pick up of 20g to provide an application
rate of 1.5~ resol resin 'B' plus to fluorochemical
based on the weight of the sample. The sample was
dried at 120°C for 20 minutes. The treated sample was
tested with results as set forth in Table 6 along with
results from Example 3 Resol 'B' containing no
fluorochemical.
TABLE 6
Example I.S. W.S. I.D. L.D.
21 8 7 3-4 3-4
3 8 7 3-4 3-4
Example 21 containing Resol 'B' resin and a
fluorochemical demonstrated no adverse affects due to
the presence of a fluorochemical when compared with
Example 3 containing only Resol Resin ' B' . It should
be noted that less stain resist chemical is required
when directly applied to the substrate via foam
methods when compared to indirect application via
exhaust methods.
CA 02202215 1997-04-09
- 26 -
EXAMPLE 22
A treating solution was formed containing:
0.4 g/1 resol A (40~ solids)
0.3 g/1 condensation product of sulfonated
naphthalene and formaldehyde
(40$ solids);
1.5 g/1 methacrylic resin (15o solids)
- having M.W. above 150,000 and
M.N. above 30,000.
The solution was adjusted to pH 2 with
phosphoric acid and sulfuric acid and was applied on a
10 g sample of Nylon 6 carpet with a pick up of 350.
The sample was steamed for 3 minutes, rinsed and
dried. Test results for the resulting dried sample
are shown in Table 7.
TABLE 7
I.S. W.S. I.D. L.D.
8 7 5 4-5
The condensation product of the sulfonated
naphthol and formaldehyde is a dispersant and improves
solubility of the resins.
Table 7 shows that surprisingly good results
were achieved in all test categories for employing the
methacrylic resin of high M.W. and M.N.
The methacrylic resin employed is a
copolymer of methacrylic acid and acrylic acid.
EXAMPLE 23
A treating solution was formed containing:
0.2 g/1 resol A (40g solids)
0.15 g/1 condensation product of sulfonated
naphthalene and formaldehyde
(40a solids);
CA 02202215 1997-04-09
- 27 -
1.0 g/1 methacrylic resin (15o solids)
having M.W. above 150,000 and
M.N. above 30,000
3 g/1 magnesium sulfate.
The solution was adjusted to pH 2 with a
combination of phosphoric acid and sulfuric acid and
was applied on a lOg sample of Nylon 66 carpet with a
pick up of 350 . The thus treated sample was steamed
for 3 minutes, rinsed and dried. Test results for the
dried sample are set out in Table 8.
TABLE 8
I.S. W.S. I.D. L.D.
8 7 5 4-5
The results are consistent with the good
results achieved in Example 22.
The treated samples in Examples 22 and 23
were also shown to display superior durability to
washing or wash fastness.
In this specification, unless indicated
otherwise the molecular weights (M. W.) are weight
average molecular weights; and the $ are o by weight
unless indicated otherwise.
