Note: Descriptions are shown in the official language in which they were submitted.
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BACKGROUND OF THE INVENTION
i) Field of the Invention
This invention relates to a fibrous polyamide or wool substrate having
durable resistance to staining by acid colorants and to a method of rendering
a fibrous polyamide or wool substrate durably resistant to staining by acid
colorants.
ii) Description of Prior Art
Fibrous polyamide substrates, such as nylon carpeting and similar
wool substrates 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 or
sulfonated phenol-formaldehyde condensation products as disclosed for
example in the following patents: US Patent 4,501,591 Ucci and Blyth; US
Patent 4,592,940 Blyth and Ucci; US Patent 4,680,212 Blyth and Ucci; US
Patent 4,780,099 Creshler, Malone and Zinnato; US Patent 4,865,885
Herlant and Al; or by treatment with compositions comprising sulfonated
novolak resins together with polymethacrylic acid as disclosed in US Patent
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 US Patent 4,937,123 Chang, Olson and Muggli.
The initial stain resistance properties imparted to polyamide or wool
substrates, such as carpeting, that have been treated using the above
mentioned compositions degenerate, significantly with each wet cleaning the
substrate receives. Improved stain resistance after wet cleaning can be
achieved by increasing the amount of the sulfonated hydroxy aromatic
CA 02292460 2003-07-17
3
formaldehyde condensation products, in the stain resist product or by
increasing the amount of stain-resist product initially applied to the
substrate, however, this generally leads to discoloration caused by yellowing
of the substrate initially and further discoloration upon exposure to oxides
of
nitrogen and/or light.
Stain-resist products currently available in the market place are
generally based on dihydroxydiphenyl sulfone and phenol sulfonic acid
condensed with an aldehyde in acid or alkaline media, or dihydroxy
diphenyl sulfone and naphthalene sulfonic acid condensed with aldehyde in
acid or alkaline media.
It is generally known that increasing the ratio of the
dihydroxydiphenyl sulfone to the phenol sulfonic acid or naphthalene
sulfonic acid increases the stain resistance properties of the resin and
subsequently causes a higher degree of yellowing or discoloration initially
and further discoloration upon exposure to oxides of nitrogen and/or light.
Conversely it is also evident that when the ratio of phenol sulfonic
acid or naphthalene sulfonic acid to dihydroxydiphenyl sulfone increases the
result is lower stain-resist properties and less discoloration.
The addition of a methacrylic resin in the form of methacrylic
polymers and/or copolymers to the previously mentioned condensation
products (novolak resin) as disclosed in US Patent 4,822,373 (Olson, Chang
and Muggli ) allows the use of a novolak resin in smaller quantities with
larger quantities of the methacrylic resin. With this combination of novolak
resin and methacrylic resin, a major improvement in the light fastness or less
discoloration is achieved due to the dramatically reduced percentage of
novolak resin in the product mentioned above, which is adjusted to obtain a
desired low level of discoloration while maintaining an acceptable level of
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durability to wash. The high level of initial stain resistance is supplied
primarily by the methacrylic resin and after wet cleaning the stain resistance
is supposedly maintained by the novolak resin, the methacrylic resin having
largely been removed during the wet cleaning process.
SUMMARY OF THE INVENTION
This invention seeks to provide fibrous polyamide or wool substrates
having durable resistance to staining by acid colorants.
Still further this invention seeks to provide a method of rendering a
fibrous polyamide or wool substrate durably resistant to staining by acid
colorants.
Still further this invention seeks to provide an aqueous formulation
for providing resistance to staining by acid colorants in a fibrous 'polyamide
or wool substrate.
In accordance with one aspect of the invention there is provided a
fibrous polyamide substrate having resistance to staining by acid colorants
comprising: a fibrous polyamide substrate having applied thereto a semi-
bleached to bleached sulfonated aromatic condensation resin, said resin
being selected from the group consisting of condensation products of i)
phenolsulfonic acid, dihydroxydiphenyl sulfone and an aldehyde; ii)
sulfonated dihydroxydiphenylsulfone, dihydroxydiphenylsulfone and an
aldehyde; iii) sulfonated dihydroxy diphenyl sulfone and an aldehyde and iv)
mixtures of i), ii) and iii).
In accordance with another aspect of the invention there is provided a
method of imparting stain resistance to acid colorants, to a fibrous
polyamide substrate comprising: contacting said fibrous polyamide substrate
with a semi-bleached to bleached sulfonated aromatic condensation resin in
an aqueous vehicle, said resin being selected from the group consisting of
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condensation products of: i) phenolsulfonic acid, dihydroxydiphenyl sulfone
and an aldehyde; ii) sulfonated dihydroxydiphenylsulfone,
dihydroxydiphenyl sulfone and an aldehyde; iii) sulfonated dihydroxy
diphenyl sulfone and an aldehyde and iv) mixtures of i), ii) and iii).
The condensation product can be applied alone or in combination
with: a semi-soluble high molecular weight methacrylic acid polymer and
optionally also a semi-soluble to insoluble high molecular weight ethyl
methacrylate polymer.
In accordance with another aspect of the invention there is provided
an aqueous formulation for providing resistance to staining by acid colorants
in a fibrous polyamide substrate comprising in an aqueous vehicle: a) a
semi-bleached to bleached sulfonated aromatic condensation resin, said resin
being selected from the group consisting of condensation products of i)
phenolsulfonic acid, dihydroxydiphenyl sulfone and an aldehyde; ii)
sulfonated dihydroxydiphenyl sulfone, dihydroxydiphenyl sulfone and an
aldehyde; iii) sulfonated dihydroxy diphenyl sulfone and an aldehyde and iv)
mixtures of i), ii) and iii) and b) a semi-soluble methacrylic acid polymer of
high weight average molecular weight and high number average molecular
weight.
DETAILED DESCRIPTION OF THE INVENTION
i) Condensation Resin
The invention employs a semi-bleached to bleached sulfonated
aromatic condensation resin.
The condensation resin may be a condensation product of phenol
sulfonic acid, dihydroxy diphenyl sulfone and an aldehyde; or a sulfonated
condensation product of dihydroxy phenyl sulfone, sulfonated dihydroxy
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phenyl sulfone and an aldehyde; or a sulfonated dihydroxy phenyl sulfone
and an aldehyde.
The aldehyde is suitably formaldehyde or a lower alkyl aldehyde in
which the lower alkyl moiety has 1 to 6, preferably 1 to 4 carbon atoms.
The condensation may be carried out in acid or alkaline media.
The dihydroxydiphenyl sulfone may, in particular, be 4,4-
dihydroxyphenyl sulfone; and similarly the sulfonated dihydroxydiphenyl
sulfone, may be sulfonated 4,4-dihydroxyphenyl sulfone.
A unit of the condensation product of phenol sulfonic acid, 4,4-
dihydroxy diphenylsulfone and formaldehyde may be represented by
formula (I):
H03S
CH2
S02
(I)
~i
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A typical unit of the condensation product of 4,4-
dihydroxydiphenylsulfone, sulfonated 4,4-dihydroxydiphenylsulfone and
formaldehyde may be represented by formula (II):
off off
so3H
CH2
_ \
S03H
S02 S02
S03H
SO3H (II)
OH
OH
The sulfonated 4,4-dihydroxydiphenylsulfone employed in the above
unit is double sulfonated, by which is meant that on average each phenyl of
the 4,4-dihydroxydiphenylsulfone has two sulfonate or sulfonic acid
substituents.
A typical unit of the condensation product of sulfonated 4,4-
dihydroxydiphenylsulfone and formaldehyde may be represented by the
formula (III):
CA 02292460 2003-07-17
s
OH
CH2 '
S03H ~ SO3H
S02 S02
S03H
OH I S03H (III)
OH
The sulfonic acid groups increase the solubility of the condensation
products.
The condensation resin may comprise one or more of the
condensation resins of the afore-mentioned three classes such as represented
by (I), (II) and (III).
Optionally the semi-bleached to bleached condensation resin of the
invention may be employed in conjunction with a bleached aldehyde
condensate of a sulfonated naphthalene, such as described in CA Patent
Application SN 2,292,888, filed December 20, 1999, Y. Elgarh~ et al. In
particular, such condensates are condensates of a naphthalene sulfonic acid,
for example, a mono-, di, or tri-sulfonic acid, such as naphthalene-2-
monosulfonic acids, an aldehyde especially formaldehyde and a
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dihydroxydiphenyl sulfone, for example, 4,4-dihydroxydiphenylsulfone.
The condensation may be in acid or alkaline media.
The above condensation products are bleached or semi-bleached to
remove or reduce colour which causes the yellowing of nylon fibres, by
techniques known in the art. By way of example the condensate may be
bleached by addition of 0.1 to 4%, by weight, sodium or zinc formaldehyde
sulfoxylate for a period of 20 to 90 minutes at a temperature below
100°C.
This typically reduces colour by 20 to 80% and prevents further
discoloration. The bleaching or partial stripping of color is preferably
carried out at a pH higher than 7 when sodium formaldehyde sulfoxylate is
employed, and at a pH lower than 7 when zinc formaldehyde sulfoxylate is
employed, and at a temperature of 50°C or higher. The reference to
bleaching, stripping or partially removing color herein refers to removal of
the part of the color in the condensate which causes the yellowing of the
fibres, bleaching, stripping or partial removal of color results in the
condensate becoming lighter in color.
The degree of bleaching or stripping depends upon the condensate
and whether it is condensed at acid or alkaline media; and also depends on
the stripping agent whether it is sodium or zinc, formaldehyde sulfoxylate,
and the bleaching or stripping conditions, for example, pH.
The time and the temperature are important factors and the
percentage of stripping of the color varies, according to the stripping
conditions, between 20 to 80%.
After the bleaching or stripping, even if the color is still dark, it is
observed that yellowing of the fibers does not occur.
The amounts of the semi-bleached to bleached sulfonated aromatic
condensation resin and the optional bleached aldehyde condensate of a
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sulfonated naphthalene deposited from an aqueous formulation on the
polyamide substrate is dependent on the process employed for the
deposition, as is well understood by persons in the art, and thus persons in
the art will well understand the concentrations required in the aqueous
formulation, based on the application technique and method parameters
employed.
The aqueous formulation is applied to the fibrous substrate by
conventional procedures, for example, the substrate may be immersed in a
bath of the aqueous formulation, or the formulation may be exhausted onto
the substrate by foam system or spray or applied in one step with
fluorochemical. Suitably, the treated substrate is rinsed with water and
dried. The treated substrate retains the deposited resins.
Suitably the resins are applied to the polyamide fibre substrate in an
aqueous vehicle at a pH of 1 to 10.
ii) Methacrylic Polymers
Methacrylic acid polymers and methacrylate polymers referred to
herein contemplates homopolymers as well as copolymers with one or more
comonomers.
These methacrylic acid and methacrylate polymers are optionally
employed in conjunction with the condensation resin.
Suitable polymers include semi-soluble methacrylic acid polymers;
and semi-soluble or insoluble ethylmethacrylate polymers.
Completely soluble acrylic and methacrylic homopolymers and
copolymers do not have durability to wet cleaning, so that their stain resist
effect diminishes with wet cleaning; whereas completely insoluble acrylic
resins have very little stain resist effect on polyamide fibers.
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The present invention preferably employs one or more lower
solubility methacrylic acid and methacrylate polymers which are resistant to
wet cleaning processes thereby providing durable stain resistance, while
providing initial stain resistance, prior to wet cleaning of a polyamide fiber
substrate, as well as a soil release effect, and a substantial improvement in
the light fastness.
The semi-soluble methacrylic acid polymer, is suitably a
homopolymer of methacrylic acid or a copolymer of methacrylic acid and at
least one comonomer, for example, ethyl acrylate, 2-ethylhexyl
methacrylate, ethyl methacrylate, methyl methacrylate, butyl methacrylate or
isobutyl methacrylate.
The methacrylic acid polymer suitably has a high weight average
molecular weight of at least 100,000, typically 100,000 to 500,000, and
preferably 150,000 to 250,000 preferably over 200,000; and a high number
average molecular weight of at least 50,000, typically 50,000, to 100,000,
and preferably 50,000 to 80,000, and more preferably 60,000 to 75,000.
Suitably the semi-soluble or insoluble ethyl methacrylate polymer is a
homopolymer of ethyl methacrylate or a copolymer of ethyl methacrylate
and at least one comonomer, for example, ethyl acrylate, methyl acrylate,
methyl methacrylate, methacrylic acid, butyl methacrylate, isobutyl
methacrylate or 2-ethyl hexyl methacrylate.
The ethyl methacrylate polymer suitably has a high weight average
molecular weight of at least 100,000, typically 100,000 to 500,000, and
preferably 100,000 to 250,000, and a high number average molecular weight
of at least 25,000 to 100,000 and preferably 35,000 to 70,000.
The ethyl methacrylate polymer and the methacrylic acid polymer,
when employed, together with semi-bleached to bleached sulfonated
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aromatic condensation products and the optional bleached aldehyde
condensate of a sulfonated naphthalene, are applied to the polyamide fiber
substrate in an aqueous vehicle in which the polymers, condensation
products and aldehyde condensate, are mixed in water.
An aqueous formulation of the methacrylic acid polymers and the
sulfonated aromatic condensation products, for treating a polyamide
substrate, typically contains an amount of the methacrylic acid polymer to
deposit on the polyamide substrate of Nylon 66 at least 0.1 %, by weight, and
at least 0.3%, by weight, on Nylon 6.
The sulfonated aromatic condensation products of this invention are
typically employed in the formulation in an amount to deposit at least
0.03%, by weight, on Nylon 66 substrate and at least 0.1%, by weight, on
Nylon 6 substrate, based on the weight of the substrate.
The amounts of suitable methacrylic polymers and the semi-bleached
to bleached aromatic condensation products of this invention, and the
optional bleached aldehyde condensate, deposited from the aqueous
formulation on the polyamide fibre substrate is dependent on the process
employed for the deposition; as is well understood by persons in the art, and
thus persons in the art will well understand the concentration required in the
aqueous formulation, based on the application technique and method
parameters employed.
The aqueous formulation is applied to the fibrous substrate by
conventional procedures for example, the substrate may be immersed in a
bath of the aqueous formulation, or the formulation may be exhausted onto
the substrate by foam system or spray or applied in one step. Suitably, the
treated substrate is rinsed with water and dried.
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The treated substrate retains the deposited polymers, condensation
products and aldehyde condensate on the fibers.
In a preferred embodiment an anionic or non-ionic fluorochemical is
also applied to the substrate. The fluorochemical can be applied from a
single bath containing the other components to be deposited, or may be
deposited from a separate bath.
In a particular embodiment there is deposited on Nylon 66 one, two
or three of the three classes of semi-bleached to bleached sulfonated
aromatic condensation resins of the invention, in an amount of at least 0.1 %,
based on the weight of the substrate; together with at least 0.2%, based on
the weight of the substrate, of the methacrylic acid polymer; and 0 to 3%
based on the weight of the substrate, of the ethylmethacrylate polymer.
In another particular embodiment there is deposited on Nylon 6 one,
two or three of the three classes of semi-bleached to bleached sulfonated
aromatic condensation resins of the invention, in an amount of at least 0.1 %,
by weight, based on the weight of the substrate; together with at least 0.3%,
by weight, based on the weight of the substrate, of the methacrylic acid
polymer; and 0% to 4%, by weight, based on the weight of the substrate, of
the ethylmethacrylate polymer.
The methacrylic acid polymer is suitably deposited from an aqueous
vehicle at an acidic pH below 7.
DESCRIPTION OF PREFERRED EMBODIMENTS
Polymer A)
In a clean reactor vessel the following were added:
Mix No. 1
92.36 parts by weight of water and 0.14 parts by weight of
ammonium persulfate.
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3 parts of dodecyl benzene sulfamic acid (sodium salt at 30 % solid)
The solution was heated to 90°C and maintained at this temperature
at all
times with continued agitation.
Mix No. 2
In a separate tank the following were added in parts by weight.
57.2 water - 29.6 methacrylic acid - 3 parts 2 ethyl hexyl
methacrylate - and another addition of ammonium persulfate was added to
obtain the mole weight required.
Mix No. 2 was added slowly to Mix No. 1 while maintaining
temperature of 90°C at all times, after the last addition the
temperature was
raised to 95°C and the reaction was continued for 90 minutes then
cooled
down to 30°C.
The above reaction resulted in an anionic hazy solution with high
viscosity and a solid content of 18 to 19 %, by weight.
The resultant methacrylic acid copolymer had a weight average
molecular weight of 210,000, and a number average molecular weight of
70,000, and is referred to in the Examples as Polymer A.
Polymer B)
To a clean reaction vessel equipped with mechanical stirrer to
produce efficient agitation the following was charged as for Mix No. 1, in
parts, by weight: 85.8 parts water and 2.2 parts ammonium persulfate 3.52
parts dodecyl benzene sulfonic acid sodium salt. The above solution was
heated to 80°C and maintained at this temperature.
In a separate tank the following were charged as Mix No. 2: 0.7 ethyl
acrylate -3.52 parts methyl methacrylate
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6.6 parts methacrylic acid, 45 parts water
26.4 parts ethyl methacrylate
then finally another addition of ammonium persulfate was added to obtain
the mole weight required.
Mix No. 2 was added slowly to mix no. 1 while maintaining the
temperature at 80°C. After the last addition the reaction continued for
90 -
120 minutes at 80-90°C, followed by cooling to 30°C. The
reaction
produced an anionic milky emulsion with approximately 25 to 26%, by
weight, solid content. The resultant ethyl methacrylate copolymer had a
weight average molecular weight of 110,000, and a number average
molecular weight of 36,000, and is referred to in the Examples as Polymer
B.
The manufacturing of semi-bleached to bleached sulfonated aromatic
formaldehyde condensation resins is as follows:
Condensation Product C
This product can be manufactured in different ways, however, the
most important factor is the bleaching of the final product which makes the
difference between the unbleached condensation product and the bleached
product.
First Method:
4,4-Dihydroxy diphenyl sulfone was sulfonated by treatment with
concentrated sulfuric acid over several hours at a temperature of 100°C
or
higher with a level of double sulfonation on eanh mole of 4,4-dihydroxy
diphenyl sulfone. The sulfonated 4,4-dihydroxydiphenyl sulfone was mixed
with 4,4-dihydroxy diphenyl sulfone at a ratio of 70 to 30 and the mixture
was condensed with formaldehyde at a pH below 7 for several hours at a
temperature of 100-110°C, the ratio of the aromatic compounds and the
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formaldehyde being adjusted at 1 mole aromatic compound to 0.55 moles of
formaldehyde.
After the reaction the condensation product was cooled down to
70°C
add bleached with 1.5% zinc formaldehyde sulfoxylate at this temperature,
for 60 minutes. This produces a product with type II units as described
hereinbefore.
Second Method:
The product also can be manufactured by a different method as
follows:
4,4-Dihydroxydiphenyl sulfone was sulfonated by concentrated
sulfuric acid at a temperature around 100°C for several hours, to
produce
sulfonation ratio around 1:1 to obtain acceptable solubility, then the
sulfonated 4,4-dihydroxy diphenyl sulfone was condensed with
formaldehyde over several hours at about 100°C at a ratio of 1 mole
sulfonated 4,4-dihydroxydiphenol sulfone to 0.7 to 0.8 moles of
formaldehyde. The condensation product was cooled down to 70°C and
bleached with 1.5% zinc formaldehyde sulfoxylate for about 60 minutes.
Condensation Product D
A second condensation product of this invention can be made as
follows: phenol sulfonic acid/dihydroxy diphenyl sulfone were dissolved in
water then condensed with formaldehyde several hours at a pH between 3 to
10, at a temperature between 105°C and 130°C. The product which
is
evaluated in this invention is made as follows:
The molecular ratio of the phenol sulfonic acid to the dihydroxy
diphenyl sulfone was 55:45.
The molecular ratio between the above mix and the formaldehyde was
adjusted to 1 to 0.55. The pH was adjusted to about 5 in water and the
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condensation was carried out for about 6 hours at 120°C. The product is
then cooled down to 70°C and bleached with zinc formaldehyde
sulfoxylate
for 60 minutes. After bleaching, the liquid is a pale amber color instead of
very dark brown. The solid content is adjusted to 40%, by weight.
The semi bleaching method of the sulfonated aromatic condensation
products of this invention was described in US Patent No. 5,457,259,
Trichromatic Carpet Inc.
TEST METHODS
In the test procedures and examples described below all percentages
are by weight unless otherwise indicated, the molecular weight (MW) is the
weight average molecular weight, and the molecular weight (MN) 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 diameter ring is placed on the sample and
20m1 of staining solution is poured into the ring and worked into the
substrate. The ring is removed and the sample is left undisturbed for 16
hours at ambient temperature. The staining solution is prepared by
dissolving 0.6 grams of Acid Red Dye No. 40, the sample is rinsed with cool
tap water and dried.
The stain resistance of the sample is visually rated by assessing the
amount of color remaining in the stained area by comparison with the
unstained portion. The sample is rated on a scale from 1 to 8 wherein 8 is
excellent stain resistance and 1 is poor stain resistance categorized as
follows:
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8 - EXCELLENT STAIN RESISTANCE
7 - GOOD STAIN RESISTANCE
6 - POOR STAIN RESISTANCE
- UNACCEPTABLE STAINING
4 - UNACCEPTABLE STAINING
3 - UNACCEPTABLE STAINING
2 - UNACCEPTABLE STAINING
1 - UNACCEPTABLE STAINING
AFTER WET CLEANING STAIN RESISTANCE ("WS")
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 a surface active agent based on lauryl sulfate) per liter 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 S 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 S represents no discoloration. 4
CA 02292460 1999-12-16
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represents acceptable discoloration and 3 or less represents unacceptable
discoloration. Exposure to light was carried out according to AATCC test
method 16E with an exposure time of 40 standard hours.
The sulfonated aromatic Condensation Products C and D before
bleaching and after bleaching were tested separately and in combination
with the Polymers A and B as follows:
EXAMPLES
1 ) Test on Nylon 66
The treatment bath was adjusted to pH 1.8 by Bartex C-4 (Trade-
mark for buffering system in liquid form of Trichromatic Carpet Inc. under
US Patent No. 5,821,177).
The amount of stainblocker used were as follow:
Example # l:
4 g/L condensation product #C unbleached manufactured by the
Second Method (hereinbefore)
Example # 2:
4 g/1 condensation product #C bleached manufactured by the Second
Method (hereinbefore)
Example # 3:
4 g/L condensation product # D unbleached
Example # 4:
4 g/1 condensation product # D bleached
Example # 5:
8 g/L methacrylic acid polymer with MW 10,000
Example # 6:
6 g/L Polymer A - 2 g/L, Polymer B
CA 02292460 1999-12-16
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Example # 7:
8 g/L Polyacrylic acid polymer with MW 100,000
Example # 8:
6 g/L Polymer A - 2 g/L condensation product #C bleached
manufactured by the Second Method (hereinbefore)
Example # 9:
6 g/L Polymer A- 2 g/L condensation product #D
Example # 10:
6 g/L polyacrylic acid polymer with MW 100,000 - 2 g/L
condensation product #C bleached manufactured by the Second Method
(hereinbefore)
2) Test on Nylon 6
The treatment bath was adjusted to pH 2.2 by Bartex C-4 (Trade-
mark for buffering system from Trichromatic Carpet under US Patent No.
5,821,177).
The amount of stainblocker used were as follows:
Example # 11:
8 g/L condensation product #C unbleached manufactured by the Second
Method (hereinbefore)
Example # 12:
8 g/L condensation product #C bleached manufactured by the Second
Method (hereinbefore)
Example # 13:
8 g/L condensation product #D unbleached
Example # 14:
8 g/L condensation product #D bleached
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Example # 15:
18 g/L methacrylic acid polymer with MW 10,000 and MW 2,300
Example # 16:
14 g/L Polymer A - 4 g/L Polymer B
Example # 17:
18 g/L polyacrylic acid polymer with MW 100000
Example # 18:
14 g/L Polymer A - 4 g/L condensation product # C bleached manufactured
by the Second Method (hereinbefore)
Example # 19:
14 g/L Polymer A - 4 g/L condensation product #D bleached
Example # 20:
14 g/L acrylic acid polymer MW 100000 - 4 g/L condensation product #C
bleached manufactured by the Second Method (hereinbefore).
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In each case Nylon 66 substrate was immersed in the stain resist bath
to obtain a pick up of about 350% on the weight of the substrate, then
steamed for 3 minutes, followed by light rinse and dried to be ready for
testing. The results appear in Table #1:
TABLE # 1
~~ ~ ~ LD
Product y ~ IS~ ~ WS ~ ~ ID
' a
;.
SAMPLE # 1 7-8 6-7 3-4 3
SAMPLE #2 7-8 6-7 4-5 4-5
SAMPLE #3 6-7 5-6 3-4 3
SAMPLE #4 6-7 5-6 4 4
SAMPLE #5 7 5 5 5
SAMPLE #6 7-8 6-7 5 5
SAMPLE #7 4 2 5 5
SAMPLE #8 8 7 5 S
SAMPLE #9 8 7 4-S 4-5
SAMPLE #10 6 5 5 5
CA 02292460 1999-12-16
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In each case Nylon 6 substrate was immersed in the stain resist bath
to obtain a pick up of 350% on weight of the substrate, then steamed for 3
minutes, followed by light rinse and dried to be ready for testing: The
results
appear in Table #2:
TABLE #2
Product ~~ ~ ~'IS WS ~ ID ~ KLD .
~ ~F< ~_ ~
.~ . .
~.n,.
~
SAMPLE # 11 7 6 3-4 3-4
SAMPLE #12 7 6 4-5 4-5
SAMPLE #13 7 6 3 3
SAMPLE #14 7 6 4 4
SAMPLE #15 6 4 5 5
SAMPLE # 16 7 6-7 5 5
SAMPLE #17 <3 <1 5 5
SAMPLE # 18 7-8 6-7 5 5
SAMPLE #19 8 6-7 4-5 4-5
SAMPLE #20 <5 <4 5 5
CA 02292460 1999-12-16
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CONCLUSION
The results in Table # 1 and Table #2 of stain resist on Nylon 66
and Nylon 6 show the following:
1. Best results of stainblockers with wash durability treated with acrylic
resin alone are obtained from Polymer A and Polymer B of this
mventlon.
2. The low molecular weight methacrylic acid polymer has acceptable
effect on the initial staining but it easily removed in alkaline wash.
3. The poly acrylic acid polymer alone has a very little effect or no
effect as stain blocker.
4. The bleached condensation product #C of this invention produces
best results as stain blocker initially and after alkaline wash alone or
in combination with Polymer A in all the examples of this
invention on Nylon 66 beside the improved light fastness.
S. Optimum results for initial staining, durability to alkaline wash,
and light fastness were obtained by the synergetic effect of the
Polymer A and the bleached Condensation Product #C or D.
In this Specification, unless indicated otherwise amounts in parts or
by % are by weight.
While the invention has been particularly described by reference to a
fibrous polyamide substrate, it applies equally to a wool substrate for the
application of the condensation products.
It will be recognized that various modifications and alterations of the
invention will be apparent to those skilled in the art without department from
CA 02292460 1999-12-16
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the scope and spirit of the invention and that the invention is not restricted
by the details and examples set forth for illustrative purposes.
