Note: Descriptions are shown in the official language in which they were submitted.
CA 02817018 2013-05-03
SPRAY-ON ANTI-SOIL FORMULATIONS FOR FIBERS, CARPETS AND FABRICS
FIELD OF THE INVENTION
The invention relates to spray-on anti-soil formulations, for all fibers and
specifically, to spray-on anti-soil formulations for polyester and olefin
fibers, carpets,
and fabrics. The anti-soil formulations comprise a synergistic blend of an
anti-soil
component and a stain blocker component. Soil repellant fibers, carpets, and
fabrics,
with improved anti-soil properties, are also disclosed. Also disclosed herein
are
processes for making soil repellant fibers, carpets, and fabrics.
BACKGROUND OF THE TECHNOLOGY
Carpets are currently treated with topical chemistries for improved stain
resistance and/or soil resistance. For nylon carpets, both stain blocker (e.g.
acid dye
blocker) and anti-soil with fluorochemicals are traditionally used. For
polyester carpets,
such as 2GT and 3GT carpets, and polypropylene carpets, either no topical
chemistry is
applied or only anti-soil is topically applied. Polyester and polypropylene
carpets
typically do not require a stain blocker topical treatment because of inherent
stain
resistance and lack of amine end groups that function as dye sites.
Topical application can be in the form of exhaust application (i.e. flex-nip
process
at high (300 ¨ 400 wt.%) wet pick-up), which is known to be an improvement
over
spray-on applications at 10-20 wt.% wet pick-up of anti-soil. Exhaust
applications
typically use higher amounts of water and energy to dry and cure the carpet.
Spray-on
fiuorochemical products are designed to use less water and energy than exhaust
applications, but do not impart satisfactory anti-soil properties.
CA 02817018 2013-05-03
While various processes are in use in the carpet industry for the dyeing and
finishing of carpets, some large scale and some small, most of the broad loom
carpet
made today is dyed and finished on a continuous dye range. This is done mainly
in one
of two ways: In one case a two stage process is employed, where the carpet is
steamed
and dyed first, steamed, rinsed, and excess water extracted, then stain
blocker (SB) is
applied, the carpet is again steamed and washed, and then fluorochemical (FC)
is
applied in the form of a foam or liquid spray and the carpet Is finally dried.
(See e.g.
U.S. Patent Nos. 5,853,814; 5,948,480 and W02000/000691). In the second,
somewhat improved case, called the co-application process, the carpet is also
steamed
and dyed first, steamed again, rinsed and extracted; and then a blend of SB
and FC is
applied together at high wet pick up, after which the carpet and chemicals are
exposed
once again to steam to fix the treatment, followed by drying. (See e.g. U.S.
Patent Nos.
6,197,378 and 5,520,962).
SUMMARY OF THE INVENTION
There is a desire to reduce the overall usage of topical anti-soil
formulations,
especially formulations that contain fluorochemicals, for environmental and
cost
reasons. Thus, anti-soil compositions that can be applied by spray-on
applicators are in
demand because spray-on processes use less water and energy to dry than
exhaust
applications. However, current spray-on compositions do not impart
satisfactory anti-
soil properties at the necessary low wet pick-up during application.
Therefore, it is desirable to develop anti-soil compositions that can be
applied via
spray-on processes at low wet pick-up. Such compositions would be ideal for
carpets
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CA 02817018 2013-05-03
made from dyed fiber that has no need for further exposure to exhaust
processes. Also,
rug mills that do not have facilities to apply anti-soil compositions via
exhaust processes
would benefit from such a spray-on composition.
The invention disclosed herein provides a spray-on anti-soil composition
comprising an anti-soil component and a stain blocker component. The spray-on
anti-
soil composition can be used with a variety of fibers, carpets, and fabrics,
such as those
manufactured with olefin and polyester polymer components. Such composition is
counter-intuitive, since certain olefin and polyester fibers, carpets, and
fabrics do not
require stain blockers because they are inherently stain resistant. Thus,
there is a
surprising synergistic effect with a composition comprising both an anti-soil
component
and a stain blacker component. The anti-soil component can be either
fluorochemical
or non-fluorochemical based. Polyester and olefin carpets treated with the
disclosed
compositions show superior anti-soil properties over the same carpets treated
with
known fluorochemical anti-soil compositions. Also disclosed are processes for
making
soil repellant fibers, carpets, and fabrics.
In one aspect, an anti-soil composition comprising an anti-soil component and
a
stain blocker component is disclosed. The anti-soil composition is adapted to
be
sprayed-on a fiber at a wet pick-up of between about 8% and about 40%. The
anti-soil
composition can be comprised of a high specific surface energy chemical or
other
material, for example a fluorochemical that imparts high specific surface
energy
properties such as high contact angles for water and oil, or even a non-
fluorochemical
particulate material having similar properties. Stain blockers can comprise
any acidic
fiber coating chemical, such as a stain blocker chemical designed to impart
acid dye
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CA 02817018 2013-05-03
stain resistance by association with positively charged dye sites such as
amine end
groups.
In another aspect, a fiber comprising a sprayed-on surface treatment
comprising
an effective amount of a stain blocker is disclosed. The stain blocker is
present at an on
weight of fiber from about 500 ppm to about 4%. The fiber can have a
polypropylene or
polyester polymer component. The fiber can be manufactured into carpet or
fabrics.
The surface treatment can further comprise an anti-soil component.
In a further aspect, a carpet treated with the disclosed anti-soil composition
having a Delta E soil resistance rating of less than about 10 at 15,000 walk
cycles is
disclosed, The carpet has an initial L value in the range from about 58 to
about 62.
In yet another aspect, a carpet treated with the disclosed anti-soil
composition
having a Delta E soil resistance rating of less than about 4 after 15,000 walk
cycles and
after one hot water extraction is disclosed. The carpet has an initial L value
in the range
from about 58 to about 62.
In yet a further aspect, a method of treating a fiber is disclosed,
comprising: (a)
contacting said fiber with, an anti-soil composition comprising an anti-soil
component
and a stain blocker component at a wet pick-up between about 10'-- 20 wt.%;
and (b)
drying said fiber. The contacting can be done by spraying. The stain blocker
is present
after drying at an on weight of fiber from about 500 ppm to about 4%. The
fiber can
have a polyester or polypropylene polymer component.
DEFINITIONS
While mostly familiar to those versed In the art, the following definitions
are
provided in the interest of clarity.
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CA 02817018 2013-05-03
OWF (On weight of fiber: The amount of chemistry that was applied as a % of
weight of fiber.
. = WPU
(Wet pick-up): The amount of water and solvent that was applied on carpet
before drying off the carpet, expressed as a % of weight of fiber.
DETAILED DESCRIPTION OF THE INVENTION
An anti-soil composition is disclosed comprising an anti-soil component and a
stain blocker component. The composition is adapted to be sprayed on a fiber,
carpet,
or fabric at a wet pick-up of between about 8 wt.% and about 40 wt.%. Anti-
soil
compositions for use in the disclosed anti-soil compositions impart high
specific surface
energy properties such as high contact angles for water and oil (e.g. water
and oil
"beads up" on surfaces treated by it). The anti-soil component can comprise a
fluorochemical dispersion, which dispersion may be predominantly either
cationic or
anionic, including those selected from the group consisting of fluorochemical
allophanates, fluorochemical polyacrylates, fluorochemical urethanes,
fluorochemical
carbodiimides, and fluorochemical quanidines. Alternatively, the
fluorochemical can
have less than or equal to eight fluorinated carbons, including less than or
equal to six
fluorinated carbons. Example fluorochemical anti-soil components include;
DuPont
TLF 10816 and 10894; Daikin TG 2511, and DuPont Capstone RCP. Non-fluorinated
anti-soil components can include: silicones, silsesquioxanes and
fluorosilanated and
fluoroalkylated particulates, anionic non-fluorinated surfactants and anionic
hydrotrope
non-fluorinated surfactants, including sulfonates, sulfates, phosphates and
carboxylates.
(See U.S. Patent No. 6,824,854, herein incorporated by reference).
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CA 02817018 2013-05-03
Stain blocker compositions for use in the disclosed anti-soil compositions
comprise an acidic moiety which associates with polymer amine end groups and
protects them from staining by acidic dye stains. The general category of
chemicals
suitable to the process of the instant invention can comprise any chemical
that blocks
positively charged dye sites. Stain blockers are available in various forms
such as
syntans, sulfonated novolacs, or sulfonated aromatic aldehyde condensation
products
(SACs). They are usually made by reacting formaldehyde, phenol,
polymethacrylic acid,
maleic anyhydride, and sulfonic acid depending on specific chemistry. Further,
the stain
blocker is typically water soluble and generally penetrates the fiber while
the anti-soil,
usually a fluorochemical, is a non-water soluble dispersion that coats the
surface of
fiber.
Examples of stain blockers include, but are not limited to: phenol
formaldehyde
polymers or copolymers such as CEASESTAIN and STAINAWAY (from American
Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock
Hill,
N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from
Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech,
Inc.,
Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and
SR-
300, SR-400, and SR-500 (from E. I. du Pont de Nemours and Company,
Wilmington,
Del.); polymers of methacrylic acid such as the SCOTCHGARD FX series carpet
'Protectors (from 3M Company, St. Paul Minn.); sulfonated fatty acids from
Rockland
React-Rite, Inc., Rockmart, Ga); and stain resist chemistries from ArrowStar
LLC,
Dalton and Tri-Tex, Canada.
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CA 02817018 2013-05-03
The anti-soil composition is adapted to be sprayed-on fibers, carpets, and
fabrics, such that the stain blocker on weight of fiber is from about 500 ppm
to about
4%, including from about 1000 ppm to about 3%, from about 0.5% to about 2%,
and
from about 0.5% to about 1%; and the fluorine based anti-soll component on
weight of
fiber is from about 50 ppm to about 800 ppm fluorine, including from about 100
to about
500 ppm fluorine, and from about 100 ppm to about 300 ppm. The wet pick-up of
composition is between about to 8 ¨ 40 wt.%, including from about 10 ¨ 20
wt.%, from
about 10¨ 15 wt.%, and from about 10¨ 12 wt%.
Common stain blockers use sulfonated moieties as part of the chemistry, which
results in the presence of sulfur on the treated fiber. The sulfur content can
range from
about 50 ppm with 5% stain blocker to about 1 ppm with 0,1% stain blocker on
weight of
fiber. Thus, based on the above stain blocker concentrations, the sulfur
content on
weight of fiber will range from about 0.5 ppm to about 40 ppm, including from
about 1
ppm to about 30 ppm, from about 5 ppm to about 20 ppm, and from about 5 ppm to
about 10 ppm. Sulfur content can be determined by x-ray diffraction or other
methods.
Carpets treated with the various aspects of the disclosed anti-soil
composition
exhibit Delta E soil resistance ratings of less than about 10, including less
than about 9,
and less than about 8, at 15,000 walk cycles, It should be noted that the
Delta E will be
a function of initial color of the carpet. The above results are with respect
to a carpet
color in the range from about 58 to about 68 L value. Further, carpets treated
with the
various aspects of the disclosed anti-soil composition exhibit improved Delta
E soil
resistance after hot water extraction compared to fluorochemical only treated
carpets.
When the carpet is darker, or L value Is less than this range specified, the
soiling delta
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= CA 02817018 2013-05-03
E will also be less (Le. it will be harder to see the color change in a carpet
that is
darker). The stain blocker from the anti-soil composition is present on the
carpet at an
on weight of fiber from about 600 ppm to about 4%, including from about 1000
ppm to
about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1%.
Also disclosed is a fiber comprising a sprayed on surface treatment comprising
an effective amount of a stain blacker. The stain blocker can be any of the
components
described above. The stain blocker is present on the fiber at an on weight of
fiber from
about 500 ppm to about 4%, including from about 1000 ppm to about 3%, from
about
0.5% to about 2%, and from about 0.5% to about 1%. The surface treatment can
further comprise any of the anti-soil components described above, Prior to
drying the
fiber, the surface treatment is present at a wet pick-up between about 10 to
about 20
wt.%, including between about 10 to about 15 wt,%, and between about 10 and
about
12 wt.%. The fiber, by itself or blended with non-treated fibers, can be
manufactured
Into carpets or fabrics. The fiber can have a polyester (e.g. PET or PPT) or
olefin (e.g.
polypropylene) polymer component. An effective amount of sprayed-on surface
treatment results in around the same as or better anti-soil characteristics as
the same
fiber treated with an exhaust process.
Further disclosed is a method of treating a fiber. The method comprises: (a)
contacting said fiber with an anti-soil composition comprising an anti-soil
component
and a stain blocker component at a wet pick-up between about 10 ¨ 20 wt.%; and
(b)
drying said fiber. The anti-soil component and stain blocker component can be
any of
the chemicals disclosed above. The contacting can be done through a spray-on
application at a low wet pick-up, The drying can be done using any type of
oven,
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CA 02817018 2013-05-03
convention dryer, or forced hot air application. Drying temperatures can range
from
about 230 F to about 280 F, including from about 245 F to about 260 F. Drying
temperatures can range from about 1 to about 4 minutes, including from about 1
to
about 3 minutes. Wet pick-ups can also range from about 10 to about 15 wt.%,
including from about 10 to about 12 wt.%, After drying, the stain blocker is
present at
an on weight of fiber from about 500 ppm to about 4%, including from about
1000 ppm
to about 3%, from about 0.5% to about 2%, and from about 0.5% to about 1%. If
a
fluorine based anti-soil component is used, the fluorine based anti-soil
component on
weight of fiber is from about 50 ppm to about 800 ppm fluorine, including from
about
100 to about 500 ppm fluorine, and from about 100 ppm to about 300 ppm. The
fiber
'can have a polyester or polypropylene polymer component.
The fiber, by itself or blended with non-treated fibers, can be manufactured
into
carpets or fabrics. Further, the disclosed method can be used to treat carpets
or
fabrics, rather than the fibers. In addition, the disclosed method can be used
for
pigmented fibers (also known as solution dyed) as well as dyed fibers. This
will include
carpets made from polyester. Polypropylene is usually solution dyed, The anti-
soil
composition= may or may not include a fluorochemical. Fluorochemical
compositions
can be cationic or anionic in their formulations, and the disclosed anti-soil
compositions
can use both.
The combination of anti-soil and stain blocker yields a surprisingly
synergistic
anti-soil composition that is more effective at improving soiling resistance
of carpet. This
is surprising because stain block, by itself, does not impart any anti-soil
characteristics
to fibers. Further, stain block typically is not usually required with
polyester (e.g. PET
9
= CA 02817018 2013-05-03
and PPT) and olefin (e.g. polypropylene) fibers because these polymers lack
amine end
groups that function as acid dye sites and are inherently stain resistant. The
combination of anti-soil and stain block components on olefins and polyesters
is
synergistic, as surprisingly low levels of application can be effective. Those
well versed
in the art can select chemistries which are not specifically used as stain
blockers but
have other closely related properties (such as sulfonated low molecular weight
polymers, polymeric binders, soft coatings etc), for blending with anti-soil
formulations to
obtain the disclosed improvements. These modifications are still considered as
part of
the invention. Further, because of the synergistic effect, the anti-soil
composition can
be applied to the fiber, carpet, or fabric via spray-on application instead of
exhaust
application, while still maintaining superior anti-stain properties.
EXAMPLES
The following are examples of polyester and polypropylene rugs treated with
the
anti-soil compositions disclosed above compared to a standard anti-soil
fluorochemical
treated rug and as well as rug with no treatment. Selection of alternative
anti-soil
components and stain blocker components, fibers and textiles having different
surface
chemistries will necessitate minor adjustments to the variables herein
described.
Test Methods
Walk Test: A description of the walk test is as follows:
1. Walk way selection: Select a walk way with a highest traffic volume
possible. The
samples should be located 20 to 30 feet from an outside entrance. Always use
walk off areas (example: carpet tiles) on both ends of the test extending at
least
CA 02817018 2013-05-03
for 6 to 8 feet. Determine the number of traffics by electric eye counters or
pad
counters. This method will not work well if groups of large number of people
come in at the same time.
2. Sample preparation and installation
Determine size of the hallway for the walk test. The length of hall way will
determine the number of samples and sample size. One can use 12" min width
(the
smallest size) to 24" width.
Method for soilino test
One set of sample carpets or multiple set of samples can be installed. Measure
the initial L, a, b (using a Minolta spectraphotometer) of samples. As the
soiling
proceeds,. take readings of L, a, b, and calculate Delta E. This delta E
represents the
color change of the sample when compared to the sample of the same carpet
prior to
soiling. When the Delta E reaches a high value, it will be time to hot water
extract
(HWE) and measure delta E after cleaning. This process can be repeated to
obtain data
over multiple cleanings and traffic cycles.
Example
In this test, a PET rug of 37 Oz weight, with a beige color having a L value
of
around 65 was sprayed on with various fluorochemical chemistries to a fluorine
level of
about 300 ppm on rug. The fluorochemical chemistries were from DuPont and
Daikin.
Table 1 shows anti-soil chemistry make up. Pieces of these carpets were
installed for a
walk test and Delta Es were measured using a Minolta Spectra photometer at
various
intervals of traffic. Measurements of L, a, b, for 5000, 10,000, 15,000, and
17,500
11
CA 02817018 2013-05-03
=
cycles of traffic were made and Delta E's were calculated. At 17,500 cycles of
traffic,
the carpets were hot water extracted with detergent. The L, a, b values were
again
recorded after cleaning and Delta Es were calculated. Table 1 data shows that
soiling
was very high (over 16 Delta E) and even after cleaning, with high Delta Es
over 9.
Therefore spray application of such chemistries do not result in improved
soiling
performance.
Table
.;;Sample,.1Spray on
Conc. of Initial DeltaE Delta E Delta E Delta E DeltaE
= Chemistry chemistry L at 5000
at at at after
= and =inünti- value cycles: 10000
150G0 17500 17500..
Application soil cycles cycles cycles and
after
cleaning
Daikin TG 25.37 65.4 15.8 10.5 16.7 17.5
9.81
2511 (8%) grams / L
2 DuPont TLF 80.9 65.9 16.9 18.8 19.1 18.9 9
10816 grams / L
(2.5%)
3 DuPont TLF 80.9 66.1 15.1 15.5 15.7 16.3
9.1
10894 grams / L
(2.5%)
Example 2
In this test, a PET rug of 30 Oz weight, with a beige color having L value of
around 58 was sprayed on with various fluorochemical chemistries to a fluorine
level of
about 300 ppm on carpet. The fluorochemical chemistries were from DuPont and
Daikin
and included a stain blocker S-801, made by INVISTA. Table 2 shows anti-soil
chemistry make up. Pieces of these carpets were installed for a walk test and
Delta E's
were measured using a Minolta Spectra photometer at various Intervals of
traffic,
Measurements of L, a, b, for 5000, 10,000, 15,000 cycles of traffic were made
and
Delta E's were calculated. At 15,000 cycles of traffic, the carpets were hot
water
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CA 02817018 2013-05-03
extracted with detergent. The L, a, b values were again recorded after
cleaning and
Delta E's were calculated. Table 2 data shows that soiling was much improved
(lower
Delta E) at 15,000 cycles (lower Delta E) for Samples 6 and 7, which were
based on the
disclosed anti-soil compositions when compared to Sample 4, which was
untreated
carpet sample and Sample 5, which was treated with a conventional application
process. Sample 7 in Table 2 uses the same fluorochemical as used in Sample 3
in
Table1, but performs much better in soiling due to using the blend as per this
invention.
Further, when the samples were cleaned after 15,000 cycles, Samples 6 and 7
showed
a Delta E improvement of 64% to 70%, while Samples 4 and 5 showed a Delta E
improvement of only about 50%. After cleaning, Delta E results of Samples 6-7
are low
enough that they are acceptable commercially. Carpets treated with the
disclosed anti-
soil compositions respond better to carpet cleaning than traditionally treated
carpets and
have superior soiling results throughout walk test including after cleaning.
Table 2
Sample Spray:on: . Conc. of. initial' ,=Delta'E at DoltaE.: Delta E
Delta E
ChemIstry chemistry L 5000 at 10000at 15000 after
and In anti-soil value cycles cycles
cycles 15000
= ' IA*116atioti.and after
-
cleanln
Untreated N/A 58.4 11.2 13.5 13.1 6.44
5 DuPont TLF 80.9 grams / 62.6 10.7 11.6 11.3
5.74
10816 (2.5%) L
Daikin 20.4 grams / 61.2 6.8 8,8 9.5 3.35
102511 (8%) L of TO
+ 5-801 2511 and
135 grams /
L of S-801
7 DuPont TLF 80.9 grams / 61.9 6.3 7.1 8.2 2.33
10894 (2.5%) L of TLF
and S-801 10894 and
135 grams!
L of S-801
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CA 02817018 2013-05-03
Example 3
Tests were conducted with polypropylene carpets having flowery carpet design.
Table 3 lists various polypropylene carpet items and how they were treated.
Chemistries
used were Daikin TG 2511, DuPont TLF 10816, TLF 10894 and Capstone RCP. All
samples were 35 ounce rug carpets and application levels of fluorochemical
were about
300 ppm Fluorine.
Table 3
Concentration
r,-:.?.,:CenoentratiOrt
8 Untreated N/A
9 Dakin TG 2511 (8%) 20.4 grams / L
Dakin TO 2511(8%) + 3-801 20.4 grams / L of TG 2511 + 135 grams / L of S-
801
11 DuPont TLF 10816 (2.5%) 80.9 grams / L
12 DuPont TLF 10894(2.5%) 80.9 grams IL
13 DuPont Capstone RCP (5%) 40.6 grams / L of RCP and 135 grams / L
of S-
and S-801 801
Because of the flowery design, the Walk Cycle test measurements of Delta E
10 were not possible. However, visual inspection showed that Sample 13
followed by
Sample 10, demonstrated superior soil resistance than the remaining samples.
This
improvement was also visible after cleaning. These samples with superior
soiling
performance were prepared by various aspects of the disclosed process.
It should be noted that Daikin TG 2511 was a cationic formulation and DuPont
chemistries were anionic formulations. This shows that the process of this
invention
works well for different types of formulations of fluoro chemical chemistries,
The invention has been described above with reference to the various aspects
of
the disclosed anti-soil composition, treated fibers, carpets, fabrics, and
methods of
making the same, Obvious modifications and alterations will occur to others
upon
14
=
CA 02817018 2013-05-03
reading and understanding the proceeding detailed description. it is intended
that the
invention be construed as including all such modifications and alterations
insofar as
they come within the scope of the claims.
=
