SILICONE SOFTENERS FOR STAIN REPELLENT

AND
STAIN RELEASE FABRIC FINISHING

Fernando Vazquez
Dow Corning Corporation
Greensboro, N.C.
ABSTRACT
During the last few years the use of fluorochemicals to
provide stain repellency and/or stain release properties to
apparel goods has rapidly grown. The use of
fluorochemicals as well as durable press resins, however,
has a detrimental effect on the fabric softness. Providing
premium softness is key to satisfy the highly demanding
aesthetic requirements of many of today’s apparel
products. Although softeners based on conventional
aminofunctional silicones are well known to provide
excellent hand, they significantly impair both the stain
repellency and the stain release properties of
fluorochemical treated fabrics. This paper presents the
results from a recent study where current and new selected
organo-modified silicones provide very good softness with
minimum–to–no impact on the fluorochemical properties.
INTRODUCTION
During the last few years the “easy care” concept has
rapidly expanded to include “stain resistant” features in
many apparel applications. The easy care concept now
encompasses both minimization of ironing and easiness to
clean garments that might have become stained in
everyday use. The use of finishes that provide stain
release and stain repellency to apparel fabrics, particularly
cotton, has shown an amazing growth during these last
years. 1, 2
Fabric manufacturers and chemical manufacturers have
made advances in finishing processes to ease stain
removal and prevent stain penetration. Today, stain
release finishing for apparel cotton fabrics is mostly
imparted by the incorporation of low surface energy
fluorochemicals. Stain release fluorochemical finishes
allow oil and water stains to penetrate the fabric; however,
when the fabric is laundered, the stains are easily
removed. 3 Fluorochemicals also dominate the stain
repellency textile apparel market. Out of all existing
textile chemicals, only fluorochemicals have shown the
unique property to provide fabrics a low surface energy
film with both high oil and water repellency properties to
resist penetration of oil and water-based stains (polar and
non polar liquids). The “repellent” products prevent the
textile substrate from wetting and soiling by repelling the
soiling substances and the adhesion of dry soil. 4
Fluorochemical hybrid finishes, also called “dual effect”,
which contain hydrophilic groups, have also been
developed and improved successfully over the most recent
years to impart both stain repellency and stain release
properties.
Most fabrics finished with durable press resins and
fluorochemicals have, however, an important drawback;
their handle is generally not acceptable and actually can
be considerably harsh. Although selected conventional
organic softeners can be used in these systems to
overcome this issue, the degree of softness they can
provide has fallen short for many apparel applications.
This is particularly true with today’s high performance
and durability requirements where normally higher levels
of finishing chemicals are used, which in turn, results in a
higher detrimental effect on the fabric handle. Even
higher levels of conventional organic softeners may not
give the softness level required or these levels may have a
negative effect on the stain repellency or release
properties, not evident when lower levels where used. In
addition to performance requirements, today’s highly
productive and complex finishing operations require the
use of “easy to use” and “trouble free” finishing products
that can offer stability over a broad range of process
conditions and compatibility with most textile chemicals. 5
Thus, the selection of the right softener in order to achieve
both premium hand and optimum processability becomes
extremely important.
SILICONE SOFTENERS FOR FLUORO-
CHEMICAL TEXTILE FINISHING
Silicones, particularly amino-modified silicones, are well
recognized as premium fabric finishing agents as they not
only provide unsurpassed softness but also improve many
fabric physical properties. 6, 7 However, conventional
aminofunctional silicones have shown to impair
significantly both the stain repellency and the soil release
properties of most fluorochemical treated fabric
substrates.
During the last several years, specialty organo-modified
silicones have been used in stain release and stain
repellency textile finishing, imparting various degrees of
softness without degrading significantly the properties
provided by fluorochemicals. These materials are
generally silicone copolymers or terpolymers and have
chemical structures where hydrophilic groups, such as
polyalkylene oxide polymers, are arranged in different
ways onto the main siloxane backbone. These organo-
modified silicone polymers may also contain additional
reactive organic groups, such as amines, amides and
epoxides, which normally contribute to the softness and/or
durability.
Most recently, modified versions of the above as well as
new silicone chemistries are being introduced which offer
improved softness coupled with the benefit of not
impacting the stain repellency and/or stain release
properties. More interestingly, some of these silicones
have even shown synergistic effects, which result in
improvements of the properties provided by the repellency performance was assessed by measuring
fluorochemicals. fabric’s oil and water repellency using AATCC methods
118-2000 and 22-2000 respectively. Softness was
In addition, some of these selected organo-modified evaluated through a hand panel where evaluators rated the
silicones are water dispersible or soluble which make fabrics by giving 5 points to the softest and 1 point to the
them extremely stable in most extreme textile finishing least soft. The average rating was recorded.
conditions and also compatible with most textile
chemicals.
Table 1. Finishing Bath Formulation
EXPERIMENTAL
The effect of several selected organo-modified silicones
Product % Weight
on stain release and stain repellency properties were Silicone Emulsion (20% actives) 7.7
evaluated. The silicone softeners included in the study Fluorochemical Emulsion a
5.0
were: 1) Conventional aminosilicone (microemulsion),
2) Reactive silicone copolymer (currently used in the Durable Press Reactantb 12.0
application), 3) Silicone terpolymer and 4) New silicone Durable Press Catalyst 3.0
copolymer. Water based emulsions and/or dispersions
were prepared containing 20% actives of each of the Wetting Agentb 0.1
silicones listed above. Water Balance Balance
a. Both the stain release fluorochemical and the stain repellent
fluorochemical have 30% total solids.
The finishing bath consisted of the silicone softener b. Buffered glyoxal reactant, 40% solids.
emulsion, a fluorochemical emulsion, a durable press c. A non-rewetting surfactant type was used for the stain repellent finish
reactant and its catalyst, and a non-rewetting wetting
agent. The bath formulation is shown in Table 1. The
systems were applied to khaki cotton twill (8 oz/sqyd) and RESULTS:
to bleached 65/35 polyester/cotton broadcloth. In
addition, a 100% interlock cotton knit was also included in STAIN RELEASE FINISHING
the stain repellency study.
Table 2 shows the stain release ratings of untreated and
treated fabrics after 1 HLTD cycle. As expected, the
The fabrics were treated by padding (65% Wet pick-up)
conventional aminosilicone had a significant impact on
and dried/cured at 170oC for 90 seconds. A fluorinated
the stain release properties of both the cotton twill and
urethane polymer was used for the stain release finishing
polycotton woven fabric.
whereas a fluoroacrylate copolymer was used for the stain
repellent finishing.
On Cotton Twill, the stain release ratings dropped 1.2 –
1.4 points when this fabric was treated with the
For the stain release testing, finishing formulations were
aminosilicone as compared to the fluorinated urethane
designed so that 1% silicone solids and 1% fluorochemical
treated fabric. In contrast, the cotton twill treated with the
solids were added on both fabrics. For the stain
selected organo-modified silicones showed minimum–to–
repellency testing also 0.5% silicone add on was used.
no impact on the stain release properties provided by the
The reasons behind using relatively high quantities of
fluorinated urethane polymer. The differences in stain
silicone on fabric were that, first, the real impact of these
release ratings between the selected organo-modified
silicones on the fluorochemical properties wanted to be
silicones and the fluorochemical only-treated fabrics go
determined and lower levels might have hidden their
from a decrease in 0.3 units (reactive copolymer/vegetable
potential impact, and second, the high amounts of
oil) to an improvement of 0.4 units (new copolymer/
finishing chemicals such as durable press resins and
motor oil). The new silicone copolymer actually shows
fluorochemicals being used in some applications may
the best average performance as compared to the
require higher levels of silicone softener in order to satisfy
fluorochemical only-treated cotton twill. As anticipated,
premium softness requirements.
all silicones improved the softness of the
resin/fluorochemical treated-only fabric. The new silicone
Stain release performance was assessed using AATCC
copolymer also provided very good softness, better than
method 130-2000. Fabrics were stained with three types
any of the other silicone polymers designed for the
of oily soils, dirty motor oil, mineral oil and vegetable oil
application and not far from that provided by the
(Wesson® corn oil) and rated after one home laundering
aminosilicone.
tumble-dry cycle (HLTD). On the other hand, stain
Table 2. Stain Release Ratingsa of Fabrics Treated with STAIN REPELLENT FINISHING
Organo-modified Silicones and Fluorinated Urethane Table 3 shows the stain repellency performance of the
Product Dirty Vegetable Mineral Softnessb treated fabrics, measured as a function of oil and water
Motor Oil Oil repellency. As expected, the conventional aminosilicone
Oil
had a significant impact on oil repellency of both the
Khaki Cotton Twill
fabrics. Overall, oil repellency rating differences for the
FC Only 2.2 4.5 3.8 1 aminosilicone went from 3.5 (for polycotton) to as high as
6.5 points (for the cotton fabrics) when compared to the
FC + fluorochemical only-treated fabrics.
1.0 3.3 2.0 5
Aminosilicone
FC + Reactive On cotton twill, the selected organo-modified silicones
Silicone 2.2 4.2 3.7 3.7 showed little-to–no impact on the oil repellent properties
Copolymer provided by the fluoroacrylate copolymer. The
FC + Silicone terpolymer gave the best performance as far as impact on
2.3 4.5 3.7 3
Terpolymer the oil repellency provided by the fluorochemical. The
FC + New new silicone copolymer provided the second best
Silicone 2.6 4.3 3.7 4.4 performance impacting the oil ratings only 0.5-1 points.
Copolymer
65/35 Polycotton Broadcloth As far as water repellency is concerned, the reactive
silicone copolymer gave the best performance on cotton
FC Only 2.3 5 4.3 1
twill and actually slightly improved the water repellency
FC + provided by the fluoroacrylate copolymer alone. When
1.0 3.6 3.5 5 compared to the fluorochemical treated-only fabric, both
Aminosilicone
the silicone terpolymer and the new silicone copolymer
FC + Reactive
Silicone 1.3 4.4 3.7 4.5 show some impact on the water repellency. In both cases,
Copolymer the water repellency performance drops as the silicone
FC + Silicone
1.9 4.8 3.8 4.5 added on increases. This is also true for the
Terpolymer aminofunctional silicone.
FC + New
Silicone 1.8 4.7 3.8 4.0 All the silicones improved the softness of the
Copolymer resin/fluorochemical treated-only fabric. The reactive
a. Ratings according to AATCC 130- 2000. silicone copolymer provided the best softness among the
b. Average rating from hand panel evaluation where 5 = Softest, 1 = Least organo-modified silicones and the second best overall
soft/harshest.
after the aminosilicone. On this fabric, the new silicone
copolymer provided the second best softness at 1%
On the 65/35 polycotton fabric, the impact of the selected
silicone add-on level and only 0.5 points away from the
organo-modified silicones on the stain release properties
aminosilicone. Overall, the reactive silicone copolymer
was higher than that seen on the cotton twill but still
provided the best balance of properties on cotton twill.
shows a very important improvement as compared to that
obtained when the fabric is treated with the aminosilicone.
On 65/35 polycotton, the results for all the three organo-
The selected organo-modified silicones impacted the stain
modified silicones were very good. The impact on either
release ratings 0.1-1 points. Both the terpolymer and the
oil repellency or water repellency was practically non-
new silicone copolymer also showed the best performance
existent. The silicone terpolymer seemed to perform
with stain release ratings only about 0.4 points (on
slightly better than the others in terms of the oil repellency
average) higher, respectively, than those obtained with the
impact on this fabric. It is interesting to notice that for the
fluorochemical only-treated fabric. As expected, softness
polycotton and cotton knit fabrics, the higher the amount
was again improved with the addition of all the silicones.
of the new silicone copolymer, the better the oil repellency
Although the best softness was obtained with the
rating.
aminosilicone, both the reactive silicone copolymer and
The softness provided by the three organo-modified
the terpolymer were very close. The new silicone
silicones was similar for the 0.5% silicone add-on levels,
copolymer provided a good hand improvement as well,
yet inferior as compared to that provided by the
however, this was perceived relatively inferior to that
aminosilicone. Overall, the reactive copolymer was the
provided by the other two silicones designed for the
closest to the aminosilicone. For the 1% add on levels, the
application.
softness gap between the amino silicone and the other On cotton knit, both the silicone terpolymer and the new
organo-modified silicones broadened showing rating copolymer had perfect performance showing no impact on
differences of as much as 2.5 points. In this particular either oil repellency or water repellency as compared to
case, the new copolymer did not provide as good softness the fluorochemical treated-only fabric. Interestingly, it
as that obtained on the cotton twill. can be seen that higher silicone add on levels on fabric
actually improve both the oil repellency and the water
Table 3. Stain Repellency Performance using repellency ratings. The new silicone copolymer provides
Organo-modified Silicones in a Fluoroacrylate Copolymer System
Oil Repellencya Water Repellencyb Softnessc the best balance of properties as it also provides a good
improvement on the fabric softness. The reactive silicone
Product 0.5 % 1% 0.5 % 1 % 0.5 % 1 %
Silicone Silicone Silicone Silicone Silicone Silicone
shows a slight impact on both water and oil repellency at
Khaki Cotton Twill 1% silicone add on levels but shows to provide the best
softness overall. Although the aminosilicone provides a
FC Only 7.0 7.0 97 97 1.3 1.3
very good hand on this type of fabric as well, it shows the
FC +
highest negative impact on both oil and water repellency.
1.0 1.5 75 50 4.6 4.4
Aminosilicone
FC +
Reactive
Silicone
6.0 6.0 100 100 4.4 3.5 CONCLUSION
Copolymer Several organo-modified silicones are available for use as
FC + Silicone premium softeners in stain repellent and stain release
7.0 6.5 90 83 2.3 3.3
Terpolymer fabric finishing. These softeners provide very good
FC + New softness with little–to–no impact on the properties
Silicone 6.5 6.5 83 82 3.3 3.9 provided by fluorochemicals. No single silicone system
Copolymer
65/35 Polycotton Broadcloth seems to provide a complete or ideal solution for all fabric
substrates or fluorochemical system. This last fact and as
7 7 100 100 1 1.2
FC Only well as the awareness that fabric hand preferences vary
with several factors such as fiber type, fabric construction
FC +
Aminosilicone
1.5 3.5 85 80 5 5 and even geographical region, suggest that a
FC +
comprehensive evaluation of the selected organo-modified
Reactive
6.5 7 100 100 4.2 3.4
silicones is needed in order to identify the optimum
Silicone solution for any given fluorochemical system and/or fabric
Copolymer
substrate.
FC + Silicone
7 7 100 100 4.3 3.1
Terpolymer

FC + New
Silicone 6.5 7 100 100 3.8 2.5
Copolymer
Cotton Interlock Knit

FC Only 6.5 6.5 90 90 1.7 1

FC +
0 0 0 0 4.1 4.8
Aminosilicone
FC +
Reactive
6.5 6.0 90 80 5 4.8
Silicone
Copolymer
FC + Silicone
6.5 7 90 100 3.2 3.3
Terpolymer

FC + New
Silicone 6.5 7 90 100 4.4 3.0
Copolymer

a. Oil repellency ratings according to AATCC 118-2000 Method.

b. Spray Ratings according to AATCC 22 –2000 for twill and polycotton.
Ratings for knit were using the water/IPA drop absorbency test.
c. Average rating from hand panel evaluation where 5 = Softest, 1 = Least
soft/harshest.
REFERENCES

1. Cote, G., “New Fluorochemical Technologies for

Protective Textile Finishes”, Book of papers,
2002, AATCC International Conference.
2. Bender, D. “Innovations in Fabric Protection”,
2004, Textile Technology International, p.66.
3. Franchina, G., “The Chemistry and Properties
Behind Designed Fluoroprotectants for Textiles”,
Book of Papers, 2001, AATCC International
Conference.
4. Nabi, W. “New Effects in Textile Finishing with
Innovative Technologies and Application of
Fluorochemicals”.
5. Vazquez, F., “Trouble Free Performance in
Finishing Conditions”, 2004, Textile Technology
International, p.58.
6. Vazquez, F., “Silicones: Beyond Softening in
Garment Finishing”, Book of Papers, 1999,
AATCC Garment Finishing Symposium.
7. Cray, S., Budden, G. Edwards, J. “Agregando
Flexibilidad al Suavizado del Tejido”, 1997,
Textiles Panamericanos.

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