Note: Descriptions are shown in the official language in which they were submitted.
133~7~
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IMPROVED ~IET~ODS AND COMPOSITIONS TO ENHANCE
STAIN RESISTANCE OF CARPET FIBERS
BACKGROUND OF THE INVENTION
This invention is related to improved methods
and compositions to enhance stain resistance of carpet
fibers. Sulfonated aromatic condensates alone in a new
process or in combination with other compounds are used to
improve stain resistance. Related technology is disclosed
in Canadian application, Serial No. 580,948, on sulfonated
benzotriazoles.
The following terms are defined for use in this
specification.
By sulfonated aromatic condensate (s.a.c.) is
meant any condensate of an aromatic compound whether
sulfonated prior to or after condensation, particularly
sulfonated aromatic formaldehyde condensate (s.a.f.c.),
effective to enhance stain resistance of fiber or carpet
fabri~.
By thiocyanate is meant any salt, organic or
inorganic, containing a cation and the thiocyanate anion.
By fluorocarbon is meant those fluorocarbon
compounds effective to improve the antisoiling properties
of fiber or carpet fabric.
By ICP is meant index of crystalline perfection,
a measured indication of the internal crystal structure of
the polymer in an oriented fiber. High ICP indicates an
open crystalline internal structure, easily dyeable
polymer fiber.
By nylon is meant the polyamide family of
polymers, nylon 6, nylon G,6, nylon 4, nylon 12 and the
other polymers containing the ~C-l3 structure along with
O H
the ~CH2~X chain.
By carpet fabric is meant carpet fiber or yarn
which has been typically tufted, woven, or otherwise
.
l~3a-~76
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constructed into fabric suitable for final use in home
furnishings, particularly as floor covering.
By fiber is meant continuous filament of a
running or extremely long length or cut or otherwise short
fiber known as staple. Carpet yarn may be made of
multiple continuous filaments or spun staple fiber, both
typically pretextured for increased bulk.
By salt having a divalent cation is meant any
such salt effective to enhance stain resistance of fiber,
particularly high ICP nylon fiber, when combined with an
efrective amount of a s.a.c.
By dispersing agent is meant any chemical
compound or combination of chemical compounds effective to
make stable, relatively nonprecipitating, noncoagulating
mixtures of other chemical compounds.
By sequestering agent is meant any chelating
agent which is effective in sequestration, which is the
suppression of certain properties of a metal without
removing it frorn the system or phase. To be practical,
the sequestering agent must not cause any undesirable
change that would render the system unsuitable for its
intended purpose. Chelation produces sequestration mainly
by reducing the coneentration of free metal ion to a very
low value by converting most of the metal to a soluble
ehelate that does not possess the properties to be
suppressed.
`:~
A chelating agent is a compound eontaining donor
atoms that ean combine by eoordinate bonding with a single
, metal atom to form a eyelie strueture ealled a chelation
complex or, simply, a ehelate. Beeause the donor atoms
are connected intramolecularly by ehains of other atoms, a
~; ~ ehelate ring is formed for eaeh donor atom after the first
whieh eoordinates with the metal. The above is from
Volume 5, beginning page 339, of the Kirk-Othmer Encyelo-
pedia of Chemieal Teehnology (John Wiley & Sons), 1979.
It is known to use sulfonated aromatic formalde-
~;~ hyde condensates ("s.a.f.c."s) in the yarn finish (during~: :
1330476
or after fiber quenching) to improve stain resistance of
carpet fiber, see U.S. 4,680,212, in the dye bath for the
same purpose, see U.S. 4,501,591 or incorporated into the
fiber for the same purpose, see U.S. 4,579,762.
Use of fluorochemical to improve both stain ahd
soil resistance in combination with s.a.f.c.'s is also
taught in U.S. 4,680,212, column 5. Other useful fluoro-
chemicals for antisoiling are taught in commonly assigned
U.S. 4,192,754, 4,209,610: 4,414,277; 4,604,316, 4,605 t 5a7.
It is known to use thiocyanates, such as ammo-
nium thiocyanate, at different process conditions as
"assists" during dyeing for various purposes. See U.S.
3,652,199; 3,576,588; 3,387,913; 2,899,262; and 2,615,718,
Use of salts containing a divalent cation, such
as magnesium sulfate, with s.a.f.c.'s to improve wet fast-
ness is known in U.S. 3,790,344, Also see page 48 of a
textbook by Rosen, M. J., Surfactants & Interficial
Phenomena (Wiley, 1978). `~
It is also known generally to use acid,
including citric acid to buffer a dye bath and to use
dispersing agents and/or sequestering agents to stabilize
a aqueous formulations of chemicals.
Nylon carpets may be permanently discolored or
stained by certain artificial colorants, such as food
dyes, or oxidizing agents, such as acne preparations
` containing benzoyl peroxide. S.A.C.'s, applied to the
fiber to provide an ionic barrier to food colorants, make
the fiber more stain resistant, but are not effective
~, ~
against oxidizing agents. Furthermore, many of the
s.a.c.'s used commercially for the preparation qf "stain
resistant" carpets are themselves, susceptible to
oxidation upon exposure to light and ozone. This results
~ in a yellowing of the s.a.c. and subsequent destruction.
;~ This has a major impact on the carpet properties. The
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1~30~76
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yellow color of the s.a.c. results in a perceptible shift
in the color of the carpet. Destruction of the s.a.c.
results in a loss of the stain resistance properties of
the carpet.
Use of fluorocarbon compound treated nylon fiber
in carpet fabric inhibits wetting of the fiber surfaces
which also inhibits any staining agent from being adsorbed
onto or absorbed into the fiber. This surface wetting
inhibition can be insufficient when the staining agent is
dropped on the carpet with enough force to break the
surface energy of the fluorocarbon surface barrier or not
cleaned from the carpet and left in contact with fibers
for extended time. Carpet treated with compositions
containing s.a.c.'s must not interfere with the
antisoiling properties of the fluorocarbon.
Application of s.a.c. to the carpet fabric must
be effective, economical, and compatible to both untreated
and fluorocarbon treated fiber, and to both continuous
dyeing and Beck or batch dyeing. The same is true of any - ;
2Q s.a.c. application formulation. The s.a.c. formulation
must achieve effective penetration into the carpet fabric.
Exhaustion of the individual active chemical components of
any s.a.c. formulation must also be effective if not
complete.
Certain nylon polymer fibers have very open
internal crystal structure, namely high ICP polymer fiber,
which require large amounts of s.a.c. to impart an
effective degree of stain resistance. High ICP polymers
are usually the result of high temperature saturated steam
heat setting processes.
Some prior compositions and methods are only
marginally acceptable regarding durability of the stain
resistance when the carpet is steam cleaned with a
;~ detergent at a high pH.
SUMMARY OF THE INVENTION
This invention is several interrelated
embodiments wherein the several new s.a.c. application
formulations are used in the several new application
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133~7~
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processes. First described is a continuous aftertreatment
for dyed nylon carpet fabric, using several combinations
of chemical compositions to apply a s.a.c.. Then the two-
step process of treating carpet fabric with a s.a.c.,
still using the continuous aftertreatment as the second
step is described. This includes batch (or
beck)-continuous and continuous-continuous two-step
treatment. The combination of s.a.c. and the
thiocyanates, and with various added chemicals, to improve
resistance of dye and s.a.c. on the fiber to oxidation is
next described. Then the method to improve stain
resistance of nylon fiber, particularly high ICP fiber,
using s.a.c., thiocyanate and a salt having a divalent
cation and with additional added chemicals is described.
The method to improve light induced yellowing of s.a.c.
treated fiber by buffering with citric acid or any acid
with a sequestering agent is an embodiment described
throughout and specifically at this point. Then the new
two-step batch-batch process is described used with
various formulations. Finally described is an improved
method to exhaust thiocyanate at low pH.
The first embodiment of this invention is a
method to continuously treat dyed nylon carpet fabric to
impart improved resistance to staining comprising
preheating the dyed carpet fabric with water at a
. temperature of between about 140 and 212F (60 and 100C)
to a wet pick-up of above about 75% by weight, and a
carpet temperature of between about 130 and 210F (54.4
and 99C), then extracting the water from the carpet
30 fabric to a wet pick-up of between about 30 to 190% by
weight, then applying an aqueous solution of an effective
amount of a sulfonated aromatic condensate to the carpet
fabric at a pH of between about 1.5 to 5.5, at a
concentration of between about 0.25 and 40 grams of solids
of said condensate per liter of aqueous solution, at a wet
pick-up between 200 and 650% by weight, an aqueous
solution liquor of between about 140 and 212F (60 and
~; 100C) to achieve a carpet fabric temperature between
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133~76
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about 130 and 210F (54.4 and 99C), then holding the
carpet in the aqueous solution for between about 0.5 to 90
seconds at a temperature above 130F (54.4C). The carpet
fabric can subsequently be washed in water. The preferred
5 sulfonated aromatic condensate has been condensed with
formaldehyde. The method of extracting can be by applying
vacuum to the wet carpet fab~ic or by squeezing the wet
carpet fabric with a pair of rollers. The preferred
concentration of the condensate is between about 0.25 and
10 10 grams per liter of aqueous solution. The preferred wet
pick-up of the aqueous solution is between about 300 and
600~ by weight. When the aqueous solution is applied by
pressurized contact with the carpet fabric, the wet
pick-up preferred maximum is 450%. When the aqueous
15 solution is applied by spray, the preferred wet pick-up
mimimum is 400~. It is preferred that the carpet fabric
be held in the aqueous solution for between about 2 and 30
seconds. The preferred wet pick-up after extracting is
between about 50 and 150~ by weight. The sulfonated
20 aromatic formaldehyde condensate can be formed by
condensation of formaldehyde with one or more phenols. At
least one of the phenols can be phenol sulfonic acid or
the alkali metal salt thereof. It is preferred that one
of the phenols be dihydroxy aromatic diphenylsulfone. It
25 is most preferred that the condensate be formaldehyde con-
r densed with the alkali metal salt of para-phenol sulfonic
acid and with 4,4'-diphenylsulfone. The beginning dyed
carpet fabric of this process may also comprise an
effective amount of a fluorocarbon compound intended to
30 improve resistance to soiling of the carpet. The
preferrèd amount of fluorccarbon present is an amount of
from about 0.05 to 0.4~ by weight of the fabric. The
fluorocarbon can contain perfluoroalkyl radical or can be
a mixture of fluorinated pyromellitate oligomers. A more
35 preferred fluorocarbon is a mixture of pyromellitate
oligomers formed by two reactions, first, the reaction of
pyromellitic dianhydride with the fluorinated alcohol, and
second, the reaction product of the first reaction further
133~7g
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reacted with epichlorohydrin. Another preferred
fluorocarbon is a reaction product of a perfluoroalkyl
alcohol or amide with a suitable anhydride or isocyanate.
Another more preferred fluorocarbon is a reaction product
of N-ethyl perfluorooctyl-sulfoamideo ethanol with toluene
diisocyanate. The aqueous solution of this method may
also contain an effective amount of a thiocyanate. The
thiocyanate cation may be ammonium, sodium, potassium,
copper, zinc, ferrous, ferric, methyl or phenyl, preferred
is ammonium. The aqueous solution of this method may also
contain an effective amount of a dispersing agent. The
dispersing agent can be a condensed naphthalenic salt,
alkyl sulfosuccinate or mixtures thereof. The preferred
dispersing agent is a mixture of a sodium salt of
condensed naphthalenic sulfonic acid and di-isobutyl
sulfosuccinate. The aqueous solution of this method may
also contain an effective amount of a salt having a
divalent cation. The preferred salt is calcium,
magnesium, zinc, or ferrous chloride, sulfate or phosphate
wherein the most preferred is magnesium sulfate. The
preferred aqueous solution would contain the combination
of a sulfonated aromatic condensate, a salt containing a
divalent cation, a thiocyanate, and a dispersing agent,
the most preferred combination would be wherein the
condensate is formaldehyde condensed with the alkali metal
salt of para-phenol sulfonic acid and with 4,4'-diphenol
sulfone, the thiocyanate is ammonium thiocyanate, the
divalent cationic salt is magnesium sulfate and the
preferred dispersing agents are di-isobutyl sulfosuccinate
and the sodium salt of condensed naphthalene sulfonic acid
in a mixture. The preferred carpet fabric would comprise
a fiber treated with a fluorocarbon. The fluorocarbon is
a mixture of pyromellitate oligomers formed by two
reactions, first the reaction of pyromellitic dianhydride
with a fluorinated alcohol, second, the reaction product
~- of the first reaction further reacted with
epichloronydrin. The amounts of the fluorocarbon present
on the carpet fabric used in the method is an amount
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between about 0.05 and 0.4% b~ weight of the fabric, the
magnesium sulfate can be present in the aqueous solution
of the method in an amount between about 0.05 and 0.8~ on
the weight of the fabric, the ammonium thiocyanate can be
present in an amount in about 0.03 to 1% on the weight of
the fabric, the sulfonated aromatic condensate can be
present in an amount of between about 0.15 and 7.5% on the
weight of the fabric, the dialkyl sulfosuccinate can be
present in an amount of between 0 and 6 parts by weight to
the parts by weight of the sulfonated aromatic condensate
and the sodium of the condensed naphthalenic acid can be
present in an amount between about 0 and 3 parts by weight
to parts by weight of the sulfonated aromatic condensate.
The preferred arnounts of the compounds are about 0.05 and
0.4% by weight of the fabric of the fluorocarbon, between
about 0.08 and 0.4% on the weight of the fabric of the
magnesium sulfate, between 0.15 and 0.7% on the weight of
the fabric of the ammonium thiocyanate and between about
0.15 and 1.5~ on the weight of the fabric of the
sulfonated aromatic condensate with the dialkyl
sulfosuccinate being present in an amount between 0 and
2.5 parts by weight to the parts by weight of the
sulfonated aromatic condensate and the sodium salt of the
condensed naphthalenic acid being present in an amount
between 0 and 2 parts by weight to parts by weight of the
sulfonated aromatic condensate. In order to improve
yellowing of the carpet fabric, any of the above aqueous
solutions can be buffered with an effective amount of
citric acid or any other acid with a sequestering agent.
The preferred aqueous solution is buffered with an amount
of citric acid between 0.3 and 5.5 grams per liter of
aqueous solution.
A two-step process embodiment of this invention
uses the aftertreatment process described above but,
preceding the initial preheating step of that after-
treatment an effective amount of the sulfonated aromatic
condensate is added during dyeing of the carpet fabric so
that the total of effective amounts of sulfonated aromatic
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condensate in both steps is less than the total effective
amount useful in either the first dye step, solely, or in
the subsequent application step, solely, or so that a more
effective degree of stain resistance of the carpet fabric
is achieved at the same total of effective amounts of
sulfonated aromatic condensate in the two steps as
compared to the same amount in either step solely. An
effective amount of the salt having a divalent cation can
be added during the dyeing so that the s.a.c. exhausts
onto the fiber at the possibly higher pH and so that the
stain resistance of the nylon fiber in the carpet fabric,
especially an easily dyed nylon fiber having a high index
of crystalline perfection and having a very open internal
crystal polymer structure, is enhanced and durability
steam cleaning of the stain resistance is enhanced, or the
effective amount of sulfonated aromatic condensate is
lower to achieve the same level of stain resistance. The
divalent salt again can be calcium, zinc, magnesium or
ferrous sulfate, chloride or phosphate. The preferred
salt is magnesium sulfate. The preferred amounts of
sulfonated aromatic condensate added during dyeing and
after dyeing are between about 0.05% on the weight of the
fiber to 0.5% on the weight of the fiber during dyeing, an
additional 0.05% on the weight of the fiber to 7.5% on the
weight of the fiber after dyeing. Also, the preferred
amounts of magnesium sulfate are 0.03 to 1~ on the weight
Gf the fiber added to the dyebath and 0.05 to 1% on the
weight of the fiber added after dyeing. The carpet fabric
used in the method can comprise a fluorocarbon present
before dyeing. The fluorocarbon again can contain
perfluoroalkyl radical or a mixture of fluorinated
pyromellitic oligomers. The preferred fluorocarbon is a
mixture of pyromellitic oligomers formed by two reactions,
first, the reaction of pyromellitic dianhydride with a
fluorinated alcohol, and second, the reaction product of
the first reaction further reacted with epichlorohydrin.
The preceding dyeing step can either be a continuous
dyeing operation or it can be batch or beck dyeing. The
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beck dyeing can be done in the presence of an effective
amount of a salt having a divalent cation so that the
stain resistance of tlle carpet fabric is enhanced. The
preferred amount of magnesium sulfate in the dyebath is an
amount between 0.2% on the weight of the fiber to 5% on
the weight of the fiber.
Another method to improve stain resistance of
nylon or wool fiber comprises treating the fiber with a
combination of an effective amount of each of a sulfonated
aromatic condensate and a thiocyanate, whereby improved
resistance to oxidation to ozone or by other stroIlg
oxidizing agents such as benzoyl peroxide is imparted to
the s.a.c. and the dye on the fiber. The preferred fiber
is carpet fiber, the preferred aromatic condensate is
sulfonated aromatic formaldehyde condensate formed by
condensation with one or more phenols. At least one of
the phenols can be a phenol sulfonic acid or the alkali
metal salt thereof. Or at least one of the phenols can be
a sulfone. The sulfone can be a dihydroxy aromatic
diphenolsulfone. The preferred condensate is formaldehyde
condensed with a alkali metal salt of para-phenol sulfonic
acid and with 4,4'-diphenolsulfone. This method of
improving stain resistance of nylon or wool fiber using a
thiocyanate with the sulfonated arornatic condensate can
use a thiocyanate selected from the group consisting of
ammonium, sodium, potassium, copper, zinc, ferrous,
ferric, methyl and phenyl thiocyanate. The most preferred
is ammonium thiocyanate. The dispersing agent can be
added to the mixture applied to the fiber in this method
also. The dispersing agent can be selected from the group
consisting of condensèd naphthalenic salt, an alkyl
sulfosuccinate or a mixture thereof. The preferred
dispersing agent is a mixture of the sodium salt of
condensed naphthalene sulfonic acid and di-isobutyl
sulfosuccinate. The preferred amounts used in this method
are between about 0.05 and 10% on weight of the fiber of
the sulfonated aromatic condensate, between about 0.1 and
5~i on weight of the fiber of the thiocyanate and the
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--11--
sodium salt of the condensed naphthalenic sulfonic acid is
added in an amount between 0 and 3 parts by weight by
parts by weight of the sulfonated aromatic condensate and
the di-isobutyl sulfosuccinate is added in amount between
0 and 6 parts by weight to the parts by weight of
sulfonated aromatic condensate.
Yet another method of improving stain resistance
of nylon fiber, particularly fiber having a high index of
crystalline perfection, for carpet comprises treating the
fiber with a combination of an effective amount each of a
sulfonated aromatic condensate, thiocyanate and salt
having a divalent cation. The sulfonated aromatic
condensate can be a condensate with formaldehyde, can
further be formed by the condensation of formaldehyde with
one or more phenols and at least one of the phenols can be
phenol sulfonic acid and the alkali metal salt thereof or
sulfone. The preferred condensate is formaldehyde
condensed with a alkali metal salt of para-phenol sulfonic
acid and with 4,4'-diphenolsulfone. The preferred
thiocyanate is ammoniurn thiocyanate but the thiocyanate
can be ammonium, sodium, potassium, copper, zinc, ferrous,
ferric, methyl or phenyl. The preferred salt is magnesium
sulfate but the salt can be calcium, magnesium or ferrous
chloride, ~ulfate or phosphate. The fiber treated can
comprise an effective amount of the fluorocarbon compound
intended to enhance soil resistance of the fiber. The
preferred fluorocarbon is a mixture of pyromellitate
oligomers formed by two reactions, first the reaction of
pyromellitic dianhydride with a fluorinated alcohol and
second a reaction product of the first reaction further
reacted with epichlorohydrin. A dispersing agent can be
added to the combination used to treat the fiber in this
method. Dispersing agents can be condensed naphthalenic
salt or an alkyl sulfosuccinate or a mixture thereof. The
preferred amounts are between 0.15 and 7.5% on weight of
the fiber of the sulfonated aromatic condensate between
~; 0.15 and 1~ on weight of the fabric of the thiocyanate,
between O.OS and 0.8% on weight of the fabric of the
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1~3~7fi
-12-
divalent cation salt, and between 0.05 and 0.4% on the
weight of the fabric of the fluorocarbon present on the
fiber before dyeing. As above the condensate and
thiocyanate can be buffered with an effective amount of
citric acid or any acid with a sequestering agent so light
induced yellowing of the stain resistant fiber is reduced.
A method of improving light induced yellowing of
stain resistant nylon in fiber treated with an effective
amount of sulfonated aromatic condensate from an aqueous
solution comprises using an effective arnount of citric
acid or any acid with a sequestering agent to buffer the
aqueous solution containing the sulfonated aromatic
condensate for treating the fiber at a pH between about 1
and 5.5.
Another two-step treatment is a method to dye
and treat in two steps (both batch or beck) nylon carpet
fabric to impart improved resistance to staining
comprising dyeing in a first step in dyed carpet fabric in
a dyebath liquor in the presence of an effective amount of
a sulfonated aromatic condensate in an aqueous solution at
an elevated temperature then removing the dyebath liquor
from the dyed carpet fabric then rinsing the dyed carpet
fabric then applying in a second step another effective
amount of a sulfonated aromatic condensate in an aqueous
solution to the dyed carpet fabric at a pE~ between 1.5 to
5.5 at a liquor temperature between 110 and 195F (60 and
91C) so that the total of effective amounts of sulfonated
aromatic condensate in both steps is less than total
effective amount useful in either the first dye steps
solely or in a subsequent application step solely or so
that a more effective degree of stain resistance of the
carpet fabric is achieved at the same total of effective
amounts of sulfonated aromatic condensate in said two
~ steps as compared to the same amount in either step
¦ 35 solely. The dyeing conditions in the first step are a
liquor to fabric ratio of about 10:1 to 100:1 at a
temperature of 158 to 212F (70 to 100C) for 15 to 90
minutes. Preferred conditions for the second step are a
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-13-
liquor to fabric ratio of about 10:1 to 100:1 for a period
of about 5 to 60 minutes. The carpet fabric can be also
rinsed subsequent to the second step. The sulfonated
aromatic condensate can be condensed with formaldehyde.
The sulfonated aromatic formaldehyde condensate can be
formed by condensation of formaldehyde with one or more
phenols. The phenols can be phenol sulfonic acid or the
alkali metal salt thereof. Or the phenol can be dihydroxy
aromatic diphenol sulfone. The preferred condensate is
formaldehyde condensed with alkali metal salt of
para-phenol sulfonic acid and with 4,4'-diphenolsulfone.
Here again the dyed carpet fabric can comprise an
effective amount of a fluorocarbon intended to improve the
resistance of soiling of the carpet. The preferred amount
of the fluorocarbon is present in an amount of from about
0.05 to 0.4~ by weight on weight of the fabric. The
fluorocarbon can contain perfluoroalkyl radical or a
mixture of fluorinated pyromellitate oligomers. The
fluorocarbon can be the reaction product of a
perfluoroalkyl alcohol or amide with a suitable anhydride
or isocyanate. The fluorocarbon can be the reaction
product of N-ethyl perfluorooctylsulfoamideo ethanol with
toluene diisocyanate. The preferred fluorocarbon is a
mixture of pyromellitate oligomers formed by two
reactions, first, the reaction of pyromellitic dianhydride
with a fluorinated alcohol, and second, the first reaction
product is further reacted with epichlorodrin. The second
step aqueous solution can also contain an effective amount
of a thiocyanate such as ammonium, sodium, potassium,
copper, ~inc, ferrous, ferric, methyl or phenyl
thiocyanate. The'preferred thiocyanate is ammonium
thiocyanate. The aqueous solution of either or both
application steps can also contain an effective amount of
;~ dispersing agent such a condensed naphthalenic salt, an
alkyl sulfosuccinate or a mixture thereof. The preferred
dispersing agent is a mixture of the sodium salt of
condensed naphthalene sulfonic acid and di-isobutyl
sulfosuccinate. The aqueous solutions of both steps of
.
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7 ~
-14-
this invention can also contain an effective amount of
salt having divalent cation such calcium, magnesium or
ferrous chloride, sulfate or phosphate, preferably
magnesium sulfate. The preferred amounts of this method
would be having the fluorocarbon present in an amount of
0.05 and 0.4% by weight of the fabric, magnesium sulfate
present in an amount of betwëen 0.25 and 4% on the weight
of the fabric, ammonium thiocyanate present in an amount
between 0.03 and 1% on the weight of the fabric, the
sulfonated aromatic formaldehyde condensate present in an
amount between 0.15 and 7.5% on the weight of the fabric
and the dialkyl sulfosuccinate present in an amount betwen
0 and 6 parts by parts by weight of the sulfonated
aromatic condensate and the sodium salt of a condensed
naphthalenic acid is present in an amount between 0 and 3
parts by weight by parts by weight of sulfonated aromatic
condensate. The more preferred amounts are where the
fluorocarbon is present in an amount of between about 0.05
and 0.4% on the weight of the fabric, the magnesium
20 sulfate is present in an amount between 0.25 and 1.5~ on
the weight of the fabric, ammonium thiocyanate is present
in an amount between 0.05 and 0.75% on the weight of the
fabric, sulfonated aromatic formaldehyde condensate is
present in an amount between 0.15 and 2.0% on the weight
of the fabric and the dialkyl sulfonsuccinate is present
in an amount between 0 and 2.5 parts by weight to the
parts by weight of the sulfonated aromatic condensate and
the sodium salt of a condensed naphthalenic acid is
present in an amount between 0 and 2 parts by weight to
the parts by weight of the sulfonated aromatic condensate.
Here again aqueous solution can be buffered with an
effective amount of citric acid or any other acid with a
sequestering agent to improve the yellowing of the carpet
; fabric.
Finally, in the last embodiment of this
invention a method of improving exhaustion of a water
soluble thiocyanate onto polyamide fiber comprising
contacting the fiber with an effective amount of the
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i33~7fi
-15-
thiocyanate at a pH between about 1 and 5 wherein the
fiber has improved resistance to fading of dye, due to
strong oxidizing agents such as benzoyl peroxide or ozone,
the dye being present in or on the fiber, is disclosed.
The thiocyanate can be ammonium, sodium, potassium,
copper, zinc, ferrous, ferric, methyl or phenyl
thiocyanate. The preferred pH of the method is between 1
and 4. The preferred amount- of thiocyanate is between
about 0.1 and 6~ on the weight of the fiber of the
thiocyanate, present in or on the fiber after dyeing. The
method improves exhaustion so that between about 0.1 and
about 12% on the weight of the fiber of the thiocyanate is
present during the contacting and at least 50% of the
thiocyanate present during the contacting is exhausted
onto or into the fiber. The preferred thiocyanate is
ammonium thiocyanate. The thiocyanate can be contacted
with the fiber in the dyebath or after dyeing of the
fiber. The fiber being treated can comprise an effective
amount of a fluorocarbon to inhibit soiling of the fiber
and a sulfonated aromatic condensate can be present either
on the fiber or with the thiocyanate. The various
fluorocarbons are as described above. An effective amount
of citric acid or any acid with a sequestering agent can
also be used to buffer for the condensate and thiocyanate
to the desired pH for this same anti-yellowing effect. It
is preferred to have between about 0.1 and 12~ thiocyanate
on the weight of the fiber and between about 0.05 and 0.4
fluorocarbon on the weight of the fiber.
PREFERRED EMBODIMENTS
Continuous Aftertreatment Process
This process is intended to continuously treat
nylon carpet fabric with sulfonated aromatic condensate
formulations, for instance on a continuous dye range after
steaming but before washing; or piece (or beck) dyed
carpets may be continuously treated in a similar fashion
by treating in-line on the wet goods dryer range prior to
the dryer. Equipment could be a spray header(s), or the
equivalent, for the heated water across the moving carpet
''~
`~?~ v~
~`` 133~76
-16-
fabric with vacuum extractors below or a set of squeeze
rolls to remove the water, followed by spray headers for
the treatment liquor with a catch pan underneath. An
alternative to spray application is use of a pressurized
applicator, such as a Kusters Fluidyer,* which presses the
carpet into contact with a narrow slot
in a conduit containing treatment liquor under pressure.
The prior art describes the application of
similar sulfonated aromatic formaldehyde condensates by a
beck (piece) aftertreatment and a continuous manner along
with dyestuffs and subsequent steaming. The continuous
process of this invention has economical advantages over
the beck aftertreatment process by approximately 4 cents
per pound of fiber produced as finished carpet (at equal
levels of the stain resist agent on the fiber). The
continuous aftertreatment process of this invention has
the following advantages over the known prior art
processes~
(a) Post dyeing process. Process conditions are
optimized for the "exhaustion" of the sulfonated aromatic
formaldehyde condensate onto the fiber. These conditions
are not necessarily compatible with the dyeing process.
Since the treatment process occurs after dyeing, there is
no interference with the dyeing process. Prior art
concurrent (with dyes) processes generally result in
~ poorer dyeing quality, a loss in dye yield and an effect; of the dyed shade of the carpet.
(b) More versatile. The process of this invention
is applicable to both continuously dyed solid or multi-
color patterns with the same process conditions. Further-
more, the process is also applicable to continuously
aftertreating piece (or beck) dyed goods at the wet goods
dryer.
~ The process involves the general principle of
`~ 35 first, preheating the carpet with heated water followed by
hydroextraction and the application of an aqueous solution
I of the sulfonated aromatic formaldehyde condensate, for
which there are specific ranges of p~, concentration, wet
,
~ : *Trademark
~ B
ijr,~
- 1330~7fi
-17-
pick-up (w.p.u.) and temperatures. This is followed by a
dwell period at which the carpet is either held at
temperature or is allowed to radiant cool prior to washing
the carpet. Prior to the treatment, the carpet has
already been dyed by either beck or continuous methods.
For beck-dyed carpets the treatment process is at the wet
goods dryer and for continuously-dyed carpets the
treatment process is in-line after steaming and prior to
the final washing step.
The process, in more detail, involves preheating
the dyed carpet with hot water followed by hydroextraction
by either squeeze or vacuum methods to a wet pick-up of 30
to 190%. The conditions of the preheating process are
established to achieve a carpet temperature of 130 to
210F (54.4 to 99C) prior to the treatment stage. The
conditions of the preheating process are generally using
200% w.p.u. to total saturation with water at 140 to 212F
(60 to 100C). As an addition in the continuous dyeing
process, this also gives the carpet a washing prior to
application of the treatment solution which aids the
carpet's receptiveness to the stain resist agent. The
treatment solution i8 an aqueous solution of the
sulfonated aromatic condensate at a 0.25 to 40 grams per
liter concentration and a pH of 1.5 to 5.5. The treatment
solution is applied at 200 to 600% w.p.u. add-on and a
-~ temperature of 140 to 212F (60 to 100C). The resulting
temperature of the carpet must be in the 130 to 210F
(54.4 to 99C) range for the treatment to be effective.
It is preferred to keep the difference in carpet fabric
temperature between pretreating and application to a
minimum. Following the application of the treatment
liquor, it is necessary to either maintain the carpet at
the application temperature for at least 0.5 to 30 seconds
or allow it to radiantly cool to no less than 130F
(54.4C).
The equipment used for the application of the
treatment liquor may be either spray or contact (e.g.
Kusters Fluidyer) in nature. The contact method is
.~
~ 3 `~. ~7 t
-18-
preferred since it is easier to achieve 100% penetration
of the treatment. Spray processes are adequate provided
that the solution penetrates to the back of the carpet,
and will generally require additional mechanical
considerations, such a squeeze or "S" rollers to achieve
complete penetration. Other application equipment may
also be used as long as the process requirements of
preheating, heated treatment and dwell time at temperature
are satisfied. The preheating and/or extracting steps of
this invention may be carried out on the previously
existing equipment.
The practical significance of this invention is
that it provides an economical and effective means to
apply sulfonated aromatic formaldehyde condensates to
impart stain resistance to dyed carpets. The process is
applicable to over 90~ of all carpets treated with
sulfonated aromatic formaldehyde condensates.
The continuous aftertreatment embodiment can
also be the second step of another two-step process
embodiment of this invention wherein an effective amount
of the sulfonated aromatic condensate is added to a
continuous dyebath or in batch or beck process for dyeing
carpet fabric. The two-step process uses less overall
amount sulfonated aromatic condensate for the same effect
level of stain resistance. Alternatively, the same total
. amount of sulfonated aromatic condensate can be used in
the two-step process to achieve a higher level of stain
resistance.
Certain nylon substrates (fiber) have very open
internal structure (orientation of the polymer chains)
which require very high amounts of the sulfonated aromatic
~ condensate composition to impart a marketable degree of
;~ stain resistance. Certain sulfonated aromatic condensate
; compositions cannot achieve a sufficient level of
3S protection on these substrates, so they must be excluded.
Also, the continuous aftertreatment method results in only
moderate durability of the stain resistance properties to
steam cleaning when a high pH detergent is used.
.~
: '
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~ ~ ' '' r ; ~
--19--
The two-step application process has all of the
advantages of the continuous aftertreatment process such
as economics, etc. over one-step batch processes. It also
has unique advantages over the aftertreatment process
alone and all other known continuous application processes
for sulfonated aromatic condensates, such as using all of
the sulfonated aromatic condensate in dyebath (currently
being practiced on a commercial scale).
The level of stain resistance imparted by a
given total amount of the sulfonated aromatic condensate
is substantially improved. The required add-on for a
marketable level of stain resistance reduced by
approximately 30% over aftertreatment and greater for
other continuous processes, providing economical
advantages. The process (with optimized sulfonated
aromatic condensate composition for aftertreatment) yields
marketable levels of stain resistance on critical
substrates described above using reasonable levels of the
sulfonated aromatic condensate composition. The
durability of the stain resistance properties to steam
cleaning (with and without a high pH detergent) is
improved over the aftertreatment only process, yielding
improved properties.
The two-step process involves the general
principle of applying a portion of the total sulfonated
aromatic condensate composition to be applied in the
standard dyebath with an appropriate amount of magnesium
sulfate (magnesium sulfate, 0 to 0.35% on the weight of
the fabric for each 1% on the weight of the fabric of the
sulfonated aromatic condensate). The balance of the total
sulfonated aromatic condensate composition (with 0 to
0.35% of magnesium sulfate) is then applied as an
aftertreatment. The amount of Epsom Salt required in both
portions depends on the sulfonated aromatic condensate and
the substrate being treated.
The dyebath composition is based on that
typically used for continuous dyeing. The appropriate
amount of the sulfonated aromatic condensate composition
.` ~ .
~ .
~33~ ~7~
-20-
(~ased on the optimum ratio and the total required for the
particular substrate) is added to the dyebath.
More specific examples of the processes are
given in the following Examples.
Preferred Treatment Compositions
In addition to a sulfonated aromatic condensate
other chemical compounds such as a thiocyanate are added
to the formulation used to treat the carpet fabric to
overcome oxidative yellowing of the sulfonated aromatic
condensate, and to provide the resulting carpet with
better resistance of the dyes to strong oxidizing agents,
such as ozone or the benzoyl peroxide found in commercial
anti-acne preparations. Also a salt containing a divalent
cation is useful to improve exhaustion of the sulfonated
aromatic condensate on high ICP polymer fibers. A
dispersing agent(s) is usually necessary in the
formulation to prevent precipitation or coagulation due to
incompatibility of the components of the formulation for
treatment and/or the components with a fluorocarbon
treated carpet fabric. Acids are used to buffer the
formulations. It has been discovered that citric acid or
any acid with a sequestering agent creates an additional
improvement in yellowing characteristics of sulfonated
aromatic condensate treated fiber or fabric.
Ammonium thiocyanate and sulfonated aromatic
condensates exhaust onto nylon fibers under comparable
application procedures. The two products may be -~
co-applied providing that the uptake of one material does
not interfere with the other. Therefore, the selection of
the sulfonated aromatic condensate is important. Some
sulfonated aromatic condensates exhaust preferentially
over ammonium thiocyanate. But to the contrary there was
a synergistic effect of IntratexXN (which is reported to
be formaldehyde condensed with an alkali metal salt of
para-phenol sulfGnic acid and with 4,4'-diphenolsulfone)
and ammonium thiocyanate on benzoyl peroxide spotting
resistance.
An additional benefit of ammonium thiocyanate in
Trademark
133~fi
-21-
the composition is as an antioxidant to prevent light
induced yellowing of Intratex N. This combination was
found to give a sufficient improvement (acceptable light-
fastness) for beck applications, but was insufficient for
continuous applications (although improved).
The combination of sequestering agents, such as
EDTA and sodium hexametaphosphate, with Intratex N was
found to result in some improvement in light induced
yellowing, but did not yield completely acceptable results
for the continuous application. Combination of Intratex N
with citric acid (sequestering and antioxidant properties)
also gave similar results. The combination of ammonium
thiocyanate and citric acid was discovered to achieve the
best results in the reduction of light induced yellowing
for continuous application, showing virtually no
yellowing. (Combinations of ammonium thiocyanate and
other sequestering agents were not as effective.)
A novel dispersant system, using Tamo~ SN and
MonawetXi`~B-45 was developed to prepare a stable
composition containing Intratex N, ammonium thiocyanate
and citric acid in concentrated form for continuous
applications. A new dispersant system was developed to
prepare a stable concentrate containing Intratex N and
ammonium thiocyanate for beck aplications.
Example Compositions:
Composition Solids, Composition Solids,
Component 1, % % 2, % %
_ _ _
Intratex N* - - 18.9 3.8
(s.a.c.)
30 Intratex N-l* 25 5
Ammonium Thiocyanate 6.00 6 - -
Citric Acid 14.30 7.15
(50% solution)
-~ Sulfuric Acid - - 1.11 1.1
35 Tamol SN ~sodium4.00 3.9 7.32 7.1
salt of condensed
naphthalene
sulfonic acid)
Trademark
; ~
^` 133~
-22-
Example compositions: (Continued)
Composition Solids, Composition Solids,
Component 1, % _ ~ 2, %
~onawet MB-4520.00 9 - -
(di-isobutyl
sulfosuccinate)
Epsom Salt 6.00 6
(Magnesium Sulfate) 24.7 2.9
Demineralized Water 33.03- 0 72.65 0
* Same concentration of same s.a.c., N-l has pH 7,
N has pH 10.5.
Any thiocyanate such as those listed in the
Summary of the Invention is expected to be effective,
although the copper, ferrous and ferric thiocyanates may
have to be color compensated.
As dispersing agents any agent that is effective
can be used, such as for any process formulation, the
condensed naphthalenic salts, the alkyl sulfosuccinates, a
mixture of them, and for batch process systems salts of
polymeric carboxylic acid, and polyethylene glycol ethers.
As sequestering agents, the polyphosphates, such
as sodium tripolyphosphate (STPP), aminocarboxylic acids,
such as ethylenediamine tetraacetic acid (EDTA), hydroxy-
carboxylic acids, such as tartaric and citric acid, and
the aminoalcohols, such as triethanolamine (TEA) are
expected to be effective. See Kirk-Othmer Encyclopedia of
Chemical Technology, supra.
Example 1 -
On a commercial dyeing range Composition 1 was
applied both in a two-step (continuous-continuous) and in
a continuous aftertreatment only process to a normal and
to a high ICP fiber carpet fabric. The normal fiber was
in an 1186 denier Superba heat set textured yarn. The
high ICP fiber was a 1700 denier textured yarn which was
heat set by a proprietary Pharr process with a high heat
history giving an ICP of 3.92 compared to normal ICP of
about 3.8. Both fibers were previously treated with a
.
. .
-~ 133B~7~
-23-
spin finish containing a soil-release fluorocarbon as
described in U.S. 4,604,316 and/or U.S. 4,192,754. The
fabric was dyed gray. The prewash and treatment
application was by spray just after t~e dryer but before
the final wash on the continuous dye range. Following are
the dyes and chemicals used in the continuous dyebath.
Control:
0.135 g/l** Nylanthrenel Orange RAR (liquid)
0.092 g/l Tectilon2 Red 2B Liq.-50
0.052 g/l Telon3 Blue B-AR (powder)
(the above dyes are the same for all dyebaths.)
3.0 g/l Alrowet2 D-70 *
1.0 g/l Chemcogen4 DCG *
0.5 g/l Defoamer AC (Fuller) *
pH 5.5 with Acetic Acid
400% w.p.u. via Kuster Fluidyer
Steam in vertical steamer 5 to 6 minutes
"4% Dyebath":
(Order of addition to bath as listed.)
3.0 g/l Alrowet D-70
1.0 g/l Chemcogen DC5 --
0.5 g/l Defoamer AC (Fuller)
10.0 g/l Composition 1
1.25 g/l Epsom Salt (Magnesium Sulfate)
0.5 g/l Sequestrene2 30A *
- Dyes above
Approximately 1 g/l Ammonia to pH 5.5
"8~ Dyebath":
- (Order of addition to bath as listed.)
3.0 g/l Alrowet D-70
1.0 g/l Chemcogen DCG
0.5 g/l Defoamer AC (Fuller)
20.0 g/l Composition 1
2.5 g/l Epsom Salt (Magnesium Sulfate)
0.5 g/l Sequestrene 30A *
Dyes above
Approximately 3 g/l Ammonia to pH 5.5
,~
~:
.
'`~'"'~'' '"'~ ~''' ~ ` " ~ v ~ " ~ ` " ~ "
--" 1330476
-24-
* Alrowet D-70 is dioctyl sulfo~iuccinate - 70% active
Chemcogen DCG is sulfonated alkyl diphenylether -
30-38% active.
Defoamer AC is a proprietary defoamer from Fuller Sales.
5Sequestrene 30A is ethylene diamine tetraacetic acid.
1 ~ of Crompton & Knowles
2 ~ of Ciba GeigY
3 ~ of Mobay
4 ~ of Lyndal Chem.
** grams per liter
The following tables-provide other operating
conditions and results, using the above dyebaths and the
shown aftertreatments. Trials 3 and 4 were omitted
because they had a slightly different, nonpreferred,
formulation.
TABLE I `
Aftertreatment (A/T) Application Data
Nominal
Comp.l Nominal Total
Add-on Comp.l Nominal Preheat
from Add-on Comp.l Liquor
Trial Dyebath, from A/T, Add-on, Temperature,
I.D.* % owf% owf % owf F (C)
25 1 0 0 0 142 (61.1)
0 11.0 11.0140 (60.0)
9 4.0 7.0 11.0141 (60.6)
4.011.0 15.0140 (60.0)
2 0 0 0 142 (61.1)
30 6 0 10.9 10.9140 (60.0)
8 4.0 7.0 11.0141 (60.6)
7 0 14.9 14.9140 (60.0)
11 4.010.9 14.9140 (60.0)
12 8.0 7.0 15.0140 (60.0)
~;~ 351~ 8.011.0 19.0140 (60.0)
:` :
"
I
~ 1330~7~
TABLE I (CONTINUED)
Aftertreatment (A/T) Application Data
Carpet Post-A/T
Temperature A/T Carpet
5 Trial Before A/T, Liquor, Temperature,
I.D.* F (C) pH F (C)
1 128 (53.3) 7.6 157-159 (69.4-70.6)
127-129 (52.8-53.9) 2.9 155-156 (68.3-68.9)
9 129-130 (53.9-54.4~ 3.0 158-159 (70.0-70.6)
1010 128-129 (53.3-53.9) 2.9 155-157 (68.3-69.4)
2 128 (53.3) 7.6156-158 (68.9-70.0)
6 127-129 (52.8-53.9) 2.9 158-160 (70.0-71.1)
8 128-131 (53.3-55.0) 3.0 158-159 (70.0-70.6~
7 128-12g (53.3-53.9) 2.8 160-162 (71.1-72.2) `
1511 129-131 (53.9-55.0) 2.9 157-158 (69.4-70.0)
12 129-130 (53.9-54.4) 3.0 160-161 (71.1-71.7)
13 130 (54.4) 2.9157-159 (69.4-70.6)
* Numbers 1, 5, 9 and 10 trials are normal carpet fabric;
remaining numbers are high ICP carpet fabric. Trials
1 and 2 are a controls.
Both fabrics are 40 oz/sq yd cut piles.`~
A/T Liquor Temperature ranged from 180-182F (82.2-83.3C).
TABLE II
SOLUTION AND CARPET ANALYSIS DATA ~ -
Concurrent Portion (in Dyebath)
Calc.
TargerNominal Anal. Comp.l
NominalComp.l Comp.l Add-on
Comp.lConc.in Conc.in from
~ 30 Trial Add-on,Dyebath, Dyebath, Analysis,
; I.D. ~ owf g/l _g/l % owf
1. 0 0 0 0
2 0 0 0 0 -
5 i o 0 0 0
6 0 0 0 0
;~ 7 0 0 0 0
8 4.0 10.0 9.2 3.7
9 4.0 10.0 9.2 3.7
4.0 10.0 9.2 3.7
11 4.0 10.0 9.3 3.7
12 8.0 20.0 16.8 6.7
13 8.0 20.0 16.8 6.7
1 ~ 3 ~ ~ 7 ~
-26-
TABLE II (CONTINUED)
SOLUTION AND CARPET ANALYSIS DATA -
Aftertreatment Portion
Actual A/T
Target Spray Total A/T
Nominal Conc.Header Liquor
Trial Add-on, Deliv.,Pres., Deliv.,
I.D. % owf GPM* psig GPM*
-
1 0 0 6.7 77
2 0 0 ~ 6.6 76
11.2 1.19 6.5 75
6 11.2 1.19 6.6 76
7 15.2 1.62 6.6 76
8 7.2 0.76 6.6 76
9 7.2 0.76 6.6 76
11.2 1.19 6.7 77
11 11.2 1.19 6.7 76
12 7.2 0.76 6.6 76
13 11.2 1.19 6.5 75
Line speed for both fabrics was 30 ft/min.
Throughput = 99.8 lb carpet/min. - =
Actual dyeing wet pick-up was 400% in all cases.
Aftertreatment wet pick-up was always between 626 and 643%.
Aftertreatment pH was always between 2.8 and 3.0 except
control was 7.6.
* gallons per minute
"
.
~: :
:;
.,
:
" ~ I
.,~
..~
~ '
'
~ ".
133~7fi
-26A-
TABLE II (CONTINUED)
SOLUTION AND CARPET ANALYSIS DATA
Aftertreatment Portion
Calc. Calc. Calc.
Nominal Anal.Comp.lComp.~l
A/ T A/ TAdd- on Add-on
Liquor Liquorfrom from
TrialConc., Conc.,Set-up,Analysis,
I.D. g/l g/l % owf % owf
1 0 0 . O
2 0 0 0 0
5 17.4 14.8 11.0 9.3
6 17.2 14.8 10.9 9.4
7 23.3 22.4 14.9 14.3
~ 11.0 11.6 7.0 7.4
9 11.0 11.6 7.0 7.4
10 17.0 18.4 11.0 11.9
11 17.2 18.4 10.9 11.7 -
12 11.0 11.2 7.0 7.1
13 17.4 13.6 11.0 8.6
. ..
,
1 ,
~ `S~ ~:; `~5~
7 ~
-26B-
TABLE II tCONTINUED)
SOLUTION AND CARPET ANALYSIS DATA
Concurrent and Aftertreatment Portion
Calc. Calc. Anal. Anal.
Comp.l Comp.l Comp.1 s.a.c.
Target Add-on Add-on Add-on Add-on
Comp.l from frorn from from
Trial Add-on, Set-up, ANALYSIS, Carpets, Carpets,
I.D. ~ owf ~ owf % owf % owf % owf
10 1 0 0 '- O O O
2 0 0 0 0 0
11.2 11.0 9.3 10.6 ~.6
6 11.2 10.9 9.4 10.9 2.7
7 15.2 14.9 14.3 16.3 4.0
15 8 11.2 11.0 11.1 10.7 2.6
9 11.2 11.0 11.1 11.1 2.7
15.2 15.0 15.6 14.0 3.5
11 15.2 14.9 15.4 15.4 3.8
12 15.2 15.0 13.8 15.8 3.9
2013 19.2 19.0 15.3 19~6 4.9
Line speed for both fabrics was 30 ft/min.
Throughput = 99.8 lb carpet/min.
Actual dyeing wet pick-up was 400% in all cases.
Aftertreatment wet pick-up was always between 626 and 643~.
Aftertreatment pH was always between 2.8 and 3.0 except
control was 7.6.
''
: ~'' ' .
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~,
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,~
.
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`~
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,,
, ~ ., .
~ 133~76
-27-
TABLE III
STAINING DATA
NominalNominal
Comp. 1Comp. 1 Total
Add-on from Add-on from Nominal Comp.l
Trial Dyebath, A/T, Add-on,
I.D. ~ owf~ owf ~ owf
0 0 0
0 - 11.0 11.0
9 4.0 7.0 11.0
4.0 11.0 15.0
2 0 0 0
6 0 10.9 10.9
8 4.0 7.0 11.0
7 0 14.9 14.9
11 4.0 10.9 14.9
12 8.0 7.0 15.0
13 8.0 11.0 19.0
Stain Ratingl (0=best 10=worst) _ -
20 Trial Time Before Blotting with Water, Hours
I.D. 1 _47 24- 4 24
Originals After s.c.* -
1 8.5 8.5 8.58.5 8.5 8.5
0.25 0.25 0.25 0.25 4.5 5.0
259 0 0 0 03.5 4.5
1 .
0 0 0 03.0 4.0
2 9.0 9.0 9.0 9.08.0 8.5
6 2.5 2.5 2.5 2.54.5 5.5
8 0.1 0.5 0.1 0.25 2.5 4.0
l ~
307 0.25 1.5 1.5 1.55.0 6.0
11 0 0.1 0.1 0.25 3.0 4.0
12 0 0 0 0.11.0 2.0
13 ~ 0 0 0 01.0 1.0 ~-
~; * steam cleaning
3 ~
2 passes of detergent solution using
conventional steam cleaning equipment. Detergent
~ .
solution: 1 oz./gal. ALL-IN-ONE (Certified Chemical &
Equipment, Cleveland, OII).
1 See Example 6, Part 2, "Performance", "Drop Test".
, ~
. . :~
-- 1330~7~
-2~-
TABLE IV
REPELLENCY AND COLORFASTNESS DATA
Comp. 1 Comp. 1 Total
Add-on Add-on Nominal
from from Cornp. 1.
5 Trial Dyebath,A/T, Add-on, Repellency3_
I.D. % owf% owf % owf 0Water
1 0 0 0 5.0 4.0
0 11.0 11.05.0 4.0
9 4.0 7.0 11.04.0 4.0
1010 4.0 11.0 15.04.5 3.5
2 0 0 0 5.0 5.0
6 0 10.9 10.95.0 4.0
8 4.0 7.0 11.05.0 5.0
7 0 14.9 14.95.0 4.0
1511 4.0 10.9 14.94.0 4.0
12 8.0 7.0 15.04.0 4.0
13 8.0 11.0 19.04.0 3.5
.
Grey Scale Rating
~:~ N02 : : .
Trial Liahtfastness Ozonefastnessl Fastness
I.D. 20 AFU* 40 AFU1 cy** 3 cy5 cy 1 cy**
1 4.5 4.0 3.0 2.01.5 3.0
255 4.5 4.0 3.5 3.02.5 2.5
9 4-5 4.0 3-5 3.0 2-5 3.0
4.S 4.0 3.5 3.02.5 3.0 ,
,, ~
~ 2 4.0 3.5 3.0 2.~1.5 3.0
: ~
6 4.0 4.0 3.0 2.52.5 2.5 ~
~ 308 4.5 4.0 3.5 3.02.5 3.0 ~ -
`~ 7 4.0 4.0 3.0 3.02.5 2.5
11 4.0 i' 3.753.5 3.0i 3-0 3-0
12 4.0 3.253.0 3.02.5 2.5
13 3.5 3.0 3.0 3.02.5 2.5 -~
'i`;~ ~ 35
I ~ ~
* AATCC 16E fading unit
** cycles
~ 1 AATCC 129
`~ 2 AATCC 164
' '
.:,
--` 133iil7~
--29--
3 Oil Repellency
- AATCC TM-118, Oil Repellency: Hydrocarbon
Resistance Test.
Water Repellency
DuPont Isopropanol/water series
1. 2/98 IPA/Water (55)
2. 5/95 IPA/Water- (47)
3. 10/90 IPA/Water (40
4. 20/80 IPA/Water (33)
10 5. 30/70 IPA/Water (28)
2~umbers in parentheses represents surface tension of the
test fluids.
TABLE V
BENZOYL PEROXIDE SPOTTING DATA*
Comp. 1 Comp. 1 Total Spot Visibility
Add-onAdd-on ~ominal 0=Invisible; 10=Bright
fromfrom Agent Benzoyl Peroxide Conc.,
Trial Dyebath, A/T, Add-on, % Soln. in Acetone
20I.D. % owf% owf % owf .01 .05 .10 1.0 5.0
-
O 0 0 6.5 -7.0 8.0 9.0 9.0
011.0 11.0 0 1.0 2.0 4.5 5.5
9 4.07.0 11.0 0 1.0 2.0 5.5 6.0
4.011.0 15.0 0 2.0 2.0 5.5 6.0
252 0 0 0 5.0 6.5 6.5 9.0 9.0
6 010.9 10.9 0 1.0 1.5 5.0 6.0
8 4.07.0 11.0 0 1.0 2.0 6.0 6.5
7 014.9 14.9 0 0.5 1.0 4.5 6.0
11 4.010.9 14.9 0 1.0 2.0 5.0 5.5
3012 8.07.0 15.0 0 0.5 1.5 4.5 5.5
13 8.011.0 19.0 0 0.5 1.5 5.0 5.5
~ , ;
* Sample spotted with l-ml of benzoyl peroxide solution
and exposed in chamber at 90F (32.2C) and 80% R.H.
35 for three days (color change ceases).
~ ~ .
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133Q47~
~,
-30-
TABLE VI
SOILING DATA
Soil Rating
Comp.l Comp.l Total (0=best, 10=worst)
Add-on Add-on Nominal Treads
from from Comp.l Accl.* Total
Trial Dyebath, A/T, Add-on, Method JTCC** Soil
I.D. % owf % owf % owf 5K 5K 10K Ratiny
1 0 0 0 5.0 5.5 7.0 17.5
10 4 0 10.9 ~0.9 5.5 6.0 7.0 18.5
0 11.0 11.0 5.5 6.0 7.5 19.0
9 4.07.0 11.0 4.5 6.0 7 5 18.0
4.011.0 15.0 4.5 6.0 7.5 18.0
2 0 0 0 5.5 4.0 5.5 15.0
15 3 0 10.9 10.9 5.5 4.5 6.0 16.0
6 0 10.9 10.9 5.5 5.5 6.5 17.5 -~
8 4.07.0 11.0 4.0 5.0 7.0 16.0
7 0 14.9 14.9 5.5 5.5 7.0 18.0
11 4.0lO.g 14.9 4.0 4.5 7.0 15.5
2012 8.07.0 15.0 4.5 5.5 7.0 17.0
13 8.011.0 19.0 4.5 5.5 7.0 17.0
* Accelerated soiling conducted at Petersburg
Rehabilitation Center using "natural soil" with 2.5
mineral oil added.
** John Tyler Community College Maintenance Hall.
: :
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-31-
Example 1 - Conclusions
The two-step process with composition gives
considerably better stain resistance than the
aftertreatment (only) process, at equal total add-on
levels. This shows potential for achieving acceptable
performance at lower total add-on levels.
The two-step process also gives acceptable stain
resistance on the "high ICP" substrate at levels
comparable to that currently being used for s.a.c. normal
substrates by aftertreatment only.
Stain resistnace improves and lightfastness is
adversely effected (yellowing) as the C~mposition 1
concentration in the concurrent portion increases, with
total add-on level constant. Acceptable yellowing and
stain resistance was achieved at 4~ on the weight of the
fiber of Composition 1 in the concurrent portion.
"Optimum" two-step systems had improved ozone
and benzoyl peroxide (B.P.) spotting xesistance
properties. Some reduction does occur as the
concentration applied by the aftertreatment portion is
reduced in favor of the concurrent portion.
Example 1 - Summary of Results
Staining Performance Table III:
In general, the standard Superba heat set (H/S)
subætrate performed beter than the high ICP substrate at
equivalent application conditions, while analyzed add-on's
were equal. This is normally observed because of undesired
deep penetration of s.a.c. into fiber of high ICP.
When applied by aftertreatment only, Composition
1 on the high ICP fabric did not yield acceptable staining
performance. When the level of Composition 1 was
increased from 11 to 15~ owf on the high ICP fabric, stain
resistance was further improved to a "Marginal"
~; performance level (stain rating of 1.5 at 4- and 24-hour
blot times).
The two-step process gave considerably better
stain resistance than the aftertreatment only process on
~ both substrates, at equal total application levels. No
I
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`
-32-
staining at 24 hours was obtained on the Superba H/S
fabric using 4% on the weight of the fiber in the Dyebath
and 7% on the weight of the fiber in the A/T. These
same levels on the high ICP substrate gave staining
performance equal to the Superba fabric aftertreated
(only) with 11% on the weight of the fiber of Composition
1 (stain rating of 0.5 at 24 hours).
Example 1 - SUMMary of Results
I
Colorfastness Table IV:
No light induced yellowing was observed at 20
AFU on any of the trials conducted, but begn to be noticed
at 40 AFU. ~-
Light induced yellowing (at 40 AFU) became more
noticeable as the amount in the concurrent portion was
increased (and aftertreatment was reduced). Trials with
~ 8% on the weight of the fiber Composition 1 in the
¦ concurrent portion (high ICP substrate) were marginal to
unacceptable for lightfastness.
The improveMent in resistance to ozone fading,
obtained with Composition 1 by aftertreatment was also
observed with Composition 1 and also using the two-step
process with Composition 1 (at lower level).
Benzoyl Peroxide Spotting Table V:
The two-step process gave only a slight
reduction in the benzoyl peroxide spotting performance
--. than the aftertreatment process, at equal add-on levels.
Repellency Table IV:
There was no significant effect in any of the
trials on oil and water repellency. As the amount of
Composition 1 (and magnesium sulfate) in the concurrent
portion was increased, the oil repellency tended to
decrease slightly.
Soiling Table VI:
Only a slight negative effect in soiling was
observed on all trial samples compared to the control.
Composition 1 showed slightly more soiling when
applied by aftertreatment, as the concentration applied
was increased.
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-33-
With total add-on constant, the two-step process
had less impact on soiling than aEtertreatment aloneO
Two-Step Process Guidelines (Best Mode)
For The Continuous Application of Composition 1
Concurrent (with dyestuffs) Portion:
For Suessen H/S Substrates: 2.0% owf
For Superba H/S Substrates: 3.0% owf
For "High ICP" Substrates- 4.0-5.0% owf
Dyebath Make-up Procedure:
1st - Wetting and leveling agents (defoamer, if
required)
2nd - Composition and Epsom Salt** (MgSO4-7H2O)
(0.5% owf Epsom Salt for each 4.0% owf Composition 1)
3rd - 0.25-0.50 g/l Sequestering agent (EDTA)
4th - Dyestuffs
5th - Adjust to desired pH with either acetic
acid, ammonia or caustic soda*
Notes:
* Composition 1 has low pH. Use in the dyebath -
20 will result in pH's of 3.0-3.5, requiring an alkalai to
adjust pH.
** Only phosphates which form water-soluble
complexes with magnesium ion may be used in the presence
of magnesium sulfate.
Aftertreatment Portion:
Composition 1 Concentration:
For Suessen H/S Substrates: 3.0% owf
For Superba H/S Substrates: 5.0% owf
For "High ICP" Substrates: 7.0 -8.0%
Application Parameters:
Preheat/wash spray at 160F (71~.1C) and extract
(vacuum) to 75-125% w.p.u. to give carpet temperature of
140F (60C).
-~ Apply treatment solution at 180F (81.2C) and
35 400-500% w.p.u. to give a post-A/T carpet temperature of
I60F (71.1C).
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-34-
Example 2
This is a further example of the continuous
aftertreatment process of the invention, using Composition
2 in the treatment of the carpet fabric. The fabrics
treated were (a) a fabric tufted from an 1186 denier
continuous filament textured medium dye fiber in a Superba
heatset (H/S) yarn to a 28-ounce cut pile fabric and (b) a
textured 3.15/2 cotton count- yarn from a 19 denier per
filament staple deep dye fiber heat in a Suessen and
tufted into 48-ounce fabric. Both were pretreated with
the fluorocarbon of Example 1 and were to be dyed light
gray. The nominal application conditions were 140F
(60C) preheat water temperature, 180F (81.2C)
application liquor temperature, 500 to 600% w.p.u.
application liquor, the dyes and dyebath additives were as
in Example 1, except no sequestrene was used. No
Composition 2 or other s.a.c. was added to the dyebath.
The following Tables show the application conditions and
results.
TABLE VII
APPLICATION DATA
Target Actual
Target Nominal A/T Target
25Nominal Nominal Epsom Spray A/T A/T
Comp.2 s.a.c. Salts Header Liquor Liuqor
- Trial Applied, Level, Level, Pres., Deliv., Conc.,
I.D. % % owf% owfpsig GPM g/l
1 0 0 0 6.2 73.3 0
2 15.0 2.8 0 6.2 73.325.0
3 0 0 0 6.5 75.2 0
4 9.0 1.7 0 6.5 75.217.2
~`
Actual w.p.u. was between 523 and 532%, pH was 8.3 for
control: 3.0 for Trial 2; 3.3 for Trial 4.
Preheat liquor temperature was 140F (60C). Carpet
temperature was 127-130F (52.8-54.4C). Application
liquor temperature was 179-182F (81.7-83.5C) and carpet
~ temperature was 156-161F (68.9-71.7C).
:~
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' 133~476
TABLE VII (CONTINUED)
APPLICATION DATA
Calc.s.a.c.
Calc. Calc. Add-on Anal.
Calc. Anal. Comp.2 s.a.c. from s~a.c. Calc.
Conc. Conc. Add-on Add-on Anal. Add-on Epsom
Comp.2 Comp.2 frorn from A/T from Salt
Trial Liquor Liquor Set-up Set-up Liquor Carpets Add-on
I.D. g/l g/l % owf ~ owf % owf % owf ~ owf
10 1 0 00 - O O O ',
2 30.4 21.217.7 3.4 2.3 2.62 0
3 0 00 0 0 0 0
4 20.9 14.410.9 2.1 1.5 1.8g 0
Actual w.p.u. was between 523 and 532%, pH was 8.3 for
control; 3.0 for Trial 2; 3.3 for Trial 4.
Preheat liquor temperature was 140F (60C). Carpet
temperature was 127-130F (52.8-54.4C). Application
liquor temperature was 179-182F (81.2-83.3C) and
carpet temperature was 156-161F (68.9-71.7C).
T~BLE VIII
STAINING PERFORMANCE, DURABILITY TO ~
STEAM CLEANING AND CHANGE-OF-SHADE DATA ~-
Nominal ~~~
Comp.2 Stain Rating (0=best, 10=worst)-
Sample Applied, Time Before Blotting with Water, Hr
I.D. % 0.05 0.5 1 4 --
: 1 0 8.5 8.5 8.5 8.5
2 15 0.25 0.25 0.75 1.5
3 0 4.5 7.0 7.0 7.0
. 30 4 9 0 0 0 0.1
Stain Rating
(0=best,10=worst)
Tlme Before
Blotting with
35 Sample Water, Hr S.C.** Shade
I.D. 8 24 4 Change *
1 8.5 8.5 7.0
2 1.75 2.0 5.0 M-N (Y)
3 7.0 7.0 7.0
40 4 0.1 0.1 3.0 M (Y)
; * N=no, acceptable; M=marginal; Y=yellow.
Letter in parentheses indicates direction of color
change frorn the control.
** steam cleaned.
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133~7~
-36-
TABLE IX
COLORFASTNESS DATA
Grey Scale Rating
Sample Nominal Comp.2 Lightfastness, AFU
5I.D. Applied, % 20 40
1 0 4.0 3.0
2 15.0 2.5 3.0
3 0 4.5 3.5
4 9.0 ~ 3.5 3.5
Grey Scale Rating
N02*
Sample Ozonefastness Fastness
I.D. 1 2 3 5 ~_~y
1 3.0 2.5 2.0 1.0 2.5
2 3.0 2.5 2.5 2.0 1.0
3 3.5 3.0 2.5 2.0 2.5
4 3.5 3.0 3.0 2.5 1.5
* High R.H. nitrogen dioxide (AATCC TM-164).
TABLE X
BENZOYL PEROXIDE SPOTTING DATA*
Spot Visibility (O=Invisible; 10=Bright)
Nominal _ Ori~inals
Comp.2 Benzoyl Peroxide Conc.,
SampleApplied, % Solution in Acetone
-r I.D.% 0.010.05 0.10 1 5.0
1 0 2.07.5 8.0 9.0 9.5
215 1.06.57.0 8.5 8.5
3 0 2.07.58.0 9.0 9.5
4 9 2.07.58.0 8.5 8.5
* Sample spotted with 1 ml of benzoyl peroxide solution
and exposed in chamber at 90F (32.2C) and 80% R.H.
for three days (color change ceases).
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-37-
TABLE X (CONTINUED)
BENZOYL PEROXIDE SPOTTING DATA*
Spot Visibility (O=Invisible; lO=Bright)
steam Cleaned - -
Benzoyl Peroxide Conc.,
Sample ~ Solution in Acetone
_
I.D. 0.01 0.05 0.10 1.0 5.0
l 1.0 5.0 7.0 9.0 9.5
2 0.25 5.0 7.0 8.5 9.0
lO 3 0.5 5.0 7.0 8.5 9.0
4 0.3 4.5 6.5 8.0 9.0
* Sample spotted with 1 ml of benzoyl peroxide solution
and exposed in chamber at 90F (32.2C) and 80~ R.H.
15 for three days (color change ceases). ~-
TAsLE XI
REPELLENCY DATA (FINISHED CARPETS)
Sample Nominal Co~np.2 Repellency
20I.D. Applied, % Oil Water
l 0 4.0 4.0
2 15.0 4.0 4.5 :~
3 0 3.0 4.0
4 9.0 3.0 4.5
~: This Example 2 demonstrates the effectiveness of
the sulfonatèd aromatic condensate with only a dispersing
- agent and further demonstrates the effectiveness of the
35 continuous aftertreatment process of this invention. ~:
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-38-
Example 3 - Part 1
This example demonstrates the effective use of
the process of this invention on fabric which has not been
previously treated with any fluorocarbon compound for
antisoiling properties. The Cornposition 2 used in the
continuous aftertreatment process (no two step) of this
invention as set forth in Example 1. Dyebath formulation
was as in Example 2. Conditions were as in Example 1,
more specifically, preheat water temperature was 195F
(90.6C) at 100% w.p.u. to achieve carpet temperature o~
135-140F (57.2 to 60C). Aftertreatment liquor
temperature was 180-185F (82.2 to 85C) to achieve carpet
temperature of 160-170F (71.1 to 7~.7C). Aftertreatment
dwell time was 30 seconds before washing at 40:1 liquor to
fabric ratio, hydroextraction and drying. Both
compositions were applied at both 1.5 and 3.0~ on the
weight of the fabric. Samples of fabric pretreated with
fluorocarbons, which are also part of the invention, were
run alongside the fabric untreated with fluorocarbon. The
results show that higher amounts of sulfonated aromatic
~ondensate must be applied to the fabric untreated with
fluorocarbon to achieve the nearly same level of s~ain
resistance. The following tables give application
conditions and results.
TABLE XII
EVALUATION OF STAIN BLOCKING FOR
CONTINUOUS AFTERTREATMENT
Stain Rating Totall 20 AFU Rank2 _ -
Nominal Fabric Fabric Fabric Fabric
Sample Add-on, With Without With Without
_I.D. ~ *Fluoro. Fluoro. Fluoro. Fluoro.
1 0i 54.0 45.0 2 3
2 3.01.5 1.4 4 7
3 3.00.3 0.3 4 9
4 3.01.2 1.5 4 9
~ .
* Samples 2 and 4 applied at pH 3. Samples 1 and 3 were
applied at pH 2.
1 Total of ratings at 1, 4, 7 and 24-hour tests.
High numbers indicate most stain.
2 Lower numbers are better.
1330~7~ -
-39-
TABLE XII (CONTINUED)
EVALUATION OF STAIN BLOCKING FOR
CONTINUO~S AFTERTREATMENT
NO2 RanX2 Soiling Rating**
Fabric FabricFabric Fabric
Sample With WithoutWith Without
I.D. Fluoro. Fluoro.Fluoro. Fluoroc
1 1 1 4 8
2 2 2 9.5 9
3 2 3 10 10
4 2 2 5.5 7.5
** Soiling evaluated under Accelerated Method, 0=best,
10=worst.
2 Lower numbers are better.
TABLE XIII
ANALYSIS DATA
S.a.c. Analyzed, ~ owf*
Sample Nominal Fabric With Fabric Without
I.D. Add-on, % Fluoro. ~ ~ Fluoro.
- O O
2 3.0 3.09 2.96 ~ ? `
3 3.0 3.47 3.36
4 3.0 2.94 2.86
Samples 2 and 4 were applied at pH 3. Samples 1 and 3
were applied at pH 2. -~
* Extracted from carpets with 0.lN NaOH for four hours and
analyzed by HPLC against original material.
Example 3 - Part 2
The conditions of Example 3 - Part 1 were
repeated except Composition 1 was used with the results
shown in the following tables. All fabric was without
fluorocarbon treatments,
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-40-
TABLE XIV
STAINING AND CHANGE-OF-SHADE DATA
... .. .
Nominal Stain Rating (0=best,10=worst)
Comp.l Time Before Blotting
Trial Add-on, With Water, HrShade
I.D. % owf 1 4 7 24Change
1 - 7.0 7.0 7.0 7O0
2 5.0 0.25 .1.0 1.00.75 M (Y)
3 6.0 0.1 0.75 0.750.5 M (Y)
4 7.0 0.1 0.25 0.250.25 M (Y)
8.0 0.1 0.25 0.250.25 M (Y)
TABLE XV
COLORFASTNESS DATA
Grey Scale Rating
Nominal NO2*
Comp.l Lightfastness, Ozonefastness, Fastness,
Trial Add-on, AFUcy cy
20 I.D. % owf 20 40 1 3
1 - 4.0 3.5 3.5 2.0 3.0
2 5.0 4.5 4.0 4.0 3.0 2.5
3 6.0 4.5 4.0 4.0 3.5 2.5
4 7.0 4.5 4.0 4.0 3.5 2.5
~.0 4.5 4.0 4.5 4.0 2.5
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-41-
TABLE XVI
ANALYSIS DATA
s.a.c.
Nominal Anal. Add-on Anal.
Comp.l A/T Based on sac Anal.
Nominal Conc. Liquor Anal. Add-on sac in
Comp.l A/T Conc. A/T from Rinse
Trial Add-on, Liquor of sac Liquor Carpets Bath
I.D. % owfg/l* g~l % owf ~ owf g/l
1 - - _ N/D** N/D
2 5.012.5 11.8 4.7 5.1 N/D
3 6.015.0 15.0 6.0 7.3 N/D
4 7.017.5 19.6 7.8 7.5 N/D
8.020.0 23.5 9.4 8.3 N/D
* Applied at 400`~ w.p.u.
** Non-detected
Example 4
The process and conditions of dyeing
formulations of Example 2 using Composition 2 were
repeated with and without citric acid to adjust pH in the
continuous aftertreatment application process of this
invention the fabric was in 32 ounce per square yard cut
pile construction of a 1185 denier bulked continuous
filament, Superba H/S, beck-dyed grey. The fiber had been
treated with fluorocarbon for antisoiling properties.
Also all dispersing agents (Tamol) were omitted from
Composition 2 for another set of samples. Epsom salt (49%
MgS04) was added to another set of samples. Citric acid
was used as a rinse and in the application liquor. Use of
citric acid in the treatment liquor or to adjust pH
resulted in improved yellowing of the sulfonated aromatic
condensate treated fiber. The combination of Epsom salt
and citric acid further reduced the tendency to yellow
whether due to exposure to ozone or to N02. The following
tables provide application conditions and results.
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-42-
TABLE XVII
EVALUATION OF CITRIC ACID -
USE FOR CONCENTRATE pH ADJUSTMENT ON
LIGHT INDUCED YELLOWING
APPLICATlON AND ANALYSIS DATA
.
Nominal
s.a.c.
SampleApplied,
10I.D. s.a.c.Used % Other Agents/Conc.
6 Not Treated 0
1 Composition 2 3.0
2 Composition 2 3.0
3 Composition 2 3.0
4 Composition 2 3.0
Composition 2 3.0 - --~
7 Composition 2 3.0 0.09 g/l Citric Acid
8 Composition 2 3.0 0.09 g/l Citric Acid
9 Composition 2 ' 3.0 0.75 g/l Citric Acid
20 10 Composition 2 3.0 0.75 g/l Citric Acid
11 Intratex N 3.0 Citr-ic Acid (pH adj) *
12 Intratex N 3.0 Citric Acid (pH adj) *
13 Intratex N 3.0 0.7,2% owf Epsom Salt &
Citric Acid (pH adj) *
25 14 Intratex N 3.0 0.72% owf Epsom Salt &
Citric Acid (pH adj) *
~ * 1.25 g/l citric acid required for pH ad]ustment.
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-43-
TABLE XVII (CONTINUED)
EVALUATION OF CITRIC ACID -
USE FOR CONC~NTR~TE pH ADJUSTMENT ON
LIGHT INDUCED YELLOWING
APPLICATION AND ANALYSIS DATA
s.a.c.
Sample Appl. Analyzed
I.D. pH Rinse
6 7.5 Normal - Cold Water 0
1 3.1 Normal - Cold Water 1.87
2 3.1 0.09 g/l Citric (pH 4.1) 2.18
3 3.1 0.25 g/l Citric (pH 3.5) 2.29
4 3.1 0.75 g/l Citric (pH 3.1) 2.32
3.1 5.9 g/l Citric (pH 2.5) 2.44
7 3.1 Normal - Cold Water 1.90
8 3.1 No Rinse 2.10
9 2.9 Normal - Cold Water 2.04
2.9 No Rinse 2.30
11 3.0 Normal - Cold Water 2.67
12 3.0 No Rinse ~ 2.39
13 3.0 Normal - Cold Water 2.89
14 3.0 No Rinse 2.89
.
Notes: Carpet temperature before A/T ranged from 132 to
138F (55.6-58.9C).
A/T liquor temperature was 183 to 185F
(83.9-85C).
Actual temperature after A/T ranged from 163 to
171F (72.8-77.2C)
.
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-44-
TABLE XVIII
EVALUATION OF CITRIC ACID -
USE FOR CONCENTRATE pH ADJUSTMENT ON
LIGHT INDUCED YELL0WING
STAINING PERFORMANCE
5AND CHANGE-OF-SHADE DATA
Stain Rating (0=best,10=worst)
Sample Time Before Blotting With Water,Hr
I.D. 0.05 0.5 1 4 8 24 Shade Change*
6 9.5 9.5 9.5 9.5 9.5 9.5
l 0 0.25 0.5 1.0 1.0 1.0 ril-N
2 0 0.25 0.25 0.5 0.5 0.75 M-N
3 0 0.25 0.25 0.5 0.75 1.0 M-N
4 0 0.25 0.25 0.5 0.75 0.75 M-N
0 0.25 0.5 0.5 1.0 1.5 M-N
7 0 0.25 0.25 0.25 0.25 0.25 M-N(Y)
8 0 0.25 0.25 0.5 1.0 1.0 M-N(B)
9 0 0.25 0.25 0.25 0.5 0.75 M-N(B)
0 0.1 0.1 0.5 0.5 0.5 M-N
20 ll 0.1 0.5 0.5 0.5 0.5 1.0 M-N
12 0 0.25 1.0 2.0 2.5 2.5 M-N
13 0 0.25 0.25 0.25 0.25 0.25 M-N(B)
14 0 0.25 0.5 0.5 0.5 0.5 M-N(B)
* M=marginal, N=none, Y=yellow, B=blue
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--45--
TABLE XIX
EVALUATION OF CITRIC ACID --
USE FOR CONCENTRATE pH ADJUSTMENT ON
LIG~lT INDUCED YELLOWING
-
COLORFASTNESS DATA
Grey 5cale Ratin
Lightfastness, NO2*
Sample AFU Ozonefastness, cy Fastness,
10I.D. 2 40 1 2 3 5 1 cy_
6 4.0 3.5 3.0 2.51.5 1.0 2.5
2.5 3.0 3.0 2.52.5 2.0 1.5
2 2.5 3.0 3.0 2.5 - - 1.5
3 2.5 3.0 3.0 2.5 - - 1.5
4 3.0 3.0 3.5 3.03.0 2.5 1.5
3.0 3.0 3.5 3.0 - - 2.0
7 2.5 3.0 3.0 3.0 - - 1.5
8 2.5 3.0 3.0 2.5 - - 1.5
9 3.0 3.0 ~3.5 3.03.0 2.5 2.0
20 10 2.5 3.0 3.5 3.03.0 2.5 1.5
11 3.0 3.5 3.5 3.0 _- - 2.0
12 3.0 3.5 3.5 3.0 - - 2.0
13 4.0 3.5 3.5 3.03.0 3.0 2.5
14 4.0 3.5 3.5 3.53.5 3.0 2.5
* High R.H nitrogen dioxide (AATCC TM-164).
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-46-
TABLE XX
EVALUATION OF CITRIC ACID -
USE FOR CONCENTRATE pH ADJUST~IENT ON
LIGHT INDUCED YELLOWING
BENZOYL PEROXIDE SPOTTING DATA*
Spot Visibility (0=Invisible; 10=Bright)
SampleBenzoyl Peroxide Conc., ~ Soln. in Acetone
I.D. 0.01 0.05 0.10 1.0 5.0
6 3.0 7.0 8.0 9.0 9.5
1 0.75 5.5 6.5 7.5 ~.0
13 0 0.25 0.5 1.5 2.5
14 0 0.25 0.5 1.5 2.5
* Sample spotted with 1 ml of benzoyl peroxide solution
and exposed in chamber at 90F (32.2C) and 80% R.H. for
three days.
Example 5
The process on the fabric of Example 4 was
repeated, also using Composition 2 with and without the
Tamol dispersant, and also adding N~4SCN to show its
benefits.
Following are the standard continuous process
aftertreatment conditions used:
Prewet/heat carpet at 195F (90.6C) and 100%
w.p.u. to achieve a carpet temperature prior to treatment ~-~
of 135 to 140F (57.2 to 60C).
Apply A/T liquor at 400% w.p.u. and 175 to 180F
(79.4 to 82.2C) to achieve a post-A/T carpet temperature
of 160 to 170F (71.1 to 76.7C).
~`! Aftertreatment, 30-second dwell time before
washing (at 40:1 liquor ratio), hydroextraction and
drying,
Summary of Results
1. Application
~-~ The addition of NH4SC~ to the Composition 2
~ -
bath was found to affect pH only at the lowest
concentration. This is an indication of the buffering
capacity of Composition 2 solutions.
~,,
133~476
..
-47-
During the make-up and running of the treatment
solutions, it was observed that considerably more foaming
occurs with Intratex-N alone than does Composition 2.
2. Stain Resistance
Composition 2 tended to exhibit better staining
performance than Intratex N alone at comparable levels.
The differences between the two diminish as the overall
concentratio`n increases.
The addition of NH4SCN did not adversely affect
the staining performance and, in fact, samples with NH4SCN
tended to perform better than corresponding samples
without NH4SCN. This difference diminishes as the
Intratex N concentration increases and overall performance
improves.
3. Light and N02 Induced Yellowing (Table XXIII)
Intratex N and Tamol SN (by themselves) were
found to behave differently when exposed to light.
Intratex N yellows/browns severely at short light
exposures (20 afu). This yellowing or browning then fades
20 as the lightfastness exposure is continued. Tamol, on the -~
other hand, greens when exposed to 20 afu and upon
continued exposure the green fades to yellow. The overall
rating of the shade change does not necessarily improve
from the 20 to 40 afu exposures. The severity of shade
change is about equal for Intratex N and Tamol SN.
The break of Composition 2 at short -
lightfastness exposures (20 afu) appears as a hybrid of
Intratex N and Tamol SN alone (at the respective levels in
Composition 2).
At both 20 and 40 afu, the break of Composition
2 samples were no worse-to-slightly better than the
corresponding Intratex N and Tamol SN only samples.
The addition of NH4SCN gives a slight
improvement in light induced yellowing. The reduction is
greatest at the lower Intratex N levels and decreases as
the Intratex N level increases. Similar behavior is
observed between Composition 2 and Intratex N alone, but
;~ Tamol SN is less affected.
.: .
1330476
-48-
Yellowing diminishes as the N~-14SCN level
increases. The yellowing is significantly reduced using
approximately 0.3% owf NE~4SCN for every l.0~ owf Intratex
N.
Tamol SN was found to be unaffected by exposure
to N02, while Composition 2 and Intratex N yellowed
severely. The addition of NH4SCN improved N02 yellowing
only slightly, but not enough to raise Grey Scale ratings
above 1-2.
4. Ozonefastness (Table XXIII)
Intratex N had a significant impact on
ozonefastness, both alone and as Composition 2. While
overall fastness ratings tended to be better at extended
cycles compared to the nontreated control, a significant
yellowing occurs.
The yellowing of Intratex N overwhelms any
improvement achieved by the addition of NH4SCN. Samples
incorporating NH4SCN tend to yellow less when exposed to
ozone and higher levels yield more improvement. The
significant improvement in ozonefastness of NH4SCN alone
~as not achieved, but were improved over nontreated
samples.
5. Benzoyl Peroxide Spotting (Table XXIV)
The dispersant, Tamol SN, had no effect on the
benzoyl peroxide spotting performance. Table XXIV shows
the benzoyl peroxide performance identical when 0.3~ owf
NH4SCN is applied with either Composition 2 or s.a.c. at
several levels.
The performance of NH4SCN is not effected at
varied s.a.c. levels (as Composition 2 or alone) as shown
, , , ,; ~ ,
in Table XXIV.
Benzoyl peroxide spotting improves as the
NH4SCN concentration is increased from 0.3 to 0.6~ owf.
The improvement becomes more noticeable at the highest
benzoyl peroxide concentration and probably beyond.
~ .
Conclusions
The dispersant, Tamol SN, contributes to the
light induced yellowing of Composition 2 but is not the
133047fi
.
-49-
sole cause. Elimination of Tamol SN from Composition 2
would not significantly improve or resolve yellowing on
Superba H/S substrates. The elimination of Tamol SN could
reduce staining performance slightly at lower add-on's and
increase the foaming of the treatment liquor upon spray
application.
Intratex N is the sole cause of yellowing upon
exposure to ~2 of Composition 2.
Tamol does not interfere with any of the NH4SCN ~-
benefits.
Intratex N has a significant impact on
ozonefastness (yellows) and overwhelms the ozonefastness
improvement benefits of NH4SCN. There is, however, a
reduction in the yellowing and an improvernent over
Composition 2 alone at a nominal 0.6~ owf NH4SCN.
NH4SCN has no adverse impacts on Composition 2
stain blocking benefits.
There is a reduction in light induced yellowing
when NH4SCN is applied with Composition 2. The degree of
improvement has varied from marginal to significant
during all internal trials. Higher NH4SCN levels always
yield greater improvernent.
- Benzoyl peroxide spotting performance may be
further improved, particularly at higher benzoyl peroxide
concentrations, by increasing the NH4SCN level to 0.6%
ow~.
' ~1,
; ~
: ::
'~: :
~ . . .
, ~ .
`~
:
::
133Q~7fi
..,,~
-50-
TABLE XXI
APPLICATION AND ANALYSIS DATA
Nominal
s.a.c. s.a.c.
5Applied Nominal Nominal Nominal Anal.
as s.a.c. Tamol SN Nl14SCN (As
Sample Comp.2, Applied* Applied* Applied Rec'd)
I.D. % % % ~i pH %
1 - - - - 7.4 0
10 28 - - - 0.3 2.8 0
2 1.0 - - - 3.5 1.05
3 1.0 - - 0.3 4.6 1.08
4 1.0 - - 0.6 4.7 1.05
2.0 - - - 3.1 1.91
6 2.0 - - 0.3 3.2 1.93
7 2.0 - - 0.6 3.2 2.16
8 3.0 - - - 3.0 3.19
9 3.0 - - 0.3 3.0 3.58
3.0 - - 0.6 3.0 3.24
20 11 4.0 - - - 2.8 3.23
12 4.0 - - ~0.3 2.9 4.20
13 4.0 - - 0.6 2.9 3.90
14 - 2.0 - - 3.2 2.10
- 2.0 - 0.3 3.2 2.43
25 16 - 3.0 - - 2.9 3.83
17 - 3.0 - 0.3 2.8 4.20
18 - 4.0 - - 2.7 4.97
19 - 4.0 - 0.3 2.7 4.73
- - 1.93 - 2.9
30 21 - - 1.93 0.3 2.9
22 - - 2.90 - 2.8
23 - - 2.90 0.3 2.8
24 - - 3.89 - 2.8
~ 25 - - 3.89 0.3 2.9
'~ 35 * Materials applied as supplied, not blended or part of a
composition.
Notes: Carpet temperature before A/T ranged from 132 to
144F (55.6-62.2C).
A/T liquor temperature was 178 to 183F (55.6-
62.2C).
Actual temperature after A/T ranged from 158 to
172F (70-77.8C)
~' 133~7~
TABLE XXII
STAINING PERFORMANCE DATA
. . .
Stain Rating (O=best,10=worst)
5 Sample Time Before Blotting With Water, Hours
I.D. 0.05 0.5 1 4 8 24
1 9.5 9.5 9~5 9.5 9.5 9.5
~ O 1.0 2.0 3.5 3.5 3.5
3 0 1.0 1.5 2.0 3.0 3.0
4 0 0.5 0.75 1.5 1.0 1.0
0 0.25 0.5 1.0 1.0 1.5
6 0 0.25 0.25 1.0 1.0 1.0
7 0 0 0.25 0.5 0.5 0.5
8 0 0.25 0.25 0.75 0.75 0.75
9 0 0 0.10 0.25 0.25 0.25
0 0 0 0.25 0.5 0.5
11 0 0 0.1 0.5 0.25 ~.5
12 0 0 0.1 0.25 0.25 0.5
13 0 0 0 0.25 0.25 0.25
20 14 0 0.5 1.0 1.5 2.0 3.0
0 0.5 1.0 1.25 2.0 2.5
16 0 0.25 0.25 0.5 0.5 0.5 ``
17 0 0 0.25 0.5 0.25 0.25
18 0 0.1 0.1 0.25 0.25 0.25
25 19 0 0 0 0.25 0.1 0.1
.,
~ .~r
~3~476
--52--
TABLE XXIII
COLORFASTNESS DATA
Grey Scale Rating
5 Lightfastness, ~O2*
Sample AFU Ozonefastness, cy Fastness,
I.D. 20 40 1 2 3 5 , 1 cy
4.0 3.0 3.0 2.5 2.0 1.0 3.0
28 4.0 3.0 3;5 3.0 3.0 3.0 3.0
102 2.5 3.0 3.0 2.5 2.5 2.0 1.5
3 3.0 3.5 3.0 2.5 2.5 2.5 1.5
4 3.5 3.5 3.0 2.5 2.5 2.5 1.5
2.5 2.5 2.5 2.5 2.0 2.0 1.5
6 2.5 2.5 3.0 2.5 2.5 2.0 1.5
157 3.0 3.0 3.0 2.5 2.5 2.5 1.5
8 2.0 2.5 2.5 2.5 2.0 2.0 1.5
9 2.0 2.5 2.5 2.5 2.5 2.0 1.5
2.5 2.5 ,3.0 3.0 2.5 2.5 1.5
11 2.0 2.0 2.5 2.5 2.0 2.0 1.5
2012 2.0 2.0 2.5 2.5 2.0 2.0 1.5
13 2.5 2.5 3.0 3.0 2.5 2.5 1.5
14 2.5 2.5 2.5 2.5 2.0 2.0 1.5
3.0 2.5 2.5 2.5 2.0 2.0 1.5
16 2.0 2.0 2.5 2.5 2.0 2.0 1.5
2517 2.5 2.5 2.5 2.5 2.5 2.0 1.5
18 2.0 2.0 2.0 2.0 2.0 2.0 1.5
19 2.5 2.0 2.5 2.5 2.0 2.0 2.0
2.5 2.5 2.5 2.5 - - 2.5
21 2.5 2.5 3.0 3.0 - - 3.0
3022 2.0 2.0 3.0 2.5 - - 3.0
23 2.0 2.0 3.0 2.5 - - 3.0
24 2.0 2.0 3.0 2.5 - - 2.5
2.0 2.0 3.0 2.5 - - 3.0
35 * High R.H nitrogen dioxide (AATCC TM-164).
~,
133~476
-53-
TABLE XXIV
-
BENZOYL PEROXIDE SPOTTING DATA*
Spot Visibility (0=Invisible;10=Bright)
5 SampleBenzoyl Peroxide Conc., % Soln. in Acetone
I.D. 0.005 0.01 0.05 0.1 1.0
_
1 0.5 1.5 6.5 8.0 9.0
28 0 0 0.75 1.0 8.0
2 0.25 2.0 6.75 8.0 8.5
3 0 0 1.25 4.0 7.0
4 0 0 0.25 0.5 2.0
0.5 1.75 5.5 6.5 7.5
6 0 0 0.5 1.0 2.0
7 0 0 0.1 0.75 3.0
8 0.25 2.0 7.25 7.5 7.5
9 0 0 0.5 1.25 2.0
0 0 0.25 0.5 0.75
11 1.0 2.5 7.5 8.0 8.5
12 0 0 0.5 1.0 3.0
20 13 0 0 0.1 . 0.5 1.25
14 0.5 1.5 6.5 7.5 ~.0
0 0 0.5 1.0 2.0
16 - - - - -
17 - - - -
25 18 0.25 1.0 6.5 7.5 8.5
` 19 0 0 0.5 0.75 1.75
* Sample spotted with l ml of benzoyl peroxide solution
and exposed in chamber at 90F (32.2C) and 80~ R.H. for
three days.
: ~ ; . , I . ' , !
; ':
,
i.
`C:~
-:~
i33~7~
-5~-
Example 6
This example demonstrates the two-step,
batch-batch (beck-beck) process embodiment of this
invention.
Prior art has shown that application of
sulfonated arornatic condensates (stain blockers) to nylon
improves resistance to staining by most food colors. In
the prior art, the preferred mode of application has been
a low temperature (120~ to 180F (48.9 to 82.2C)
treatment with the stain blocker after dyeing has been
completed. Also, prior art includes application of stain -~
blockers concurrent with dye application. This invention
embodies application of a portion of the total stain
blocker concurrently with dye application, and application
of the remainder in a low temperature aftertreatment step.
(two-step process).
The two-step p~ocess results in a level of stain
performance superior to that which is achieved by the
prior art at the same total add-on concentration of stain
blocker. In addition, use of ammonium thiocyanate in the
aftertreatment step improves dye fastness to ozone,
benzoyl peroxide (acne medications) and light.
It is theorized that the improvement over prior
art is achieved by maximization of the concentration of
stain blocker in a thin zone near the fiber surface and
that this condition results in better stain resistance.
The two-step process promotes this condition by sorption
of a portion of the stain blocker during the dyeing
operation which is fully penetrated into the cross-section
of the nylon fiber. The sorption of the portion of stain
blocker subsequently applied in the low temperature
aftertreatment step in retarded by the presence of the
~` existing portion already on the fiber, therefore,
increasing the effective concentration near the fiber
surface. The presence of magnesium sulfate in both steps
of the process accelerates rate of sorption of the stain
blocker by increasing the bath electrolyte concentration
.
~'`.' '',,';` '' ',''.''~"'`.'"'''''"`'' " ""'` " ''"" ' `' ' ` '' '`'"' ' ' '' . '.'.'`j'`'` ' ' ',': .,', ,,
7 ~
-55-
and by complexing with the stain blockers thus reducing
molecular mobility in the nylon.
Example 6 - Part 1
This example shows that two-step process is
superior to either concurrent or aftertreatment.
Carpet Fabric:
1185 denier fluorocarbon treated Superba Heat Set
Process:
A total of 2.0% owf Intratex N was applied to
carpet.
The total was distributed between dyebath and
aftertreatment in the following ways:
Dyebath, % Aftertreatment, %
O 1()0
15 50 50
100 0
Varying amounts of Magnesium Sulfate were used
(0% owf to 4% owf~. ;
Dyebath conditions were typical of industry
practice.
Dyeing procedure as follows:
1. Load fabric and wet out at 20:1 Liquor
Ratio
2. Add 1.0% owf Dowfax 2Al-sodium mono-and
didodecyl disulfonated diphenyl oxide (45% active)
3. Add the specified amount of Intratex N-l
4. Add the specified amount of Magnesium
Sulfate
5. Run 5 minutes
6. Add~0.5% Sequestrene 30A (EDTA) or equiv.
7. Add 1% owf ammonium sulfate
8. Add 0.5% owf ammonium hydroxide
9. Add predissolved dyes
10. Run 10 minutes
~; 35 11. Raise temperature to boil
,~ 12. Boil 30 minutes
13. Drop and rinse cold
`~
.
.
1~30476
, .
-56-
14. Aftertreat if indicated
Aftertreatment procedure as follows:
1. Reill Beck at 20:1 Liquor Ratio
2. Add specified amount of Magnesium Sulfate
3. Add specified amount of Intratex Nl
4. Run 10 minutes
5. Lower pH to 2.0 to 2.1 with sulfamic acid
6. Raise temperature to 160F (71.1C).
7. Hold at temperature 20 minutes
8. Drop bath and rinse cold
Performance:
Reference samples Nos. 17 through 31 in Table
XXV. Samples 23, 24 and 25 prepared with the 50%/50%
two-step process are superior. Those samples which passed
the dip test were further tested by the drop test.
Test Protocols:
1. "Dip Test" - Immerse a 5 gram sample of
unfinished carpet into a large excess of Cherry Kool-Aid
(unsweetened) at room temperature for 30 minutes. Rinse
with cold water, dry and assess the stain.
2. "Drop Test"- Drop 30 ml. Cherry Kool-Aidl
(unsweetened) onto the finished carpet from a height of 12
inches. Allow to stand for seven hours. Blot with paper
towels using water spray to aid in removal.
Example 6 - Part 2
-~ This example shows use of ammonium thiocyanate
in two~step process for improved resistance to benzoyl
peroxide and light fading.
Carpet Fabric:
~ -
170Q denier Superba Heat Set (High ICP fiber)
Process:
., .
Using the process of Part 1, a total of 2.8%
Intratex N was applied using the 50%/50% two-step mode.
A second sample was prepared in the same way but an
Intratex N pre-formulated rnixture containing ammonium
thiocyanate (Composition 3) was used in the aftertreatment
step. Composition 3 is 40% Intratex N-l, 12~ ammonium
thiocyanate, 21.5% Monawet MB45, 26.5~ ater.
1 Registered ~ of General Foods Corporation.
~ ~ 330476
-57~
Performance:
Reference samples "H" and "I" in Tables XXVI to
XXVIII. Using the "Drop Test" Protocol from Example 1,
sample "I" has good stain resistance (somewhat poorer than
"H") but very significant improvements in benzoyl peroxide
and light fading.
Example 6 - Part 3
This example shows that 50%/50~ two-ste~ mode is
preferred and the 2% magnesium sulfate is optimum.
10Carpet Yabric:
1185 denier fluorocarbon treated autoclave Heat
Set (high ICP fiber)
Process:
Using the process of Part 1, a total of 3.0%
Intratex N-l was applied using the two-step mode.
The total was distributed between dyebath and
aftertreatment in the following ways:
Dyebath, % Aftertreatment, %
10.0
Varying amounts of magnesium sulfate were used
-~ (0% owf to 4% owf)
Performance:
;~ Reference samples 2 through 23 Table XXIX.
Using the test protocols from Example 1, samples 20
30 through 23 (50%/50% application mode) have best stain
resistànce. Samplè 20 is best of group (uses 2~ and 2%
owf magnesium sulfate). ~ -
: '~
. ~, .
~`
.
`~` 133~476
-58-
TABLE XXV
Dyebath Aftertreatment K/A** "Dip"
No. s.a.c. ES* s.a.c. ES* Test***
1 0 0 - - F
2 0 0 1.6 0 F
3 0 0 1.6 2.0 F
4 0 0 1.6 ' 4.0 F
0.8 0 0.8 . 0 F
10 6 0.8 0 0.8 2.0 F
7 0.8 0 0.8 4.0 F
8 0.8 2.0 0.8 0 S
9 0.8 2.0 0.8 2.0 P
0.8 2.0 0.8 4.0 S
1511 0.8 4.0 0.8 0 S
12 0.8 4.0 0.8 2.0 S
i3 0.8 4.0 0.8 4.0 P
14 1.6 0 - - F
1.6 2.0 - - F
~; 2016 1.6 4.0 - - S
17 0 0 2.0 0 F
18 0 0 2.0 2.0 F
~: 19 0 0 2.0 4.0 F
~ 20 1.0 0 1.0 0 F
:; 2521 1.0 0 1.0 2.0 F
22 1.0 0 1.0 4.0 F
23 1.0 2.0 1.0 0 P
; 24 1.0 2.0 1.0 2.0 P
1.0 2.0 1.0 4.0 P
3026 1.0 4.0 1.0 0 S
~
~` 27 1.0 4.0 1.0 2.0 P
28 1.0 i4.0i 1.0 4.0 P
: 29 2.0 0 - - F
:,~ 30 2.0 2.0 - - F
3531 2.0 4.0 - - F
32 0 0 2.8 0 F
33 0 0 2.8 2.0 F
* Epsom salt
~:: ** Kool Aid
***F=fail P=pass S=slight stain
,~
~ .:; ~
~ ~33~`~7~
-59-
TABLE XXV (CONTINUED)
Dyebath Aftertreatment K/A "Dip"
5 No. s.a.c. ES* s.a.c. ES* Test
34 0 0 2.8 4.0 F
1.4 0 1.4 0 F
36 1.4 0 1.4 2.0 F
37 1.4 0 1.4 4.0 F
1038 1.4 2.0 1.4 0 S
39 1.4 2.0 1.4 2.0 P
1.4 2.0 1.4 4.0 P
41 1.4 4.0 1.4 0 P
42 1.4 4.0 1.4 2.0 P
1543 1.4 4.0 1.4 4.0 P
44 2.8 0 - - F
2.8 2.0 - - P
46 2.8 4.0 - - P
P = Pass (No Stain)
F = Fail (Noticeably Stained)
S = Slight Stain (Just Detectable)
* Epsom salt
TABLE XXV (Continued)
Gray Scale
7-Hour Xenon
Kool-AidLight-Fastness Shade
No. Staining* 20 AFU Change
1 7.5 3.0
2 - 3.0 3.5
3 - 3.0 3.5
4 - 3.5 3.0
- 3.0 3.0
6 - 2.5 4.0
7 ' - ` 3.0 ' 3.5
8 1.5 3.5 3.0
9 0-75 3-5 3.5
1.0 3.5 3.0
11 1.0 3.5 3.0
12 0.75 3.5 2.5
40 13 0.25 4.0 3.0
*Drop test
~ .
.
'
133~47fi
-60-
TABLE XXV (CONTI~UED)
Gray Scale
7-HourXenon
Kool-Aid Light-Fastness Shade
5 No. Staining 20 AFU Change
.
14 - 2.5 3.5
- 2.0 3.5
16 1.03.0 3.5
17 - 4.0 3.5
18
19 - 4.0 3.0
- 4.0 3.5
21 - 3.5 3.5
22 - 3.5 3.5
23 0.5 4.0 3.0
24 0 3.5 3.5
0.1 3.5 3.5
26 0.5 ' 3.5 3.5
27 0 3.0 3.5
28 0 3.0 - 3.5
29 - 2.5 3.0
- 2.5 3.0
31 - 2.5 3.0
32 - 3.5 3.0
33 - 4.0 3.5
34 - 4.0 3.0
- 2.5 3.5
;~ 36 - 2.5 3.5
37 - 2.5 2.5
38 0.5 2.0 3.5
39 0.1 j ~ 2.5 , 3.5
0 2.5 3.5
41 0 3.0 3.5
42 0 3.0 4.0
43 0
44 - 2.0 2.5
0.1 2.5 2.5
46 0.1 3.0 2.5
133~.~7fi
" ` ~
-61-
TABLE XXVI
Original Samples
Before Blot, Hours
No. Description
5 A Control 7.50
Aftertreatments
B 5.0% Intratex N-1+4% ES* 0.10
C 10% Composition 3 0.75
D 10% Composition 3+4~ ES 0.75
E 12.5% Composition 3 0.25
Two-Step
1 _ 2
F 1.0~ IntratexN-1+2.0%ES 1.0% Intratex +2.0%ES 4.50
1.4% IntratexN-1+2.0~ES 1.4~ Intratex +4.0%ES 1.00
H 1.4~ IntratexN-1+4.0%ES 1.4% Intratex +4.0~ES 0.10
I 1.4~ IntratexN-1+2.0~ES 3.5% Comp. 3 +4.0~ES 1.00
* ES-Epsom salt
Original Samples s.a.c. ~
20Before Blot, ~ by Steam Cleaned
Hours ** analysis Before Blot, Hours
No. 4 7 _24 % 1 4 7 24
A8.00 8.00 8.00 - -~~
B0.25 0.50 0.50 13.58*2.00 3.50 3.00 3.50
C1.00 1.50 1.00 4.45 2.50 4.00 3.50 4.00
D1.00 1.00 1.50 4.64 4.00 3.00 4.00- 4.00
E1.00 1.00 1.50 5.83 1.50 4.50 3.50 4.00
F3.50 4.00 3.00 1.69 6.00 5.50 6.50 6.50
G2.00 2.00 1.50 2.14 4.00 4.00 5.00 4.50
30 H0.10 0.25 0.50 2.57 5.50 4.50 4.50 5.00
I1.00 1.50 0.75 2.14 4.00 5.00 5.00 4.50
* Error in application
Note: All aftertreatments at pH = 2, 160F ( C).
** Drop test 0=~est 10 worst
:~
. .
- 1330~76
. .
-62-
TABLE ~YVII
Spot Visibility *
Benzoyl Peroxide Spotting Data
5 No. 0.005 0.01 0.05 0.1 1.0
A 3.50 6.50 7.50 9.00 9.00
B 3.00 6.50 7.50 8.00 8.00
C 0 0.50 - 1.00 2.00 2.50
D 0 0.25 1.00 3.00 3.00
E 0 0.10 0.75 1.50 1.00
F 3.00 6.50 7.50 8.00 9.00
G 4.50 6.50 7.50 8.00 8.50
H 4.00 6.00 7.00 8.00 8.50
I 0.25 0.75 1.50 3.00 3.00
* 0 = Invisible: 10= Bright
TABLE XXVIII
Gray Scale Rating
Ozone No. 2
Lightfastness, Fastness, Fastness,
AFU Cycles ~ Shade
No. 20 40 60 1 2 1 Change
A 4 3 2-3 3-4 2-3 2
B 3 2-3 2-3 4-5 4 2 3
C 4 3-4 3 4-5 4 2-3 3-4
D 4 3-4 3 4 3-4 2-3 3-4
E 4 3-4 3 4-5 4 3 4
F 4-5 4 4 4-5 4 2-3 2
G 4 3-4 3 4 3-4 2-3 3
~ 3-4 3 3 4 3-4 2 2-3
I 4 3 3-4 4 3-4 3 3
~:
~ .
-- 133~476
-63-
TAsLE XXIX
Dyebath %owf Aftertreat ~owf . K~A t**
No. s.a.c. ES* s.a.c. ~A Dlp es
1 0 o - - 23
2 o o 3.0 2.022
3 o 0 3.0 4.021
4 0.15 2.0 2.85 2.0 20
0.15 2.0 -2.85 4.0 17
6 0.15 4.0 2.85 2.0 13
7 0.15 4.0 2.85 4.0 16
~ 0.3 2.0 2.7 2.0 14
9 0.3 2.0 2.7 4.0 18
0.3 4.0 2.7 2.0 12
15 11 0.3 4.0 2.7 4.0 15
12 0.6 2.0 2.4 2.0 9
13 G.6 2.0 2.4 4.0 19
14 0.6 4.0 ~ 2.4 2.0 10
0.6 4.0 2.4 4.0 11
20 16 0.9 2.0 2.1 2.~0 7
17 0.9 2.0 2.1 4.0 8
18 0.9 4.0 2.1 2.0 5
19 0.9 4.0 2.1 4.0 6
1.5 2.0 1.5 2.0
25 21 1.5 2.0 1.5 4.0 4
22 1.5 4.0 1.5 2.0 2
" 23 1.5 4.0 1.5 4.0 3
* ES Ep-Epsom salt
** Forced ranking (K/A = Kool-Aid)
1 = Best
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TABLE XXIX (CONTINUED)
s.a.c.
7-Hour Xenon by
Kool-Aid Lightfastness Shade analysis
No. Staining* 20 AFU Change
1 7.50 3-4
2 2.50 4 4 3.78
3 3.00 4 4-5 3.93
4 1.00 4 5 3.38
1.50 3-4 5 3.4B
6 1.50 4 4-5 3.38
7 1.50 4 4-5 3.60
8 1.00 4-5 4-5 3.60
9 1.50 3 4 3.60
1.00 3-4 4 3.38
11 1.50 3 4-5 3.29
12 1.00 '4 4-5 3.24
13 1.00 3-4 4 3.00
14 1.50 4 -~ 4-5 3.15
1.50 3-4 4 3.22
16 0.75 3 4 3.15
17 0.50 3-4 4-5 ~3.00
18 0.75 4 4-5 3.03
19 1.00 3-4 4 3.10
0.10 3-4 4 2.72
21 0.50 3-4 4 2.86
22 0.10 3-4 4 2.82
23 0.75 3 4-5 2.91
* drop test
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-65-
Example 7
This example describes use of a sequestering
agent in the continuous aftertreatment process of this
invention. The general procedure was as in Example 2.
Experimental Summary
Substrate
1185 denier fluorocarbon treated Superba H/S
in 32 ounce per square yard cut pile fabric construction
and beck dyed into Argent Grey shade.
Continuously aftertreated using nominal add-on
15.9% owf Composition 2 (3.0~ owf Intratex N) with no
additional pH adjustment tactual pH 2.9).
Calquest ADP (Mfrs. Chem.) added to treatment
bath containing Comp. 2 at levels corresponding to 0.5 and
1.0~ owf.
Standard Continuous Process
Prewet/heat carpet at 195F t90.6C) and 100~
w.p.u. to achieve a carpet temperature prior to treatment
of 135 to 140F (S7.2 to 60C).
Apply A/T liquor at 400~ w.p.u. and 175 to 180F
(79.4 to 82.2C) to achieve a post-A/T carpet temperature
of 160 to 170F (71.1 to 76.7C).
After treatment, 30-second dwell time before
washing (at 40:1 liquor ratio), hydroextraction and
drying.
-, Summary of Results
;~ The change in the dyed shade was reduced (went
more to the blue side) when the sequestering agent was
used.
Light induced yellowing was improved between 1/2
to 1 gray scale unit at 20 AFU using the sequestering
; agent. ~o further improvement was noted going from the
low to the high concentration. There also appeared to be
more of an improvement (or fading) of the yellowing in
going from 20 to 40 AFU's when the sequestering agent was
included.
Yellowing upon exposure to ozone was also mini-
mized when the sequestering agent was included. Only a
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slight reduction in the yellowing upon exposure to nitro-
gen dioxide was observed.
There was no impact on staining, but a slight
reduction in the Intratex ~ analyzed on carpet level was
observed when the sequestering agent was used.
Conclusions
The use of sequestering agent in the Composition
2 formulation shows reduced yellowing at low lightfastness
exposures and upon exposure to ozone.
TABLE XXX
EFFECT OF SEQUESTERING AGENTS ON LIGHT INDUC~D
YELLOWING (NOMI~AL 3.0~ OWF INTRATEX
ANALYSIS, STAINING PERFORMANCE,
CHANGE-OF-SHADE AND COLORFASTNESS DATA
Nominal Stain Rating
Nominal Seq. (0=best,10=worst)
Comp. 2 Agent Intratex N Time Before Blotting
Sample Conc., Conc.,~ Analyzed, With Water, Hours
20I.D. % owf% owf* ~ 0.05 0.5 1 4
1 N.T. - 0 7.0 8.5 8.50 8.5
2 3.0 - 4.22 0 0 0 0.1
3 3.0 0.5 3.41 0 0 0 0.1
4 3.0 1.0 3.66 0 0 0 0.1
Stain Rating Grey Scale Rating
: (O=best,10=worst) ~2***
Time Before Light- Ozone- Fast- ~-
, -r Blotting Withfastness, fastness ness,
30 Sample Water, Hours Shade AFU cy cy
I.D. 8 24Change 20 60 1 2 1 ~ -
1 8.58.5 - 3.5 2.53.02.5 2.5
2 0.10.1M(B) 2.5 3.03.02.5 1.0
3 0.1~0.1, M-Y(B) 3.5 4.03.03.0 1.5
4 0.10.1M-Y(B) 3.5 3.53.03.0 1.5 ~ -
~ * Calquest ADP (Manufacturers Chemical)
1 i ~ ** N.T. = Not treated
~ *** High R.H. ~itrogen Dioxide. A~TCC TM-164.
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-67-
Other sequestering agents would also be useful,
for example, the polyphosphates, such as Calgon which is
sodium hexametaphosphate, aminocarboxylic acids, such as
EDTA or ethylenediaminetetraacetic acid, the amino
alcohols, and the hydroxycarboxylic acids, including
citric acid.
TABLE XXXI
!
ADDITION OF SEQUESTERING AGE~TS TO
INHIBIT LIGHT INDUCED YELLOWING
(1185 Fluorocarbon Treated Superba Substrate,
Nominal 15.9% owf Composition 2 - 3.0% Intratex N)
-
Analysis and Colorfastness Data
Sample s.a.c.
I.D. Additives A/T pH Analyzed
15 1 Not Treated - 0
2 No Additive (Comp. 2 only) 3.0 2.4G
3 0.50% owf Calquest ADP 3.3 2.95
4 0.10% owf Sequestrene 30A 3.2 2.75
0.25% owf Sequestrene 30A 3.7 3.02
20 6 0.50% owf Sequestrene 30A 3.3** 2.54
7 0.10% owf SHMP* 3.0 2.80
8 0.25% owf SE~MP* 3.3 2.95
9 0.50% owf SHMP* 3.6 3.09
Grey Scale Rating
N02*
Lightfastness, Ozonefastness, Fastness,
-~ Sample _ AFIJ cy cy
I.D. 20 40 1 2
1 5.0 4.5 3.0 2.5 2.5
2 3.0 3.5 3.5 3.0 1.5
3 3.0 3.5 4.0 3.0 2.0
4 ; 4-0 4.0 3.5 3.0 2.0
4.0 3.5 4.0 3.0 2.0
6 4.0 3.5 3.5 3.0 2.0
7 4.0 3.5 3.5 3.0 2.0
8 3.5 3.5 3.0 2.5 2.0
9 3.5 3.5 3.5 3.0 2.0
* Sodium Hexametaphosphate.
** Sulfamic Acid required to lower pH after the additive
added to A/T liquor.
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133~476
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TABLE XXXII
ADDITION OF SEQUESTERING AGENTS TO
INHIBIT LIGHT INDUCED YELLOWING
STAINING ~ATA
Stain Rating (0=best 10 worst
Time Before Blotting
SampleWith Water, E~ours
I.D. A/T pEI 1 4 8 24 Shade Change*
1 - 9.5 9.5 9.5 9.5
2 3.0 0.25 0.250.75 1.25 M-N
3 3.3 0.75 0.750.75 0.75 M-N
4 3.2 0.25 0.750.75 0.75 M-N
3.7 0.5 1.01.25 1.25 N
15 6 3.3 0.5 0.5 1.0 1.5 M-N - ;
7 3.0 0.25 0.750.75 0.75 N
8 3.3 0.5 1.0 1.0 1.0 N
9 3.6 0.25 0.5 1.0 1.0 N
* M=moderate N=none
Example 8
Method for Exhausting Ammonium Thiocyanate Onto Dyed ~ylon
Fiber to Improve its Resistance to Oxidizing Agents
Description of the Embodiment
Dyed carpet fiber, especially that made from
nylon, whether or not it is treated with a sulfonated
aromatic condensate or other treatments, is susceptible to
significant color fadiny due to exposure to ozone, benzoyl
-~ peroxide and products containing chlorine. The problem
was lessened to some extent when the dye industry changed
over to acid dyes from disperse dyes. Acid dyes were less
able to migrate and be destroyed by ozone because they
were electronlcally bound to the nylon. However, the use
of acid dyes did not eliminate these color fastness
problems.
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There are many antioxidants and antiozonants
available on the market. These products are usually
aromatic and contain amine or sulfur functionalities.
These products have several disadvantages: arornatics
usually yellow the fiber upon further heat treatment, and
the amines and sulfur functionalities cause a reduction in
nylon lightfastness. Also, these chemistries probably act
as sacrificial agents and it has been difficult to apply
enough onto the fiber to have long term benefit.
The thiocyanates, such as ammonium thiocyanate,
are antiozonants that are well known. The cation of the
thiocyanate may be ammonium, sodium, potassium, zinc,
copper, ferrous, ferric, methyl or phenyl. They had the
additional advantage over the other antioxidants in that
]5 they do not reduce lightfastness. However, it has not
been economically possible to apply enough of the
thiocyanate during dyeing to have long term effectiveness
as it is also a sacrificial agent. (Ammonium thiocyanate
also appears to aglomerate the dye raolecules which also
improves ozone fastness.)
In order to apply ammonium thiocyanate economic-
ally, it is necessary to devise a process in which
it essentially exhausts onto the fiber. At pH=7 and 212F
( C) (normal dyeing conditions), the ammonium thiocya-
nate will not exhaust onto the fiber as it is water
. soluble and not very substantive to nylon. However, it
has been found that at acidic pH's, especially at about pH
1.5 to pH 5, the ammonium thiocyanate will exhaust onto -
I the nylon.
Comparison of Various Thiocyanates
A comparison was made of the performance of
several organic and inorganic thiocyanate compounds which
- had been aftertreated onto fluorocarbon treated nylon
carpet fiber knitted into sleeves at pd=2, 140'F (60~C),
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1330476
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20:1 liquor:goods and 20 minutes. No dyes were added.
The following thiocyanates were evaluated:
Added as Received, % Thiocyanate Activity,
0.30 NH4SCN 100
0.32 NaSCN 100
0.38 KSCN 100
0.48 CuSCN 100
2.57 CH2(SCN)2 10
3.13 Ph(S)N=CCH2SCN 30
The amounts added introduced an equivalent
quantity of thiocyanate concentration onto the fiber.
The ammonium, sodium and potassium thiocyanates -
were all equally superior to untreated nylon in resistance
to ozone, benzoyl peroxide and chlorine bleach fastness.
The other 15 thiocyanates were slightly more resistant to
these color fade tests than the untreated nylon. The
xenon lightfastness of all the samples were similar to
untreated nylon except CuSCN which was more resistant and
the phenyl-based thiocyanate which was much worse.
Effect of pH
Using the same conditions as above but varyiny
pH and using only NH4SCN, the percent exhaustion of
N~4SCN onto fiber was measured at the pH levels shown. -
pHExhaustion, %
1 60
-. 2 60
3 40
4 10
6 8
7 9
Effect of Temperature
In another test at the same conditions pH 2
~ `:
temperature was varied to achieve the following exhaustion
levels.
133~47~
-71-
Temperature, Exhaustion,
F( C)
7523.9 70
10037.8 66
1204~3.9 63
14060.0 60
18082.2 75
20093.3 9~
Thus by raising the temperature, it is expected that more
complete exhaustion can be achieved at higher pH levels.
In a separate test at the same conditions but
varying time, it was found that time between 5 and 50
minutes had little effect on exhaustion levels. On the
other hand, increasing the concentration of NH4SCN lowers
the level of exhaustion. It was also found that putting
increasing amounts of NH4SCN on the fiber has only a very
small effect on ozonefastness over 2,000 ppm, a little
effect over 1,000 ppm, but a large effect between 0 and
1,000 ppm. It was noted that the ~ E in the standard
5-cycle AATCC ozonefastness changed from 6 at 500 ppm
to only 2 at 1,000 ppm. -
DISCUSSION
The above examples are but a few of the many
embodiments and variations of this invention. One skilled
in the art would be able to select the proper conditions
and amounts of chemical compounds for other embodiments of
this invention to achieve the results desired after
~;~ learning the teachings of this invention, including the
Examples and the broader teachings of the Summary of the
Invention above. The broader teachings are based on
economic, technical and practical limitations to practice
the invention. However, it may sometimes be useful to
operate outside these economic or practical limitations
for special reasons.
; ~
The following discussion will describe some of
the practical, economical and/or technical limitations of
the parameters of the embodiments of this invention.
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~33~76
-72-
First, regarding the operating conditions of the
continuous aftertreatment method, including two-step
application methods, of this invention, the following
table lists reasons for the limitations given.
Limitation Variation Reason
preheat water temp. below less uniform application
140F (60C) and carpet during the following treat-
temp. below 130F (54.4C) ment and less effective
- or economic to heat carpet
10 preheat water temp. above atmospheric process, water
212F (100C) and carpet cannot be heated above the
above 210F ( C) boiling point
less than 75% w.p.u. less uniform, poor
preheat step penetration
15 extracting to less than less uniform, poor
30% w.p.u. penetration
extracting to above 190% dilutes following appli-
w.p.u. cation liquor, less
effective
20 application pH below 1.5~ corrosive
application pH above 5.5 less effective, due to
compounds of aqueous soln.
penetrating too deep into
fiber, at very high pH no
exhaustion of cornpositions
application less than less effective
200% w.p.u.
application over 650% carpet fabric cannot hold
w.p.u. much more aqueous solution
30 conc. of s.a.c. less than less effective
0.25 g/l
conc. of s.a.c. over 40 g/l uneconomical
application soln. temp. less effective
under 140F (60C) and
35 carpet temp. under 130F
(54.4C)
. ~ , .
application soln. temp. atmospheric process, water
over 212F (100C) and cannot be heated above the
carpet temp. over 210F boil
40 (99C)
less than 0.05% owf MgSO4 less effective
more than 0.8% owf MgSO4 adverse color fastness
results
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~ 133~47fi
-73-
less than 0.03% owf Nii4SCN less effective
more than 1% owf NH4SCN uneconomical
less than 0.15% owf s.a.c. less effeetive
more than 7.5% owf s.a.c. uneconomical
5 more than 6 or 3 parts to uneconomical, possible
parts of s.a.c. of the adverse chemical activity
respective dispersing
agents
The following table lists reasons for limitation
parameters for the two-step, batch-batch method of this
invention.
Limitation Variation Reason
second step pH below 1.5 corrosive
seeond step pH above 5.5 less effeetive, due to
compounds of aqueous soln.
penetrating too deep into
fiber, at very high pH no
exhaustion of compositions
second step temp. below uneconomical, takes too
20 110F ( C) long
second step temp. above less effective, due to
195F ( C) eompounds of aqueous soln.
penetrating too deep into
fiber
first & seeond step liquor: less uniform, poor wetting
fabrie ratio below 10 and penetration
first & seeond step liquor: uneeonomieal
fabric ratio above 100
- first step temp. below uneeonomical, nonuniform
30 158F (70C) applieation, takes too
long
; first step temp. above atmospherie proeess, water
212F (100C) eannot be heated above the
boil
35 first step treating time blotches and streaks,
less than 15 minutes nonuniform
first step treating time uneconomical
over 90 minutes
` seeond step treating time nonuniform application
40 under 5 minutes
less than 0.05% owf fluoro- does not provide anti-
earbon on pretreated fabric soiling effect
over 0.4% owf fluorocarbon uneconomical
on pretreated fabric
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133Q476
-74-
Limitation Variation Reason
. . .. . . _ . __ _
below 0.25~ owf MgS04 ineffective
over 4% owf MgS04 poor lightfastness,
uneconomical, poor
dyeing, shade changes
below 0.03~ owf NH4SCN ineffective
above 1% owf NH4SCN uneconomical
below 0.15% owf s.a.c. ineffective
above 7.5~ owf s.a.c. fabric discolors, fabric
stiff, poor dye yield,
yellowing
The benefits of the best mode of this invention
using Composition 1 in a two-step, continuous-continuous
process as described above in Example 1 are given below.
Most or some of the individual benefits given are also
achieved by the other embodiments of this invention.
- improved stain resistance, particularly for
carpet fabric of high ICP nylon fiber,
- substantially eliminates light induced
yellowing of sulfonated aromatic condensate treated fiber,
- reduces N02 yellowing of sulfonated aromatic
condensate treated fiber,
- improves resistance of dye on sulfonated aro-
matic condensate treated fiber to fading from ozone and
oxidation by benzoyl peroxide,
- improves penetration of sulfonated aromatic
condensate and treatment chemicals into the carpet fabric,
including the base or backing,
- does not significantly impact the soil
resistance of the fluorocarbon treatment on the fiber of
the carpet fabric, ~ ~
- improves durability of the sulfonated aromatic
condensate and treatment chemicals to steam cleaning with
high pH detergents.
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