Note: Descriptions are shown in the official language in which they were submitted.
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APPARATUS AND PROCESS FOR DISPERSING ISOCYANATE
TERMINATED POLYURETHANE PREPOLYMERS
Cross Reference to Related Application
This application is a conLillualion-in-part of Copending application
Serial No. 08/528936, filed September 15, 1995.
Field Of The Invention
This invention relates to an apl,c~dl~ls and process for dispersing
isocyanate-termin~ted polyurethane prepolymers in water.
Background Of The Invention
It is known that dynamic mixers, which have a pitched blade turbine
within a draft tube to generate axial flow, are useful for continuously
emulsifying, homogenizing and dispersing materials. References describing
such mixers include:
J~r~nçse Utility Model Patent No. 1148021(Canan KK) discloses
turbine dynamic mixers which are designed to generate axial flow within the
vessel.
A product brochure entitled, "T.K. Homomic Line Flow" from
Tokushu Kika Kogyo Co., Ltd, (Osaka, Japan) describes turbine dynamic
mixers which are useful for emulsifying, homogenizing and dispersing
materials which are transferable by metering feed pumps. The mixers are also
described as being useful for continuously dissolving several kinds of resin
solutions in solvent. The reference fails to disclose the use of said mixers fordispersing isocyanate terrnin~te~ polyurethane prepolymers in water.
Generally, water dispersible isocyanate-terminated polyurethane
prepolymers are formed by reacting a stoichiometric excess of polyisocyanate
30 with compounds cont~ining active hydrogen atoms such as polyols and
polyamines. The prepolymers are dispersed in water using mechanical
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agitation and then reacted with compounds such as water soluble ~mines The
resulting product is a water-based polyurethane-urea polymer.
The ap~dlus most often used to disperse these prepolymers are stator-
rotor and pin dynamic mixers. Such mixers are designed to rapidly disperse
the prepolymers in water using a high energy per unit volume input and short
residence times. For example, U.S. Pat. No. 4,742,095, Mobay Corporation
(Pittsburg, PA) describes stator-rotor and pins dynamic mixers operating at a
speed of about 500 revolutions per minute (rpm) to 8,000 rpm, a mixing
wattage of about 0.3 watts/cu.cm. to 10.0 watts/cu.cm. and a mixing volume of
at least about 0.1 liters. The average residence time in said mixers being from
about 1-second to 30-seconds.
Other related patents, which fail to disclose the apparatus and process
ofthe present invention, include British Pat. No. l,414,930, Pat. No.
1,432,112, Pat. No. 1,428,907 and German Offenlegungeschrift Pat. No.
lS 2,347,299.
A disadvantage with these dynamic mixers is that reduced residence
times may not generate a uniform particle dispersion, and a high energy per
unit volume input can cause shear induced destabilization generating increased
sedimentation.
To enhance the performance characteristics of water-based
polyurethane-urea polymers, it is often nçcess~ry to form isocyanate-
termin~ted polyurethane prepolymers which are characterized as having
increased hydrophobicity, crystallinity and viscosities. Such prepolymers are
not easily dispersed in water, require extended residence times, and lower
energy per unit volume input to generate uniform particle dispersions
which are substantially free of sedimentation.
Therefore, there remains a need for an apparatus and process which can
disperse isocyanate-termin~t~d polyurethane prepolymers in water using
extended residence times and a lower energy per unit volume input.
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Summary Of The I~.v~ltion
The present invention is directed to an appaldlus and process for
dispersing isocyanate-te- " ~ d polyurethane prepolymers in water. The
a~ Lus comprises:
a) at least one reaction vessel CO~ g a water dispersible NCO-
tPnnin~ted polyurethane prepolymer which is the reaction
product of;
1) at least one polyisocyanate; and
2) at least one polyol and/or polyamine component which
may be substituted with at least one hydrophilic moiety;
b) at least one supply vessel containing at least one compound
such as water, organic materials and inorganic materials;
c) at least one dynamic mixer, which has a pitched blade turbine
within a draft tube to generate axial flow, configured to
1 5 provide:
1) a mixing zone volume greater than about 0.1 liters;
2) an average tip speed greater than about 100 meters/min.;
3) an average power per unit volume input less than about
0.60 watts/cu.cm.;
4) an average residence time of at least about 1 0-seconds;
with
S) an average of at least about 5-passes through the mixing
zone; and
d) at least one fini~hing vessel wherein the dispersion is further
reacted to form a water-based polyurethane-urea polymer.
The invention is further characterized by a process for dispersing
NCO-terminated pol,vurethane prepolymers, comprising the steps of:
a) combining an aqueous solution of organic and inorganic
ingredients with at least one water dispersible isocyanate-
30 t~ d polyurethane prepolymer to form a materials
llli~L~c;
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b) feeding the materials mixture into at least one axial flow
dynamic mixer and lltili~ing a dispersing process comprising;
1) an average tip speed greater than about 100 meters/min.;
2) an average power per unit volume input less than about
0.60 watts/cu.cm.;
3) an average residence time of at least about 1 0-seconds;
with
4) an average of at least about 5-passes through the mixing
zone;
5) an average flow rate greater than about 30 liters/llours;
and
c) transferring the dispersion to at least one fini~hing vessel and
completing the isocyanate reaction to forrn a water-based
polyurethane-urea polymer.
Surprisingly, the inventive appaldllls and process generates uniform
prepolymer dispersions using extended residence times and lower energy per
unit volume input.
Brief Description Of The Dr~
Figure 1 is a side fragmentary view, in partial cross-section, of a axial
flow dynamic mixer used in the app~lus and process of the invention.
Figure 2 is a schematic diagram of an a~upaldLus of the invention.
Det~iled Description Of The Invention
The present invention is directed to an app~L~Is and process for
dispersin~ NCO-termin~t~cl polyurethane prepolymers. The appa~lus is a
turbine mixer which has a pitched blade turbine within a draft tube. The
turbine mixers, which generate axial flow within the mixing vessel, can be
configured to provide a lower energy per unit volume, extended residence
times and multiple passes through the mixing zone. Such mixers have proven
useful for processing prepolymers which are difficult to disperse in water.
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Suitable dynamic mixers are commercially available from Tokushu
Kika Kogyo Co., Ltd., Osaka, Japan under the product name T.K. Homomic
Line Flow. Such mixers can be configured to provide:
1) a mixing zone volume greater than from about 0.1 Iiters;
2) a tip speed of about 100 meters/min. to about 5,000
meters/min., and more preferably from about 2S0 meters/min.
to about 1500 meters/min.;
3) a power per unit volume input from about 0.01 watts/cu.cm. to
about 0.60 watts/cu.cm., and more preferably from about 0.10
watts/cu.cm. to about 0.30 watts/cu.cm.;
4) an average residence time from about 10-seconds to about 120-
seconds, and more preferably from about 10-seconds to about
60-seconds; with
5) an average number of passes through the mixing zone from
about 2-passes to about 150-passes, and more preferably from
about 10-passes to about 60-passes; and
6) a flow-out rate greater than about 100 liters/hr.
The average residence time and the average number of passes through
the mixing zone can be varied with the material feed rates and the tip speed. Ifdesired, greater quantities of dispersion may be produced per unit time by
using more than one mixer at a time.
Figure 1 illustrates a dynamic mixer of the type used in the ~J,aldlus
and process of the invention. The mixer includes a motor 12 mounted to a
motor base 14 which is connected to a bearing case 16. The bearing case 16
mounts the motor on the vessel lid 18.
A mixing vessel 20 is removably mounted to lid 18. Pitched blade
turbine 26 and draft tube 28 define a mixing zone. The blade is mounted to a
shaft 32 operatively connected to the motor shaft via a mechanical seal 34.
The vessel is double chambered having a central mixing chamber 21, a
recirculation zone 22 and a smaller annular exit chamber 24. An inlet 36
provides feed access to the mixing chamber 21 while outlet 38 provides for
exit of the dispersed product emerging from the mixing chamber.
SU13~ l 11 U ~ t S~ l (RUI~
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In Figure 1, the direction of flow is indicated by the arrows. Material
entering the vessel via inlet 36 is directed through the mixing zone 21 and
cycles through the draft tube 28 and the recirculation zone 22 in an axial flow.The dispersed material exits from the recirculation zone through outlet 38.
S Figure 2 is a schematic rep,csen~alion of an app~dlus in accordance
with the invention. A water dispersible isocyanate-termin~ted polyurethane
prepolymer is p,c~cd in reaction vessel 100 and fed via metering pump 110
into dynamic mixer 300. The conte"ls of supply vessel 200 is fed to mixer
300 via meter pump 210, which joins conduit 110 to provide a single feed line
into mixer 300. The prepolymer dispersion exiting mixer 300 is fed via
conduit 310 to a stirred fini.~hing vessel 500. The contents of supply vessel
400 can be added to the dispersion in several locations. For example, the
supply vessel contents can be fed into the mixing vessel 300 via meter pumped
conduit 410 or into conduit 310 via meter pumped conduit 420 or into the
fini.~hing vessel 500 via meter pumped conduit 430. Alternatively, supply
vessel 400, conduit 410,420 and 430 can be omitted. Once the components
are within the fini~hin~ vessel ~00, the prepolymer dispersion is stirred to
complete the isocyanate reaction and form a water-based polyurethane-urea
polymer.
At least one reaction vessel is used in the appa~ s and process of the
invention. If desired, multiple reaction vessels may be used. Such vessels
may contain isocyanate-terrnin~te~l polyurethane prepolymers of different
composition.
At least one axial flow turbine mixer, which is mounted in a draft tube,
is used in the invention. The term "draft tube" refers to an open cylinder
which sepal~es the mixing zone from the recirculation zone. The draft tube
generates axial flow and allows recirculation through the mixing vessel. If
desired, multiple mixers may be used to disperse large quantities of
prepolymer thus increasing the total volume of dispersion produced per unit
time.
At least one supply vessel is used. The vessel contains at least one
component which may include ~mines, antioxidants, biocides, coalescing aids,
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coloring agents, defoamers, dispersed pigments, emulsifiable waxes, fillers,
fire retardant agents, fungicides, ionic and/or nonionic emulsifiers, natural
polymer dispersions, non-polyurethane based emulsifiable synthetic resins,
organic co-solvents, perfume-like materials, plasticizers, sequestering agents,
UV stabilizers, water, wetting agents and their mixtures.
The isocyanate-termin~ted polyurethane prepolymers and the supply
vessel conte,l~ can be transferred using metering pumps which may include
centrifugal pumps, diaphragm pumps, gear pumps, piston pumps, peristaltic
pumps, progressive cavity pumps, lobe pumps, screw pumps and vane pumps.
Alternatively, said materials may be transferred using gravity feed and/or
complessed gasses including nitrogen which may require the use of control
valves. Preferably, a conduit system comprising pipes or tubes is used to
channel the materials throughout the apparatus of the invention.
At least one fini~hing vessel is used and is preferably equipped with
mechanical agitation. Also, multiple fini.ching vessels may be used to react theprepolymer dispersions with rli~imil~r compounds having active hydrogen
atoms. Such a process is used to generate water-based polyurethane-urea
polymers which differ in composition.
To enhance the performance characteristics of water-based
polyurethane-urea polymers, it is often necessary to form isocyanate-
termin~ted polyurethane prepolymers having ploptllies such as increased
hydrophobicity, crystalinity and viscosity. Examples include the hydrophobic
prepolymers described in U.S. Pat. No. 5,354,807 (H.B. Fuller Company) and
the crystalline polymers described in copending application Serial No.
08/528936, incol~uld~ed herein by reference. Said prepolymers can have
viscosities ranging from about 10,000 m.Pas to about 100,000 m.Pas, and
more preferably from about 15,000 m.Pas to about 50,000 m.Pas. These
prepolymers are more likely to develop a uniform particle dispersion when
extended residence times and lower energy per unit volume inputs are utilized.
The prepolymers are plepared by reacting a stoichiometric excess of
polyisocyanate with at least one polyol and/or polyamine compound which
may be ~ub~lilu~d with at least one hydrophilic moiety. The materials can be
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reacted at a telllyelaLule in a range from about 25C to about 1 00C, and more
preferably from about 60C to about 90C. The percent isocyanate, present in
the finished prepolymer, can be in a range from about 1.0% by weight to
about 15.0% by weight, and more preferably from about 4.0% by weight to
about 8.0% by weight, based on total prepolymer solids.
The prepolymers are preferably dispersed using distilled and/or
deionized water. The water temperature is greater than 0C and preferably in a
range from about 5C to about l 00C, and more preferably from about 25C to
about 50C.
The water-based polymers of the present invention can have a solids
content in the range from about 20.0% by weight to about 80.0% by weight,
and preferably from about 30.0% by weight to about 50.0% by weight.
Once the isocyanate-terminated polyurethane prepolymer has been
dispersed and transferred to a fini~hin~ vessel, the dispersion may be charged
with the contents of a second supply vessel, which may contain de-ionized
water and water soluble ~rnin~s, to form a dispersion mixture. Said mixture
may or may not be agitated and can be reacted at a tell~ L~Ire from about 5C
to about 1 00C, and preferably from about 25C to about 65C.
The following description of compositions is illustrative of the types of
dispersible products which are advantageously prepared using the apl)a,allls
and process of the present invention. Those skilled in the art will recognize
that alternative products may be formed using other reactants.
The polyisocyanates may be linear aliphatic, cyclic aliphatic, aromatic,
and mixtures thereof. The polyisocyanate is preferably a mixture including
hindered polyisocyanate and non-hindered polyisocyanate. The term
"hindered polyisocyanate" is defined as an isocyanate moiety which is less
sensitive to the water-isocyanate reaction due to the proximity of adjacent
aliphatic character. The hindered polyisocyanate may be present in the
polyisocvanate mixture in a range from about 1 part to about 95 parts, and
more preferably from about 25 parts to about 75 parts, based on 100 parts total
polyisocyanates. Examples of commercially available hindered
polyisocyanates include Vestanat~ IPDI which is 3-isocyanatomethyl-3,5,5-
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trimethylcyclohexyl isocyanate from HULS America, Inc. (Piscataway, NJ)
and TMXDI~ which is 1,3-bis (1-isocyanato-1-methylethyl) benzene from
Cyanamid (Wayne, NJ). Examples of commercially available non-hindered
polyisocyanates include Luxate~ HM which is 1,6-hexamethylene
diisocyanate from Olin Corporation (Stamford, CT), diphenylmethane
diisocyanate from Upjohn Polymer chemicals (E~ m~700, MI), Desmodur~
W which is Dicyclohexylmethane- 4,4'-diisocyanate from Mobay Corporation
(PiLl~bul~,h, PA) and toluene diisocyanate (TDI).
The presence of a hindered polyisocyanate is preferred in the process
of the invention. It is surmised such sterically hindered polyisocyanates are
less likely to be completely reacted during prepolymer synthesis. The
resulting isocyanate-termin~ted polyurethane prepolymers, which are less
sensitive to the isocyanate/water reaction, can be dispersed in water allowing
further reaction with ~mines,
If desired, the water dispersible isocyanate-tçnnin~ted polyurethane
prepolymers may be subjected to complete hydrolysis. Such prepolymers,
which are preferably based on sulfonate character, generate polyurethane-urea
polymers having enhanced ~lop.,.lies such as water- resistance and heat
resistance and are described in the above mentioned copending application
Serial No. 08/528936.
Other polyisocyanates which may be used include modified
polyisocyanates ~l~pa ed from hexamethylene diisocyanate, isophorone
diisocyanate and toluylene diisocyanate. The modified diisocyanates can have
functionalities such as urethanes, uretdiones, isocyanurates, biurets and
mixtures thereof.
Examples of small molecular weight polyols which may be used in the
plepdl~tion of the water dispersible isocyanate-termin~ted polyurethane
prepolymers can have hydroxyl numbers, as determined by ASTM designation
E-222-67 (Method B), in a range from about 130 to about 1250, and preferably
from about 950 to about 1250. Examples of preferred small molecular weight
polyols include trimethylolpropane, diethylene glycol, 1,4-butanediol, 1,6-
hexanediol, glycerol and the aliphatic diols described in U.S. Pat. No.
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5,039,732, Sherwin-Williams Company (Baltimore, MD), incorporated herein
by ,efe,e"ce.
The prepolymer of the invention may be rendered water dispersible by
the chemical incorporation of anionic moieties, non-ionic moieties, cationic
moieties and mixtures thereof. Anionic polyurethane-urea polymers are
p,ere.,ed and prepolymers cont~ining a combination of sulfonate and
carboxylate groups are most plere"~d. Examples of ionic moieties which may
be incorporated into the prepolymer include dimethylopropionic acid and 1,4-
dihydroxybutane sulfonic acid described in U.S. Pat No. 3,412,054 and U.S.
Pat No. 4,108,814, incorporated herein by reference.
The anionic groups can be neutralized with bases such as alkali metal
hydroxides, organic tertiary amines, ammonia and mixtures thereof.
Conversion of the anionic groups to ionic groups (salts) may be accomplished
before, during or after the prepolymer has been dispersed in water.
Polymeric diols used in the p,epa,dlion ofthe prepolymers can have
hydroxyl numbers, as determined by ASTM designation E-222-67 (Method
B), in a range from about 20 to about 140, and preferably from about 55 to
about 110. The polymeric polyols can have melting temperatures from about
10C to about 200C, and more preferably from about 25C to about 95C.
The polyols can be selected from the group consisting of polyester polyols,
polyether polyols, polycarbonate polyols, polyurethane polyols, polyacetal
polyols, polyacrylate polyols, polycaprolactone polyols, polyesteramide
polyols, polythioether polyols, and mixtures thereof. The preferred polymeric
polyols are those described in the above mentioned copending application
Serial No. 08/528936 and U.S. Pat No. 5,334,690 (Hoechst Aktiengesellschaft,
Fed.), incol~o,ated herein by reference.
The inventive process generates water-based polyurethane-urea
polymers which are characterized as having enhanced properties including
heat and water resistance. Said process is also useful in the preparation of
water-based polyurethane-urea polymer blends and hybrids containing
polyacrylic and/or polyvinyl polymers. Examples include the compositions
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described in copending U.S. application 08/561197, filed November 21, 1995,
H.B. Fuller Company (St. Paul, MN) incorporated herein by reference.
The invention is illustrated by the following non-limiting examples.
E:xample 1
Example 1 describes the prel,alalion of a highly crystalline water-based
polyurethane-urea polymer.
To a reaction vessel was charged 45.39 kgs. (44.5 hydroxyl
equivalence) Rucoflex~ XS-5483-55 which is a sulfonated polyester polyol
from Ruco Polymer Corporation (Hicksville, NY), 2.13 kgs. (15.9 hydroxyl
equivalence) dimethylolpropionic acid, 2.39 kgs. (53.0 hydroxyl equivalence)
1,4-butanediol, 6.60 kgs. grams (59.4 isocyanate equivalence) isophorone
diisocyanate, 9.99 kgs. (118.8 isocyanate equivalence) hexamethylene
diisocyanate and 4.24 kgs. anhydrous acetone. The mixture was mildly
agitated and heated to 70C for approximately 2.5-hours then charged with
1.27 kgs. triethylamine and stirred an additional 15-minutes before dispersing.
The prepolymer (80C) and de-ionized water (60C) were combined in-
line and transferred to a T.K. Homonic Line Flow model 100S axial flow
dynamic mixer from Tokushu Kika Kogyo Co., Ltd. (Osaka, Japan). The
prepolymer was transferred from the reaction vessel using a gear pump set at a
rate of 3.60 kgs. per minute while the water was transferred from a supply
vessel using a progressive gravity pump set at a rate of 6.40 kgs. per minute.
The mixer was configured to provide an average residence time of 61 -seconds
using a shaft speed of 3,600 rpm and a tip speed of 1,000 meters/min.
The dispersion was transferred to a finiching vessel equipped with a
turbine agitator and run at a circulation rate of about 10 min-l for
approximately 20 minutes. To the dispersion was charged a mixture
cont~ining ethylene diamine in de-ionized water. The dispersion was stirred
an additional 30-minutes at 60C to generate a water-based polyurethane-urea
polymer. The polymers properties are described below:
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pH=7.9
Solids = 31.38%
Mean diameter article size = 189 nm.
Viscosity = 40 m.Pas
Example 2
Example 2 describes the prepd,alion of a hydrophobic water-based
polyurethane-urea polymer.
To a reaction vessel was charged 28.53 kgs. (56.0 hydroxyl
equivalence) Rucoflex~ S-102-10 which is a polyester polyol from Ruco
Polymer Corporation (Hicksville, NY), 0.348 kgs. (7.8 hydroxyl equivalence)
trimethylolpropane,3.48 kgs. (50.0 hydroxyl equivalence)
dimethylolpropionic acid,30.18 kgs. TMXDI~ which is tetramethylxylene
diisocyanate from Cyanamid (Wayne, NJ), 0.362 kgs. Irganox~ 1076 which is
a hindered phenol antioxidant from Ciba-Giegy Corporation (Hawthorne, NY)
and 2.50 kgs. triethylamine. The mixture was mildly agitated and heated to
90C for ~-hours.
The pre-prepolymer was charged with 6.60 kgs. (47.0 amine
equivalence) Tomah~-14 which is isodecyloxypropyl-1,3-diaminopropane
from Tomah Products (Milton, WI). The amine was charged to the reactor
over a 1- hour period keeping the temperature below 90C.
The prepolymer, which had a viscosity of approximately 15,000 m.Pas
at 90C, was processed as similarly described in Example 1. The exception
being the prepolymer was metered at 4.4 kgs./min., the water (62C) was
metered at a rate of 7.0 kgs./min., the turbine tip speed was 1,000 meters/sec.
and the average residence time was 53-seconds.
The dispersion was transferred to a fini~hing vessel equipped with a
turbine agitator and run at a circulation rate of about 10 min-l for
approximately 20-minutes. To the dispersion was charged a chain extender
solution consisting of 12.65% diethylene triamine,39.62% ethylene diamine
and water. The dispersion was stirred an additional 30-minutes to generate a
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water-based polyurethane-urea polymer. The polymers properties are
described below:
pH = 9.12
Solids = 36.7%
Viscosity = 20 m.Pas
13
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Claims
1. An appdldlus for dispersing isocyanate-terrnin~ted polyurethane
prepolymers comprising:.
a) at least one reaction vessel cont~ining a water dispersible
isocyanate-t~rrnin~ted polyurethane prepolymer;
b) at least one supply vessel;
c) at least one supply conduit system;
d) at least one dynamic mixer which has a pitched blade turbine
within a draft tube; and
e) at least one fini~hing vessel.
2. A reaction vessel as described in Claim 1, vherein said water
dispersible isocyanate-terminated polyurethane prepolymer is the
reaction product of:
a) at least one polyisocyanate; and
b) at least one isocyanate reactive component which may be
substituted with at least one hydrophilic moiety.
3. A water dispersible isocyanate-terrnin~ted polyurethane prepolymer as
described in Claim 2 wherein said polyisocyanate is selected from the
group consisting of aliphatic polyisocyanates, cyclic aliphatic
polyisocyanates, aromatic polyisocyanates and mixtures thereof.
4. A polyisocyanate mixture as described in Claim 2, comprising a
hindered polyisocyanate.
5. A hindered polyisocyanate as described in Claim 4, including
isophorone diisocyanate, tetramethylxylene diisocyanate and mixtures
thereof.
6. An appaldlus as described in Claim 1, wherein said supply vessel
contains at least one compound selected from the group consisting of
amines, antioxidants, biocides, coalescing aids, coloring agents,
defoamers, dispersed pigments, emulsifiable waxes, fillers, fire
retardant agents, fungicides, ionic and/or nonionic emulsifiers, natural
polymer dispersions, non-polyurethane based emulsifiable synthetic
resins, organic co-solvents, perfume-like materials, plasticizers,
14
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