U.S. patent application number 11/966213 was filed with the patent office on 2008-09-25 for stain and fouling resistant polyurea and polyurethane coatings.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to Stephen E. Amos, Robert P. Messner.
Application Number | 20080229976 11/966213 |
Document ID | / |
Family ID | 39588993 |
Filed Date | 2008-09-25 |
United States Patent
Application |
20080229976 |
Kind Code |
A1 |
Amos; Stephen E. ; et
al. |
September 25, 2008 |
STAIN AND FOULING RESISTANT POLYUREA AND POLYURETHANE COATINGS
Abstract
Transporters, e.g., ore carriers, vehicles, materials handling
equipment, etc. having fluorinated polyurea and fluorinated
polyurethane coatings thereon.
Inventors: |
Amos; Stephen E.;
(Minneapolis, MN) ; Messner; Robert P.; (St. Paul,
MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
39588993 |
Appl. No.: |
11/966213 |
Filed: |
December 28, 2007 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60882790 |
Dec 29, 2006 |
|
|
|
Current U.S.
Class: |
106/287.25 |
Current CPC
Class: |
C08K 7/28 20130101; C08G
18/712 20130101; C08G 18/73 20130101; C09D 175/02 20130101; C08G
18/6685 20130101; C09D 175/02 20130101; C08G 2150/50 20130101; C08L
75/02 20130101; C08L 2666/20 20130101 |
Class at
Publication: |
106/287.25 |
International
Class: |
D21H 17/46 20060101
D21H017/46 |
Claims
1. A transporter having a coating on at least a portion of the
surface thereof, said coating selected from the group consisting of
polyureas, polyurethanes, and combinations thereon which are the
reaction products of precursors including at least one
fluorochemical compound.
2. The transporter of claim 1 wherein said transporter is selected
from the group consisting of rail cars, trucks, automobiles,
wheelbarrows, carts, carriers, conveyor belts, tanks, tankers,
aircraft, watercraft, pipelines, and sluices.
3. The transporter of claim 1 wherein said fluorochemical compounds
is a fluorinated isocyanate.
4. The transporter of claim 3 wherein said fluorinated isocyanate
is a fluorinated monoisocyanate.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 60/882,790, filed Dec. 29, 2006.
FIELD
[0002] The present invention relates to polyurea compositions and
polyurethane compositions for forming coatings and coatings formed
from such compositions. In particular the invention relates to
stain and fouling resistant coatings, e.g., for use on rail cars,
containers, vehicles, etc.
BACKGROUND
[0003] It has been known to use polyurethane compositions and
polyurea compositions for forming coatings on substrates for a
variety of purposes. Such compositions have been applied in a
variety of approaches including spraying.
[0004] Although such coatings have been used in a variety of
applications, a deficiency has been the tendency of such coatings
to stain and/or foul. Such staining or fouling may be of mere
aesthetic concern or may, in some cases, represent an important
functional or performance deficiency.
[0005] A developing energy source is oil from oil sands and tar
sands. Such sands tend to stick to equipment and vehicles used to
move and process them. As a result, efficiency is reduced as the
deposits build up, increasing the weight of moving vehicles,
clogging handling chutes, etc. It is common practice today to
remove vehicles used in such operations from service for one or two
days each week for extensive spray washing to remove the build up
of deposits from the vehicle in addition to an extensive solvent
wash done on a monthly basis.
[0006] An established energy source is coal which is mined in one
location and then shipped to another location via such means as
rail car. When removed from the mine, coal commonly contains
significant water content and has a temperature of about 40 to
about 50.degree. F. (4 to 10.degree. C.). During cool months when
the coal is placed in rail cars which are at an ambient temperature
close to or below 32.degree. F. (0.degree. C.), the coal will tend
to stick to the surfaces of the rail car. When the rail car is
emptied significant quantities of the load remain stuck to the car.
As a result, as much as 25% of the potential load carrying capacity
of the rail cars might be lost. Removal is a labor and cost
intensive exercise.
[0007] A need exists for conveniently applied polyurethane
compositions and polyurea compositions that provide durable, light
weight coatings which exhibit oil-repellency, water-repellency, and
stain resistance.
SUMMARY OF INVENTION
[0008] The present invention provides novel polyurethane
compositions and polyurea compositions and novel coatings formed
therefrom, and transporters, e.g., carriers, vessels, and vehicles,
having such coatings thereon.
[0009] In brief summary, the compositions of the invention comprise
reactive precursors for forming a polyurethane or polyurea coating
and at least one fluorochemical fluorochemical compound.
[0010] The compositions of the invention can be applied in
convenient manner, e.g., spraying, to form films or coatings on
substrates. The resultant films or coatings can exhibit exceptional
physical properties such as high hardness, flexibility, abrasion
resistance, and chemical resistance. Durable and light weight,
films and coatings of the invention exhibit oil-repellency,
water-repellency, and stain resistance. The invention provides
polyurethane and polyurea coatings that provide heretofore
unattainable resistance to staining and fouling.
DETAILED DESCRIPTION OF INVENTION
[0011] Compositions of the invention comprise reactive precursors
for forming polyurethane and/or polyureas and at least one
fluorochemical compound. In preferred embodiments, the
fluorochemical compound is reactive with one or more of the
reactive precursors.
[0012] Polyurethanes can be prepared by reacting one or more
isocyanates with one or more polyols. Polyureas can be prepared by
reacting one or more isocyanates with one or more amines.
[0013] An illustrative class of fluorochemical compounds suitable
for use herein include the fluorochemical monoisocyanates disclosed
in U.S. Pat. No. 7,081,545 (Klun et al.) which is incorporated
herein by reference in its entirety.
[0014] Fluorochemical alcohols that are useful in carrying out the
invention include those represented by the following formula:
C.sub.nF.sub.2n+1SO.sub.2NCH.sub.3(CH.sub.2).sub.mOH wherein n=2 to
5, and m=2 to 4 (preferably, n=2 to 4; more preferably, n=4).
Fluorochemical alcohols that are useful starting compounds include
C.sub.2F.sub.5SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.2F.sub.5SO.sub.2NCH.sub.3(CH.sub.2).sub.3OH,
C.sub.2F.sub.5SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH,
C.sub.3F.sub.7SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.3F.sub.7SO.sub.2NCH.sub.3(CH.sub.2).sub.3OH,
C.sub.3F.sub.7SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.3OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH,
C.sub.5F.sub.11SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.5F.sub.11SO.sub.2NCH.sub.3(CH.sub.2).sub.3OH,
C.sub.5F.sub.11SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH, and mixtures
thereof. Preferred fluorochemical alcohols include, for example,
C.sub.2F.sub.5SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH, and mixtures
thereof. More preferred fluorochemical alcohols include, for
example, C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH,
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.4OH, and mixtures
thereof. A most preferred fluorochemical alcohol is
C.sub.4F.sub.9SO.sub.2NCH.sub.3(CH.sub.2).sub.2OH. Useful
fluorochemical alcohols can be purchased from 3M (St. Paul, Minn.),
or can be prepared essentially as described in U.S. Pat. Nos.
2,803,656 (Ahlbrecht et al.) and 6,664,345 (Savu et al.).
[0015] The above-described fluorochemical alcohols can be reacted
with 4,4'-diphenylmethane diisocyanate in a solvent to form the
corresponding monoisocyanates. 4,4'-Diphenylmethane diisocyanate is
commonly known as "methylene diisocyanate" or "MDI". In its pure
form, MDI is commercially available as ISONATE.TM. 125M from the
Dow Chemical Company (Midland, Mich.), and as MONDUR.TM. M from
Bayer Polymers (Pittsburgh, Pa.).
[0016] The process of the invention can be carried out with a molar
ratio of fluorochemical alcohol:MDI from about 1:1 to about 1:2.5.
Preferably, the molar ratio of fluorochemical alcohol:MDI is from
about 1:1 to about 1:2. More preferably, the molar ratio is from
about 1:1.1 to about 1:1.5.
[0017] The process of the invention can be carried out in a solvent
in which the resulting monoisocyanate is not soluble (that is, the
solvent is one in which the monoisocyanate partitions out of so
that it no longer participates in the reaction). Preferably, the
solvent is a nonpolar solvent. More preferably, it is a nonpolar
non-aromatic hydrocarbon or halogenated solvent.
[0018] Representative examples of useful solvents include
cyclohexane, n-heptane, hexanes, n-hexane, pentane, n-decane,
i-octane, octane, methyl nonafluoroisobutyl ether, methyl
nonafluorobutyl ether, petroleum ether, and the like, and mixtures
thereof. A mixture of methyl nonafluoroisobutyl ether and methyl
nonafluorobutyl ether is available as HFE-7100 NOVEC.TM. Engineered
Fluid from 3M. Preferred solvents include, for example, methyl
nonafluoroisobutyl ether, methyl nonafluorobutyl ether, petroleum
ether, n-heptane, and the like.
[0019] Preferably, the solvent has a Hildebrand solubility
parameter (6) of less than about 8.3 (cal/cm.sup.3).sup.1/2 (about
17 MPa.sup.1/2) and a hydrogen bonding index of less than about 4.
The Hildebrand solubility parameter is a numerical value that
indicates the relative solvency behavior of a specific solvent. It
is derived from the cohesive energy density (c) of the solvent,
which in turn is derived from the heat of vaporization: .delta.
.times. .times. c _ = [ .DELTA. .times. .times. H - RT V m ] 1 2 (
2 ) ##EQU1##
[0020] wherein:
[0021] .DELTA.H=heat of vaporization,
[0022] R=gas constant,
[0023] T=temperature, and
[0024] Vm=molar volume
[0025] For example, n-heptane has a Hildebrand solubility index of
about 7.4 (cal/cm.sup.3).sup.1/2 (about 15 MPa.sup.1/2), and water
has a Hildebrand solubility index of about 23.4
(cal/cm.sup.3).sup.1/2 (about 48 MPa.sup.1/2) (Principles of
Polymer Systems, 2.sup.nd edition, McGraw-Hill Book Company, New
York (1982)).
[0026] The hydrogen bonding index is a numerical value that
indicates the strength of the hydrogen bonding that occurs in a
solvent. Hydrogen bonding values range from -18 to +15. For
example, n-heptane has a hydrogen bonding value of about 2.2, and
water has a hydrogen bonding value of about 16.2 (Principles of
Polymer Systems, 2.sup.nd edition, McGraw-Hill Book Company, New
York (1982)).
[0027] The reaction can be carried out by combining the
fluorochemical alcohol and MDI in the solvent. Preferably, the
fluorochemical alcohol is added to MDI, which is in the solvent,
over time. Optionally, the fluorochemical alcohol can first be
dissolved in a solvent such as, for example, toluene, and then
added to the MDI in solution. Preferably, the reaction mixture is
agitated. The reaction can generally be carried out at a
temperature between about 25.degree. C. and about 70.degree. C.
(preferably, between about 25.degree. C. and about 50.degree.
C.).
[0028] Optionally, the reaction can be carried out in the presence
of a catalyst. Useful catalysts include bases (for example,
tertiary amines, alkoxides, and carboxylates), metal salts and
chelates, organometallic compounds, acids, and urethanes.
Preferably, the catalyst is an organotin compound (for example,
dibutyltin dilaurate (DBTDL)) or a tertiary amine (for example,
diazobicyclo[2.2.2]octane (DABCO)), or a combination thereof. More
preferably, the catalyst is DBTDL.
[0029] After the reaction is carried out, the reaction product can
be filtered out and dried. The reaction product typically comprises
greater than about 85% of the desired fluorochemical monoisocyanate
(preferably, greater than about 90%; more preferably, greater than
about 95%).
[0030] Fluorochemical monoisocyanates that can be prepared using
the process of the invention can be represented by the following
formula: ##STR1## wherein n=2 to 5, and m=2 to 4.
[0031] Preferred fluorochemical monoisocyanates that can be
prepared using the process of the invention include, for example:
##STR2## More preferred fluorochemical monoisocyanates prepared
using the process of the invention include, for example:
##STR3##
[0032] Fluorochemical monoisocyanates prepared using the process of
the invention can be useful starting compounds in processes for
preparing fluorinated acrylic polymers with water- and
oil-repellency properties.
[0033] For example, fluorochemical monoisocyanates prepared using
the process of the invention can be reacted with active
hydrogen-containing compounds, materials, or surfaces bearing
hydroxyl, primary or secondary amines, or thiol groups. The monomer
produced by reacting a fluorochemical monoisocyanate prepared by
the process of the invention with a hydroxy alkyl acrylate such as
hydroxy ethyl acrylate, for example, can be polymerized (alone or
with comonomers) to provide polymers that have useful water- and
oil-repellency properties.
[0034] In some preferred embodiments, compositions of the invention
will further comprise filler materials such as glass microspheres,
glass bubbles, ceramic microspheres, or other particles.
[0035] The surprising combination of properties exhibited by films
and coatings of the invention makes them advantageously suited for
a variety of applications.
[0036] For example, coatings of the invention can be used as
coatings on motor vehicle bodies, undercarriages, truck beds,
carriers and vessels used for transporting materials, etc. The
coatings exhibit good adhesion to metal substrates coupled with
oil-repellency, water-repellency, and stain resistance.
[0037] An illustrative application of the compositions and coatings
of the invention is on equipment and vehicles used in mining
operations, e.g., for oil sands and tar sands. Despite the tendency
of such sands to stick to equipment and vehicles used to move and
process them, use of coatings of the invention will reduce the
maintenance time required to clean conventional equipment and
vehicles, thereby reducing downtime and increasing efficiency of
operations. With the improved release properties achieved in
accordance with the present invention, such costly down-time
operations can be reduced, resulting in greater productivity, lower
operating costs, etc. Similarly, railcars can outfitted with
coatings of the invention to reduce the build up of coal, resulting
in increased transportation efficiency.
[0038] The invention may be used to advantageous effect in a
variety of applications where durable, abrasion-resistant coatings
exhibiting oil-repellency, water-repellency, and stain resistance
and desired.
[0039] Coatings of the invention exhibit good adhesion to metal
substrates.
[0040] Coatings of the invention preferably contain glass
microspheres and or bubbles to impart improved insulative
properties (e.g., thermal insulation, noise dampening, vibration,
etc.), reduce effective weight of the coating. In some embodiments,
coatings of the invention are made in combination with open celled,
foamed construction.
[0041] Coatings of invention can be made with superior abrasion
resistance and hardness.
[0042] Compositions of invention can be applied by any of a variety
of techniques. In some embodiments, compositions of the invention
can be applied by such convenient techniques as spraying.
[0043] Coatings of the invention can applied over other, less
durable insulation materials to provide optimized, composite
properties. For example, the present invention may be used to
provide a polyurea insulation coating sprayed over other insulation
materials such as polystyrene or polyurethane open cell foam
insulation, or other insulative material.
[0044] Films and coatings of the invention may be used in
conjunction with other materials and layers to make multilayer
composite constructions offering desired performance. For example,
Compositions of the invention can be coated over blast and tear
resistant films to impart improved blast and/or projectile
resistance.
[0045] The combination of convenient application and high
performance provided by compositions and coatings of the invention
makes them well suited for a wide variety of applications. Some
examples include protective coatings to protect the cab, passenger
compartment, load area, or other chambers of vehicles including
aircraft, watercraft and land vehicles. For example, the invention
provides advantageous results on wheeled and tracked vehicles,
e.g., trucks, HUMVEEs, tanks, etc., airplanes, space vehicles,
helicopters, boats and other enclosed cockpit vehicles, from heat
from engines or ambient sources. Other examples include protective
coatings on equipment and vehicles or vehicle components that are
used in extreme environments, e.g., trucks, tanks, airplanes, space
vehicles, helicopters, boats, pipes, bridges, off-shore oil
platforms, and other metallic substrates used in extreme
environments or washed with bleach and other corrosive materials to
provide corrosion resistance for the metal substrates. The
invention can be used on a variety of materials handling equipment
including wheelbarrows, pipelines, sluices, etc.
EXAMPLES
[0046] The invention will be further explained with the following
illustrative examples.
Test Methods
[0047] Dynamic Contact Angle Measurement
[0048] Advancing and receding contact angles on the polyurea
samples were measured using a CAHN Dynamic Contact Angle Analyzer,
Model DCA 322 (a Wilhelmy balance apparatus equipped with a
computer for control and data processing, commercially available
from ATI, Madison, Wis.). Water was used as the probe liquid.
[0049] Static Contact Angle Measurement
[0050] The treated substrates were tested for their contact angles
versus water using an Olympus TGHM goniometer (Olympus Corp,
Pompano Beach, Fla.). Contact angles were measured at least 24 hrs
after cure. The values are the mean values of 4 measurements and
are reported in degrees. The minimum measurable value for a contact
angle was 20. A value less than 20 means that the liquid spreads on
the surface.
[0051] Thermal Conductivity Test Method 1
[0052] Thermal conductivity was measured using a Model 2021 Thermal
Conductivity Apparatus (available from Anter Corporation,
Pittsburgh, Pa.) following ASTM E 1530 (Test Method for Evaluating
the Resistance to Thermal Transmission of Thin Specimens of
Materials by the Guarded Flow Meter Technique).
[0053] Thermal Conductivity Test Method 2--Hot Face vs. Cold
Face
[0054] A 4 inch.times.6 inch (10.16 cm.times.15.24 cm) rectangular
hole was cut in the top of a lab furnace (Econo-Kiln, Model K 14, L
& L Manufacturing Co., Twin Oaks, Pa.; maximum temperature of
1832.degree. F. (1000.degree. C.)). The sample to be tested was
placed over the rectangular hole in the furnace such that the edges
of the sample fully overlapped on all sides of the opening. Two
thermocouples (Type K Thermocouple Thermometer, Model 650, Omega
Engineering, Inc., Stamford, Conn.) were placed in the center of
the sample and held in contact with a foil tape. One thermocouple
measures the external face temperature (T.sub.Outside) of the
sample (that portion outside the oven) and one thermocouple
measures the internal face temperature T.sub.Inside of the sample
(that portion inside the furnace). The furnace oven was turned on
and the I.sub.Inside of the sample was adjusted to 200.degree. F.
(93.3.degree. C.). After several minutes, the T.sub.Outside was
recorded. Additionally, Model ThermaCAM.TM. P65 infrared camera,
available from Flir Systems Inc., Portland, Oreg., was used to
analyze the temperature of the external face surface of the
sample.
Comparative Example 1
[0055] A two component polyurea (Part A and Part B) was formulated
as follows. Part A contained hexamethylene diisocyanate (85.2% by
weight, obtained from Rhodia, Inc., Cranbury, N.J., under the trade
designation "TOLONATE.TM. HDT LV2"), glass microspheres (13.5% by
weight, obtained from 3M Company under the trade designation
"3M.TM. GLASS MICROSPHERES K37") and a modified polyurea (1.3% by
weight, obtained from BYK Chemie, Wesel, Germany, under the trade
designation "BYK.TM. 410"). Part B contained diethyltoluenediamine
(32.4% by weight, obtained from Albemarle Corporation, Bayport,
Tex., under the trade designation "ETHACURE.TM. 100"),
polyoxypropylenediamine (39.6% by weight, obtained from Huntsman
Corporation, Salt Lake City, Utah under the trade designation
"JEFFAMINE.TM. D-2000"), an aromatic secondary diamine (6.5% by
weight, obtained from UOP, A Honeywell Company, Tonawanda, N.Y.,
under the trade designation "UNILINK.TM. 4200"), a trifunctional
amine (2.4% by weight, obtained from Huntsman Corporation under the
trade designation "JEFFAMINE.TM. T-5000"), glass microspheres
(18.2% by weight, obtained from 3M Company under the trade
designation "3M.TM. GLASS MICROSPHERES K37"), a modified polyurea
(0.8% by weight, obtained from BYK Chemie, under the trade
designation "BYK.TM. 410") and a liquid organic pigment to produce
the desired color (0.1%).
[0056] Parts A and B were sprayed from a plural component
proportioning sprayer (obtained from Graco, Minneapolis, Minn.,
under the trade designation "REACTOR H-XP2" using a "FUSION MP"
spray gun with nozzles. Each part (A and B) was kept separate until
they exited the spray gun. The two components, A and B, were
stirred, in separate pots, in the spray unit and maintained at a
temperature of 160.degree. F. (71.degree. C.) during the spray
process. The materials (Parts A and B) were sprayed on to a cold
roll steel panel that was previously sprayed with a release agent
(from Sierra Paint Co., Minnetonka, Minn., under the trade
designation "TK-709 UR") and also waxed paper. The formulation
cured within about 20 seconds. After a period of time the sprayed
panels were peeled from the metal substrate and waxed paper and
tested as described above. The contact angle data is listed in
Table 1. Thermal conductivity data is listed in Table 2.
Example 1
[0057] A two component polyurea (Part A and Part B) was formulated
as follows. Part A contained hexamethylene diisocyanate (85.2% by
weight, obtained from Rhodia, Inc., Cranbury, N.J., under the trade
designation "TOLONATE.TM. HDT LV2"), glass microspheres (13.5% by
weight, obtained from 3M Company under the trade designation
"3M.TM. GLASS MICROSPHERES K37") and a modified polyurea (1.3% by
weight, obtained from BYK Chemie, Wesel, Germany, under the trade
designation "BYK.TM. 410"). Part B contained diethyltoluenediamine
(31.6% by weight, obtained from Albemarle Corporation, Bayport,
Tex., under the trade designation "ETHACURE 100"),
polyoxypropylenediamine (38.7% by weight, obtained from Huntsman
Corporation, Salt Lake City, Utah, under the trade designation
"JEFFAMINE.TM. D-2000"), an aromatic secondary diamine (6.3% by
weight, obtained from UOP, A Honeywell Company, Tonawanda, N.Y.
under the trade designation "UNILINK.TM. 4200"), a trifunctional
amine (2.4% by weight, obtained from Huntsman Corporation under the
trade designation "JEFFAMINE.TM. T-5000"), glass microspheres
(17.8% by weight, obtained from 3M Company under the trade
designation "3M.TM. GLASS MICROSPHERES K37"), a modified polyurea
(0.7% by weight, obtained from BYK Chemie, under the trade
designation "BYK.TM. 410"), deionized water (2.4% by weight) and a
liquid organic pigment to produce the desired color (0.1%).
[0058] Parts A and B were sprayed from a plural component
proportioning sprayer (obtained from Graco, Minneapolis, Minn.,
under the trade designation "REACTOR H-XP2" using a "FUSION MP"
spray gun with nozzles. Each part (A and B) was kept separate until
they exited the spray gun. The two components, A and B, were
stirred, in separate pots, in the spray unit and maintained at a
temperature of 160.degree. F. (71.degree. C.) during the spray
process. The materials (Parts A and B) were sprayed on to a cold
roll steel panel that was previously sprayed with a release agent
(from Sierra Paint Co., Minnetonka, Minn., under the trade
designation "TK-709 UR") and also waxed paper. The formulation
cured within about 20 seconds. After a period of time the sprayed
panels were peeled from the metal substrate and waxed paper. The
contact angle data is listed in Table 1. Thermal conductivity data
is listed in Table 2.
Example 2
[0059] A two component polyurea (Part A and Part B) was formulated
as follows. Part A contained hexamethylene diisocyanate (84.4% by
weight, obtained from Rhodia, Inc., Cranbury, N.J., under the trade
designation "TOLONATE.TM. HDT LV2"), glass microspheres (12.3% by
weight, obtained from 3M Company under the trade designation
"3M.TM. GLASS MICROSPHERES K37"), a modified polyurea (1.3% by
weight, obtained from BYK Chemie, Wesel, Germany, under the trade
designation "BYK.TM. 410") and a fluorochemical urethane (2% by
weight, obtained from 3M Company under the trade designation
"SRC-220". Part B contained diethyltoluenediamine (32.4% by weight,
obtained from Albemarle Corporation, Bayport, Tex., under the trade
designation "ETHACURE.TM. 100"), polyoxypropylenediamine (39.6% by
weight, obtained from Huntsman Corporation, Salt Lake City, Utah
under the trade designation "JEFFAMINE.TM. D-2000"), an aromatic
secondary diamine (6.5% by weight, obtained from UOP, A Honeywell
Company, Tonawanda, N.Y. under the trade designation "UNILINK.TM.
4200"), a trifunctional amine (2.4% by weight, obtained from
Huntsman Corporation under the trade designation "JEFFAMINE.TM.
T-5000"), glass microspheres (18.2% by weight, obtained from 3M
Company under the trade designation "3M.TM. GLASS MICROSPHERES
K37"), a modified polyurea (0.8% by weight, obtained from BYK
Chemie, under the trade designation "BYK.TM. 410"), and a liquid
organic pigment to produce the desired color (0.1%).
[0060] Parts A and B were sprayed from a plural component
proportioning sprayer (obtained from Graco, Minneapolis, Minn.,
under the trade designation "REACTOR H-XP2" using a "FUSION MP"
spray gun with nozzles. Each part (A and B) was kept separate until
they exited the spray gun. The two components, A and B, were
stirred, in separate pots, in the spray unit and maintained at a
temperature of 160.degree. F. (71.degree. C.) during the spray
process. The materials (Parts A and B) were sprayed on to a cold
roll steel panel that was previously sprayed with a release agent
(from Sierra Paint Co., Minnetonka, Minn., under the trade
designation "TK-709 UR") and also waxed paper. The formulation
cured within about 20 seconds. After a period of time the sprayed
panels were peeled from the metal substrate and waxed paper and
tested as described above. The data is listed in Table 1.
Example 3
[0061] A two component polyurea (Part A and Part B) was formulated
as follows. Part A contained hexamethylene diisocyanate (76.8% by
weight, obtained from Rhodia, Inc., Cranbury, N.J., under the trade
designation "TOLONATE.TM. HDT LV2"), glass microspheres (12.2% by
weight, obtained from 3M Company under the trade designation
"3M.TM. GLASS MICROSPHERES K37"), a modified polyurea (1.0% by
weight, obtained from BYK Chemie, Wesel, Germany, under the trade
designation "BYK 410") and a fluorochemical urethane (10% by
weight, obtained from 3M Company under the trade designation
"SRC-220". Part B contained diethyltoluenediamine (32.4% by weight,
obtained from Albemarle Corporation, Bayport, Tex., under the trade
designation "ETHACURE.TM. 100"), polyoxypropylenediamine (39.6% by
weight, obtained from Huntsman Corporation, Salt Lake City, Utah
under the trade designation "JEFFAMINE.TM. D-2000"), an aromatic
secondary diamine (6.5% by weight, obtained from UOP, A Honeywell
Company, Tonawanda, N.Y., under the trade designation "UNILINK.TM.
4200"), a trifunctional amine (2.4% by weight, obtained from
Huntsman Corporation under the trade designation "JEFFAMINE.TM.
T-5000"), glass microspheres (18.2% by weight, obtained from 3M
Company under the trade designation "3M.TM. GLASS MICROSPHERES
K37"), a modified polyurea (0.8% by weight, obtained from BYK
Chemie, under the trade designation "BYK.TM. 410"), and a liquid
organic pigment to produce the desired color (0.1%).
[0062] Parts A and B were sprayed from a plural component
proportioning sprayer (obtained from Graco, Minneapolis, Minn.,
under the trade designation "REACTOR H-XP2" using a "FUSION MP"
spray gun with nozzles. Each part (A and B) was kept separate until
they exited the spray gun. The two components, A and B, were
stirred, in separate pots, in the spray unit and maintained at a
temperature of 160.degree. F. (71.degree. C.) during the spray
process. The materials (Parts A and B) were sprayed on to a cold
roll steel panel that was previously sprayed with a release agent
(from Sierra Paint Co., Minnetonka, Minn., under the trade
designation "TK-709 UR") and also waxed paper. The formulation
cured within about 20 seconds. After a period of time the sprayed
panels were peeled from the metal substrate and waxed paper and
tested as described above. The data is listed in Table 1.
Example 4
[0063] A two component polyurea (Part A and Part B) was formulated
as follows. Part A contained hexamethylene diisocyanate (81.8% by
weight, obtained from Rhodia, Inc., Cranbury, N.J., under the trade
designation "TOLONATE.TM. HDT LV2"), glass microspheres (13.0% by
weight, obtained from 3M Company under the trade designation
"3M.TM. GLASS MICROSPHERES K37"), a modified polyurea (1.2% by
weight, obtained from BYK Chemie, Wesel, Germany, under the trade
designation "BYK.TM. 410") and a fluorochemical monoisocyanate (4%
by weight, as prepared in U.S. Pat. No. 7,081,545 (Klun et al.)
Example 5, which is incorporated by reference to the extent that it
is not inconsistent with the present disclosure). Part B contained
diethyltoluenediamine (32.4% by weight, obtained from Albemarle
Corporation, Bayport, Tex., under the trade designation
"ETHACURE.TM. 100"), polyoxypropylenediamine (39.6% by weight,
obtained from Huntsman Corporation, Salt Lake City, Utah under the
trade designation "JEFFAMINE.TM. D-2000"), an aromatic secondary
diamine (6.5% by weight, obtained from UOP, A Honeywell Company,
Tonawanda, N.Y., under the trade designation "UNILINK.TM. 4200"), a
trifunctional amine (2.4% by weight, obtained from Huntsman
Corporation under the trade designation "JEFFAMINE.TM. T-5000"),
glass microspheres (18.2% by weight, obtained from 3M Company under
the trade designation "3M.TM. GLASS MICROSPHERES K37"), a modified
polyurea (0.8% by weight, obtained from BYK Chemie, under the trade
designation "BYK.TM. 410"), and a liquid organic pigment to produce
the desired color (0.1%).
[0064] Parts A and B were sprayed from a plural component
proportioning sprayer (obtained from Graco, Minneapolis, Minn.,
under the trade designation "REACTOR H-XP2" using a "FUSION MP"
spray gun with nozzles. Each part (A and B) was kept separate until
they exited the spray gun. The two components, A and B, were
stirred, in separate pots, in the spray unit and maintained at a
temperature of 160.degree. F. (71.degree. C.) during the spray
process. The materials (Parts A and B) were sprayed on to a cold
roll steel panel that was previously sprayed with a release agent
(from Sierra Paint Co., Minnetonka, Minn., under the trade
designation "TK-709 UR") and also waxed paper. The formulation
cured within about 20 seconds. After a period of time the sprayed
panels were peeled from the metal substrate and waxed paper and
tested as described above. The data is listed in Table 1.
TABLE-US-00001 TABLE 1 Static Contact Angle H2O Dynamic Advancing
Sprayed Contact Angle (H.sub.2O) Dynamic Receding Contact Sprayed
On Sprayed On Angle (H.sub.2O) On Waxed Sprayed Waxed Sprayed On
Sprayed On Steel Paper On Steel Paper Steel Waxed Paper Comparative
73.1 65 78.2 72.2 42.5 45.6 Example 1 Example 2 76.8 65.8 77.9 77.4
48.0 46.8 Example 3 91.2 97.9 99 100 33.1 32 Example 4 90 81.5 79.5
74.8 58.0 49.3
[0065] TABLE-US-00002 TABLE 2 Test Method Comparative Example 1
Example 1 Thermal 250.degree. F./115.degree. F. 250.degree.
F./104.degree. F. Conductivity Test Method 2- Hot Face vs. Cold
Face Thermal K = 0.1 W/mK @ 58.degree. C. K = 0.07 W/mK @
58.degree. C. Conductivity Test Method 1
[0066] Various modifications and alterations to this invention will
become apparent to those skilled in the art without departing from
the scope and spirit of this invention. It should be understood
that this invention is not intended to be unduly limited by the
illustrative embodiments and examples set forth herein and that
such examples and embodiments are presented by way of example only
with the scope of the invention intended to be limited only by the
claims set forth herein as follows.
* * * * *