U.S. patent application number 10/898773 was filed with the patent office on 2005-01-06 for hydrophobic coating compositions and articles coated with said compositions.
This patent application is currently assigned to Cytonix Corporation. Invention is credited to Brown, James F..
Application Number | 20050003203 10/898773 |
Document ID | / |
Family ID | 46277453 |
Filed Date | 2005-01-06 |
United States Patent
Application |
20050003203 |
Kind Code |
A1 |
Brown, James F. |
January 6, 2005 |
Hydrophobic coating compositions and articles coated with said
compositions
Abstract
Hydrophobic coating compositions are provided as are processes
to coat articles with the compositions. Extremely hydrophobic
coatings are provided by the compositions. Durable, weatherable and
scratch-resistant coatings are provided by compositions comprising
a trifluoromethyl-containing component and a hardenable material.
Weatherable coatings are also provided by compositions comprising a
mobile non-volatile fluorinated component and a hardenable
material. Processes are also provided for forming hydrophobic
coatings on articles.
Inventors: |
Brown, James F.; (Clifton,
VA) |
Correspondence
Address: |
KILYK & BOWERSOX, P.L.L.C.
3603 CHAIN BRIDGE ROAD
SUITE E
FAIRFAX
VA
22030
US
|
Assignee: |
Cytonix Corporation
Beltsville
MD
|
Family ID: |
46277453 |
Appl. No.: |
10/898773 |
Filed: |
July 26, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10898773 |
Jul 26, 2004 |
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10272982 |
Oct 17, 2002 |
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6767587 |
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10272982 |
Oct 17, 2002 |
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09823853 |
Mar 30, 2001 |
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6495624 |
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09823853 |
Mar 30, 2001 |
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09593847 |
Jun 14, 2000 |
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6447919 |
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09593847 |
Jun 14, 2000 |
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09220884 |
Dec 28, 1998 |
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6156389 |
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09220884 |
Dec 28, 1998 |
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08795316 |
Feb 3, 1997 |
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5853894 |
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Current U.S.
Class: |
428/413 ; 522/1;
525/88 |
Current CPC
Class: |
C09D 127/18 20130101;
C09D 133/16 20130101; C08L 2205/18 20130101; C09D 133/16 20130101;
C09D 133/16 20130101; Y10T 428/31511 20150401; C08L 27/18 20130101;
C08L 2666/54 20130101; C08L 2666/04 20130101; C09D 127/18 20130101;
C08L 2666/28 20130101; C08L 2666/54 20130101; C08L 2666/14
20130101; B01L 3/50 20130101; C09D 133/16 20130101 |
Class at
Publication: |
428/413 ;
525/088; 522/001 |
International
Class: |
B32B 027/38; C08L
053/00; C08L 063/00; C08F 002/46 |
Claims
What is claimed is:
1. A composition of matter comprising the reaction product of a
first monomer and a second monomer and formed by a first reaction
mechanism, said composition comprising at least 15 percent by
weight said first monomer, and from about 1 to about 10 percent by
weight said second monomer, said first monomer comprising a
trifluormethyl-containing monomer, said second monomer differing
from the first monomer and including a functional group that is
capable of being activated by a second reaction mechanism, wherein
said second reaction mechanism differs from the first reaction
mechanism and comprises a radiation induced linkage.
2. A composition as in claim 1, wherein the second reaction
mechanism comprises activation by visible light.
3. A composition as in claim 1, wherein the second reaction
mechanism comprises activation by ultraviolet light.
4. A composition as in claim 1, wherein said functional group is at
least one of an epoxy group, a vinyl group, an acrylate group, or a
methacrylate group.
5. A composition as in claim 1, further comprising a catalyst for
said second reaction mechanism.
6. A composition as in claim 1, further comprising a solvent.
7. A composition as in claim 6, wherein said solvent comprises a
fluorinated solvent.
8. A composition as in claim 1, wherein the first monomer comprises
at least one of a peroxide catalyzed linkage, an azo catalyzed
linkage, a free radical induced linkage, a cationically induced
linkage, a radiation induced linkage, a vinyl linkage, a
methacrylate linkage, a urethane linkage, an epoxy linkage, a
condensation linkage, a silane linkage, and a siloxane linkage.
9. A composition as in claim 1, further comprising a
non-perfluorinated functional monomer present in an amount of from
about 15 to about 95 percent by weight.
10. A composition as in claim 7, wherein said additive comprises an
epoxy.
11. The composition of claim 1, further comprising hydrophobic
particles having an average particle size diameter of less than
about 100 microns.
12. An article coated with the composition of matter of claim
1.
13. An article coated with the composition of matter of claim
2.
14. An article coated with the composition of matter of claim
3.
15. An article coated with the composition of matter of claim
4.
16. An article coated with the composition of matter of claim
5.
17. An article coated with the composition of matter of claim
8.
18. An article coated with the composition of matter of claim
9.
19. An article coated with the composition of matter of claim
10.
20. An article coated with the composition of matter of claim 11.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a continuation of U.S. patent
application Ser. No. 10/272,982, filed Oct. 17, 2002, and allowed
on Apr. 1, 2004; which in turn is a divisional of U.S. patent
application Ser. No. 09/823,853, filed Mar. 30, 2001, now U.S. Pat.
No. 6,495,624, issued Dec. 17, 2002; which in turn is a
continuation-in-part of U.S. patent application Ser. No.
09/593,847, filed Jun. 14, 2000, now U.S. Pat. No. 6,447,919,
issued Sep. 10, 2002; which in turn is a divisional of prior
application Ser. No. 09/220,884, filed Dec. 28, 1998, now U.S. Pat.
No. 6,156,389, issued Dec. 5, 2000; which in turn is a
continuation-in-part of prior application Ser. No. 08/795,316,
filed Feb. 3, 1997, now U.S. Pat. No. 5,853,894, issued Dec. 29,
1998.
FIELD OF THE INVENTION
[0002] The present invention relates to compositions for coating
surfaces, surfaces coated with compositions, and methods of forming
coated surfaces. More particularly, the present invention relates
to hydrophobic coatings for laboratory vessels and other articles.
The present invention also relates to processes for forming a
hydrophobic coating on a surface of an article.
BACKGROUND OF THE INVENTION
[0003] Hydrophobic coatings are useful for many applications, for
example, to prevent rain from wetting-out or collecting on a
windshield. Another application of hydrophobic coatings is in the
field of laboratory vessels. Laboratory vessels including chambers,
microtiter plates, vials, flasks, test tubes, syringes,
microcentrifuge tubes, pipette tips, selectively coated microscope
slides, coverslips, films, porous substrates and assemblies
comprising such devices are often used to handle, measure, react,
incubate, contain, store, restrain, isolate and/or transport very
precise and sometimes minute volumes of liquid, often biological
samples. When samples are quantitatively analyzed, it can be of
critical importance that precise and representative amounts of
sample are transferred, or else inaccurate results are obtained.
Due to the different affinities of some materials to adhere to the
walls of a laboratory vessel, qualitative analyses such as
concentrations of materials may also be adversely affected if
certain materials in a sample selectively adhere to operational
surfaces of the vessel walls.
[0004] Unfortunately, materials typically used in the manufacture
of laboratory vessels do not sufficiently repel many biological
sample fluids nor do they sufficiently resist the adherence of
molecular constituents of such a sample fluid. The sample fluids
often wet the surface of the vessel causing residual quantities of
liquid sample to cling to an operational surface of the vessel when
the sample is removed. In some cases, significant quantitative
and/or qualitative errors result. It is therefore desirable to
provide extremely hydrophobic coatings for laboratory vessels which
will reduce the wetting of the operational surfaces of the vessels
and reduce clinging by even the most adherent samples so that
virtually no sample remains in the vessel when poured, ejected or
vacuumed therefrom.
[0005] In some laboratory techniques, it is important to restrain,
isolate or limit the position of liquid samples to prescribed
locations within or on a laboratory vessel, while keeping adjacent
surfaces of the vessel substantially free of liquid sample. Such
techniques can be used to facilitate chemical and biological
reactions, as well as improving sample recovery. The prescribed
locations may (1) have surfaces that are reactive, (2) have a
surface that exhibits a specific affinity, (3) optimize the sample
volume to area ratio, (4) restrict sample movement during at least
some vessel motion, and (5) have porous surfaces.
[0006] Vessels for handling, measuring, storing and transporting
liquids have previously been rendered less wettable and less
adherent to fluids by application of silicone compounds to the
vessel surfaces which come in contact with the fluid. For example,
silane monomers and polymers have been added to polyolefins prior
to injection molding, resulting in laboratory vessels with an
improved repellency to many sample fluids and their constituents.
These materials produce surfaces with surface energies potentially
as low as 22 ergs per square centimeter. In practice, however,
silane treated vessels exhibit surface energies that measure 25 to
30 dynes/cm.
[0007] Drawbacks associated with silane treatments include a
continued wetting of the vessel, adherence to the vessel walls by
many samples, chemical reactivity with many reagents, and a
tendency for the vessel to become wettable following the common
practice of autoclaving for sterilization. Silicones are known to
freely migrate, leading to worries over sample integrity. Many
pipette tips are plugged with porous filters to prevent sample
contamination from the pipettor barrel, yet these free silicones
make the pipette tips slippery and cause the filters to become
loose or dislodged. Additionally, silicones must typically be added
at a level of 2 percent by weight to be effective, making the cost
prohibitive for many price sensitive applications.
[0008] Fluorination processes have been used to treat laboratory
vessels and have resulted in vessels having interior surfaces with
surface energies approaching 22 dynes/cm. These processes generally
involve the full or partial replacement of superficial hydrogen by
fluorine using chemical processes or the plasma polymerization of
fluorine containing gases. U.S. Pat. No. 4,902,529 to Rebhan et al.
discloses a plasma torch process using CF.sub.4 or SiF.sub.6 to
fluorinate the interior of resin articles and containers in an
attempt to eliminate the use of dangerous mixtures of fluorine and
inert gases. This method is impractical, however, for treating the
vast quantities of small vessels consumed by industrial, clinical
and research establishments. Furthermore, improvements in
performance over silicone processes are only marginal.
[0009] The plasma polymerization of perfluorobutene onto the
exterior surface of various articles has been reported to produce
exterior surfaces with up to 24 percent --CF.sub.3 groups, and a
high percentage of --CF.sub.2-- groups. Resultant surface energies
of 22 to 24 dynes/cm are obtained due to the presence of
cross-linkages and numerous monofluorinated carbons.
Time-consuming, carefully controlled RF plasmas employing
fluorine-containing monomers have also been used to reduce the
wettability and adhesion of laboratory vessels, producing exterior
surface energies of 12 to 15 dynes/cm and surface populations of up
to about 25% by area CF.sub.3 groups on exterior non-operational
surfaces. Interior operational surfaces, however, are still not
reduced to below 22 dynes/cm. While these methods offer
improvements over silicon-based treatments, the time, expense and
equipment required are not appropriate for high commercial volume
articles that are often for one-time use and require very low
inherent cost.
[0010] Perfluoroalkyl polymers and carefully prepared monolayer
films of perfluoroalkyl surfactants are widely recognized as having
surface energies below 20 dynes/cm. FEP and PFA Teflons.RTM.,
available from DuPont's Polymer Products Department, Wilmington,
Del., have surface energies of 15 to 16 dynes/cm with --CF.sub.3
populations as high as 25 percent. Extruded and fused Teflon.RTM.
vessels are currently manufactured for special applications
involving exceptionally harsh reagents but are expected to have a
long service life because of their high material cost when compared
to the cost of glass or polypropylene vessels.
[0011] Fluoroalkyl polymers have been used to produce oleophobic,
hydrophobic membrane surfaces that are not wetted by common organic
solvents. Membranes coated with such polymers are disclosed in U.S.
Pat. No. 4,954,256 to Degen et al. These membranes have surface
energies ranging from about 6 to about 15 dynes/cm but require a
manufacturing procedure which involves soaking a membrane with a
solution containing polymerizable monomers, exposing the
solution-wetted membrane to high doses of ionizing radiation, and
then washing the ionized membrane with organic solvent to remove
unreacted monomer. While no attempts are known to coat laboratory
vessels by such a procedure, it is expected that difficulties would
arise as well as high cost in coating such vessels because of the
shear bulk of the polymerizable solution to be irradiated and
problems with fully washing the coated vessel.
[0012] Methods of making disposable, one-time use laboratory
vessels such as pipette tips can involve a substantial loss of
costly solvent when a coating solution is used to form a
hydrophobic coating. A need exists for a process of coating
laboratory vessels at a cost of a few cents per thousand with an
insignificant loss of solvent.
[0013] Recent patents may suggest the practice of solvent recovery
in the application of certain branched fluoropolymers, such as
Teflon AF, to articles of manufacture. U.S. Pat. No. 5,356,668 to
Paton et al. and U.S. Pat. No. 5,006,382 to Squire are incorporated
herein in their entireties by reference. The mere suggestion of
such a recovery practice, however, does not provide a commercially
viable method for coating many low cost, one-time-use articles,
such as pipette tips and laboratory vessels.
[0014] Environmental concerns about pollution by volatile solvents,
especially chlorine-containing materials such as perchoroethylene,
have motivated significant improvement in dry cleaning equipment,
resulting in significant reductions in solvent losses. Cleaning and
coating equipment used in the semiconductor, plastics, and metal
parts industries have made similar strides. Better seals and welded
ducts account for some of the upgrades.
[0015] Operation of these machines according to their suggested
protocols using fluorinated solvents, however, still results in
large, expensive losses. For example, the Renzacci Company of Italy
manufactures perchloroethylene-based cleaning machines that are
widely recognized to be among the best in the industry in terms of
minimal solvent loss. But loaded with 60,000 pipette tips in
mono-filament mesh bags and using Renzacci's standard automated
programs, these machines loose about 5 pounds of FC84 (3M Company,
St Paul, Minn.) per cycle. This translates to solvent consumption
costs of over one dollar per thousand tips. Higher boiling point
fluorocarbon solvents have lower loss rates, but the solvent
expense is about the same due to their higher cost per pound.
[0016] The Renzacci standard automated program partially fills a
cleaning/coating tank of approximately one-half cubic meter with
solvent at ambient temperature from a solvent reservoir. Articles
in the tank are then tumbled in the solvent for several minutes,
followed by drain, spin and spin-rinse cycles. With continued
tumbling, a heat pump and a supplementary heat source (electric,
steam, etc.) heat air blown through the tank, while passing air
returns from the tank over chilled condensation coils where solvent
vapor is liquified and returned to the reservoir. Water is
circulated through the heat pump system to remove excess heat.
However, the temperature in the tank can still rise to over
50.degree. C. and the reservoir temperature can rise to more than
30.degree. C. At the end of the process cycle, heating is
discontinued and the tank and reservoir are cooled to about
30.degree. C. When the tank door is opened to remove the
cleaned/coated articles, a small blower draws air out of the tank
through a carbon filter in order to reduce the odor of remaining
perchloroethylene solvent.
[0017] Unfortunately, at 30.degree. C. the solvent FC84 has a vapor
pressure of over one fifth atmosphere, and the half cubic meter
tank volume contains about two pounds of solvent as dense vapor
(about 14 times that of air), even without agitation. Opening the
tank door results in the immediate loss of this material, at a
current cost of about $45 (US). Since the machine will handle about
60,000 tips per run, the loss per thousand is about 50 cents. The
carbon recovery filter is at the top of the tank and is of little
practical economic value.
[0018] Additional losses accrue during the heat cycle at 50.degree.
C. when the machine fittings and seals are challenged by pressures
approaching 1.2 atmospheres. Furthermore, it is apparent from other
studies that low molecular weight fluorocarbon solvents, having
boiling points between 80.degree. and 120.degree. C. are
particularly "slippery" in passing through rubber and silicone
gaskets and seals. No machines investigated had more aggressive
containment systems for leak-free operation under these
conditions.
[0019] A need exists for a method of coating large numbers of
laboratory vessels which results in a very low loss of solvent at a
surprising and significant cost savings.
[0020] Described by Dettre and Johnson in 1964 are phenomena
related to rough hydrophobic surfaces. Dettre and Johnson developed
a theoretical model based on experiments with glass beads coated
with paraffin or TFE telomer. For even moderately hydrophobic
surfaces (e.g. about 40 dynes/cm or less) with high levels of
microscopic roughness, where the average height of bumps is close
to or exceeds their average width, an aqueous liquid, especially
one without surfactant activity, in contact with the surface only
wets the top of the bumps, forming what is known as a "composite"
air-liquid-solid interface. For example, water at rest on a surface
of this kind may exhibit contact angles greater than 160 degrees.
This unusual property has been practiced and is the basis for a
variety of proprietary microscope slide, plate and membrane
products using coatings sold by Cytonix Corporation, in Beltsville,
Md. However, such products are based on Teflon.RTM. and the
hydrophobic properties of difluoromethylene (--CF.sub.2--) groups,
which at best exhibit surface energies of from about 18 to about 20
dynes/cm.
[0021] Hydrophobic coatings are also used on antennas and radomes.
Microwave signals are significantly, and in some cases about
equally, attenuated by atmospheric precipitation and by water films
on antennas and radomes. Higher microwave frequencies have resulted
in greater communication bandwidth, but the shorter wavelengths are
even more susceptible to rain attenuation. Airports report losses
of vital satellite links during heavy precipitation, and most home
viewers of satellite TV are familiar with programming disruption
during even light rain. As bandwidths expand commercial and private
use of microwave links, the problem of rain attenuation will become
even more critical.
[0022] Numerous companies have addressed the problem of water
filming on microwave radomes and dishes by using hydrophobic
coatings to shed water as small, microwave-transparent beads. The
smooth silicones and fluoropolymer coatings allow formation of
large beads that can form rivulets and films during moderate to
heavy rain. As these coatings degrade over time due to sunlight and
pollution, they become less hydrophobic and their effectiveness is
diminished.
[0023] Several companies, notably Vellox (Salisbury, Mass.) and
Boyd (Hudson, Mass.), have addressed the problem of rain fade using
hydrophobic coatings that comprise micropowders of Teflon.TM. or
fumed silica dispersed in a hardenable resin, such as an alkyd or
diisocyanate. These composite coatings have good performance
initially but begin to form water films in an hour or less of
moderate to heavy rain. After months or just weeks of exposure to
mid-latitude summer sunlight these types of coatings wet out even
more quickly. Herein, mid-latitude summer sunlight is defined as
average mid-day uv radiation during the summer months in regions of
the United States from a latitude of 25.degree. to a latitude of
40.degree., and moderate to heavy rain is defined as 1 to 6 inches
per hour. Drying fully after being swamped, the Boyd Teflon.TM.
dispersion coating CRC6040 recovers most of its previous
performance, but the hydrophobic performance of the Vellox LC-410
fumed silicate coating is permanently lost. Both coatings must be
reapplied every year or two.
[0024] It is believed that sunlight damages at least the surfaces
of all solid polymers to some degree. Generally, unsaturated
materials degrade faster than aliphatics, and aliphatics degrade
faster than some fluoropolymers. But all hydrocarbon resins suffer
at least superficial changes that render them more wettable; and
this is also true for most fluoropolymers. The fluoropolymer
exceptions are those that degrade to hydrophobic by-products, such
as PTFE; but even the exceptions can be rendered somewhat more
hydrophilic and receptive to adhesives by ionizing radiation
treatment. Once surface damage has taken place, the new surface is
a permanent feature of the solid. Tests of all common fluorinated
and non-fluorinated plastics show increases in surface wettability
after exposure to the equivalent of months in mid-latitude summer
sunlight.
[0025] A need exists for a method of manufacturing a coating which
exhibits, on all or part of an operational surface thereof,
interfacial contact angles to aqueous samples of 120.degree. and
above, even as high as 160.degree., and surface energies well below
20 dynes/cm. According to some desirable applications, a need also
exists for vessels having surface energies of below 10 dynes/cm.
This need is especially acute but difficult to achieve for
one-time-use vessels costing only a few dollars per thousand.
[0026] There is also a need for extremely hydrophobic coatings that
are durable, for example, coatings for articles such as
windshields, rainshields, and satellite and/or radar dishes, other
signal receivers and transmitters, and radomes. A need exists for a
composition which can provide an extremely hydrophobic and durable
coating on a surface of an article. Problems associated with water
film formation on radomes, and problems of radar desensitization in
rain are described, for example, in the Honeywell Technical
Newsletter entitled RADAR DENSENSITIZATION IN RAIN, WATER FILMS ON
RADOMES, AND HYDROPHOBIC COATINGS, Nov. 2, 1998, re-published by
Cytonix Corporation with permission from Honeywell, Inc., said
newsletter being incorporated herein in its entirety by reference.
A need exists for a coating composition for a signal transmitter or
receiver, wherein the composition can be applied and form an
extremely hydrophobic coating that does not interfere with signal
transmission or reception.
[0027] A need also exists for a composition that forms a
hydrophobic surface useful as a surface for articles which could
benefit from hydrophobic properties, for example, radomes and
antennas, vehicular surfaces, architectural surfaces, outdoor
furniture, household goods, and kitchen and bath articles.
SUMMARY OF THE INVENTION
[0028] According to the present invention, extremely hydrophobic
coatings are provided. According to an embodiment of the present
invention, the invention provides a durable, weatherable, and
erosion-resistant hydrophobic coating. The coatings of the present
invention can be used on a signal transmitter or receiver, for
example, a microwave, infra-red, light, radar, electromagnetic, or
the like emitter or receiver such as a radome. The coatings of the
invention do not adversely affect reception or transmission of a
signal.
[0029] According to another embodiment of the present invention, a
process is provided for forming an extremely hydrophobic coating on
a surface of an article. An embodiment of the present invention is
based on the discovery that methods can be provided to coat
laboratory vessels with an extremely hydrophobic coating at a cost
of only a few cents per thousand vessels.
[0030] According to embodiments of the present invention, a surface
is coated with a composition which includes or provides a reaction
product, for example, a polymerization product, of a fluorinated
reactant, for example, a fluorinated monomer containing from about
3 to about 20 carbon atoms and at least one terminal
trifluoromethyl group. According to embodiments of the invention,
the coating composition also includes a hardenable material, for
example, a urethane resin or TEFLON AF from DuPont. Hardenable
materials that may be employed include non-fluorinated hardenable
resins, fluorinated hardenable resins, and perfluorinated
hardenable resins. The resulting surfaces are extremely hydrophobic
and highly resistant to removal by weathering and/or solvents.
[0031] Herein, the term "fluorinated" includes both perfluorinated
and non-perfluorinated monomers and/or polymers. The present
invention relates to fluorinated compositions, coatings, and coated
surfaces which may be part of or parts of laboratory vessels,
signal transmitters, signal receivers, signal reflectors, radomes,
vehicular surfaces, architectural surfaces, outdoor furniture,
household goods, kitchen articles, kitchen surfaces, bathroom
articles, bathroom surfaces, antennae, microwave antennae, dishes,
reflectors, signs, visual signaling devices, scanner windows,
lenses, liquid crystal displays, and video displays. In addition,
the present invention relates to processes of coating small article
surfaces, for example, laboratory vessels, with nominal solvent
loss.
[0032] Processes of forming the extremely hydrophobic coatings of
the present invention may include applying a solution, suspension
or other liquid containing a coating composition and allowing the
solution, suspension or other liquid to harden, dry and/or cure on
a surface. The coating composition includes a trifluoromethylated
agent, which may be a reactant, a monomer, a reaction product,
and/or a polymerization product. The present invention also
provides a method wherein a solution or suspension of such agent is
partially, selectively or conformally coated onto at least a
portion of a surface of an article, for example, a laboratory
vessel, a radar dish, a radome, a windshield, a rainshield, a
vehicular surface, an architectural surface, outdoor furniture, a
household good, a kitchen article, a kitchen surface, a bath
article, a bathroom surface, an antenna, a microwave antenna, a
dish, a reflector, a sign, a visual signaling device, a scanner
window, a lens, a liquid crystal display, and/or a video display.
Then, the composition including the agent is subsequently hardened,
dried, and/or cured to remove solvent and/or suspension medium. The
coatings provide surfaces exhibiting extremely low surface energies
and, for some cases, preferably also provide a high resistance to
solvent removal. Some compositions according to the present
invention may desirably be removed with one or more organic
solvent, for example, with methylethylketone (MEK).
[0033] A surprising discovery about the economics and commercial
success of coating low cost, especially one-time-use, articles with
fluoropolymer coatings is that process efficiency in recovering
carrier solvents can be a more important factor than the relatively
high cost of the coating fluoropolymers. While high quality
unsaturated fluoromonomers currently can cost $250 (US) to over
$1000 (US) per pound in bulk quantities, articles such as pipette
tips may only require 10 to 20 milligrams of fluoropolymer per
thousand pipette tips at a current cost of less than 10 cents per
thousand. Conventional coating/washing equipment, for example,
equipment from Renzacci of America Inc., Absecond, N.J., and from
Fluoromatic Ltd., Villa Park, Ill., and processes that are designed
to recover solvents, can consume over 25 grams of solvent per
thousand pipette tips at a current cost of about five cents per
gram or $1.25 (US) per thousand. In many situations, particularly
coating methods using expensive perfluoropolymers, this is an
unacceptable added cost to articles otherwise costing only a few
dollars per thousand to manufacture. According to the present
invention, solvent loss is significantly reduced compared to the
conventional machines and processes.
[0034] According to some embodiments of the invention, a
hydrophobic coating may be formed from a coating composition of the
invention applied or co-injected as a resin, powder, particle or
mixture which is dried, melted, sintered, fused cured or otherwise
formed on a surface of an article.
[0035] Moreover, the present invention is based on the discovery
that laboratory vessel surfaces of low surface energy can be
provided by coating a solution, suspension, other liquid, resin,
powder, particle or mixture of a trifluoromethylated agent
according to the invention, admixed with microscopic particles
and/or fibers. In some embodiments, foaming and/or pore-forming
agents may additionally, or alternatively, be admixed with the
coating compositions of the present invention. The
trifluoromethylated agent may include a trifluoromethylated
reactant, monomer, reaction product and/or polymerization product.
Upon subsequent drying, melting, solidifying, sintering, fusing or
curing of the coating formulation, a laboratory vessel is produced
exhibiting extraordinarily high contact angles to aqueous
liquids.
[0036] The present invention is also based on the discovery that
coatings of trifluoromethylated agents containing 3 to 20 carbon
atoms and at least one terminal trifluoromethyl group are extremely
hydrophobic and can provide populations of 30% by area or greater
of trifluoromethyl groups on exposed coating surfaces. According to
the present invention, a reaction product of a reactant
trifluoromethylated agent may be coated from a formulation onto at
least a portion of an operational surface of a laboratory vessel,
for example, a vessel surface which contacts or restrains a liquid
sample. The coatings have tightly packed, exposed trifluoromethyl
groups.
[0037] According to some embodiments, at least about 30% of the
area of the exposed coating surface is covered by trifluoromethyl
groups. According to more preferred methods of the invention, the
exposed coating surface is covered with a population of
trifluoromethyl groups of from about 50% to 100% by area of the
surface. According to some embodiments, at least about 15% by area
of the exposed coating surface is covered by trifluoromethyl groups
and the coating includes a hardenable resin in addition to a
reaction product of a trifluoromethylated agent.
[0038] According to the present invention, the coating composition
comprises a trifluoromethylated agent comprised of a fluorocarbon,
hydrofluorocarbon, epoxy, urethane, silicone, acrylic or other
material that has a terminal trifluoromethyl group and contains
from about 3 to about 20 carbon atoms. Preferably, coatings made
from such compositions exhibit tightly packed trifluoromethyl
groups on the exposed coating surface. According to some
embodiments of the invention, coating polymers made from
substantially non-branched fluorinated monomers having carbon
chains of from about 3 to about 20 carbon atoms in length, and more
particularly from about 6 to about 12 carbon atoms in length,
enable a dense packing of the terminal trifluoromethyl groups and
thus can form hydrophobic surfaces of very low surface energy,
having critical surface tensions of about 10 dynes/cm or lower at
20.degree. C., and having high resistance to solvent removal and
low retention of biological samples.
[0039] According to yet other embodiments of the invention,
laboratory vessels and other articles are coated with hydrophobic
coating formulations containing terminal trifluoromethyl groups and
optionally further containing reaction products, polymers,
reactants, polymerizable monomers and/or other additives which also
become incorporated in the hydrophobic coatings.
DETAILED DESCRIPTION OF THE INVENTION
[0040] According to embodiments of the present invention, an
extremely hydrophobic coating can be formed on the surface of an
article and comprises the reaction product of a reactant containing
a terminal trifluoromethyl group. According to embodiments of the
present invention, an extremely hydrophobic coating can be formed
from a composition consisting essentially of the reaction product
of a reactant containing a terminal trifluoromethyl group with or
without a hardenable resin, for example, a urethane resin.
Particular articles which can be coated according to the present
invention include those having an operational surface comprising
plastic, sintered material, woven material, textured material,
semiconductor, glass, ceramic, or metal, or a primed or pre-coated
surface. The invention can also be used on operational surfaces
which are porous, smooth, rough, pitted, foamed, grooved,
cross-hatched, striated, or having patterned physical features.
[0041] Laboratory vessels according to an embodiment of the present
invention have at least one operational surface. Many vessels
according to the invention have at least one interior wall which
defines a reservoir portion for containing a volume of liquid, and
at least one opening in communication with the reservoir portion.
According to some embodiments of the invention, a laboratory vessel
having an interior wall and an opening is coated on the interior
wall and on the area surrounding and forming the opening, with a
polymer coating according to the invention.
[0042] According to embodiments of the present invention, methods
are provided for forming extremely hydrophobic coatings on small
articles such as laboratory vessels. Measures to curtail
fluorinated solvent losses, according to the present invention,
focus on better containment, improved solvent recovery, and reduced
solvent vapor pressure throughout the coating operation. According
to embodiments of the invention, the general design of the Renzacci
Patriot 350, from Renzacci of America, may be employed for the
coating machine and process of the present invention, but with some
major modifications. According to the present invention, it has
been determined that rubber and silicone seals are significantly
not leak-proof to fluorocarbon solvents. According to the present
invention, sealing means comprising a rubber derived from
vinylidene fluoride and hexafluoropropene, for example, VITON.TM.
seals are substituted for other rubber or silicone seals. The
generally lower permeability of VITON.TM. seals to hydrophobic
gases such as methane and tetrafluoromethane prevent a significant
amount of fluorocarbon solvent and/or gas loss as a result of a
coating process.
[0043] Metal tubing and swaged fittings are preferred over plastic
piping and threaded pipe connections. If the Renzacci machine is
modified to form an apparatus according to the present invention,
the carbon "recovery" system of the Renzacci model is preferably
eliminated.
[0044] According to embodiments of the present invention, solvent
recovery is enhanced by lowering the cooling coil temperature and
by slowing the air flow over the coils. Longer recovery times are
programmed to further improve solvent recovery according to
embodiments of the present invention. According to embodiments of
the invention, significant benefits in reducing solvent loss are
achieved by operating the entire coating cycle at temperatures that
keep solvent vapor pressure low relative to atmospheric pressure,
that is, at about or below atmospheric pressure. Although removing
solvent from wetted articles according to the invention requires
somewhat more time, the increased cost of machine time is only
hundredths of a cent per thousand pipette tips. Solvent
consumption, however, is reduced to only barely detectable levels,
providing overall savings of more than $60 (US) per cycle.
[0045] According to embodiments of the present invention, a process
is provided wherein laboratory vessels can be coated with a
composition which forms a coating having at least a 15% by area
trifluoromethyl surface, and solvent loss resulting from the
process of less than 20 grams of fluorosolvent lost per pound of
processed laboratory vessels. More preferably, solvent loss
resulting from the process is less than 10 grams of fluorosolvent
lost, more preferably less than 5 grams of fluorosolvent lost, per
pound of processed laboratory vessels. Even more preferably,
fluorosolvent loss according to an embodiment of the present
invention is only one gram of fluorosolvent lost per one pound of
processed laboratory vessels.
[0046] According to embodiments of the present invention, a process
is provided wherein articles, for example, laboratory vessels, can
be coated with a composition which forms a coating having at least
a 15% by area trifluoromethyl surface, and solvent vapor pressure
within the coating chamber is maintained substantially below
atmospheric pressure. Preferably, solvent vapor pressure within the
coating chamber is maintained at below about 25% of atmospheric
pressure, more preferably, at below about 10% of atmospheric
pressure, for example, below about 5% of atmospheric pressure. Even
more preferably, solvent vapor pressure is maintained at less than
1% of atmospheric pressure. Temperature control can be used to
maintain low pressure. The solvent loss is substantially minimized
according to the process of the present invention wherein after
coating the articles the seal of the sealed chamber is broken while
the vapor pressure within the chamber is below atmospheric
pressure, preferably below about 25% of atmospheric pressure.
[0047] According to the present invention, laboratory vessels are
provided with coatings having at least a 15% surface area
population of trifluoromethyl groups by a process wherein solvent
temperature is maintained substantially below its boiling point
during the coating and solvent recovery process. Preferably, a
fluorinated solvent is used. Preferably, solvent temperature is
maintained below 75%, for example, below 50% of the absolute value
of the difference between the boiling point of the solvent and
25.degree. C. For example, if the solvent has a boiling point of
85.degree. C., the temperature is preferably maintained at or below
70.degree. C., which is at or below 75% of the absolute difference
between 85.degree. C. and 25.degree. C. More preferably, solvent
temperature is maintained below 25% of the absolute value of the
difference between the boiling point of the solvent and 25.degree.
C. Cooling water chillers or heat exchangers can be used, for
example, to lower the temperature of the coating solution or
suspension.
[0048] Articles such as laboratory vessels to be coated according
to a process of the present invention may contain or consist of
plastic, metal, or glass. Preferred materials used to manufacture
the coated laboratory vessels of the present invention include
polypropylene, polyethylene, polyethyleneterephthalate,
polystyrene, polycarbonate and cellulosics. More expensive plastics
such as polytetra-fluoroethylene and other fluorinated polymers may
be used. Some vessels made from these plastics are hydrophobic
without any additional coating. Herein, the term "hydrophobic"
refers to a surface exhibiting an average surface energy of about
40 dynes/cm or less. Because polypropylene is inexpensive and quite
hydrophobic itself, it is a particularly preferred material for
laboratory vessels, including pipette tips, used for handling and
transporting minute and precise amounts of biological sample.
[0049] In addition to the materials mentioned above, examples of
other suitable materials for the laboratory vessels of the present
invention include polyolefins, polyamides, polyesters, silicones,
polyurethanes, epoxies, acrylics, polyacrylates, polyesters,
polysulfones, polymethacrylates, polycarbonate, PEEK, polyimide,
polystyrene, and fluoropolymers such as PTFE Teflon.RTM., FEP
Teflon.RTM., Tefzel.RTM., poly(vinylidene fluoride), PVDF, and
perfluoroalkoxy resins. Glass products including silica glass are
also used to manufacture laboratory vessels. One exemplary glass
product is PYREX.RTM. (available from Corning Glass, Corning,
N.Y.). Ceramic or oxide surfaces can be coated according to
embodiments of the invention. Cellulosic products such as paper and
reinforced paper containers can be coated to form coated laboratory
vessels according to the invention. Metal surfaces can be coated
according to the invention, as can surfaces of glass, silicon,
silicon compounds or ceramics that have or have not been primed
with silane containing materials or other adhesion promoting
materials. Primed metal, primed glass, primed ceramic and primed
oxide surfaces can be coated according to embodiments of the
invention. Vessel surfaces that have been pre-coated with epoxies,
silicones, urethanes, acrylics, or other materials can also be
coated according to embodiments of the invention.
[0050] Although some wash-off of polymerized coating material or
coating monomer might be expected after repeated usage, the
coatings of the present invention do not measurably wash off most
laboratory vessel surfaces. It is believed that little if any
wash-off occurs because the coating solution causes softening and
swelling of the vessel material, especially in uncross-linked
plastics, and enables entanglement of coating and vessel substrate
molecules allowing strong Van der Waals and other bonding forces
which hold the prepolymerized product where applied to an
operational surface of the vessel. The linear swelling of many
polymers and elastomers, including some fluoroelastomers and some
silicones, is reported in Table 8 of the 1996 Technical Information
sheet for Vertrel.TM. XF, available from DuPont's Polymer Products
Division, Wilmington, Del. Little if any wash-off occurs from other
vessel materials because of the extremely low solubility of the
coatings of the present invention in most solvents and limited
solubility in fluorinated solvents. Preferably, even exposure to
water wash conditions of 1500 psi causes no substantial reduction
in hydrophobic properties of the coating or material having a
surface of the present invention.
[0051] According to some embodiments of the present invention,
hydrophobic reaction products having terminal trifluoromethyl
groups are coated from a fluorinated agent/fluorosolvent solution
or suspension onto linear, hydrophobic, essentially uncrosslinked
polymers such as polyolefins and TEFLON.RTM., and show particular
resistance to removal even by chlorinated solvents. According to
the present invention, swelling of the polyolefin surface during
application of the fluorinated agent solution or suspension and
subsequent entanglement of the reaction product, for example,
polymerization product, at the interface, result in strong
hydrophobic bonds between the coating and the polyolefin surface.
Surprisingly, the coatings according to embodiments of the
invention are not measurably removed, even with chloroform or
chloroethene.
[0052] According to some embodiments of the invention, the
laboratory vessel comprises a microscope slide or other
substantially flat device having an operational surface at least
partially coated with a coating formulation according to the
invention. According to some embodiments of the invention, a
delineated area of a laboratory vessel surface, for example, a
portion of the surface of a microscope slide, is not coated with
the coating formulation, but is instead surrounded by the coating.
The coating thus forms a boundary to restrain, contain or isolate a
fluid sample on the non-coated area of the surface, while adjacent
surfaces remain free of liquid sample, thus isolating and
facilitating chemical and biological reactions as well as improving
sample recovery. The uncoated locations may have surfaces that, for
example, are reactive or have specific affinities, optimize the
sample volume to area ratio, or restrict sample movement during
some vessel motion. The uncoated region may be surrounded by a
hydrophobic coating material according to the invention which
comprises microparticles and the reaction product, for example, the
polymerization product, of a trifluoromethyl-containing reactant,
for example, a trifluoromethyl-containing monomer.
[0053] According to some embodiments of the invention, the
operational surface of a vessel such as a microscope slide is
partially coated with a hydrophobic coating formulation according
to the invention and partially coated with nonfluorinated material
in delineated regions to isolate or constrain the position of a
liquid sample to prescribed locations that do not contain the
hydrophobic coating formulation.
[0054] According to embodiments of the invention, an operational
surface comprises a sample retaining barrier of a rough surface
composite coating according to the invention. The barrier may
isolate and restrain an aqueous sample. Surrounding the composite
coating may be a smooth coating material which does not contain a
sufficient amount of microparticles and does not exhibit surface
roughness. The surrounding smooth coating permits the run-off of
non-aqueous liquids therefrom, such as organic solvents, for
example, acetone or xylene.
[0055] According to some embodiments, a laboratory vessel is
provided with a low surface energy coating of the present invention
and further comprises a second coating. The second coating
comprises the reaction product, for example, the polymerization
product, of a second fluorinated reactant, for example, a
fluorinated monomer. The second fluorinated reactant preferably has
from about 3 to about 20 carbon atoms, at least one terminal
trifluoromethyl group, and is combined with a surface roughening
agent, for example, a micropowder which provides the second coating
with a rough surface. The second coating has an exposed surface
area populated with 30% by area or more trifluoromethyl groups and
a surface energy of about 22 dynes/cm or less at 20.degree. C. The
second coating forms a continuous sample retaining barrier for
retaining an aqueous sample within the barrier, and the low surface
energy coating is substantially free of surface roughness and
surrounds the second coating.
[0056] Articles other than laboratory vessels can also be coated
with two different coating compositions according to embodiments of
the present invention. According to some embodiments of the present
invention, an article is coated with a first composition and then
with a second, different, composition. At least one of the
coatings, for example, the first coating, preferably comprises the
polymerization product of at least one fluorinated monomer. At
least one of the coatings can comprise the polymerization product
of tetrafluoroethylene. At least one of the coatings can comprise
the polymerization product of perfluoro-2,2-dimethyl-1,3-dioxole
(PDD). At least one of the coatings can comprise the polymerization
product of tetrafluoroethylene and PDD. Preferably, both coatings
provide a trifluoromethyl group surface area population of about
15% by area or greater, more preferably, of about 30% by area or
greater.
[0057] According to embodiments of the invention, regions on a
surface of a laboratory vessel such as a microscope slide are used
to isolate or constrain aqueous sample, and the regions are defined
by a first coating comprising microscopic particles and the
reaction product of a trifluoromethyl-containing reactant. The
first coating may surround a portion of a surface coated with a
second coating wherein the second coating comprises the reaction
product of a trifluoromethyl-containing reactant. The
microparticle-containing coating provides a greater hydrophobicity
to aqueous liquids and thus a greater water repelling nature than
the region coated with the polymerization product coating that does
not contain the microparticles.
[0058] In some embodiments of the present invention, microscopic
fibers such as cellulose or glass microfibers may be used with or
in place of microparticles to provide surface roughness and
preferably contact angles to water of about 150.degree. and
greater. Preferably, cellulose and/or glass microfibers are used
which have average diameters of from about one to about 20 microns
and lengths from about 20 to several hundred microns. The
microfibers can be admixed to increase the mechanical strength of
the coating.
[0059] According to embodiments of the invention, rough hydrophobic
surfaces having a high repellency to water may be produced by
employing foaming and/or pore-forming agents in the compositions
and processes of the invention. Foaming and pore-forming agents
that may be used include spirocarbonates, diazo compounds,
compressed gases, dissolved gases, volatile liquids, and
combinations thereof The agents may be activated by heat, light, or
vacuum during the drying, curing and/or hardening of the coating
composition.
[0060] According to embodiments of the invention, regions on a
surface of a laboratory vessel such as a microscope slide are used
to isolate or constrain an organic solvent-based liquid sample, and
the regions are defined by a coating comprising the reaction
product of a trifluoromethyl-containing reactant, surrounding a
portion of the surface coated with a formulation comprising
microparticles and the reaction product of a
trifluoromethyl-containing reactant. The microparticle-containing
coating provides a greater affinity to organic solvent-based
liquids than the region coated with the reaction product coating
not containing the microparticles.
[0061] A preferred coating is provided by adhering a surface
roughening agent, for example, a micropowder, to the surface of a
reaction product according to the present invention, wherein the
coating has an exposed surface area populated with 30% or more
trifluoromethyl groups. A preferred coating can be formed with a
surface roughening agent having a surface area populated with 30%
by area or more trifluoromethyl groups, wherein the surface
roughening agent is adhered to a hydrophobic surface. The adherence
of the surface roughening agent to the surface may be due to one or
more mechanisms including, but not limited to, sintering the agent
onto the surface, curing a component of the surface and/or a
component of the agent, melting the surface and/or the agent, and
the like, or any combination thereof The surface roughening agent,
for example, a micropowder, can be dusted onto the surface.
[0062] The present invention also provides processes of preparing
surface roughening agent-containing hydrophobic surfaces. According
to an embodiment of the invention, a hydrophobic coating
formulation is applied to a surface of an article to form a coating
having an exposed surface area populated with at least 30% by area
trifluoromethyl groups. Then, fluidized hydrophobic surface
roughening agent microparticles are applied and adhered to the
coating to provide a rough surface having an exposed surface area
populated with at least 30% by area trifluoromethyl groups. The
adherence of the agent to the coating may be due to one or more
mechanisms including, but not limited to, sintering the agent onto
the surface, curing a component of the coating and/or a component
of the agent, melting the coating and/or the agent, and the like,
or any combination thereof
[0063] According to an embodiment of the invention, a hydrophobic
coating formulation is applied to a surface of an article to form a
coating having an exposed surface area populated with at least 30%
by area trifluoromethyl groups. Then, fluidized hydrophobic surface
roughening agent microparticles having an exposed surface area
populated with at least 30% by area trifluoromethyl groups are
adhered to the coating to provide a surface having a population of
trifluoromethyl groups of 30% by area or more. The adherence of the
agent to the coating may be due to one or more mechanisms
including, but not limited to, sintering the agent onto the
surface, curing a component of the coating and/or a component of
the agent, melting the coating and/or the agent, and the like, or
any combination thereof.
[0064] According to some preferred embodiments of the invention,
laboratory vessels are provided having an operational surface
coated with a polymer comprising the polymerization product of
trifluoromethyl-terminated, substantially unbranched and
fluorinated monomers containing from 6 to 12 carbon atoms. Coatings
made from such products are extremely hydrophobic, oleophobic, and
highly resistant to solvent removal and biological sample
retention.
[0065] A particularly preferred coating solution for forming
coatings according to the invention comprises the polymerization
product of a trifluoromethyl terminated, substantially unbranched
perfluorooctyl monomer. Coating solutions containing at least about
50% by weight of a product of such a perfluorooctyl monomer are
particularly preferred for printing applications.
[0066] The coating compositions of the present invention may be
diluted with an appropriate solvent or medium to obtain a coating
solids content, or a non-volatile components content, of from about
0.01% by weight to about 50% by weight, preferably from about 0.1%
by weight to about 2% by weight, depending upon the application
technique and desired coating properties.
[0067] According to an embodiment of the present invention, a
coating composition is provided for forming an extremely
hydrophobic coating surface on the surface of an article, wherein
the composition includes a fluorosilane, a fluorinated acid
anhydride or fluoroanhydride, and a fluorinated solvent. The
fluorosilane may preferably be used in an amount of from about 0.1%
by weight to about 50% by weight, for example, 2% by weight, based
on the weight of the composition. The fluorosilane is preferably a
fluoroalkylsilane. More preferably, the fluorosilane may include a
fluoroalkyl alkoxysilane, for example, perfluorooctyl
trimethoxysilane. The fluorinated acid anhydride or fluoroanhydride
preferably is capable of a condensation reaction with an oxide
surface to form an extremely hydrophobic surface, and preferably
reacts under ambient conditions or under heat. The fluorinated acid
anhydride or fluoroanhydride may comprise, for example,
trifluoroacetic acid anhydride, trifluorobutyric acid anhydride,
and combinations thereof, both available from Aldrich Chemicals.
The fluorinated solvent preferably has a boiling point above
100.degree. C. Preferred fluorinated solvents include FC 70
(boiling point of 215.degree. C.), and FC 40 (boiling point
155.degree. C.), both available from 3M.
[0068] The terminal trifluoromethyl groups of the coating polymer
or monomer preferably constitutes the entire operational surface of
the coating. According to preferred embodiments of the invention,
the polymer coating is applied in a manner such that the exposed
coating surface comprises from about 30% by area to about 100% by
area trifluoromethyl (--CF.sub.3) groups. In other words, of the
molecules and substituent groups making up the exposed operational
surface of the coating, from about 30% by area to 100% by area of
the exposed surface area of the coating is made up of --CF.sub.3
groups. The exposed surface of the coating exhibits an extremely
low surface energy which can approach about six dynes/cm, depending
upon the percentage or "population" of --CF.sub.3 groups making up
the exposed surface of the coating and the vessel material coated
according to the invention. In more preferred embodiments of the
invention, from about 50% by area to 100% by area of the exposed
surface is populated with trifluoromethyl groups, and even more
preferably, at least about 75% by area is populated with
trifluoromethyl groups.
[0069] The hydrophobicity and solvent resistance of the operational
surface coating of the invention depends on a number of factors
including the material of the laboratory vessel which is coated and
the amount or population of terminal trifluoromethyl groups present
on the exposed surface of the coating. For example, it has been
determined according to the invention that when an operational
surface of a polypropylene vessel is coated with a hydrophobic
polymer solution to form a coating comprising 30% by area or more
trifluoromethyl-terminated, substantially unbranched perfluorinated
monomer having from 6 to 12 carbon atoms, the coating exhibits a
surface energy of below 20 dynes/cm with high resistance to solvent
removal and low retention of biological samples.
[0070] It has also been determined according to the invention that
when an operational surface of a polypropylene vessel is coated
with a hydrophobic polymer solution to form a coating comprising
50% by area or more trifluoromethyl-terminated, substantially
unbranched perfluorinated monomer having from 6 to 12 carbon atoms,
the coating exhibits a surface energy of below 15 dynes/cm with
high resistance to solvent removal and low retention of biological
samples.
[0071] It has also been determined according to the invention that
when an operational surface of a polypropylene vessel is coated
with a hydrophobic polymer solution to form a coating comprising
80% by area or more trifluoromethyl-terminated, substantially
unbranched perfluorinated monomer having from 6 to 12 carbon atoms,
the coating exhibits a surface energy of about 10 dynes/cm with
high resistance to solvent removal and low retention of biological
samples.
[0072] It has also been determined according to the invention that
when an operational surface of a polypropylene vessel is coated
with a hydrophobic polymer solution to form a coating comprising
100% by area or more trifluoromethyl-terminated, substantially
unbranched perfluorinated monomer having from 6 to 12 carbon atoms,
the coating exhibits a surface energy of below 10 dynes/cm or lower
with high resistance to solvent removal and low retention of
biological samples.
[0073] The most hydrophobic properties are achieved when the
coating has an exposed surface consisting entirely of
trifluoromethyl (--CF.sub.3) groups, that is, 100% by area, with no
other substituent groups exposed at the surface.
[0074] According to some embodiments of the invention, branched
fluoroalkyl monomers containing terminal trifluoromethyl groups may
also be used as reactive monomers or polymerized product in the
coating solutions used according to the present invention. An
example of a suitable branched monomer for such purposes is a
perfluorinated iso-octyl monomer having two terminal
trifluoromethyl groups.
[0075] According to embodiments of the invention, the carbon chain
length of the trifluoromethyl-containing monomers used to form the
polymer coatings of the invention, and any functional groups used
to form linkages between the fluoropolymer and the laboratory
vessel, should be selected to provide an exposed surface of the
coating which mainly comprises --CF.sub.3 groups. The --CF.sub.3
groups, which provide extremely hydrophobic properties, prevent
liquids and samples contained in the vessel from infiltrating the
exposed coating and reacting with the intermediate carbon groups
and linkage groups of the polymerized monomer. Such infiltration is
particularly prevented when the coating consists of monomers of
substantially uniform length of greater than 6 carbon atoms, rather
than a mixture of monomers of substantially different lengths.
[0076] According to embodiments of the invention, a polymer coating
formed from a fluoroalkyl methacrylate monomer which has the
chemical formula C.sub.7F.sub.15CH.sub.2OCOC(CH.sub.3).dbd.CH.sub.2
is provided. Coatings made with the polymerized product of this
monomer or similar fluoroalkyl monomers having a trifluoromethyl
group, have exposed coating surfaces comprising tightly packed
terminal --CF.sub.3 groups. The resultant coating has a low surface
energy, or critical surface tension, which can be as low as about 6
dynes/cm at 20.degree. C. depending upon the population of
trifluoromethyl groups on the exposed surface and depending upon
the material of the vessel which is coated. However, when a surface
population of 100% by area trifluoromethyl groups is achieved, the
vessel material is irrelevant to the hydrophobicity of the
surface.
[0077] As the packing of terminal trifluoromethyl groups increases,
the surface energy of the packed surface decreases, such that
coatings having the lowest critical surface tension have the
closest packed --CF.sub.3 groups. The replacement of a single
fluorine atom by a hydrogen atom in each terminal trifluoromethyl
group of such a surface would more than double the critical surface
tension of the surface. Critical surface tensions of teflon vessels
and teflon coated vessels are only as low as about 18 dynes/cm at
20.degree. C. because such surfaces mainly comprise --CF.sub.2--
groups. Although it is difficult to obtain an exposed surface
entirely composed of tightly packed --CF.sub.3 groups, extremely
low surface tensions can be achieved by the formation of exposed
coating surfaces which contain 30% or more, by surface area,
--CF.sub.3 groups. Preferably, an exposed surface having 50% or
more --CF.sub.3 groups can be achieved according to the processes
of the present invention. These processes tend to result in
coatings having critical surface tensions ranging from about 6
dynes/cm to about 22 dynes/cm when formed on hydrophobic vessel
materials.
[0078] Critical surface tensions, also referred to as surface
energies, of as low as about 6 dynes/cm can be obtained according
to the processes of the present invention, depending upon which
terminal trifluoromethyl group-containing polymer or mixture of
polymers is used to form the hydrophobic coating, the population of
trifluoromethyl groups on the exposed surface, and the material of
the vessel to be coated. According to embodiments of the invention
wherein the exposed surface area of the hydrophobic coating
material is populated with from about 50% by area to about 100% by
area trifluoromethyl groups, surface energies of about 10 dynes/cm
or less can be provided, particularly if the coating is formed on a
polypropylene or other substantially hydrophobic laboratory vessel
material, for example, a vessel material which exhibits a surface
energy of 40 dynes/cm or less. Such surface energies are even lower
than those of Teflon.RTM. which generally provides a surface energy
of from about 18.5 to about 20 dynes/cm. Although Teflon.RTM. is
formed from polymerized fully fluorinated monomers, most of the
surface structure of a Teflong coating consists of --CF.sub.2--
groups as opposed to closely packed terminal trifluoromethyl
(--CF.sub.3) groups. Even the most hydrophobic forms of
Teflon.RTM., FEP Teflon.RTM. and PFA Teflon.RTM., which comprise
mixtures of fully fluorinated polypropylene and polyethylene
polymerized monomers, only provide surface energies of about 16.5
dynes/cm. As with other forms of Teflon.RTM., the exposed surface
of an FEP Teflon.RTM. coating consists mainly of --CF.sub.2--
groups as opposed to closely packed terminal trifluoromethyl
(--CF.sub.3) groups. Teflon.RTM. and FEP Teflon.RTM., are available
from DuPont Polymer Products Department, Wilmington, Del.
[0079] According to the present invention, lower surface tensions
are obtained when the coating polymer comprises the polymerization
product of a perfluoroalkyl monomer, when compared to coatings
comprising the product of a partially non-fluorinated monomer.
Substantially non-branched fluoroalkyl and perfluoroalkyl
ethylenically unsaturated monomers are preferred for producing the
coating polymers of the invention. According to other embodiments,
a methacrylate group is used as a preferred ethylenically
unsaturated monomer for making the polymeric coating material of
the invention. Other monomers which can be used include silicones,
epoxies and urethanes. Other reactants which may be used include
anhydrides, amines, polyols, vinyls, vinyl ethers, and mixtures
thereof Polymers made from mixtures of acrylates and epoxies or of
acrylates and silicones are particularly preferred according to
some embodiments of the invention. Polymeric coating materials
comprising urethane monomers and/or polymers are preferred for some
applications wherein a durable coating is needed.
[0080] According to embodiments of the present invention, articles
can be provided with a coating thereon comprised of a
prepolymerized fluoroalkyl, or preferably perfluoroalkyl,
ethylenically unsaturated monomer having a terminal trifluoromethyl
group. More particularly, the present invention relates to such a
coating which consists essentially of a polymerization product of a
fluoroalkyl or perfluoroalkyl ethylenically unsaturated monomer
having a terminal trifluoromethyl group and an average carbon atom
chain length of from 3 to about 20 atoms, more preferably from
about 6 to about 14 atoms, and optionally a durable resinous
component such as a urethane or polyurethane component.
[0081] According to a preferred embodiment of the present
invention, prepolymerized terminal trifluoromethyl-containing
monomers having a uniform pendant group length of from 8 to 10
carbon atoms and substantially free of branching can be deposited
on laboratory vessels to form coatings with low surface energies
and critical surface tensions of about 10 dynes/cm or less. The
coatings also exhibit exceptional resistance to many solvents with
the exception of substantially fluorinated solvents. Coating
solutions containing polymers of such monomers produce a highly
ordered, densely packed polymer with a predominantly
trifluoromethyl surface.
[0082] Solutions of polymers made from monomers having terminal
trifluoromethyl groups are commercially available. One solution
which can be used to form polymeric hydrophobic coatings according
to the invention is available from The 3M Company as FC-722. Other
trifluoromethyl group-containing polymer solutions in
fluorosolvents are available from Cytonix Corporation of
Beltsville, Maryland as the PerFluoroCoat and FluoroPel products
lines. The coating solutions used according to embodiments of the
present invention comprise fluoropolymers having terminal
trifluoromethyl groups. The solutions can be used full strength but
may be diluted with a fluorosolvent to form low concentrations of
coating polymer. The polymer solution used to make the coatings of
the invention preferably have a coating polymer content of from
about 0.01% by weight to about 50% by weight.
[0083] Methods of making fluoropolymer coating solutions or
suspensions for use with the invention comprise prepolymerizing a
fluoroalkyl ethylenically unsaturated monomer having a terminal
trifluoromethyl group to form a polyfluoroalkyl polymer, and
dissolving or suspending the polymer in a fluorinated solvent. When
making such solutions, the fluoroalkyl ethylenically unsaturated
monomer preferably has a carbon chain length of from about 3 to
about to 20 carbon atoms, with carbon chain lengths of from about 6
to about 12 atoms being more preferred. Carbon chain lengths of
from 8 to 10 atoms are particularly preferred. Mixtures of
different fluoroalkyl ethylenically unsaturated monomers having
different carbon chain lengths may be employed, however, when the
polymerized monomers have essentially uniform carbon chain lengths,
hydrophobic coatings of extremely low and repeatable surface
tension can be provided.
[0084] According to embodiments of the invention, hydrophobic
coatings are provided which may preferably comprise, and more
preferably consist essentially of, a polymerization product of a
substantially non-branched perfluoroalkyl monomer. Coatings
according to the invention may comprise polymerized products of
monomers having terminal trifluoromethyl groups, including
fluorinated or perfluorinated monomers such as hexyl ethylenically
unsaturated monomers, heptyl ethylenically unsaturated monomers,
octyl ethylenically unsaturated monomers, nonyl ethylenically
unsaturated monomers, decyl ethylenically unsaturated monomers,
undecyl ethylenically unsaturated monomers, and dodecyl
ethylenically unsaturated monomers. Mixtures of two or more
different monomers may also be used and are preferred when it is
desired to adjust surface energy properties to precise values.
[0085] The coatings of the present invention may comprise or
consist essentially of a polymerization product of a fluoroalkyl
ethylenically unsaturated monomer having a terminal trifluoromethyl
group and a carbon chain length of from 3 to 20 atoms, preferably
from 6 to 12 carbon atoms in length, and more preferably from 8 to
10 carbon atoms in length. In particular, polymerization products
of fluoroalkyl methacrylates are preferred. According to some
embodiments of the invention, polymerization products of
perfluorohexyl methacrylate, perfluoroheptyl methacrylate,
perfluorooctyl methacrylate, perfluorononyl perfluorodecyl
methacrylate, perfluoroundecyl methacrylate or perfluorododecyl
methacrylate, and mixtures thereof, are preferred. Acrylates of
such perfluoroalkyls are also preferred. According to one
particularly preferred embodiment, the polymer coating consists
essentially of a polymerization product of perfluorooctyl
methacrylate.
[0086] Exemplary materials for making the coatings of the present
invention include PerFluoroCoat and FluoroPel, both available from
Cytonix Corporation, the fluorinated materials FC-722, FX-13,
FX-14, FX-189, L-9187, L-9186, Fluorel.TM. FC 2174 and Fluorel.TM.
FC 2181, all available from Commercial Chemicals Division/3M, St.
Paul, Minn., silastic fluorosilicone rubbers from Dow Corning STI
identified as LS-2249U, LS-2332U, LS-2840 and LS-2860, and
fluorinated materials from DuPont including materials traded under
the name ZONYL.
[0087] The solvent for the coating solutions used according to the
invention may comprise a fully fluorinated non-branched
fluorocarbon having a carbon chain length of 7 or 8 carbon atoms.
Such a solvent exhibits a boiling point of about 80.degree. C.
Perfluorinated fluorocarbon solvents are preferred according to
some embodiments of the invention.
[0088] According to embodiments of the invention, preferred
fluorinated solvents include the Fluorinert.RTM. line of
fluorinated solvents, FC-71, FC-75, FC-40, FC-70, FC-77 and FC-84,
all from the 3M Company. Other fluorinated solvents which may be
used include Vertrel.RTM. XF (C.sub.5H.sub.2F.sub.10) or Freon TF
from DuPont, Wilmington, Del., the fluorinated polyethers HT70,
HT85, HT90, HT100, HT110, HT135, HT200, HT230, HT250 and HT270, and
the perfluorinated polyethers sold as GALDEN, all from Ausimont
USA, Inc. The Ausimont USA, Inc. solvent designations indicate the
boiling point of each solvent. Higher boiling solvents, for
example, HT270 and HT250, would form coatings requiring more heat
to dry than coatings made with the lower boiling solvents, for
example, HT70. The lower boiling Ausimont USA, Inc. solvents more
rapidly evaporate when compared to the higher boiling solvents.
[0089] Other fluorocarbon solvents may be used and typically have
boiling ranges of from about 30.degree. C. to about 250.degree. C.,
depending upon a number of factors including the length of the
carbon chain. At least partially fluorinated solvents are
preferred, particularly those fluorocarbon solvents having at least
about 20% by weight fluorine atoms per molecule. Solvents
exhibiting surface energies of 18 dynes/cm or lower are preferred,
with solvents having surface energies of 13 dynes/cm or lower being
more preferred and those having 9 dynes/cm being even more
preferred. In preferred embodiments of the methods of the present
invention, the solvent is substantially recovered after a coating
procedure. Volatile fluorinated surfactants may be included in the
coating formulations of the present invention.
[0090] Additives may be incorporated into or polymerized with the
coating polymers and monomers used to provide coatings according to
the invention having improved toughness, chemical resistance,
hardness, softness, processability, elasticity, adhesion, color,
texture, thickness and/or uv-resistance. Hydrophobic additives are
preferred. Chemically resistant additives are preferred. Additives
including non-trifluoromethyl-containi- ng reactants and/or
monomers may be added in amounts ranging from 1 to about 95% by
weight and are described in more detail below.
[0091] According to an embodiment of the present invention,
extremely hydrophobic surfaces on a variety of articles not limited
to laboratory vessels can be formed. The compositions of the
present invention are useful for any article which is intended to
be exposed to elements, that is, exposed to the environment,
exposed to precipitation, unprotected, unsheltered. The
compositions of the present invention provide surfaces that are
preferably weatherable, rust resistant, corrosion resistant, able
to maintain the appearance of a surface, able to withstand contact
with precipitation without degradation, chemically resistant and
mechanically resilient. Compositions are provided that combine
relatively soft polymers of unbranched trifluoromethyl-containing
monomers, and tough, chemically resistant non-fluorinated resins
such as acrylics, cellulosics, epoxy, polyesters, silicones,
urethanes, anhydrides, amines, polyols, vinyls, vinyl ethers, and
combinations thereof These mixtures may produce surfaces that are
rich in trifluoromethyl groups and interior compositions that are
substantially non-fluorinated.
[0092] The coating compositions for articles not limited to
laboratory vessels, according to the present invention, can include
functionalized fluoropolymers that have cross-linkable chemical
groups, for example, Lumiflon.RTM. FE3000, FE4100, FE4200, FE4400,
LF100, LF200, LF302, LF400, LF600X, LF710N, LF800, LF910LM, and
LF916N, from Asahi Glass Co., Tokyo, Japan. The coating
compositions of the present invention can include fluorourethanes,
for example, those available from Century 2000 Coatings,
Alexandria, Va., and those disclosed in U.S. Pat. No. 4,132,681 to
Field, which is herein incorporated in its entirety by reference.
Particularly preferred are fluorourethanes comprising polymers of
polyisocyanates and fluorine-containing diols, resulting in good
chemical and mechanical properties. These fully or partially
fluorinated resins may be used as primers for other coatings of the
present invention or as mixtures with polymers and/or monomers
according to the present invention.
[0093] The coating formulations for articles can produce extremely
hydrophobic substantially unbranched highly populated
trifluoromethyl surfaces and interior compositions that are
unfluorinated, partially fluorinated or perfluorinated. The phrase
"highly populated" applies to surface populations of 15% by area or
greater trifluoromethyl groups.
[0094] The coating compositions for articles not limited to
laboratory vessels, of the present invention, can comprise: a
copolymer of at least one fluorine-containing monomer; a
perfluoropolymer; tetrafluoroethylene;
perfluoro-2,2-dimethyl-1,3-dioxole (PDD); fluoroethylene-propylene;
a polymer containing difluoromethylene; a functionalized
fluoropolymer; the polymerization product of a branched
trifluoromethyl (TFM) containing monomer; or combinations
thereof.
[0095] According to some embodiments of the present invention, the
coating composition for articles includes an aromatic or aliphatic
polyurethane. According to some embodiments of the present
invention, the coating preferably comprises the polymerization
product of an isocyanate-containing monomer. Optionally, the
coating can further comprise a cellulosic; a polyester; the
polymerization product of an unsaturated monomer; a condensation
polymer; a silicone polymer; an epoxy; or combinations thereof.
[0096] The present invention also provides a coated formed rough
surface for articles not limited to laboratory vessels. The coating
comprises at least one fluorinated component including a
fluorinated monomer or a polymerization product thereof. The
fluorinated monomer has from about 3 to about 40 fluorine atoms and
at least one trifluoromethyl group. The formed rough surface has
features smaller than about 100 microns. The coated surface
provides a surface area populated with 30% by area or more
trifluoromethyl groups and a surface energy of about 22 dynes/cm or
lower. The formed rough surface can comprise a pattern of
features.
[0097] According to some embodiments of the invention, hydrophobic
coatings are made of a polymerization product of a fluorinated
monomer having a terminal trifluoromethyl group, and further
containing small amounts of co-monomers, for example, silanes, that
serve to promote adhesion to metal, glass or ceramic vessels
without compromising the extremely low surface energy of the
coating. Coupling agents may also be used as adhesion promoting
monomers and include those listed in Table 1 under the heading
"Coupling Agents" in the Polymer Encyclopedia. Exemplary coupling
agents include vinyltrimethoxysilane, chloropropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, and
3-methacryloxypropyl-trimethoxysilane. Such silanes and coupling
agents, if present, can be present in amounts of from 1% by weight
to 10% by weight, more preferably from about 2% by weight to about
5% by weight. If co-monomer is added, the amount added is not so
much as to cause the surface population of trifluoromethyl groups
to be less than 30% by area.
[0098] Other adhesion promoting monomers can be added to the
coating formulations of the invention. If used, adhesion promoting
monomers other than silanes are preferably added in amounts of from
about 1% by weight to about 40% by weight, more preferably from
about 5% by weight to about 20% by weight, based on the weight of
the polymerization product making up the coating material. Adhesion
promoting monomers which may be used include alkoxy terminated
monomers and methacrylate esters and acrylate esters listed as
adhesion promoting monomers on page 16 of the 1994 Sartomer Product
Catalog, including mono-, di- and trifunctional acrylate or
methacrylate ester monomers.
[0099] Other additives which may be incorporated or polymerized
with the terminal trifluoromethyl-containing monomers or products
of the inventive coatings include high glass transition temperature
(high T.sub.g) perfluorinated or non-perfluorinated monomers, and
low T.sub.g perfluorinated or non-perfluorinated monomers. High
T.sub.g monomers can be included to form hard hydrophobic coatings
for laboratory vessels, which are highly resistant to solvent
removal and retention of biological sample. Preferably, the coating
composition comprises a fluoropolymer having a T.sub.g of greater
than 100.degree. C., more preferably, greater than 140.degree. C.
The hard coatings are harder than similar coatings which differ
only in that they do not incorporate the high T.sub.g component.
High T.sub.g monomers which may be employed include those
fluorochemical acrylate or methacrylate monomers which form
homopolymers exhibiting T.sub.g's of 50.degree. C. or higher.
Exemplary additives of this category are available from the 3M
Company as FX-14 (homopolymer T.sub.g=60.degree. C.), L-9187
(homopolymer T.sub.g=60.degree. C.), and L-11913 (homopolymer
T.sub.g=116.degree. C.). Of the exemplary monomers denoted above,
L-11913 is a preferred monomer, and has the formula:
cyclo-C.sub.6F.sub.11CH.sub.2OCOC(CH.sub.3).dbd.CH.sub.2. If
L-11913 is incorporated, it is preferably employed in an amount of
from about 1% by weight to about 60% by weight, based on the weight
of the coating.
[0100] Low T.sub.g monomers can be included to form soft,
hydrophobic coatings for laboratory vessels, which are highly
resistant to solvent removal and retention of biological sample.
The soft coatings are softer than similar coatings which differ
only in that they do not incorporate the low T.sub.g component. Low
T.sub.g additive monomers can be used to form hydrophobic pressure
sensitive adhesive coatings, which find many uses including the
ability to adhere to covering materials such as Teflon tape or high
T.sub.g coatings of the present invention, even underwater. Low
.sub.g monomers which may be employed include fluorochemical
acrylate or methacrylate monomers which form homopolymers having
T.sub.g's of about 5.degree. C. or lower, preferably about
0.degree. C. or lower. More preferred low T.sub.g monomers have
terminal trifluoromethyl groups. Exemplary additives of this
category are available from the 3M Company as FX-189 (homopolymer
T.sub.g=3.degree. C.), L-9186 (homopolymer T.sub.g=0.degree. C.),
L-9911 (homopolymer T.sub.g=-53.degree. C.), L-12044 (homopolymer
T.sub.g=-23.degree. C.), L-12043 (homopolymer T.sub.g=-5.degree.
C.), and L-9367 (homopolymer T.sub.g=-120.degree. C.). Of the
foregoing monomers, L-9186 is a preferred monomer and has the
formula: C.sub.7F.sub.15CH.sub.2OCOCH.dbd.CH.sub.2. Combinations of
different low T.sub.g and high T.sub.g monomers may be added to the
coating formulations of the present invention to provide the
coating with a specific hardness or pressure sensitive
adhesiveness.
[0101] Other additives which may be added to the coating solutions
of the invention include perfluorinated and non-perfluorinated
plasticizers. Plasticizers can be added in amounts of from about 1%
by weight to about 30% by weight, more preferably 5% by weight to
about 10% by weight, based on the weight of the coating. Exemplary
plasticizers include high boiling point Fluorinert solvents from
the 3M Company including FC-71, and high boiling point
perfluorinated polyethers available from Ausimont USA, Inc.,
including HT 270.
[0102] Cross-linkable monomers may be incorporated into the coating
solutions, suspensions and formulations according to embodiments of
the present invention. Cross-linkable monomers may preferably be
used for some applications in amounts ranging from about 1% by
weight to about 95% by weight, preferably from about 5% by weight
to about 70% by weight, and even more preferably from about 10% by
weight to about 20% by weight. Cross-linkable monomers which may be
incorporated include epoxies such as novolac epoxies, bisphenol A
epoxies, acrylates, silicones, urethanes, anhydrides, and
silicates.
[0103] Reactive non-fluorinated monomers and resins can also be
added to the coating formulations of the invention to provide
different properties to the coatings. According to embodiments of
the invention, reactive monomers and resins such as methacrylate
monomers, silicone monomers, epoxy monomers, urethane monomers and
oximes can be included in the coating formulations.
[0104] According to embodiments of the invention, coating
formulations are provided comprising epoxy monomer or resin in
amounts of from about 20% by weight to about 95% by weight, based
on the total weight of the coating formulation. Preferably, from
about 30% by weight to about 70% by weight epoxy monomer may be
included in a curable coating formulation. Epoxy resins may be used
including the EPON Resins from Shell Chemical Company, Houston,
Tex., for example, EPON Resins 1001F, 1002F, 1007F and 1009F, as
well as the 2000 series powdered EPON Resins, for example, EPON
Resins 2002, 2003, 2004 and 2005. Preferably, the epoxy monomer or
resin has a high crosslink density, a functionality of about 3 or
greater, and an epoxy equivalent weight of less than 250. Exemplary
epoxies which may be employed according to embodiments of the
invention include The Dow Chemical Company (Midland, Mich.) epoxy
novolac resins D.E.N. 431, D.E.N. 438 and D.E.N. 439.
[0105] If an epoxy is included in the coating formulation, a curing
agent for the epoxy may be added in amounts of from about 1% by
weight to about 10% by weight of the epoxy component. The curing
agent may be a catalyst or a reactant, for example, the reactant
dicyandiamide. From about 1% by weight to about 50% by weight epoxy
solvent, based on the weight of the coating formulation, may also
be included in the coating formulations. Epoxy solvents can be
added to liquify the epoxy monomer or resin or adjust the viscosity
thereof Preferred epoxy solvents are triethylphosphate and ethylene
glycol. A separate epoxy solvent may not be needed according to
some embodiments of the invention wherein the epoxy is liquid at
room temperature or wherein a fluorinated monomer or surfactant
component of the coating formulation acts as a solvent for the
epoxy.
[0106] Even when a large amount of non-fluorinated epoxy is
included in a coating formulation according to the invention,
surface populations of trifluoromethyl groups of about 30% by area
or more can nonetheless be achieved on the coating. Prepolymerized
trifluoromethyl-containing monomers and/or reactive
trifluoromethyl-containing monomers in the coating formulation tend
to migrate to the surface of the coating during heat curing of the
epoxy. The trifluoromethyl-containing components are mobile during
epoxy curing due to thermal forces, convective forces, evaporative
forces and diffusion forces. If included in a formulation, volatile
trifluoromethyl-containing monomer is mostly driven off during heat
curing of the epoxy, but can be polymerized into the coating in the
presence of peroxide or azo compound catalysts, initiators or
promoters.
[0107] According to some embodiments of the invention, the coating
formulation comprises an aqueous suspension of the
trifluoromethyl-containing component such as ZONYL NWA, from
DuPont. Suspension formulations according to the invention, may
further include additives as discussed above, including epoxy
resins. Exemplary waterborne epoxy resins which may be used in
aqueous suspension coating formulations according to the invention
include the EPI-REZ Resins from Shell Chemical Company, for
example, the EPI-REZ Resins WD-510, WD-511, WD-512, 3510-W-60,
3515-W-60, 3519-W-50, 3520-WY-55 and 3522-W-60. The coating
composition may comprise microparticles, microfibers, foaming
and/or pore-forming agents, and may be dried, cured, and/or
hardened so as to produce sufficient surface roughness to provide
high contact angles to water.
[0108] According to some embodiments of the invention, a coating
solution or suspension is provided which comprises prepolymerized
fluorinated monomer, reactive non-polymerized fluorinated monomer,
and an additional additive, for example, at least one of the
additives discussed above. The additional additive may be added in
substantial amounts, for example, up to 95% by weight, provided the
resultant coating has a surface population of trifluoromethyl
groups which is about 30% by area or more. Preferably, coating
techniques which involve application of a solution containing
unreacted monomer further include a step of recovering unreacted
monomer after coating.
[0109] According to some embodiments of the invention, an
operational surface of a laboratory vessel is at least partially
coated with trifluoromethyl-containing monomers and
non-trifluoromethyl-containing monomers followed by polymerization
of the monomers and removal and recovery of unreacted monomers.
According to some embodiments, the monomers are applied from a
coating solution which further includes a fluorinated solvent.
Preferably, when reactive fluorinated monomers are used to coat an
operational surface, and subsequently polymerized, unreacted
monomer is removed and substantially recovered after coating and
curing.
[0110] According to some embodiments of the invention, the coating
solution comprises the polymerization product of substantially
terminal trifluoromethyl-containing monomers, and unreacted
terminal trifluoromethyl-containing monomers. After coating an
operational surface, the coating is then subsequently polymerized
to form polymer from the unreacted monomer in the coating solution.
Such a procedure results in extremely hydrophobic coatings. When
partially unreacted coating solutions are used, they may also
include from about 15% by weight to about 95% by weight, based on
the weight of the coating, of non-perfluorinated functional
monomer, such as an epoxy.
[0111] Linkage mechanisms for binding the
trifluoromethyl-containing monomer or polymer of the present
coating formulations to an operational surface of a vessel include
functional linkage groups such as peroxide catalyzed linkages, azo
catalyzed linkages, free radical induced linkages, cationically
induced linkages, radiation induced linkages, vinyl linkages,
methacrylate linkages, urethane linkages, epoxy linkages,
condensation linkages, silane linkages, and siloxane linkages.
[0112] According to embodiments of the invention, prepolymerized
hydrophobic coatings according to the invention comprise a
polymerization product of a substantially
trifluoromethyl-containing monomer, that is, having at least about
15%, preferably 30%, of the terminal groups of the reactant monomer
or monomers comprising trifluoromethyl groups, and from about 1% by
weight to about 10% by weight of additional comonomers. The
additional comonomers having functionality that is polymerizable by
a second, different mechanism than the mechanism used to polymerize
the substantially trifluoromethyl-containing monomer. The second
polymerization mechanism may be activated during or following
application of the hydrophobic coating to an operational surface,
allowing the hydrophobic coating to become crosslinked with itself
or with the vessel walls. For example, the initial polymerization
may be carried out as an addition reaction of acrylates or
methacrylates using a free radical catalyst, whereas the second
polymerization may be carried out as a cationic reaction of
epoxides using a cationic or acid catalyst. An exemplary material
having epoxy functionality and acrylate functionality is
glycidyl-methacrylate. Peroxides will attach hydrocarbon groups to
hydrocarbons on the surface of the vessel.
[0113] According to some embodiments of the invention, low surface
energies can be obtained when a terminal trifluoromethyl-containing
monomer is coated onto the operational surface of a vessel and
subsequently polymerized after coating. Substantially non-branched
fluoroalkyl and perfluoroalkyl ethylenically unsaturated monomers
are preferred according to embodiments of the invention. According
to some embodiments, a methacrylate group is used as the preferred
ethylenically unsaturated monomer. Other monomers which can be used
include fluorinated or perfluorinated silicones, epoxies, urethanes
and oximes. Polymers made from mixtures of acrylates, urethanes and
epoxies are particularly preferred. According to some embodiments,
both prepolymerized fluorinated monomer and reactive
non-polymerized fluorinated monomer are used in the coating
formulation, and after application to an operational surface, the
reactive monomer is then polymerized or volatilized. Preferably,
the reactive monomer is polymerized.
[0114] Another method of forming a coating according to embodiments
of the invention is by using monomers capable of free radical
linkages. Such monomers can be attached to vessel surfaces if the
vessel surfaces are first treated by ionizing radiation or other
means to generate free radicals across the surface. A monomer
capable of free radical linkages can be formed by mixing a
fluoroalkyl ethylenically unsaturated monomer dissolved in a
suitable fluorocarbon solvent with an effective amount of a free
radical initiator. Vessels coated with the mixture are then heated
to the temperature at which the free radical initiator initiates
free radical generation. Many conventional azo compounds have an
appropriate activation temperature, particularly within the range
of 30-200.degree. C. Many azo compounds may be used which are
activated by visible or ultraviolet light.
[0115] According to some embodiments of the invention, when working
with liquids which only slightly wet fluorinated surfaces, for
example, when the contact angle between the liquid and the surface
is greater than 90.degree., it may be desirable to provide a rough
surface coating on a laboratory vessel to more effectively prevent
runoff of the liquid as might occur from a smooth hydrophobic
coating. Such would be the objective when it is desired to maintain
a drop of liquid sample on a microscope slide. A microscopically
roughened or porous hydrophobic surface which will not be wetted
can be made according to the present invention by adding
microscopic particles of a surface roughening agent, for example, a
micropowder, to the hydrophobic coating material or to the surface
to which the coating polymer is to be applied. According to
embodiments of the invention, microscopic particles can be added to
coating formulations of the present invention which comprise (1) a
polymerization product of a trifluoromethyl-containing monomer, (2)
an unreacted trifluoromethyl-containing monomer, or both (1) and
(2). Microscopic particles can also be added to coating
formulations which further include a fluorinated solvent.
[0116] While many microparticles may be used as surface roughening
agents according to the present invention, micropowders are a
preferred class of surface roughening agents. Micropowders are
defined herein as those powders or particles having average
diameters of from submicron sizes up to 100 microns. A preferred
micropowder average diameter is about 10 microns or less.
Hydrophobic materials are particularly preferred for the
micropowders. Suitable micropowders include silicon glass particles
with and without silane coatings, pigments, Teflon.RTM. powders,
flour, cornstarch, siliconized glass, fluorosiliconized inorganic
pigments, and micronized cellulosics. According to embodiments of
the invention, a composite surface is formed by adding a
substantially uniformly sized micropowder to a fluoropolymer or a
fluoromonomer which is to be subsequently coated and then
polymerized. The use of micropowders exhibiting wide particle size
distributions also provides preferred coatings according to some
embodiments of the present invention.
[0117] Inert micropowders are preferred, particularly for
applications where the resultant coating is exposed to liquids
which are other than aqueous in nature. One particularly preferred
micropowder is a siliconized glass particulate material having a
0.3 micron average particle size diameter available as TULLANOX HM
250 or TULLANOX HM 250D, from Tulco, Inc., Ayer, Mass. Another
preferred micropowder is Teflon.RTM. MP 1200, available from DuPont
Polymer Products Department, Wilmington, Del., and having an
average particle diameter of about 4 .mu.m.
[0118] Microfibers are another class of surface roughening agents
and may be used in the coating compositions of the present
invention. Inert microfibers are preferred according to some
embodiments of the invention, for example, some embodiments
requiring mechanical strength. A preferred microfiber is a
cellulose microfiber having an average diameter of about 4 microns
and an average length of about 40 microns, for example, TECHNOCELL
40.TM. available from EastTec, of Pennsylvania. Microfibers of
longer lengths are also preferred.
[0119] The methods of the present invention may comprise diluting a
trifluoromethyl-containing coating polymer solution or suspension
prior to applying the solution or suspension to an operational
surface of a laboratory vessel. The coating solution or suspension
is preferably diluted to between about 0.01 and 2 percent by weight
coating polymer. Higher weight percentages of the polymer may be
used although higher concentrations tend to clog small orifices
such as the opening at the end of a pipette tip for a volumetric
pipettor, or small orifices such as nozzles and nozzle openings in
ink jet printer print heads.
[0120] One preferred method for applying a coating polymer solution
or suspension comprises dip-coating a laboratory vessel or other
articles into a polymer solution or suspension. Other coating
methods may also be used, including spray coating, tumbling in
solution, brush coating, padding, spraying, fogging, transferring,
painting, printing, stenciling, screen printing, pad printing, ink
jet printing, injection molding, laminating and doctoring. For
articles having interior walls defining a reservoir portion, the
area of the article around and defining an opening to the reservoir
is preferably also coated. For simultaneously coating a large
number of small articles, each having a reservoir portion, a
tumbling method of coating is preferred.
[0121] Dip coating may be used according to some embodiments of the
invention to apply the coating polymer from a solution of the
polymer dissolved in a fluorosolvent or from a suspension of the
polymer. After coating the polymer solution, the coating is allowed
to dry and solvent or carrier is driven off.
[0122] After forming a first coating of polymer according to the
invention, the methods of the invention may also comprise applying
at least one other coating formulation comprising a polymer having
terminal trifluoromethyl groups. According to some embodiments of
the invention, one or more coatings of the same or different
terminal trifluoromethyl-containing polymers may be applied,
depending upon the desired surface energy properties of an
operational surface being coated.
[0123] According to some embodiments of the invention, the coating
formulation is not a polymer solution or suspension but instead
comprises a fluidized micropowder of the polymerization product of
entirely or substantially trifluoromethyl-containing monomers. The
micropowder formulation can be applied to at least a portion of an
article surface, for example, an operational surface of a
laboratory vessel, and melted to form a hydrophobic coating having
an extremely low surface energy, a high resistance to solvent
removal, and for laboratory vessels, a low retention of biological
samples. According to some embodiments, the coating formulation
comprises a fluidized micropowder of the polymerization product of
entirely or substantially trifluoromethyl-containing monomers, and
at least one substantially non-perfluorinated resin. The
micropowder and resin are applied to a surface, for example, an
operational surface of a laboratory vessel and heated to melt the
fluidized micropowder.
[0124] According to embodiments of the invention, the coating
polymer or coating monomer formulation of the invention is applied
as a micropowder along with at least one of a curable resin and a
non-curable resin. Preferably, the at least one resin is
substantially non-perfluorinated. Curable resins which can be used
in formulations of micropowder coating material include epoxy
resins, urethane resins, acrylate resins, methacrylate resins.
Highly cross-linked resins provide excellent solvent resistance
according to embodiments of the invention. An exemplary resin
having a high crosslink density is the epoxy novolac resin D.E.N.
439, available from Dow Chemical Co., Midland, Mich.
[0125] According to other embodiments, resins with low cross-link
densities may be employed for coatings subsequently used with
aqueous mediums. An exemplary low crosslink density resin is the
fusion solid EPON Resin 1004F available from Shell Chemical
Company, Houston, Tex. EPON Resin 1004F is a bisphenol A epoxy
resin having a melting point of about 100.degree. C. Other EPON
Resins from Shell Chemical Company may also be used, including
1001F, 1002F, 1007F and 1009F, as well as the 2000 series powdered
EPON Resins, for example, EPON Resins 2002, 2003, 2004 and
2005.
[0126] Non-curable resins which may be employed include powdered
ethyl cellulose, powdered polyethylene, powdered polypropylene and
powdered polyvinylidenedifluoride. Cellulose acetate butyrate
pellets also be jet milled and applied as a powder. Cellulose
acetate butyrate is typically non-curable but can be cross-linked
with peroxides.
[0127] The substantially non-perfluorinated resin is preferably
non-fluorinated according to some embodiments of the invention.
[0128] The micropowders and resins used according to embodiments of
the invention can be formed, for example, by jet milling. The
micropowders and resins are preferably particles having an average
diameter of about 50 microns or less, with average diameters of 10
microns or less being more preferred. The powders can be
electrostatically sprayed onto a surface with or without a curing
agent.
[0129] Micropowders according to the present invention may also be
prepared as latexes in aqueous suspensions, subsequently separated
from the liquid phase, and dried. Nanopowders and micropowders with
substantially trifluoromethyl surfaces may be prepared in radio
frequency and microwave plasmas of trifluoromethyl-containing
gases.
[0130] In another embodiment of the invention, the coating is
formed from a fluidized micropowder product of
trifluoromethyl-containing monomer and substantially
non-perfluorinated resin, wherein the micropowder is applied and
melted on an operational surface.
[0131] In another embodiment of the invention, a fluidized
micropowder of a non-perfluorinated resin is coated with the
polymerization product of a substantially
trifluoromethyl-containing monomer. The powder is subsequently
melted to form a hydrophobic coating.
[0132] In another embodiment of the invention, a surface is coated
with a coating formulation comprising a fluidized micropowder of a
polymerization product of substantially trifluoromethyl-containing
monomer, and a hydrophobic non-melting micropowder that does not
melt at temperatures required for formation of the coating. The
formulation is then heated or sintered to melt the fluidized
polymerization product micropowder without melting the non-melting
micropowder. The non-melting micropowder is preferably selected
from the group consisting of Teflon micropowders, Tefzel.TM.
micropowders, Kynar.TM. micropowders, polyvinylidene difluoride
micropowders, and polypropylene micropowders.
[0133] According to embodiments of the invention which involve
forming coatings by melting micropowders, the coating formulations
may be applied as a suspension to the operational surface and
subsequently dried prior to melting.
[0134] Another method of forming laboratory vessels having
hydrophobic coatings according to the present invention involves
preinjecting or coinjecting a coating formulation prior to or
during the laminar flow of molten materials injected into a mold or
through an orifice to form articles, for example, laboratory
vessels. The coating formulation comprises the prepolymerization
product of a trifluoromethyl-containing monomer, preferably a
product which has from about 50% to 100% of exposed terminal groups
being trifluoromethyl groups. The preinjected or coinjected coating
formulation may also comprise a thermoplastic resin and/or a
thermosetting resin. The injectable coating formulation may
comprise mixtures of trifluoromethyl-containing monomer, catalyst,
and resin. The injectable coating formulation may comprise mixtures
of molten prepolymerized trifluoromethyl-containing monomer and
microparticles, to form coatings exhibiting extraordinarily high
contact angles of 160.degree. or more to aqueous liquids. The
injectable coating formulations may comprise mixtures of molten
prepolymerized entirely or essentially trifluoromethyl-containing
monomers, other resins, and microparticles, which are preinjected
or coinjected to or during the laminar flow of molten materials
injected into a mold or through an orifice to form coatings on the
resultant vessels having extraordinarily high contact angles to
aqueous liquids, high resistance to solvent removal, and low
retention of biological samples.
[0135] According to yet other embodiments of the invention, a
tubular laboratory vessel such as a microcentrifuge tube or test
tube is provided and comprises a tubular body having an interior
sidewall and a closed lower end having an interior surface. A
hydrophobic coating according to the invention is applied to the
interior sidewall but not to the interior surface of the closed
lower end, or the interior closed end is substantially free of the
coating. An aqueous sample placed in the tubular body tends to be
retained at the closed lower end of the vessel and tends not to
creep or advance onto the coated interior sidewall, even during
movement of the vessel.
[0136] Other applications of the coating compositions of the
present invention include their use on ink-jet ink print heads to
form hydrophobic surfaces surrounding ink jet nozzle orifices.
Hydrophobic properties in such regions of an ink jet print head are
particularly beneficial in the use of organic solvent based ink jet
inks which have even a greater tendency to wet-out on the print
head than do aqueous based ink jet inks. The hydrophobic nature of
such a print head design prevents nozzle clogging and
cross-contamination between individual orifices of the print head.
The entire print head surface containing the ink jet nozzle
orifices can be coated with the hydrophobic coating composition of
the present invention or only in areas surrounding the individual
orifices. The compositions for such uses can may or may not contain
a hardenable material along with the trifluoromethyl-containing
component.
[0137] In yet another embodiment of the present invention, it has
been discovered that certain composite coatings can be rendered
substantially resistant to water film formation and loss of
performance due to ultraviolet light degradation by including in
the composite coating a hydrophobic liquid that is mobile, even as
a component of a coated composition. Preferably, the mobile
component remains mobile throughout the period of intended use of
the coating. Herein, the term "mobile" refers to a component of a
coating composition or coated composition that can migrate or move
through the composition to become present at a surface of a coating
made from the composition. The mobile component is preferably a
substantially or fully non-volatile fluorinated compound.
Preferably, the mobile component is a non-volatile fluorinated
liquid that remains liquid at at least one temperature within the
range of from about -30.degree. C. to about 30.degree. C.
Preferably, coating compositions according to this embodiment of
the present invention contain the mobile fluorinated liquid, in an
amount sufficient to improve the hydrophobicity and/or the lifespan
of the hydrophobic nature of the coating. Preferably, the mobile
fluorinated liquid is present in the coating composition in an
amount of from about 0.001 to about 20 percent by weight based on
the total non-volatile components weight of the coating
composition, more preferably from about 2 to about 10 percent by
weight.
[0138] According to embodiments of the present invention, a
composition of matter is provided that includes a hardenable resin,
hydrophobic microparticles having an average particle size diameter
of from about 1 nanometer to about 100 microns, and a substantially
nonvolatile mobile fluorinated compound that is a liquid at at
least one temperature in the range of from about -30.degree. C. to
about 30.degree. C. Preferably, the fluorinated compound is a
perfluorinated compound, for example, a perfluoroether.
Fluoro-chloro compounds are also preferred. The fluorinated
compound is preferably resistant to degradation by sunlight.
Preferably, the fluorinated compound produces a surface comprising
at least fifteen percent trifluoromethyl groups.
[0139] According to preferred embodiments of the invention, the
melting point of the mobile fluorinated compound is below about
30.degree. C., and the compound is preferably liquid at below about
20.degree. C. Preferably, the melting point of the fluorinated
compound is below about 30.degree. C. More preferably, the
fluorinated compound is substantially nonvolatile at or below
-30.degree. C.
[0140] According to embodiments of the invention, the coating
composition has a volume of hardenable resin that is less than the
volume of hydrophobic microparticles in the composition. The
microparticles preferably comprise a polytetrafluoroethylene
material, a polytetrafluoroethylene copolymer, or combinations
thereof The microparticles may also be composed of organic and/or
inorganic substances having a hydrophobic coating that is
preferably weather and uv resistant. The microparticles may be
porous or may comprise clusters of smaller particles. The
hydrophobic microparticles may have an average particle size
diameter of from about 1 micron to about 100 microns. The
composition, in place of or in addition to the hydrophobic
microparticles, may include or comprise nanoparticles having an
average particle size diameter of less than about 100 nanometers.
Preferably, the coating composition includes both microparticles
and nanoparticles, for example, up to about 30% by weight
nanoparticles based on the weight of the microparticles, preferably
up to about 10% by weight nanoparticles, such as from about 5% by
weight to about 10% by weight nanoparticles. Nanoparticles smaller
than 30 nanometers are preferred. The hydrophobic microparticles
may be clusters of nanoparticles.
[0141] Preferably, the composition further comprises a volatile
solvent. The volatile solvent may be at least partially
fluorinated, and can be perfluorinated. The volatile solvent may
contain hydrogen, chlorine, methoxy groups, ethoxy groups, or other
halogens.
[0142] The hardenable resin of the composition is preferably
hardenable by radiation, by moisture, by oxidation, by the addition
of a hardener or co-resin, by heat, or by evaporation of a solvent.
The hardenable resin preferably has a functionality of at least
two, for example, a functionality of at least three.
[0143] The hardenable resin may be at least one resin of an
acrylate, an alkyd, a urethane, an isocyanate, an epoxy, a
fluorocarbon, a silicone, a siloxane, a silicate, a ceramic, a
metal, a polyester, a vinyl, an anhydride, a polyimide, a polyol,
or a combination thereof Preferably, the hardenable resin includes
or comprises polyhexamethylene diisocyanate, methylene bis hexane
isocyanate, and/or an ethoxylated acrylic. The hardenable resin is
preferably weather resistant.
[0144] Coating compositions are also provided according to the
present invention that do not necessarily include a mobile
fluorinated component but which do include a hardenable resin,
hydrophobic microparticles having an average particle size diameter
of from about 1 micron to about 100 microns, and/or hydrophobic
nanoparticles having an average particle size diameter of less than
about 100 nanometers. Preferably, in such compositions, the
nanoparticles have an average particle size diameter of less than
about 20 nanometers. The microparticles may be made of
polytetrafluoroethylene, a polytetrafluoroethylene copolymer, or a
combination thereof. The microparticles may be coated with a
hydrophobic coating, such as a silane or fluorosilane. Such
compositions may also include a volatile solvent, for example, an
at least partially fluorinated volatile solvent. The hardenable
resin preferably is of the type described above with reference to
the coating compositions containing a mobile fluorinated
component.
[0145] According to an embodiment of the present invention, a
composition of matter is provided that includes a volume of
hardenable resin, and a volume of hydrophobic nanoparticles having
an average particle size diameter of less than about 100
nanometers, wherein the volume of the hydrophobic nanoparticles is
equal to or greater than the volume of the hardenable resin.
Preferably, the volume of the nanoparticles is more than twice the
volume of the hardenable resin. The nanoparticles preferably have
an average particle size diameter of less than about 20
nanometers.
[0146] Articles having a coating on a surface thereof are also
provided according to the present invention, wherein the coating is
a coating as described herein. The present coatings are
particularly useful on articles that in use are exposed to weather
or the elements. The present coatings are particularly useful on
articles that in use are intended to reflect or conduct
electromagnetic radiation. Articles that benefit from the coatings
of the present invention may also include laboratory vessels or
components thereof.
[0147] The present invention also relates to processes of improving
a coating, which processes include applying to the coating a
fluorocarbon film or layer onto and conforming to at least the
interstitial surfaces of the coating. The fluorocarbon film or
layer may preferably include a hardenable resin and a volume excess
of hydrophobic particles. The film or layer may have a thickness of
less than about 2 microns, or a thickness of less than about half
of the average interstitial pore size diameter of the interstitial
pores of the coating. The film may have a thickness of less than
about 50 nanometers. The hydrophobic particles preferably have an
average particle size diameter of less than about 100 microns. The
fluorocarbon film or layer may also include a substantially
nonvolatile liquid, more preferably, a mobile non-volatile
fluorinated compound. The fluorocarbon film or layer may include
nanoparticles having an average particle size diameter of about 100
nanometers or less. The fluorocarbon film or layer preferably
comprises a copolymer of polytetrafluoroethylene. A fluorocarbon
film comprising Dupont Teflon.RTM. AF or Ausimont Hyflon.RTM. AD is
preferred. Fluorocarbon films comprising fluorinated dioxol
polymers and copolymers are preferred.
[0148] The present invention also relates to processes of improving
a surface having rough, porous, striated, embossed,
particle-covered, or micropatterned features, which processes
include applying to the surface a fluorocarbon film or layer onto
and conforming to the surface. The features have at least one width
dimension of about 100 microns or less and are spaced about 100
microns or less apart. Features that have a height greater than
about half their width dimension are preferred. The features may be
created using abrading, etching, machining, micromachining,
photolithography, laser ablation, molding, embossing or any means
that produces a microfeatured surface. The fluorocarbon film or
layer may include a hardenable resin and/or a volume excess of
hydrophobic particles. The film or layer may have a thickness of
less than about 10 microns, or a thickness of less than about half
of the average distance between the rough, striated, embossed,
particle-covered, or micropatterned features of the surface. The
film may have a thickness of less than about 50 nanometers. The
hydrophobic particles preferably have an average particle size
diameter of less than about 100 microns. The fluorocarbon film or
layer may also include a substantially nonvolatile liquid, more
preferably, a mobile non-volatile fluorinated compound. The
fluorocarbon film or layer may include nanoparticles having an
average particle size diameter of about 100 nanometers or less. The
fluorocarbon film or layer preferably comprises a copolymer of
polytetrafluoroethylene. A fluorocarbon film comprising Dupont
Teflon.RTM. AF or Ausimont Hyflon.RTM. AD is preferred.
Fluorocarbon films comprising fluorinated dioxol polymers and
copolymers are preferred.
[0149] According to the present invention, it has been discovered
that nonvolatile silicone oils are effective as mobile components
and extend the performance of Teflon.RTM. dispersions in each of:
moisture-curable polyisocyanate resin coating compositions;
uv-curable ethoxylated triacrylate coating compositions;
epoxy-amine coating compositions; and urethane alkyd coating
compositions. Low T.sub.g polymers of diisocyanate perfluoroethers
and perfluorodiols, such as Ausimont's (Morristown, N.J.)
Fluorolink.RTM. B and Fluorolink.RTM. D4000, are even more
effective, according to the present invention, than silicones in
reducing ultra-violet (uv) degradation. Preferably, such low
T.sub.g polymers have a glass transition temperature of from about
-150.degree. C. to about -100.degree. C. Polychlorotrifluoro-oils,
such as Halocarbon's H1000 oil (River Ridge, N.J.), are also
effective and useful as the mobile component in accordance with the
present invention. According to a more preferred embodiment of the
present invention, a nonvolatile fluorinated polyether is included
in a coating composition as the mobile component, such as
Ausimont's Fomblin Y45 and Dupont's Krytox.RTM. GPL107. These
fluorinated polyether oils remain liquids even at temperatures of
about -30.degree. C.
[0150] According to the present invention, it has been discovered
that when the surface of a hydrophobic liquid resin or polymer,
such as a hydrocarbon or fluorocarbon oil, is degraded and made
more hydrophilic, the changed surface is rapidly drawn into the
interior of the liquid and replaced with a new surface which is
similar to the original surface. This process of surface energy
minimization occurs until all of the liquid is degraded, which in
the case of fluoropolymer oils, can be many years, or even decades.
According to the present invention, a solid surface coating which
includes a hydrophobic liquid resin or polymer and that has been
degraded to a higher surface energy is also regenerable such that
the degraded surface is drawn into the interior of the coating and
replaced with a new surface when the solid is melted.
[0151] According to embodiments of the present invention, solid
films of PTFE Teflon.RTM., Teflon.RTM. AF, polyperfluorooctyl
methacrylate, Cytonix Corporation's FluoroPel.TM. 804A (Beltsville,
Md.), polyethylene, hardened epoxy, and hardened epoxy coated with
a 1 micron film of Ausimont Y45 oil, were tested. After exposure to
the equivalent of one year in mid-latitude summer sun, the
polyperfluorooctyl methacrylate surface had changed in contact
angle to water from 120.degree. to 60.degree.. For polyethylene and
hardened epoxy, the changes were from 90.degree. to 20.degree. and
from 70.degree. to 10.degree., respectively. However, the
fluorocarbon oil-coated epoxy retained its contact angle of
100.degree.. Furthermore, when the polyperfluorooctyl methacrylate
and polyethylene were melted, their contact angles were restored.
Virgin PTFE surfaces and Teflon.RTM. AF showed only slight changes
from initial contact angles of about 115.degree. to contact angles
after exposure of about 105.degree..
[0152] It has also been discovered according to the present
invention that during heavy rainfall, only hard, presumably
water-resistant resins prevented hydrophobic particles on the
surface from being washed away. It is believed that the Vellox
coating permanently looses performance due to erosion of fumed
silica from its alkyd resin matrix. Experiments with formulations
involving 25 parts of a resin, 100 parts dispersed Dupont ZONYL
MP1000 micropowder (Wilmington, Del.), 6 parts Ausimont Y45 and 900
parts volatile fluorochloro solvent have shown that hardness is a
critical factor in limiting extreme heavy rain erosion. The resin
to micropowder volume ratio was about one to about four. Extreme
heavy rain was defined as 60 inches per hour at drop velocities of
50 miles per hour. Silicones and elastomeric urethanes eroded after
a few inches of extreme heavy rain, and fluoropolymers, epoxies and
acrylics with moderate hardness eroded after 10 to 20 inches. Hard
epoxies, polyurethanes and acrylics with high cross-link densities
were exceptionally durable, showing little erosion after 60 inches
of extreme heavy rain.
[0153] A further discovery according to the present invention was
that the inclusion in a coating composition of mobile fluorinated
liquid according to the present invention, in an amount of from
about 0.1 percent by weight to about 15 percent by weight based on
the total non-volatile components weight of the coating
composition, more preferably from about 4 percent by weight to
about 7 percent by weight, improved the rain performance of
formulations that were not exposed to uv radiation. It is believed
that the mobile fluorinated liquid covers the exposed hard resin
present in the interstitial spaces between hydrophobic particles,
inhibiting moisture accumulation. The mobile hydrophobic liquid can
also help to hold clusters of nano-sized or micro-sized particles
together by hydrophobic bonding. For example, in experiments
wherein Ausimont Y45 oil is added to a Boyd Teflon.TM. dispersion
coating at 6 percent of total solids, which as supplied would wet
out after 5 minutes of extreme heavy rain, performance of the Boyd
Teflon.TM. coating was substantially improved for coatings exposed
to the equivalent of 5 years of mid-latitude summer sunlight.
[0154] A further aspect of the invention is that the addition of
extremely fine hydrophobic micropowders having average particle
size diameters of from about 1 to about 100 nanometers (nm),
further improves the rain performance of composite hydrophobic
coatings, particularly in amounts of from about 1.0% by weight to
about 30% by weight based on the total non-volatile components
weight of the coating composition. Average particle sizes of from
about 1 nm to about 50 nm are preferred. Average particle sizes of
from about 1 nm to about 10 nm are even more preferred. For
example, hard resin formulations including Dupont's ZONYL 5069,
having nanoparticles with average particle size diameters in the
range of from about 10 nanometers to about 100 nanometers, and
added in an amount of about 10 percent by weight based on the
weight of Dupont's ZONYL MP1000 in the formulation, significantly
improved both heavy and extreme rain performance compared to the
performance of similar formulations but containing no ZONYL 5069.
Formulations replacing the larger particle sized ZONYL MP1000
completely with ZONYL 5069 showed little further improvement over
the 10 percent by weight addition described above. It is believed
that the small polytetrafluoroethylene (PTFE) particles decrease
the surface area of exposed interstitial hardened resin,
functioning in a similar way as the non-volatile hydrophobic
liquid. Extremely fine hydrophobic nanoparticles may also change
the interstitial pore geometry to a more conical, more
water-ejecting, shape.
[0155] In yet another embodiment of the present invention, it was
has been discovered that the rain performance of composite coatings
comprising a hardenable resin and a volumetric excess of
hydrophobic micropowder could be improved by overcoating the
interstitial surfaces with a nonvolatile fluorinated liquid, a
uv-resistant fluorinated film, and/or a uv-resistant fluorinated
nanopowder. These results were observed after spraying, blotting,
and dipping uncured composite coatings in dilute 0.01 percent by
weight to 2.0 percent by weight suspensions of hydrophobic
nanoparticles in a volatile solvent, or after spraying, blotting,
and dipping uncured composite coatings in dilute about 0.01 percent
to about 1.0 percent nonvolatile fluorinated liquids in a volatile
fluorinated solvent. The rain performance of composite coatings
overcoated with dilute solutions, for example, from about 0.01
percent to about 1.0 percent solutions, of Dupont Teflon.RTM. AF,
3M FK800, or Ausimont Hyflon.RTM. AD, were also substantially
improved.
[0156] The present invention is exemplified with reference to the
following Examples. In the Examples below, the surface energies of
the coatings was determined as follows. A series of hydrocarbon
oils with known surface tensions were used to develop a graph of
liquid surface tensions verse the cosines of the liquid contact
angles for each oil. The interpolated intercept of the graphed line
at a cosine of one indicates the surface energy of the coating.
EXAMPLE 1
[0157] A plurality of polypropylene pipette tips were enclosed in a
monofilament polyester mesh bag and the bag was placed in a
tumbling or agitating device. The mesh bag permitted treatment of
the pipette tips by allowing coating solution to pass through the
bag and substantially wet the surfaces of the pipette tip,
including surfaces at and around the tip openings. The tumbling
device was fitted with special gaskets to render the machine
interior air-tight and fluid-tight. To the machine interior was
also added a sufficient amount of coating solution to at least
partially immerse the bag of pipette tips. The coating solution
comprised a diluted solution of a fluorocarbon polymer having
terminal trifluoromethyl groups. The fluorocarbon polymer solution
is available as FluoroPel from Cytonix Corporation. The FluoroPel
solution provides the polymer completely dissolved in a fully
fluorinated solvent of perfluorinated fluorocarbons having an
average carbon chain length of from about 7 to about 8 carbon
atoms. The solvent exhibited a boiling point of from about
90.degree. C. to about 100.degree. C. Additional perfluorinated
solvent or similar perfluorinated fluorocarbon solvent was added as
a diluent to the FluoroPel solution to provide a coating solution
having a solids content, or a non-volatile components content, of
coating polymer of about 0.5% by weight.
[0158] The tumbling device was equipped with a blower for removing
volatile solvent from the coating and interior airspace, and with a
heater for heating air to be blown by the blower. The tumbling
device was run to agitate and tumble the pipette tips and the
coating solution, thus evenly distributing the coating solution
on-the surfaces of the tips and sufficiently wetting the surfaces
of the tips, including surfaces at or around the tip openings. The
interior of the device was maintained at or below room temperature
during solution coating of the tips. After a few minutes of
tumbling, a drain in the interior of the device was opened to allow
excess coating solution to drain out from the tumbling device
interior during further tumbling. After a few minutes of draining
with continued tumbling, the blower and heater were turned on and
air having a temperature of about 80.degree. C. was blown through
the device interior, and exhausted. The heated air evaporated
solvent from the coated solution and from the interior airspace of
the tumbling device. The bag of pipette tips continued to tumble
during the drying process. The drained and evaporated solution and
solvent was collected, reconcentrated and recycled. The coating
polymer was not volatile under exposure to the 80.degree. C.
air.
[0159] The coated and dried pipette tips were removed from the
device interior and mesh bag. Both exterior and interior surfaces
of the tips were coated by the process. The coated surfaces had a
resultant surface energy of less than about 10 dynes/cm and an
estimated surface population of trifluoromethyl groups of about 50%
by area or more.
EXAMPLE 2
[0160] A highly chemically and solvent resistant hydrophobic
coating for a microscope slide was prepared. The coating was
provided from a coating formulation having the following
ingredients:
[0161] 50 parts by weight high functionality novolac epoxy resin,
available as D.E.N. 439 from The Dow Chemical Company, Midland,
Mich., having an epoxy functionality of 3.9, an epoxy equivalent
weight of about 220, and a high cross-link density;
[0162] 8% by weight dicyandiamide as a reactant agent for curing
the epoxy, based on the weight of the epoxy;
[0163] 50 parts by weight calcinated pigment;
[0164] 10 parts by weight epoxy solvent triethylphosphate to
liquify and reduce the viscosity of the epoxy;
[0165] 10 parts by weight trifluoromethyl-containing polymer,
comprising PerFluoroCoat (PFC) 468MP (a solution of polymerized and
non-polymerized perfluoroalkyl monomers) available from Cytonix
Corporation; and
[0166] 1 part by weight 3-glycidoxypropyltrimethoxysilane.
[0167] The coating formulation was mixed, screen printed on a
microscope slide, heat cured and allowed to dry. The resultant
cured and dried coating exhibited a contact angle to water of
120.degree., was very hard, could not be scratched with a #8H
pencil, and was chemically resistant to removal in a plurality of
common lab solvents including acetone, water, chloroform,
trichloroethane and trifluoroethane, at 20.degree. C. The coating
exhibited a very low surface energy, and the population of
trifluoromethyl groups on the exposed surface of the coating
exceeded 80% by area as determined by surface energy analysis.
EXAMPLE 3
[0168] A composite hydrophobic coating was prepared and provides a
rough surface upon curing. The coating can exhibit extremely high
contact angles to water. The coating was prepared as follows:
[0169] 50 parts by weight D.E.N. 438 epoxy, 70 parts by weight
triethylphosphate, 4 parts by weight dicyandiamide, and 1 part by
weight 3-glycidoxypropyltrimethoxysilane were thoroughly mixed
together. Then, 50 parts by weight TiO.sub.2 having an average
particle size diameter of about 1 .mu.m was added and the mixture
was again mixed thoroughly. Then, 100 parts by weight Teflon.RTM.
MP 1200 powder was added and the mixture was again mixed
thoroughly. Then, 100 parts by weight Teflon.RTM. MP 1200 powder
was added and the mixture was again mixed thoroughly. Then, 10
parts by weight PFC 468MP was added and the mixture was again mixed
thoroughly. The resulting formulation was applied to an operational
surface of a laboratory vessel and allowed to cure for 3 minutes at
200.degree. C.
EXAMPLE 4
[0170] A composite hydrophobic coating was prepared and provides a
rough surface upon curing. The coating can exhibit extremely high
contact angles to water. The coating was prepared as follows:
[0171] 90 parts by weight Shell 1004-QX-55 (bis-A epoxy in xylene
and propylene glycol monomethyl ether acetate), 1 part by weight
imidizol (optional), 40 parts by weight ethylene glycol, and 10
parts by weight organic pigment were thoroughly mixed together.
Then, 10 parts by weight Tullanox glass micropowder was added and
the mixture was again mixed thoroughly. Then, 10 parts by weight
PFC 468TF (solution of perfluoroalkyl polymer in Freon TF),
available from Cytonix Corporation, was added and the mixture was
again mixed thoroughly. The resulting formulation was applied to an
operational surface of a laboratory vessel and allowed to dry at
room temperature for 24 hours.
EXAMPLE 5
[0172] A highly chemical and solvent resistant hydrophobic coating
for spraying or dipping was prepared. The coating was provided from
a coating formulation having the following ingredients:
[0173] Part A
[0174] 5 parts Futurathane 660 part A (Futura Coatings,
Inc.-USA)
[0175] 5 parts acetophenone (Aldrich Chemical)
[0176] 20 parts Vertrel MCA
[0177] Part B
[0178] 33 parts Vertrel MCA (Dupont)
[0179] 10 parts Asakalin 225 (Asahi Glass)
[0180] 0.5 part 9187 polymer (Cytonix)
[0181] 1.5 parts 9187 monomer (3M)
[0182] 15 parts Futurathane 660 part B (Futura Coatings, Inc.
-USA)
[0183] Parts A and B were mixed and sprayed onto glass, plastic and
metal articles and allowed to dry and cure under ambient conditions
for 72 hours. The resultant coatings were scratch resistant to a #6
pencil, had a contact angle to water of 1200, and were not altered
by acetone, toluene or chloroethane. The population of
trifluoromethyl groups at the surface exceeded 80 percent.
EXAMPLE 6
[0184] A highly chemical and solvent resistant hydrophobic coating
for spraying or dipping was prepared. The coating was provided from
a coating formulation having the following ingredients:
[0185] Part A
[0186] 5 parts Futurathane 660 part A (Futura Coatings,
Inc.-USA)
[0187] 5 parts acetophenone (Aldrich Chemical)
[0188] 20 parts Vertrel MCA
[0189] 24 parts Zonyl 1300 micropowder (Dupont)
[0190] Part B
[0191] 33 parts Vertrel MCA (Dupont)
[0192] 10 parts Asakalin 225 (Asahi Glass)
[0193] 0.5 parts 9187 polymer (Cytonix)
[0194] 1.5 parts 9187 monomer (3M)
[0195] 15 parts Futurathane 660 part B (Futura Coatings,
Inc.-USA)
[0196] Parts A and B were mixed and sprayed onto glass, plastic and
metal articles and allowed to dry and cure under ambient conditions
for 72 hours. The resultant coatings had a contact angle to water
of 150.degree., and were not altered by acetone, toluene or
chloroethane. The population of trifluoromethyl groups at the
surface exceeded 80 percent.
EXAMPLE 7
[0197] A highly hydrophobic coating composition for spraying or
dipping was prepared. A coating was provided from the coating
formulation which had the following ingredients:
[0198] 100 parts Asakalin 225 (Asahi Glass)
[0199] 5 parts 9187 polymer (Cytonix)
[0200] 25 parts 9187 monomer (3M)
[0201] 100 parts HelmsMan Spar Urethane (Minwax, Upper Saddle
River, N.J.)
[0202] Ingredients were mixed and sprayed onto glass, plastic and
metal articles and allowed to dry and cure under ambient conditions
for 24 hours. The resultant coatings were scratch resistant to a #2
pencil and had a contact angle to water of 120.degree..
EXAMPLE 8
[0203] A highly hydrophobic coating for spraying or dipping was
prepared. the coating was provided from a coating formulation
having the following ingredients:
[0204] 200 parts Asakalin 225 (Asahi Glass)
[0205] 5 parts 9187 polymer (Cytonix)
[0206] 25 parts 9187 monomer (3M)
[0207] 120 parts Zonyl 1300 micropowder
[0208] 100 parts HelmsMan Spar Urethane (Minwax, Upper Saddle
River, N.J.)
[0209] Ingredients were mixed and sprayed onto glass, plastic and
metal articles and allowed to dry and cure under ambient conditions
for 24 hours. The resultant coatings had a contact angle to water
of 150.degree..
EXAMPLE 9
[0210] A highly hydrophobic coating for spraying or dipping was
prepared. The coating was provided from a coating formulation
having the following ingredients:
[0211] 200 parts Asakalin 225 (Asahi Glass)
[0212] 5 parts 9187 polymer (Cytonix)
[0213] 25 parts 9187 monomer (3M)
[0214] 80 parts TechnoCel.RTM. 40 (available from Cellulose Filler
Factory, Chestertown, Md.)
[0215] 100 parts HelmsMan Spar Urethane (available from Minwax,
Upper Saddle River, N.J.)
[0216] The ingredients were mixed and sprayed onto glass, plastic
and metal articles and allowed to dry and cure under ambient
conditions for 24 hours. The resultant coatings had act angle to
water of 150.degree..
EXAMPLE 10
[0217] A highly hydrophobic coating for printing or painting was
prepared. The coating was provided from a coating formulation
having the following ingredients:
[0218] 100 parts by weight N68 from Norland
[0219] 10 parts by weight Asakalin 225 from Asahi Glass
[0220] 10 parts by weight Zonyl TA-N from DuPont
[0221] The ingredients were mixed and painted onto glass, plastic
and metal articles and cured in mid-day summer sunlight in Virginia
for one hour. The resulting coatings had a contact angle to water
of 120.degree.. The surface area population of trifluoromethyl
groups exceeded 70%.
EXAMPLE 11
[0222] A highly hydrophobic coating for spraying or dipping was
prepared. The coating was provided from a coating formulation
having a perfluorinated hardenable resin. The coating formulation
had the following ingredients:
[0223] 10 parts by weight Teflon AF 1600 from DuPont
[0224] 100 parts by weight FC-40 from 3M
[0225] 1 part by weight L-9187 polymer from Cytonix Corporation
[0226] The ingredients were mixed and heated to 120.degree. C. for
two hours. The resultant material was then painted onto glass, PTFE
and metal articles and cured in an oven at 200.degree. C. for one
hour. The resulting coatings had a contact angle to water of
120.degree.. The surface area population of trifluoromethyl groups
exceeded 90%. The surface energy of the coating was below 9
dynes/cm compared to the surface energy of articles coated with
Teflon AF alone, which was about 16 dynes/cm. The properties of the
inventive coating indicate a substantially perfluorooctyl surface
on the coatings of the present invention.
EXAMPLES 12-14
[0227] Examples 12-14 illustrate exemplary coating compositions
according to the present invention which contain a non-volatile
fluorinated mobile compound that is liquid at at least one
temperature within the range of from about -30.degree. C. to about
0.degree. C.
EXAMPLE 12
[0228] Air-Curable Urethane Alkyd Coating
[0229] An air-curable urethane alkyd coating material was made as
follows:
[0230] 100 parts by weight Zonyl.RTM. MP1000 (Dupont, Wilmington,
Del.) and six parts by weight Fomblin.RTM. Y45 (Ausimont USA, Inc.,
Morristown, N.J.) were dispersed thoroughly in 900 parts by weight
room temperature Asahiklin AK-225 (Asahi Glass Co., Tokyo, Japan).
Then 38 parts by weight MinWax.RTM. Helmsman Spar Urethane (The
Thompson-MinWax Company, Upper Saddle River, N.J.) was blended
thoroughly with the resulting dispersion to form a coating
material.
EXAMPLE 13
[0231] UV-Curable Acrylic Coating
[0232] A uv-curable acrylic coating material was made as
follows:
[0233] 100 parts by weight Zonyl.RTM. MP1000 (Dupont, Wilmington,
Del.) and six parts by weight Fomblin.RTM. Y45 (Ausimont USA, Inc.,
Morristown, N.J.) were dispersed thoroughly in 900 parts by weight
room temperature Asahiklin AK-225 (Asahi Glass Co., Tokyo, Japan).
Then, 25 parts by weight SR 454 ethoxylated triacrylate (Sartomer
Company, Exton, Pa.) and one part KTO46 UV-catalyst (Sartomer
company, Exton, Pa.) were blended thoroughly with the resulting
dispersion to form a coating material.
EXAMPLE 14
[0234] Moisture-Curable Acrylic Coating
[0235] A moisture curable acrylic coating material was made as
follows:
[0236] 100 parts by weight Zonyl.RTM. MP1000 (Dupont, Wilmington,
Del.) and six parts by weight Fomblin.RTM. Y45 (Ausimont USA, Inc.,
Morristown, N.J.) were dispersed thoroughly in 900 parts by weight
room temperature Asahiklin AK-225 (Asahi Glass Co., Tokyo, Japan).
Then 25 parts by weight Sigma-Aldrich 41,801-3 polyhexamethylene
diisocyanate (Sigma-Aldrich, Milwaukee, Wis.) and one part by
weight Sigma-Aldrich 29, 123-4 dibutyl tin dilaurate
(Sigma-Aldrich, Milwaukee, Wis.) were blended thoroughly with the
resulting dispersion to form a coating material.
[0237] Although the present invention has been described in
connection with preferred embodiments, it will be appreciated by
those skilled in the art that additions, modifications,
substitutions and deletions not specifically described may be made
without departing from the spirit and scope of the invention
defined in the appended claims.
* * * * *