U.S. patent application number 15/010302 was filed with the patent office on 2016-05-26 for low surface energy touch screens, coatings, and methods.
The applicant listed for this patent is Cytonix, LLC. Invention is credited to James F. Brown.
Application Number | 20160145450 15/010302 |
Document ID | / |
Family ID | 48744110 |
Filed Date | 2016-05-26 |
United States Patent
Application |
20160145450 |
Kind Code |
A1 |
Brown; James F. |
May 26, 2016 |
Low Surface Energy Touch Screens, Coatings, and Methods
Abstract
Substrates, surfaces, assemblies, kits, compositions, and
methods are provided for forming touch screens and other appliance
surfaces exhibiting good hydrophobicity, oleophobicity, and
abrasion resistance. Methods are provided for increasing a
population density of hydroxyl groups on a touch surface of a touch
screen substrate without affecting the compressive strength of the
back surface. The treated touch surface of the substrate can then
be coated with a coating that includes an organo-metalic and/or
silane, for example, a fluorosilane such as a perfluoropolyether
alkoxysilane. A substrate can retain its compressive resistance to
breakage by impact applied to the touch surface while minimizing
any decrease in compressive strength against impact against the
touch surface. Examples of such substrates include touch screens
for mobile and desktop electronic devices, components of 3D display
devices, and components for electrowetting display devices.
Inventors: |
Brown; James F.; (Clifton,
VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cytonix, LLC |
Beltsville |
MD |
US |
|
|
Family ID: |
48744110 |
Appl. No.: |
15/010302 |
Filed: |
January 29, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14687475 |
Apr 15, 2015 |
9249050 |
|
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15010302 |
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|
13544360 |
Jul 9, 2012 |
9035082 |
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14687475 |
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61545556 |
Oct 10, 2011 |
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Current U.S.
Class: |
428/142 ;
106/481 |
Current CPC
Class: |
C09D 7/20 20180101; C03C
2217/29 20130101; C08G 65/00 20130101; C08K 9/10 20130101; C03C
17/28 20130101; C03C 2217/78 20130101; C08G 2650/48 20130101; C09D
171/00 20130101; Y10T 428/24355 20150115; C08G 65/005 20130101;
C08G 65/336 20130101; Y10T 428/31663 20150401; Y10T 428/24612
20150115; C09D 7/63 20180101; C03C 2217/76 20130101 |
International
Class: |
C09D 7/12 20060101
C09D007/12; C03C 17/28 20060101 C03C017/28 |
Claims
1. A micro-sized or nano-sized object coated with a
perfluoropolyether silane composition consisting of a
perfluoropolyether silane and optionally a non-volatile fluorinated
oil, the perfluoropolyether silane having the formula:
R.sub.f--CH.sub.2--O.sub.w--R--Si(Y).sub.3 wherein R.sub.f
represents a K type perfluoropolyether or a Y type
perfluoropolyether, Y represents a hydrolysable group independently
selected from a chloro group, an alkoxy group, an acyloxy group,
and an aryloxy group, R represents an alkyl group of 1 to 4 carbon
atoms, and w is 0 or 1.
2. The micro-sized or nano-sized object of claim 1, wherein the
object is a powder or a fiber.
3. A coating comprising the micro-sized or nano-sized object of
claim 1, wherein the object is in the coating, at a surface of the
coating, or both.
4. The micro-sized or nano-sized object of claim 1, wherein the
perfluoropolyether silane composition consists of the
perfluoropolyether silane and the non-volatile fluorinated oil.
5. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 1, wherein the rough surface has a
repeating or random topography, a relief, an impression, a texture,
a pattern, a design, a feature, or a combination thereof.
6. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 1, wherein the rough surface has a
pattern.
7. A surface comprising the coating of claim 3, wherein the surface
exhibits a contact angle to water of 170.degree. or greater.
8. A micro-sized or nano-sized object coated with a
perfluoropolyether silane composition consisting of a
perfluoropolyether silane and optionally a non-volatile fluorinated
oil, the perfluoropolyether silane having the formula:
R.sub.f--CH.sub.2--R--Si(Y).sub.3 wherein R.sub.f represents a K
type perfluoropolyether or a Y type perfluoropolyether, Y
represents a hydrolysable group independently selected from a
chloro group, an alkoxy group, an acyloxy group, and an aryloxy
group, and R represents an alkyl group of 1 to 4 carbon atoms.
9. The micro-sized or nano-sized object of claim 8, wherein the
object is a powder or a fiber.
10. A coating comprising the micro-sized or nano-sized object of
claim 8, wherein the object is in the coating, on a surface of the
coating, or both.
11. The micro-sized or nano-sized object of claim 8, wherein the
perfluoropolyether silane composition consists of the
perfluoropolyether silane and the non-volatile fluorinated oil.
12. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 8, wherein the rough surface has a
repeating or random topography, a relief, an impression, a texture,
a pattern, a design, a feature, or a combination thereof.
13. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 8, wherein the rough surface has a
pattern.
14. A surface comprising the coating of claim 10, wherein the
surface exhibits a contact angle to water of 170.degree. or
greater.
15. A micro-sized or nano-sized object coated with a
perfluoropolyether silane composition consisting of a
perfluoropolyether silane and a non-volatile fluorinated oil, the
perfluoropolyether silane having the formula:
R.sub.f--CH.sub.2--O--R--Si(Y).sub.3 wherein R.sub.f represents a K
type perfluoropolyether or a Y type perfluoropolyether, Y
represents a hydrolysable group independently selected from a
chloro group, an alkoxy group, an acyloxy group, and an aryloxy
group, and R represents an alkyl group of 1 to 4 carbon atoms.
16. The micro-sized or nano-sized object of claim 15, wherein the
object is a powder or a fiber.
17. A coating comprising the micro-sized or nano-sized object of
claim 15, wherein the object is in the coating, at a surface of the
coating, or both.
18. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 15, wherein the rough surface has a
repeating or random topography, a relief, an impression, a texture,
a pattern, a design, a feature, or a combination thereof.
19. An article comprising a rough surface that is coated, at least
in part, by a coating composition comprising the micro-sized or
nano-sized object of claim 15, wherein the rough surface has a
pattern.
20. A surface comprising the coating of claim 17, wherein the
surface exhibits a contact angle to water of 170.degree. or
greater.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. patent
application Ser. No. 14/687,475, filed Apr. 15, 2015, now U.S. Pat.
No. 9,249,050 B2, which in-turn is a Continuation of U.S. patent
application Ser. No. 13/544,360, filed Jul. 9, 2012, now U.S. Pat.
No. 9,035,082 B2, which in-turn claims priority to U.S. Provisional
Patent Application No. 61/545,556 filed Oct. 10, 2011, all of which
are incorporated herein in their entireties by reference.
FIELD
[0002] The present teachings relate to substrate coatings that
increase hydrophobicity, oleophobicity, and abrasion
resistance.
BACKGROUND
[0003] The explosive growth of both portable and desktop touch
screen devices has meant a heightened need to keep such surfaces
clean. Use of a touch screen device, by name, involves touching by
a user's fingers. Any oils, moisture, or various other materials
found on one's fingertips can be transferred to the surface of a
touch screen device. Overtime, these materials can accumulate and
deleteriously affect the functionality, viewability, and general
appearance of the device. Existing coating compositions and/or
methods have proved unsatisfactory in terms of cost, efficient use
of materials, longevity and/or the ability to resist abrasion,
water, cleaning agents and lipids.
[0004] Glass hardening has been used to strengthen touch screen
substrates against breakage, scratching and abrasion. Conventional
hardening techniques, however, result in glass surfaces having
reduced population densities of hydroxyl groups that could be used
for bonding with an organo-metalic and/or silane coating material.
Treating substrates to increase hydroxyl group population densities
destroys or removes surface-compression elements, such as large
atoms or ions, and strength gains from pre-hardening procedures are
lost. Accordingly, there exists a need for better pre-hardened
glass substrates for touch screens, and for coating methods and
compositions for forming touch screen surfaces.
SUMMARY
[0005] According to various embodiments of the present teachings, a
pre-hardened glass substrate is provided that comprises a treated
front surface having a first exposed hydroxyl population density
and a back surface having a second exposed hydroxyl population
density, wherein the first exposed hydroxyl population density is
greater than the second exposed hydroxyl population density. The
pre-hardened glass substrate can retain atoms or ions, such as
potassium, hardened into the back surface while providing a touch
surface that can be optimally coated with an organo-metalic and/or
silane-containing coating material. The coating material may also
comprise metals, metal compounds, other elements or their
compounds, and combinations thereof. As a result, a touch screen
can be formed from the pre-hardened glass substrate, which has a
touch surface that exhibits improved longevity, wear resistance,
lubricity, oleophobicity, and hydrophobicity, without sacrificing
the benefits enured to the back surface from a glass hardening
procedure. Compressive strength gains from a pre-hardening
procedure are not destroyed on the back surface while the touch
surface provides an increased population density of reactive sites
for organo-metalic and/or silane treatment. Methods and
compositions for treating such pre-hardened glass substrates, for
further treating such substrates with organo-metalic compounds,
co-agents and silanes are also provided. In other embodiments,
surface groups naturally present or absent on various substrates
may be increased or added in addition to hydroxyl groups.
[0006] According to various embodiments, methods more generally for
treating substrates, pre-hardened substrates, flexible substrates,
rigid substrates, polymeric substrate, glass substrates, metalic
substrates, inorganic substrates, and the like, are provided.
[0007] According to various embodiments of the present teachings,
an assembly for quantitatively treating a surface is provided. The
assembly can comprise a first adhesive surface having a first area.
The assembly can comprise a second surface having a second area,
facing and spaced substantially uniformly apart by a distance from
the first adhesive surface. The second surface may be adhesive or
non-adhesive. A capillary volume can be defined by and between the
first adhesive surface and the second surface. A first fluid can be
loaded into the capillary. The first fluid can comprise a chemical
composition or molecule having a number of adhesion functional
groups. The functional groups, when disposed as a monolayer, can
make up a third area substantially equal to a first fraction of the
first area. The fraction can be one, more than one, or less than
one.
[0008] According to various embodiments of the present teachings, a
method of coating substrate surface is provided. The substrate can
be rigid, flexible, glass, plastic, metal, inorganic, a combination
thereof, or the like. A fluid comprising molecules comprising
adhesion functional groups is applied to a first adhesive substrate
surface having a first area. A second substrate surface having a
second area is placed on first adhesive substrate surface. The
second substrate surface may be adhesive or non-adhesive. The
second substrate may be non-adhesive to the adhesion functional
groups, may be repellant to the adhesion functional groups, yet may
have an affinity for a part of the molecule which is not adhesive.
A substantially uniform layer of the fluid can then be formed
between and in contact with the first adhesive substrate surface
and the second substrate surface. The molecules can then be caused
to adhere to the first and/or second substrate surfaces. The amount
of the molecules comprising adhesion functional groups that can be
applied can be such that, when disposed in a monolayer, the
adhesion functional groups have a third area substantially equal to
a fraction of the first and second areas. The fraction can be one,
more than one, or less than one. The first and second substrate
surfaces can then be separated after a period of time.
[0009] According to various embodiments of the present teachings, a
method of manufacturing a treated substrate is provided. A
substrate can be provided having a first surface comprising exposed
hydroxyl groups and a second surface comprising exposed hydroxyl
groups. The substrate can be rigid, flexible, glass, plastic,
metalic, inorganic, a combination thereof, or the like. The first
surface can be treated to increase the population density of
exposed hydroxyl groups and form a treated surface, without
treating the second surface. The method can provide a higher
population density of exposed hydroxyl groups on the first surface
than on the second surface, wherein the treated substrate retains
its resistance to breakage by impact or pressure applied to the
first surface because surface-compressive elements in the second
surface have not been removed or destroyed.
[0010] According to various embodiments of the present teachings, a
method of treating a substrate comprising a surface having exposed
hydroxyl groups is provided. The method can comprise contacting a
surface with a composition comprising components A and B combined
together, a composition comprising A followed by a composition
comprising B, or a composition comprising B followed by a
composition comprising A, wherein component A is at least one
fluorochemical polyether alkoxy or chloro organo-metalic and/or
silane compound of formula (1):
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. Component B can
comprise tetraalkoxysilane, in an amount of 8% by weight or less
based on the total weight of components A and B, when combined
together. In other embodiments, Component B can be a metal or
element comprising 3 or more hydrolyzable groups, for example, a
tetraalkoxysilane, and may further comprise any suitable additives.
The composition can further comprise forming a coating from the
composition on the surface by causing components A and B to undergo
a substantially complete condensation reaction.
[0011] According to various embodiments of the present teachings, a
composition comprising the reaction product obtained after a
substantially complete condensation reaction of components A and B
is provided. Component A can comprise at least one fluorochemical
polyether alkoxy or chloro organo-metalic and/or silane compound of
formula (1):
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. Component B can
comprise a tetraalkoxysilane in an amount of 8% by weight or less
based on the total weight of components A and B, when combined
together. In other embodiments, Component B can be a metal or
element comprising 3 or more hydrolyzable groups, for example, a
tetraalkoxysilane, and may further comprise any suitable additives,
such as additives comprising a reactive functionality.
[0012] According to various embodiments of the present teachings, a
kit equipped for substrate coating is provided comprising a first
container and a second container packaged in a third container. The
first container can comprise at least one fluorochemical polyether
alkoxy or chloro organo-metalic and/or silane compound of the
formula (1):
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. A second container
comprises a tetraalkoxysilane and/or one or more metals or elements
comprising hydrolyzable groups, and may further comprise any
suitable additives. In some embodiments, the amount of
tetraalkoxysilane can be 8% by weight or less based on the total
weight of the combined contents of the first container and second
container.
[0013] The present teachings also provide a touch screen that
exhibits a water contact angle of 100.degree. or more after 3000
double rubs with 0000 steel wool at a pressure of 2.5 grams per
square millimeter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] A better understanding of the features and advantages of the
present disclosure will be obtained by reference to the
accompanying drawings, which are intended to illustrate, not limit,
the present teachings.
[0015] FIG. 1 is a schematic representation of substrate surfaces
comprising free hydroxyl groups in accordance with various
embodiments of the present teachings and comparing the population
density of hydroxyl groups to the density on a glass surface.
[0016] FIG. 2 is a perspective view of an assembly for
manufacturing treated and coated substrate surfaces in accordance
with various embodiments of the present teachings.
[0017] FIG. 3 is a flow chart illustrating a method of coating
substrate surfaces in accordance with various embodiments of the
present teachings.
[0018] FIG. 4 is a flow chart illustrating a method of
manufacturing a treated substrate in accordance with various
embodiments of the present teachings.
[0019] FIG. 5 is a flow chart illustrating a method of treating a
substrate in accordance with various embodiments of the present
teachings.
[0020] FIG. 6 is a partial cutaway view of a kit in accordance with
various embodiments of the present teachings.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0021] According to various embodiments of the present teachings, a
perfluoropolyether silane is provided, of the formula:
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z
[0022] wherein R.sub.f represents a pendant polyfluoropolyether,
R.sup.1 represents a C.sub.1-C.sub.8 alkyl group, Y represents a
hydrolysable group independently selected from a chloro group, an
alkoxy group, an acyloxy group, and an aryloxy group, each R
independently represents hydrogen or an alkyl group of 1 to 4
carbon atoms, z is 2, 3, or 4, and each x is independently 0 or 1.
The pendant perfluoropolyether can be any type of
perfluoropolyether, for example, a K type or Y type
perfluoropolyether. The pendant perfluoropolyether can have a
molecular weight of from about 500 to about 10,000 amu, for
example, from about 2000 to about 5000 amu. The hydrolysable group
can comprise a chloro group, a methoxy group, an ethoxy group, a
combination thereof, or the like. A composition comprising the
perfluoropolyether silane and one or more additives is also
provided. The additives can comprise, for example, a tetraalkoxy
silane, a polysilane, a polyorganometalic compound, a dipodal
silane, a dipodal organometalic compound, a combination thereof,
and the like. The composition can instead, or additionally,
comprise a fluorinated solvent as an additive. According to various
embodiments, articles, for example, display devices, can be coated
with the perfluoropolyether silane. In some cases, the article can
comprise a smooth surface that is coated, at least in part, by the
perfluoropolyether silane. In some cases, the article can comprise
a rough surface that is coated, at least in part, by the
perfluoropolyether silane, and the rough surface can have a
repeating or random topography, a relief, an impression, a texture,
a pattern, a design, a feature, a combination thereof, or the like.
The article can comprise a touch screen that is coated, at least in
part, by the perfluoropolyether silane, or a 3D imaging screen that
is coated, at least in part, by the perfluoropolyether silane, or
an electrowetting display screen that is coated, at least in part,
by the perfluoropolyether silane.
[0023] According to various embodiments of the present teachings, a
perfluoropolyether silane is provided of the formula:
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z
[0024] wherein R.sub.f represents a pendant polyfluoropolyether, Q
represents a divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. The pendant
perfluoropolyether can be any type of perfluoropolyether, for
example, a K type or Y type perfluoropolyether. The pendant
perfluoropolyether can have a molecular weight of from about 500 to
about 10,000 amu, for example, from about 2000 and about 5000 amu.
The hydrolysable group can comprise a chloro group, a methoxy
group, an ethoxy group, a combination thereof, or the like. A
composition comprising the perfluoropolyether silane and one or
more additives is also provided. The additives can comprise, for
example, a tetraalkoxy silane, a polysilane, a polyorganometalic
compound, a dipodal silane, a dipodal organometalic compound, a
combination thereof, and the like. The composition can instead, or
additionally, comprise a fluorinated solvent as an additive. In
some cases, the perfluoropolyether silane can comprise the reaction
product of a pendant perfluoropolyether vinyl ether and
Cl.sub.3SiH. The methods can comprise reacting a pendant
perfluoropolyether vinyl ether and Cl.sub.3SiH together. In some
cases, the perfluoropolyether silane comprises the reaction product
of a pendant perfluoropolyether trichlorosilane and one or more
alcohols selected from methanol, ethanol, and propanol, and the
methods herein can comprise reacting these reactants together.
According to various embodiments, articles, for example, display
devices, can be coated with the perfluoropolyether silane. In some
cases, the article can comprise a smooth surface that is coated, at
least in part, by the perfluoropolyether silane. In some cases, the
article can comprise a rough surface that is coated, at least in
part, by the perfluoropolyether silane, and the rough surface can
have a repeating or random topography, a relief, an impression, a
texture, a pattern, a design, a feature, a combination thereof, or
the like. The article can comprise a touch screen that is coated,
at least in part, by the perfluoropolyether silane, or a 3D imaging
screen that is coated, at least in part, by the perfluoropolyether
silane, or an electrowetting display screen that is coated, at
least in part, by the perfluoropolyether silane.
[0025] According to various embodiments of the present teachings, a
pre-hardened glass substrate is provided that comprises a first
surface having a first exposed hydroxyl population density and a
post-treated second surface having a second exposed hydroxyl
population density. The first exposed hydroxyl population density
can be less than the second exposed hydroxyl population density and
the second surface can be coated to form a touch surface. The
pre-hardened glass substrate can retain its compressive resistance
to breakage by impact or pressure applied to the second surface
while minimizing any decrease in tensile strength of the first
surface.
[0026] The second exposed hydroxyl population density can have a
range of densities, for example, from about 2.0 to about 5.0, from
about 2.0 to about 2.5, or about 2.2 hydroxyl groups per square
nanometer. In some embodiments, the second exposed hydroxyl
population density has a density greater than about 2.2 hydroxyl
groups per square nanometer. In some embodiments, the first exposed
hydroxyl population density is less than about 1.8 hydroxyl groups
per square nanometer. The second exposed hydroxyl population
density can be greater than the first exposed hydroxyl population
density by about 0.1 to about 3.2, from about 0.25 to about 2.5, or
about 0.4 hydroxyl groups per square nanometer. According to the
present teachings, the second exposed hydroxyl population density
can be equivalent to the amount of a first organo-metalic and/or
silane that will be used to coat the surface, such that each first
organo-metalic and/or silane molecule will substantially only
attach to a single hydroxyl group and not to a neighboring
organo-metalic and/or silane. Such stoichiometry forms a coating
that is not a two-dimensional network of molecules. Adjacent first
organo-metalic and/or silanes, once bonded to the surface, can be
crosslinked to one another simultaneously or subsequently by a
second organo-metalic and/or silane. The second organo-metalic
and/or silane can be the same as the first.
[0027] The post-treated second surface can have been treated by any
suitable process to selectively increase the second exposed
hydroxyl population density. In some embodiments, the process to
selectively increase the second exposed hydroxyl population density
comprises a plasma process, including a plasma jet process, or an
abrasive precess. The process to selectively increase the second
exposed hydroxyl population density can comprise exposure to steam,
ammonia, hydrogen peroxide, an acid, a base, fluorine, a halogen
compound, an oxidizing agent, a reducing agent, or a combination
thereof. In some examples, the touch surface can be treated to
increase the hydroxyl group population density by contacting the
touch surface with a solution comprising from about 3% by volume to
about 30% by volume ammonium hydroxide, from about 3% by volume to
about 30% by volume hydrogen peroxide, and from about 40% by volume
to about 94% by volume water. Another exemplary treating solution
that can be used comprises from about 3% by volume to about 30% by
volume concentrated sulfuric acid, from about 3% by volume to about
30% by volume hydrogen peroxide, and from about 40% by volume to
about 94% by volume water. Another exemplary treating solution that
can be used comprises from about 0.1% by weight to about 10% by
weight ammonium bifluoride, and from about 90% by weight to about
99% by weight water. Dilute solutions of aqueous hydrofluoric acid
are also preferred, as are concentrated solutions of sodium
hydroxide. In other embodiments, surface groups naturally present
or absent on various substrates may be increased or added, in
addition to hydroxyl groups, by the present teachings.
[0028] After treating to increase hydroxyl group population
density, the post-treated second surface can be reacted with a
touch screen coating composition. In some embodiments, the
post-treated second surface can be reacted with a first
organo-metalic and/or silane, for example, a monoorgano-metalic
and/or monosilane, a diorgano-metalic and/or disilane, a
triorgano-metalic and/or trisilane, a tetraorgano-metalic and/or
tetrasilane, a polyorgano-metalic and/or polysilane, or a
combination thereof, each comprising one, two, three, four or poly
hydrolysable groups, respectively. For purposes of the present
teachings, chlorine will be considered a hydrolysable group. Silane
and other organo-metalic groups can form from one to about four
hydrolyzable linkages, by way of example, a disilane can have from
2 to about 6 linkages, and a tetrasilane can have from 4 to about
12 hydrolyzable linkages. In some embodiments, the post-treated
second surface can be reacted with at least a second organo-metalic
and/or silane. The first organo-metalic and/or silane and/or the
second organo-metalic and/or silane can comprise a fluorinated
organo-metalic and/or silane, for example, a perfluorinated
organo-metalic and/or silane. The organo-metalic and/or silane can
be applied in the presence of an anhydride. In some embodiments,
the anhydride can comprise a fluorinated anhydride. The fluorinated
organo-metalic and/or silane can comprise a perfluoropolyether. The
fluorinated organo-metalic and/or silane can comprise a
polyorgano-metalic and/or silane comprising two or more
organo-metalic and/or silane groups. In some embodiments, the
post-treated second surface is substantially covered by a layer of
a fluorinated solution, for example, containing an amount of
organo-metalic and/or silane sufficient to form a monomolecular
layer or more of organo-metalic and/or silane.
[0029] The post-treated second surface, or touch surface, can be
reacted with any suitable number of organo-metalic and/or silane
groups per square nanometer to form single or multiple layers. A
continuous monolayer of organo-metalic and/or silane groups can be
formed from about 6 to about 10 groups per square nanometer. For
example, to form a monolayer, the post-treated second surface can
be reacted with a quantity of first organo-metalic and/or silane
groups at from about 1 group to about 2 groups, and then
subsequently reacted with a quantity of second organo-metalic
and/or silane groups at from about 4 groups to about 9 groups. The
post-treated second surface can be exposed to a quantity of
organo-metalic and/or silane groups, which, when disposed as a
monolayer, would cover an area substantially equal to a fraction or
multiple of the area of the second surface or a selected portion
thereof. In some embodiments, the post-treated second surface has
been reacted with sufficient hydrolyzable organo-metalic material,
for example, tetra-hydrolyzable silicon, such as tetraethoxysilane,
or a combination of organo-metalic materials to form at least one
or more monolayer(s) of silicate or silicate composite, and
simultaneously or secondarily exposed to a quantity of second
organo-metalic and/or silane molecules, which, when disposed as a
monolayer, would cover an area substantially equal to the area of
the second surface or a selected portion thereof. The quantity of
first organo-metalic and/or silane molecules and/or quantity of
second organo-metalic and/or silane molecules can comprise
perfluoropolyether organo-metalics and/or silanes. The
perfluoropolyether organo-metalic and/or silanes can have a
molecular weight of between from about 500 and about 10,000. In
some embodiments, the quantity of a first organo-metalic and/or
silane is about 2 molecules per square nanometer, and the quantity
of a second organo-metalic and/or silane is from about 2 to about 7
molecules per square nanometer. The post-treated second surface can
be first reacted with a quantity of organo-metalic and/or silane
groups of a polyorgano-metalic and/or silane having organo-metalic
and/or silane functional adhesive groups substantially equalling
the number of hydroxyl groups on the second surface, and then
secondarily exposed to a quantity of second organo-metalic and/or
silane molecules, comprising monofunctional organo-metalics and/or
silanes, which, when disposed as a monolayer, would cover an area
substantially equal to a remaining area of the second surface. In
other embodiments, the second fluid may comprise adhesive
functional groups that are different from the first adhesive
functional groups, and the molecules comprised in the first or
previous fluid may comprise functional groups which would be
selectively adhesive to molecules comprising the second or previous
fluid. Such a combination of differing functional groups may be
drawn from any of the reactive chemical groups which are well know
in the art, for example, nucleic acid base pairs, enzymes, epoxies,
amines, alcohols, isocyanates, vinyls, or (meth)acrylics, to name a
few. In some embodiments, the second or subsequent molecules may be
crosslinked by additional functional adhesive groups or adhesive
pairs of groups drawn from a similar list.
[0030] The post-treated second surface can be a hydrophobic and/or
oleophobic surface useful as a touch surface for a touch-controlled
electronic device. In some embodiments, the touch-controlled
electronic device further comprises a mechanism for polarizing or
directing light to produce 3D images. In various embodiments, the
coated surface may be part of an article or an appliance, such as a
display device.
[0031] According to various embodiments of the present teachings,
an assembly for quantitatively treating a surface is provided. The
assembly can comprise a first surface having a first area. The
assembly can comprise a second surface having a second area, facing
and spaced substantially uniformly apart from the first surface, by
a distance. The first surface, the second surface, or both surfaces
may be adhesive to an adhesion functional group. The first and
second surfaces may be positioned together such that a capillary
volume can be defined by and between the first surface and the
second surface. The assembly can comprise a first fluid within the
capillary volume, for example, to fill the capillary volume. The
fluid may be dispensed onto the first or second substrate prior to
positioning the surfaces to form the capillary, or the fluid may be
loaded into the volume after the surfaces are positioned to form
the capillary. The fluid can comprise a chemical composition or
molecule having a number of adhesion functional groups. The
adhesion groups, when disposed as a monolayer, can be of sufficient
area to cover a third area that is substantially equal to a first
fraction of the first area. The adhesive functional groups may be
activated by the presence or absence of a substance, a polarizing
electric field, electromagnetic excitation, heat, or combinations
thereof.
[0032] The adhesive properties of the first adhesive surface and
the second surface can vary or be the same. In some embodiments,
the second surface is not adhesive to the adhesion functional
group. In some embodiments, the second surface is not adhesive to
the adhesion functional group and further comprises means or
devices for introducing the fluids. In some embodiments, the second
surface is not adhesive to the adhesion functional group and
comprises a flexible film or sheet. In some embodiments, where the
second surface is not adhesive to the adhesion functional group,
the second surface may be porous to atoms or molecules, allowing
transport into and out of the capillary volume, for example, to
molecules of water or a catalyst. In some embodiments, the second
surface is adhesive to the adhesive functional group, the first and
second areas are essentially equal, and the third area is equal to
a first fraction of the combined first and second areas. The first
fraction can be any suitable fraction of the first area, for
example, the first fraction can be from about 1/8 to about 10/8, or
from about 1/5 and about 12/10 of the first area. In some
embodiments, the first fraction is less than or equal to about 1.
In some embodiments the first fraction can be a multiple of about
1. In some embodiments, the first fraction can be substantially
greater than one. The assembly can comprise a device for
introducing and/or withdrawing the first fluid and/or any
additional fluid. The capillary can comprise one or more spacers.
The spacers may be free in the fluid, introduced between the
surfaces, or attached to one or both of the first and second
surfaces. The spacers may be solid, liquid or gas, or a combination
thereof. The first and second surfaces may be spaced substantially
uniformly apart because of a balance between capillary forces and
the fluid viscosity or a balance between gravity and
electromagnetic forces. The first and/or second adhesive surface
can comprise glass, and the adhesion functional group can be any
chemically reactive group well know in the art, for example an
organo-metalic group, such as a silane group, or a combinations
thereof. The chemical composition or molecule can comprise a
perfluoropolyether. The distance between the first adhesive surface
and the second surface can be any appropriate distance. For
example, the distance can be less than about 5 mm, less than about
1 mm, less than about 100 .mu.m, less than about 25 .mu.m, from
about 1 mm to about 10 nm, from about 100 .mu.m to about 25 nm, or
from about 30 nm to about 100 nm.
[0033] According to various embodiments of the present teachings, a
method of coating substrate surfaces is provided. A fluid
comprising molecules comprising adhesion functional groups is
applied to a first substrate surface having a first area. A second
substrate surface having a second area is placed on the first
substrate surface. A substantially uniform layer of the fluid is
formed between the first and second substrate surfaces. The first
substrate surface and/or the second substrate surface may be
adhesive to the adhesive functional groups. The molecules are
adhered or caused to adhere to the adhesive substrate surface. The
molecules comprising adhesive functional groups in the fluid can
have a concentration such that when the functional groups are
disposed in a monolayer they have a third area substantially equal
to a fraction of the first and/or second areas. The first and
second substrate surfaces can then be separated after a time,
whereafter a stage of an adhesion has occurred. In some
embodiments, at least a second fluid having a concentration of
molecules having adhesive functional groups capable of adhering to
the remaining adhesive substrate surface(s) and/or to adhesive
groups comprised in the first fluid is applied. In some
embodiments, the adhesive functional groups of the second fluid can
be the same as those of the first or a previous fluid. At least one
spacer can be positioned or located between the first and second
adhesive substrate surfaces. In some embodiments, the at least one
spacer is attached to one or both adhesive substrate surfaces, or
is present in the fluids. The method can comprise collecting one or
more of the fluids for reuse. In some embodiments, at least one of
the adhesive substrate surfaces is a touch screen surface, an
appliance, or a display device.
[0034] According to various embodiments of the present teachings, a
method of manufacturing a treated substrate is provided. A
substrate can be provided having a first surface comprising exposed
hydroxyl groups and a second surface comprising exposed hydroxyl
groups. The first surface can be treated to increase the population
density of exposed hydroxyl groups and form a treated surface
without treating the second surface to increase the population
density of exposed hydroxyl groups. The method can provide a higher
population density of exposed hydroxyl groups on the first surface
than on the second surface, wherein the treated substrate retains
its compressive resistance to breakage by impact applied to the
first surface while minimizing any decrease in tensile strength of
the second surface. In some embodiments, the substrate used in the
method comprises a glass material. A glass material can be hardened
prior to the treating. In some embodiments, the glass material is
embedded with one or more kinds of large atoms or ions, such as
potassium ions, to place the substrate surfaces under compression,
increasing resistance to breakage. In some embodiments, the glass
surface is hardened by cooling the surfaces rapidly from a
temperature above the Tg for the glass. The treating can comprise
buffing or treating with at least one of ammonia, hydrogen
peroxide, an acid, a base, bleach, fluorine, hydrofluoric acid,
halogen compounds, an oxidizing agent, a reducing agent, a plasma,
steam, or a combination thereof, or any of the solutions described
herein or known to in the art for such purpose.
[0035] The method of manufacturing a treated substrate can further
comprise applying one or more coating to the treated surface. A
coating composition can be applied to the treated surface, and the
coating composition can comprise a first organo-metalic and/or
silane, for example an alkoxy or chloro organo-metalic and/or
silane compound. In some embodiments, the first organo-metalic
and/or silane compound comprises a first perfluoropolyether alkoxy
or chloro organo-metalic and/or silane compound. The first
perfluoropolyether organo-metalic and/or silane compound can have a
molecular weight of from about 500 to about 10,000 atomic units,
from about 500 to about 4,000 atomic units, from about 1000 to
about 2500 atomic units, or more than about 10,000 atomic units. In
some embodiments, the first organo-metalic and/or silane is a
fluoroalkyl organo-metalic and/or silane. In some embodiments, a
tetra-hydrolyzable organo-metalic compound, for example,
tetraethoxysilane, is applied to the treated surface. In some
embodiments, the tetra-hydrolyzable organo-metalic and/or silane
compound is applied to the treated surface at the same time the
perfluoropolyether organo-metalic and/or silane compound is applied
to the treated surface, and they may be combined together prior to
application to the treated surface. In some embodiments, the
tetra-hydrolyzable organo-metalic is applied to the treated surface
prior to applying the perfluoropolyether organo-metalic and/or
silane compound to the treated surface. In some embodiments the at
least first organo-metalic and/or silane may be a
chloro-organo-metalic or a chlorosilane, for example, titanium
tetrachloride or silicon tetrachloride. In some embodiments,
organo-metalic compounds that are mono-hydrolyzable,
di-hydrolyzable, or tri-hydrolyzable, that is, having one, two or
three hydrolyzable linkages per atom, may be used as all or part of
the first or second coating treatments. In some embodiments the at
least first organo-metalic and/or silane may be a monofunctional
organo-metalic and/or silane, that is an organo-metalic and/or
silane having, for example, one triethoxy organo-metalic and/or
silane group. In some embodiments the at least first organo-metalic
and/or silane may be a di-functional organo-metalic and/or silane,
that is an organo-metalic and/or silane molecule having, for
example, two triethoxy organo-metalic and/or silane groups or,
other embodiments, two trichloro organo-metalic and/or silane
groups. The coating composition may further comprise organo-metalic
compounds. In some embodiments, a tetra-hydrolyzable or tetrachloro
organo-metalic and/or silane may be combined with one or more other
silanes, organo-metalic compounds, organic compounds, elements,
polyvalent elements, and compounds of elements. In some preferred
embodiments, a hydrolyzable organo-metalic and/or silane, such as
tetraethoxysilane, and any other selected ingredients, additives or
co-agents may be prepared as a sol-gel before application to a
surface. In some preferred embodiments, the sol-gel may include a
fluorinated organo-metalic and/or silane, for example a
perfluoropolyether organo-metalic and/or silane. In some
embodiments, the coatings and application methods of the present
teachings may be applied to surfaces which have not been treated to
increase the hydroxyl population density.
[0036] The method of manufacturing the treated and/or coated
substrate can further comprise installing the treated and/or coated
substrate in an appliance, a touch screen, a 3D device, an
electrowetting display device, a combination thereof, and the like.
A treated and/or coated substrate manufactured according to the
present methods is also provided. The treated and/or coated first
surface of the substrate can be a hydrophobic and/or oleophobic
surface, for example, useful as a touch surface for a
touch-controlled electronic device.
[0037] According to various embodiments of the present teachings, a
method of treating a substrate comprising a surface having exposed
hydroxyl groups is provided. The method can comprise contacting a
surface with a composition comprising components A and B combined
together, a composition comprising A followed by a composition
comprising B, or a composition comprising B followed by a
composition comprising A, wherein component A is at least one
fluorochemical polyether alkoxy or chloro organo-metalic and/or
silane compound of formula (1)
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms z is
2, 3, or 4, and each x is independently 0 or 1. Component B can
comprise a tetraalkoxysilane in an amount of 8% by weight or less
based on the total weight of components A and B, when combined
together. In other embodiments, Component B can be a metal or
element comprising 3 or more hydrolyzable groups, for example,
tetramethoxysilane, and may further comprise any suitable
additives, such as additives comprising a reactive functionality.
The method can further comprise forming a coating from the
composition on the surface by causing components A and B to undergo
a substantially complete condensation reaction.
[0038] The method of treating a substrate can be performed by
varying or keeping constant the timing of the mixing of components
A and B or the individual preparation of components A and B as
separate components. In some embodiments, components A and B are
first mixed together before they contact the surface. In some
embodiments, components A and B are mixed together and diluted in a
solvent comprising a fluorosolvent to form a coating solution
having a concentration of about 0.001% to about 2%, or from about
0.02% to about 0.2% by weight or less of components A and B
combined, and the method comprises contacting the surface with the
coating solution. In some embodiments, components A and B are mixed
together and diluted in a solvent comprising a fluorosolvent to
form a coating solution having a concentration of about 0.02% to
about 0.05% by weight or less of components A and B combined. The
fluorosolvent can comprise a fluorochlorosolvent. In some
embodiments, the surface is first contacted with component B and
then with component A, either or both of which may be diluted with
a solvent. In some embodiments, the surface is first contacted with
component A and then with component B, either or both of which may
be diluted with a solvent. In some embodiments, the surface is
first contacted with a diluted solution of component B in a solvent
comprising a fluorosolvent and then subsequently contacted with a
diluted solution of component A in a solvent comprising a
fluorosolvent. In some embodiments, the surface is first contacted
with a diluted solution of component A in a solvent comprising a
fluorosolvent and then subsequently contacted with a diluted
solution of component B in a solvent comprising a fluorosolvent.
The solvent may further comprise water, organic solvents,
anhydrides, initiators, catalysts, and acid or base catalysts. In
some embodiments, the solvent may further comprise an fluorinated
anhydride. In some embodiments, the molar amount of water may equal
or exceed the molar amount of hydrolyzable groups comprised in the
organo-metalic and/or silane molecule. In some embodiments, the
solvent pH may be adjusted to a pH which promotes dense
organo-metalic and/or silane condensation having a preferred
thickness, for example, in a pH range of between about 9 and about
12 and a thickness of between about 100 nm and about 1 nm. The
method of treating a substrate can be performed wherein the surface
comprises exposed hydroxyl groups and the method further comprises
treating the surface to increase the number of exposed hydroxyl
groups before the surface is contacted with the composition.
Component A can comprise a perfluoropolyether organo-metalic and/or
silane having any suitable weight average molecular weight, for
example from about 250 to about 10,000, from about 500 to about
5000, or from about 1,000 to about 2,500 Daltons. In some
embodiments, the perfluoropolyether may be coupled to one or more
chloro organo-metalic and/or silanes and/or alkoxy organo-metalic
and/or silanes. The perfluoropolyether may be a pendant
organo-metalic and/or silane. In some embodiments the
perfluoropolyether organo-metalic and/or silane may be the silyl
ether, for example, the derivative of a PFPE-Z and/or a PFPE-M
perfluoropolyether. In some embodiments, the surface treated in the
method comprises a touch screen surface, a 3D device, an
electrowetting display device, a combination thereof, and the
like.
[0039] According to various embodiments of the present teachings, a
composition comprising the reaction product obtained after a
substantially complete condensation reaction of components A and B
is provided. Component A can comprise at least one fluorochemical
polyether chloro organo-metalic and/or silane or alkoxy
organo-metalic and/or silane compound of formula (1):
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. Component B can
comprise a tetraalkoxysilane in an amount of 8% by weight or less
based on the total weight of components A and B, when combined
together. In other embodiments, Component B can be a metal or
element comprising 3 or more hydrolyzable groups, for example, a
tetraaryloxysilane, and may further comprise any suitable
additives, such as additives comprising more than one chemical or
reactive functionality. In some embodiments, component B is present
in an amount of from about 1% by weight to about 7% by weight based
on the total weight of components A and B combined. Component A can
comprise a perfluoropolyether organo-metalic and/or silane, for
example an alkoxy organo-metalic and/or silane or chloro
organo-metalic and/or silane, having any suitable number average
molecular weight, for example from about 250 to about 10,000, from
about 500 to about 5000, or from about 1,000 to about 2500 Daltons.
In some embodiments, the composition is coated on a surface of a
substrate as a coating, wherein the coating has a thickness of from
about 2.0 to about 4.0 nanometers, or less than 4.0 nanometers. In
some embodiments, the composition is coated on a surface of a
substrate as a coating, wherein the coating comprises two layers,
and the layer comprising component B has a thickness of from about
1 nanometer to about 100 nanometers. The coating can comprise a
mono-molecular layer of the reaction product, the monomolecular
layer continuous with the underlying substrate so as to constitute
a monolithic surface comprising exposed fluorine compounds. In some
embodiments, the composition is in the form of a coating on a touch
screen surface, a 3D device, an electrowetting display device, a
combination thereof, and the like. In some embodiments, the coating
is substantially in the form of a monolayer.
[0040] According to various embodiments of the present teachings, a
kit equipped for substrate coating is provided comprising a first
container and a second container packaged in a third container. The
first container comprises at least one fluorochemical polyether
organo-metalic and/or silane compound of formula (1):
R.sub.f-[Q-CR.sub.2Si(Y).sub.3-x(R.sup.1).sub.x].sub.z (1)
wherein R.sub.f represents a polyfluoropolyether segment, Q
represents an organic divalent linking group, R.sup.1 represents a
C.sub.1-C.sub.8 alkyl group, Y represents a hydrolysable group
independently selected from a chloro group, an alkoxy group, an
acyloxy group, and an aryloxy group, each R independently
represents hydrogen or an alkyl group of 1 to 4 carbon atoms, z is
2, 3, or 4, and each x is independently 0 or 1. A second container
comprises a tetraalkoxysilane, in an amount of 8% by weight or less
based on the total weight of the combined contents of the first
container and second container and/or a metal or element comprising
3 or more hydrolyzable groups and may further comprise any suitable
additives. The contents of the first container can comprise a
perfluoropolyether organo-metalic and/or silane, for example an
alkoxy organo-metalic and/or silane or a chloro organo-metalic
and/or silane, having any suitable number average molecular weight,
for example from about 250 to about 10,000, from about 500 to about
5000, or from about 1,000 to about 2500 Daltons. In some
embodiments, the contents of the second container are present in an
amount of from about 0.05% by weight to about 7% by weight based on
the total weight of the contents of the first and second
containers.
[0041] The compositions, coatings, polymers, chemicals, solvents,
substrates, surfaces, assemblies, kits, and methods as described,
for example, in the following publications can be used in
conjunction with various embodiments of the present teachings: U.S.
Pat. No. 4,861,667; U.S. Pat. No. 6,270,903 B1; U.S. Pat. No.
6,447,919 B1; U.S. Pat. No. 6,495,624 B1; U.S. Pat. No. 6,767,587
B1; U.S. Pat. No. 7,268,179 B2; U.S. Pat. No. 7,579,056 B2; U.S.
Pat. No. 7,781,027 B2; U.S. Pat. No. 7,803,894 B2; U.S. Pat. No.
7,824,043 B2; U.S. Pat. No. 7,871,675 B2; U.S. Pat. No. 7,999,013
B2; U.S. Patent Application Publication Nos. US 2001/0019773 A1; US
2003/0124361 A1; US 2003/0138643 A1; US 2003/0139620 A1; US
2004/0091720 A1; US 2004/0092675 A1; US 2006/0010537 A1; US
2008/0220264 A1; US 2009/0197048 A1; US 2009/0326146 A1; US
2010/0015344 A1; US 2010/0053547 A1; US 2010/0210769 A1; US
2010/0239823 A1; US 2010/0285275 A1; US 2010/0304086 A1; US
2010/0324205 A1; and US 2011/0003098 A1, which are incorporated
herein in their entireties by reference.
[0042] With reference now to the drawings, FIG. 1 is a schematic
representation of substrate surfaces comprising free hydroxyl
groups 50 in accordance with various embodiments of the present
teachings. Hydroxyl (OH) groups are randomly located on quartz and
glass, typically about 5 groups and 2 groups per square nanometer,
respectively. The outer circle of each free hydroxyl group 50
corresponds to the attachment zone for a single OH group with the
understanding that the hydroxyl groups are not mobile.
Tetra-hydrolyzable organo-metalic and/or silane and
PFPE-tri-hydrolyzable organo-metalic and/or silane groups can be
bonded onto the surface. As can be seen, the quartz surface
provides a much greater population density of hydroxyl groups than
does the glass surface, for example, 5 hydroxyl groups per square
nanometer. The probability of PFPE diorgano-metalic and/or disilane
molecules, that is, having two organo-metalic or silane groups,
being bonded at both ends is unlikely above stoichiometric levels
pairing surface hydroxyl groups with silane or organo-metalic
groups. A condensed layer of tetra-hydrolyzable silane can convert
the glass surface to a quartz-like surface, providing up to about 5
hydroxyl groups per square nanometer. The addition of other
organo-metalic compounds to the surface can provide hydroxyl groups
or other desirable properties.
[0043] FIG. 2 is a perspective view of an assembly 120 for
manufacturing treated and coated substrate surfaces in accordance
with various embodiments of the present teachings. Assembly 120 can
be constructed from a first substrate 122 and a second substrate
124. First substrate 122 can have a first inwardly facing surface
126. Second substrate 124 can have a second inwardly facing surface
128. First and second substrates 122, 124 can be separated from
each other by a first spacer 130 and a second spacer 132. The
region between the first and second inwardly facing surfaces 126,
128 can constitute a capillary volume 134 capable of holding one or
more fluids. The fluid to be loaded into capillary volume 134 can
comprise adhesive molecules capable of adhering to at least one of
the first and second inwardly facing surfaces 126, 128.
[0044] FIG. 3 is a flow chart for a method 220 of coating substrate
surfaces in accordance with various embodiments of the present
teachings. In a step 230, a fluid can be applied to a first
adhesive surface. The fluid can contain one or more kinds of
molecules having adhesion groups. In step 240, a second adhesive
substrate can be placed on the covered first adhesive surface. In a
step 250, a substantially uniform layer of a fluid between the
first and second substrate surfaces can be formed. The molecules
can adhere to the first and second adhesive surfaces in step 260.
In step 270, the first and second adhesive surfaces can be
separated.
[0045] FIG. 4 is a flow chart for a method 320 of manufacturing a
treated substrate in accordance with various embodiments of the
present teachings. In a step 330, a substrate is provided having a
first surface comprising exposed hydroxyl groups, and a second
surface comprising hydroxyl groups. The first surface can be
treated in a step 340 to increase the population density of exposed
hydroxyl groups and form a treated surface, without treating the
second surface.
[0046] FIG. 5 is a flow chart for a method 420 of treating a
substrate in accordance with various embodiments of the present
teachings. In a step 430, a surface is contacted with a composition
comprising component A and component B, wherein component A and
component B are as described herein. A coating is formed on the
surface from the composition in a step 440 by causing components A
and B to undergo a substantially complete condensation
reaction.
[0047] FIG. 6 is a cross-sectional, partial cutaway view of a kit
520 in accordance with various embodiments of the present
teachings. Kit 520 can comprise a first container 522 containing
first contents 524. First contents 524 can comprise component A as
described herein. Kit 520 also comprises a second container 526
containing second contents 528. Second contents 528 can comprise
component B as described above. First container 522 and second
container 526 can each independently be a vial, a tube, a jar, an
ampule, a box, a dish, or the like. First container 522 and second
container 526 can be packaged together in a third container 530,
for example, a box. The kit can further comprise instructions for
use of first contents 524 and second contents 528 to coat a
surface.
[0048] According to various embodiments of the present teachings,
less, rather than more, of a coating is used to coat a substrate
and form in a two-dimensional network. According to various
embodiments of the present teachings, an exact amount of a coating
component is used to coat an area of a substrate and form in a
two-dimensional network. According to various embodiments of the
present teachings, exact amounts of coating components are used to
coat an area of a substrate and form in a layered three-dimensional
network. Substrates that can be used include glass that has been
immersed in a bath of molten minerals, for example salts, to
exchange sodium ions for potassium ions, putting the surface under
compression. In some embodiments, substrates that can be used
include glass that has been heated above its Tg and then the
surface cooled quickly, putting the surface under compression. In
some embodiments, substrates that can be used include glass that
has been strengthened or hardened by other means well known in the
art. The subsequent coating treatment can be applied to one side of
the resulting glass substrate but not the other. For an optimal
polyorgano-metalic and/or silane coating treatment, the number of
exposed hydroxyl groups can be substantially the same as the number
of reactive groups intended to react with the surface. For an
optimal mono-organo-metalic and/or silane coating treatment, the
number of exposed hydroxyl groups can be less than the number of
reactive groups intended to react with the surface, for example,
about 4 to 5 times less, in other words, the number of reactive
groups can be 4-5 times greater than the number of hydroxyl groups
in order to form a continuous monolayer. Increasing the exposed
hydroxyl group population density increases the adhesion of a
network of organo-metalic and/or silanes. Increasing the exposed
hydroxyl group population density can be particularly useful when a
surface has been hardened, for example, heated above 500.degree.
C., which can reduce the density of available hydroxyl groups for
long periods of time. Glass, generally, has a density of about 2.2
hydroxyl groups per square nanometer, high temperature treated
glass often has a density of about 1.7 hydroxyl groups per square
nanometer, and quartz generally has a density of about 5 hydroxyl
groups per square nanometer.
[0049] In some embodiments, the substrate is a touch screen and the
surface enhanced in exposed hydroxyl group population density is
the side (surface) that will be coated and subsequently "touched"
by a user. In various embodiments, the substrate is an appliance or
display device, for example a 3D and/or electrowetting display
device. The chemical coating can be applied to the touch surface
using any means, for example, spraying, spinning, dipping,
brushing, fogging, vacuum deposition, or the like. Tin oxide and
circuitry, if present on the back surface, can remain unaffected
during that process. Other circuitry such as piezoelectric sensors
can also remain unaffected by the coating process on the touch
surface. Glass is strong under compression and weak under tension,
and when impacted, the touch surface is generally under compression
while the back surface may become under tension. Hardened or
strengthened glass surfaces are pre-compressed, such that impacts
are less likely to put the back surface under tension, therefore it
is beneficial to preserve compressive treatments to the back side
of a touch surface. The population density of hydroxyl groups can
generally be increased, for example, to about 2.0 per square
nanometer, to about 2.5 per square nanometer, or greater. The
process of increasing hydroxyl group concentration on the touch
surface can start with unhardened glass or a glass substrate that
is hardened on one or both sides. The process of increasing
hydroxyl group concentration on a touch surface may remove
compressive elements or compressed layers at the surface without
disturbing compressive elements or compressed layers at the back
surface. The treated side can become more quartz-like than
glass-like, if the treated side is subsequently coated with
silicate. In some embodiments, the composition used for treatment
comprises 10% to 20% by weight ammonium hydroxide, 60% to 80% by
weight water, and 10% to 20% by weight hydrogen peroxide, based on
the total weight of the composition. In some embodiments, the
composition used for treatment comprises 10% to 20% by weight
sulfuric acid, 60% to 80% by weight water, and 10% to 20% by weight
hydrogen peroxide, based on the total weight of the composition.
The resulting hydroxyl group content of the treated surface can be
determined using the techniques of X. M. Liu, J. L. Thomason, about
F. R. Jones from the University of Sheffield and the University of
Strathclyde. Any type of glass can be used, for example,
GORILLA.RTM. Glass available from Corning, Inc. of Corning, N.Y.
B270 glass available from Schott North America, Inc. of Elmsford,
N.Y., can be used.
[0050] Difunctional organo-metalic and/or silanes, as well as other
polyorgano-metalic and/or silanes, can be used in the
surface-coating protocol and can be disposed on the surface at a
level not to exceed the amount required to form a two dimensional
networked monolayer of organo-metalic and/or silane groups on the
surface. In some embodiments, it is preferred that the level of
organo-metalic and/or silane groups disposed on the surface not
exceed the amount required to bond with every hydroxyl group
present on the surface, and thus not forming a networked monolayer.
If used as a 0.02 to about 0.06% by weight of an about 4000
molecular weight difunctional organo-metalic and/or silane by total
weight of a composition, a substrate can be dipped in the
composition for about 30 seconds to about 5 minutes. In some
embodiments, a disilane and/or diorgano-metalic can be used in the
form of a 1/10% to 4.0% by weight solution for spray and spin
application of FLUOROSYL FSD4500, a perfluoropolyether with two
ethoxysilane terminal groups, available from Cytonix LLC of
Beltsville, Md. In some embodiments, an approximately 2000
molecular weight disilane may be used with adjustments in laydown
according to the molecular weight, for example, Solvay
FLUOROLINK.RTM. S10, a perfluoropolyether with two ethoxysilane
terminal groups, available from Solvay Solexis, Inc. of West
Deptford, N.J. The quantity of organo-metalic and/or silane to form
a monolayer is approximately proportional to its molecular weights.
Using a significant excess of organo-metalic and/or silanes can
compromise abrasion resistance, oleophobicity, and hydrophobicity,
as exposed organo-metalic and/or silane or hydrolyzed groups may be
present at the exposed surface. Exposed hydroxyl groups at the
surface contribute to wettability and friction. Instead, a
relatively stoichiometric amount of organo-metalic and/or silane
relative to the amount of hydroxyl groups and free surface area, is
used. A PFPE disilane, a trisilane, a tetrasilane, and silane
molecules with higher numbers of silane or organo-metalic groups
can be used, as can PFPE molecules with still larger numbers of
silane or organo-metalic groups. A polysilane or a different
polyorgano-metalic molecule may have silane or organo-metalic
groups located at one end of the molecule, at both ends of the
molecule, or distributed in any way. In some embodiments, dipodal
organo-metalic and/or silanes are preferred. Polysilanes and other
polyorgano-metalics may have pendant groups that are organic,
fluorinated, inorganic, functional, or combinations thereof. Upon
application to the treated surface, the hydrolysable group, for
example an alkoxy or a halogen group, can hydrolyze releasing an
alcohol or halogen acid, which may come off in the air. SiOH then
condenses and SiOSi is formed on the surface. In some cases the
disilanes, FLUOROSYL FSD1500, FLUOROSYL FSD2500 or FLUOROSYL
FSD4500, available from Cytonix LLC of Beltsville, Md., can be
used. In some embodiments a tetrasilane may be used, such as
FSQ3000 from Cytonix LLC of Beltsville, Md. For optimum hydrophobic
and wear resistance, organo-metalics and/or silanes having a
functionality of greater than one require that a relatively
stoichiometric amount of organo-metalic and/or silane relative to
the amount of hydroxyl groups and/or free surface area be used.
[0051] For a spray application of the polyorgano-metalic and/or
silane compositions, there are at least three factors that can be
considered. These three factors are rate of delivery, belt
speed/pan rate, and concentration. In some embodiments of the
present teachings, solvents with boiling points greater than
90.degree. C. to greater than 150.degree. C. may be used, and
fluorinated oils may be used which are not volatile. The coated
surface can be tested for water contact angle, water contact angle,
roll-off (slip) angle, and abrasion resistance. Various surface
analysis techniques can be used, for example, those described by
Liu et al., slip angle testing, x-ray techniques, and laser
techniques involving burning off a layer and testing by
chromatography. An abrasion test can use materials such as but not
limited to cotton, rubber, leather, sand paper, abrasives or steel
wool rubbed repeatedly at a pressure of about 1 pound per square
inch or higher against the treated surface. A contact angle of
about 110.degree. or greater for water is desirable. After, for
example the steel wool application, the water contact angle should
remain at least about 100.degree.. According to various embodiments
of the present teachings, touch screens are provided that exhibit a
water contact angle of at or above 100.degree. after 6000 rubs with
0000 steel wool at 1 pound per square inch pressure and 3000 rubs
at 2.5 grams per square millimeter. In other tests measuring the
retention of stains from liquids commonly found in homes and
offices, it is desirable to have no visible retention.
[0052] Depending on the type of organo-metalics and/or silanes
used, a cross-linker or bridging agent can be used to bring
together isolated organo-metalic and/or silane molecules into
two-dimension networks of interconnected organo-metalic and/or
silanes bonded to the surface of the treated substrate by all
available hydroxyl groups exposed on the substrate surface.
Examples of cross-linkers and bridging agents include metals and
metal oxides, organo-metalic compounds, tetraalkoxysilanes, dipodal
organo-metalic and/or silanes, disilanes, tetrasilanes, or
combinations thereof. In some embodiments of the present teachings,
organo-metalic compounds may be used individually or in
combination, which include those comprising vanadium, aluminum,
titanium, zirconium, tin, and others well known in the art. In some
embodiments, about 1% by weight to about 8% by weight
tetraalkoxysilane may be used, based on the 4500 molecular weight
of FLUOROSYL FSD 4500 molecules, a perfluoropolyether disilane
available from Cytonix LLC of Beltsville, Md. It is preferred that
there be a molar equivalent of water present equal to or greater
than the molar weight of silol on the disilane and/or other silanes
and other organo-metalic compounds which might be present. The
concentration of organo-metalic and/or silane for applying in a
formulation comprising a fluorosolvent or fluorochlorosolvent can
be from about 0.001% to about 4% depending on the application
process and conditions. Alcohol can be added with water, acids,
tetraalkoxysilanes, alkoxyorgano-metalics, or other organic
components to promote solubility in the fluorinated solvent. An
acid or base may be used to catalyze the hydrolyzation step and
promote silol formation. Anhydrides and other catalysts are known
to promote silol formation. Examples of solvents that can be used
include dichloropentafluoropropane (FREON 225), available from E.I.
duPont deNemours (DuPont) of Wilmington, Del., ASAHIKLIN AK-225,
available from Asahi Glass Co., Ltd. of Tokyo, Japan, and
VERTREL.RTM. MCA, available from DuPont. In some embodiments, a
solvent blend is used that includes a fluorinated solvent, 8.0% by
weight alcohol and 0.5% by weight acid based on the total weight of
the solvent blend. Examples of acids include 3.0% HCl by weight of
the total weight of an acid solution, citric acid, and vinegar
(acetic acid).
[0053] According to various embodiments of the present teachings,
the silyl ethers of pendant perfluoropolyethers are particularly
preferred. The coating composition can comprise a first reaction
product of a vinyl ether functionalized pendent, as opposed to a
linear, perfluoropolyether (PFPE), and a second reactant comprising
a trichloro-silane, for example, a pendant perfluoropolyether
trichlorosilane. In some embodiments the coating composition can
comprise a reaction product of the first reaction product, for
example, a second, subsequent reaction product of the first
reaction product and a third reactant comprising at least one of
trimethylortoformamate, triethylorthoformamate,
tripropylorthoformamate, or a triarylorthoformamate.
[0054] Exemplary pendent PFPEs, second reactants, first reaction
products, third reactants, fourth reactants, and second reaction
products that can be used and formed include those shown in the
reaction scheme below:
##STR00001##
wherein n is from about 3 to about 30 or larger. In some
embodiments, n in any of the formulae above can instead be from
about 3 to about 25, from about 4 to about 20, from about 5 to
about 20, or from about 10 to about 20. Methylorthoformamate, shown
in the above example, can be substituted by any alkylorthoformamate
or arylorthoformamate. Perfluoropolyether polysilanes, for example
perfluoropolyether disilanes, can be formed according to the
reaction scheme illustrated above, and other reaction schemes are
known in the art for forming the first, second and polysilane
reaction products. Methods that include carrying out the reactions
according to one or more of these schemes are included in the
present teachings. The present teachings also relate to methods
that include coating substrates and forming such coating
compositions on substrates. Exemplary pendant perfluoropolyethers
that can be used in the first reaction scheme include KRYTOX, a
PFPE-K available from DuPont de Nemours, of Wilmington, Del., and
Fomblin-Y, a PFPE-Y available from Solvay Solexis, Inc., West
Deptford, N.J. In some embodiments, the second of these two
reaction schemes is used but wherein the methoxy group (OCH.sub.3)
shown in the second reactant can instead be an alkoxy group, an
aryloxy group, for example ethoxy or phenoxy, or a combination
thereof. Exemplary precursors for forming di-functional
perfluoropolyethers that can be used in the first reaction scheme
to produce disilanes are FluoroLink D10, Fluorolink D10H,
Fluorolink D, and FluoroLink D4000, and an exemplary precursor for
forming a tetra-function perfluoropolyether that can be used in the
first reaction scheme to produce a tetrasilane available from
Solvay Solexis, Inc., West Deptford, N.J. Compositions of the
present teachings can comprise a wide range of additives and
co-agents, including but not limited to, nano-sized and micro-sized
objects of all shapes and properties, such as particles, fibers,
nano-tubes and other natural, manufactured and engineered
components, said objects can have dimensions which are smaller than
the wavelengths of visible, ultraviolet and infrared light or
selected ranges therein. In some embodiments, one or more of said
objects may comprise a volume which is greater or less than the
total volume of the composition, substantially greater than the
total volume, and may be present at or on the surface of coatings
comprising the composition. In some embodiments, the composition
may comprise non-volatile fluids, for example, fluorinated fluids,
which can be present in the composition, dispersed in the
composition, at the surface of the composition, or combinations
thereof. In some embodiments, the composition can comprise
solvents, such a fluorinated and/or halogenated solvents,
initiators, catalysts, resins, reactants having more than one
reactive functionality, monomers, polymers, organic and inorganic
substances. In some embodiments, the composition itself can be
formed into articles, films, powders, and objects as described
herein. In some embodiments, the surface of the composition can be
formed to have a continuous or discontinuous, repeating or random
topography, shape, relief, impression, texture, a roughness,
pattern, design, feature, a height to width aspect ratio of a
feature, a volume of a feature, or combinations thereof. In some
embodiments, surfaces formed by or of the composition can be
superhydrophobic, with contact angles to water that are greater
than about 120 degrees to greater than about 170 degrees. In some
embodiments, surfaces formed by or of the composition can be
exceptionally resistant to adhesion by stains, marks, snow, ice,
organic oils, common household and industrial substances, and
pollutants. In some embodiments, surfaces formed by or of the
composition can be exceptionally slippery, lubricious, and have an
exceptionally low coefficient of friction. Touch screens can be
coated with such coating compositions, and other articles,
including those having various and substantially different
properties and uses, can also benefit from such coatings, for
example, smooth, rough, patterned, lithographed, micro and/or nano
featured, superhydrophobic, textured, designed, printed, imprinted,
porous, tubular, sintered, striated, reliefed, impressioned,
hollowed, foamed edged, powdered, powder-coated, etched,
selectively-located, embossed, woven, non-woven, molded or formed
surfaces, lotus-effect surfaces, electrowetting surfaces,
laboratory vessels, fluidic devices, medical devices, powders,
fibers, optical fibers, optical or electrical components, 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, electrowetting displays, 3D
displays, and video displays.
[0055] In some embodiments, the composition comprises the reaction
product obtained after a substantially complete condensation
reaction of components A and B, wherein: component A comprises at
least one of a pendent perfluoropolyether trichloro-silane shown in
the first reaction, a pendent perfluoropolyether aryloxy-silane
shown in the first reaction scheme below, scheme below, or a
pendent perfluoropolyether alkoxysilane shown in the second
reaction scheme below
##STR00002##
wherein n is from 3 to about 30; and component B comprises a
tetraalkoxysilane in an amount of 8% by weight or less based on the
total weight of components A and B combined together. Component B
can be a tetraalkoxysilane present in an amount of from about 1% by
weight to about 7% by weight, or from about 2% by weight to about
6% by weight based on the total weight of components A and B
combined together. Component B can comprise organo-metalic
compounds, metals, metal compounds, organic compounds, inorganic
compounds, or any combination thereof, and Component B may be
present in an amount greater than about 10% by weight of the total
weight of components A and B. For example, Component B may be
present in the applied coating at from about 1% by weight to about
99% by weight of the total weight of components A and B. In some
embodiments Component A can be applied without Component B, or, in
other embodiments, Component B may be applied a substantial period
of time before the application of Component A. Component A can have
a number average molecular weight of from about 500 to about
10,000, or from about 1,000 to about 5,000, or from about 2,000 to
about 4,500. A coated substrate is also provided wherein the
coating composition is coated on a surface of the substrate and the
coating has a thickness of from about 2 nanometers (nm) to about 4
nm, from about 1 nm to about 5 nm, or of less than 2 nm. The
coating can comprise a mono-molecular layer of the reaction product
and the monomolecular layer can be continuous with the underlying
substrate so as to constitute a monolithic surface comprising
exposed fluorine compounds. In some embodiments, component B forms
a continuous, substantially condensed layer on the underlying
substrate that can be from about 1 monolayer in thickness (<1
nanometer) to about 100 nm or more, and component A forms a
substantially homogeneous, condensed, continuous monolayer on
component B so as to constitute a monolithic surface comprising
exposed fluorine compounds. Component B can further comprise an
organo-metalic component or other suitable component known in the
art, such as an organo-metalic compound. In some embodiments
throughout the present teaching, Component A may be applied by any
means without the presence of a Component B to from a continuous,
substantially condensed layer on the underlying substrate, where a
fraction of the molecules of the composition are bound to the
underlying substrate surface and to adjacent molecules, and the
remaining fraction are bound only to adjacent molecules,
functioning as cross-linking or bridging agents. Compositions of
the present teachings can comprise a wide range of additives and
co-agents, including but not limited to, nano-sized and micro-sized
objects of all shapes and properties, such as particles, fibers,
nano-tubes and other natural, manufactured and engineered
components, said objects can have dimensions which are smaller than
the wavelengths of visible, ultraviolet and infrared light or
selected ranges therein. In some embodiments, one or more of said
objects may comprise a volume which is greater or less than the
total volume of the composition, substantially greater than the
total volume, and may be present at or on the surface of coatings
comprising the composition. In some embodiments, the composition
can comprise non-volatile fluids, for example, fluorinated fluids,
which can be present in the composition, dispersed in the
composition, at the surface of the composition, or combinations
thereof. In some embodiments, the composition can comprise
solvents, such a fluorinated and/or halogenated solvents,
initiators, catalysts, resins, reactants having more than one
reactive functionality, monomers, polymers, organic and inorganic
substances. In some embodiments, the composition itself can be
formed into articles, films, powders, and objects as described
herein. In some embodiments, the surface of the composition can be
formed to have a continuous or discontinuous, repeating or random
topography, shape, relief, impression, texture, a roughness,
pattern, design, feature, a height to width aspect ratio of a
feature, a volume of a feature, or combinations thereof. In some
embodiments, surfaces formed by or of the composition can be
superhydrophobic, with contact angles to water that are greater
than about 120 degrees to greater than about 170 degrees. In some
embodiments, surfaces formed by or of the composition can be
exceptionally resistant to adhesion by stains, marks, snow, ice,
organic oils, common household and industrial substances, and
pollutants. In some embodiments, surfaces formed by or of the
composition can be exceptionally slippery, lubricious, and have an
exceptionally low coefficient of friction. In some cases a touch
screen device is provided comprising a touch screen and a coating
on the touch screen, wherein the coating comprises the composition.
In some cases a 3D imaging device is provided comprising a screen
and a coating on the screen, wherein the coating comprises the
composition. In some cases an electrowetting display device is
provided comprising a screen and a coating on the screen. In some
cases a touch screen, a 3D imaging device, and an electrowetting
display device may be present in a display device. More generally,
any article can be coated with the composition, for example,
smooth, rough, patterned, lithographed, micro and/or nano featured,
superhydrophobic, textured, designed, printed, imprinted, porous,
tubular, sintered, striated, reliefed, impressioned, hollowed,
foamed, edged, powdered, powder-coated, etched,
selectively-located, embossed, woven, non-woven, molded or formed
surfaces, lotus-effect surfaces, electrowetting surfaces,
laboratory vessels, fluidic devices, medical devices, powders,
fibers, optical fibers, optical or electrical components, 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, electrowetting displays, 3D
displays, and video displays. In addition, the present invention
relates to processes of coating small article surfaces, for
example, smart phone touch screens, tablet computer screens, and
the like, with nominal solvent loss.
[0056] In yet other embodiments of the present teachings, a
composition is provided that comprises at least one pendent
perfluoropolyether trichloro-silane of the formula
##STR00003##
wherein n is from 3 to about 30. The pendent perfluoropolyether can
comprise, for example, a PFPE-K or a PFPE-Y. The composition can
further comprise a solvent comprising a fluorinated solvent.
Compositions of the present teachings can comprise a wide range of
additives and co-agents, including but not limited to, nano-sized
and micro-sized objects of all shapes and properties, such as
particles, fibers, nano-tubes and other natural, manufactured and
engineered components, said objects can have dimensions which are
smaller than the wavelengths of visible, ultraviolet and infrared
light or selected ranges therein. In some embodiments, one or more
of said objects may comprise a volume which is greater or less than
the total volume of the composition, substantially greater than the
total volume, and may be present at or on the surface of coatings
comprising the composition. In some embodiments, the composition
can comprise non-volatile fluids, for example, fluorinated fluids,
which can be present in the composition, dispersed in the
composition, at the surface of the composition, or combinations
thereof. In some embodiments, the composition can comprise
solvents, such a fluorinated and/or halogenated solvents,
initiators, catalysts, resins, reactants having more than one
reactive functionality, monomers, polymers, organic and inorganic
substances. In some embodiments, the composition itself can be
formed into articles, films, powders, and objects as described
herein. In some embodiments, the surface of the composition can be
formed to have a continuous or discontinuous, repeating or random
topography, shape, relief, impression, texture, a roughness,
pattern, design, feature, a height to width aspect ratio of a
feature, a volume of a feature, or combinations thereof. In some
embodiments, surfaces formed by or of the composition can be
superhydrophobic, with contact angles to water that are greater
than about 120 degrees to greater than about 170 degrees. In some
embodiments, surfaces formed by or of the composition can be
exceptionally resistant to adhesion by stains, marks, snow, ice,
organic oils, common household and industrial substances, and
pollutants. In some embodiments, surfaces formed by or of the
composition can be exceptionally slippery, lubricious, and have an
exceptionally low coefficient of friction. In some cases a touch
screen device is provided comprising a touch screen and a coating
on the touch screen, wherein the coating comprises the composition.
In some cases a 3D imaging device is provided comprising a screen
and a coating on the screen, wherein the coating comprises the
composition. In some cases an electrowetting display device is
provided comprising a screen and a coating on the screen. More
generally, any article can be coated with the composition, for
example, smooth, rough, patterned, lithographed, micro and/or nano
featured, superhydrophobic, textured, designed, printed, imprinted,
porous, tubular, sintered, striated, reliefed, impressioned,
hollowed, foamed, edged, powdered, powder-coated, etched,
selectively-located, embossed, woven, non-woven, molded or formed
surfaces, lotus-effect surfaces, electrowetting surfaces,
laboratory vessels, fluidic devices, medical devices, powders,
fibers, optical fibers, optical or electrical components, 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, electrowetting displays, 3D
displays, and video displays.
[0057] In some embodiments a composition is provided that comprises
at least one pendent perfluoropolyether alkoxysilane of the
formula
##STR00004##
wherein n is from 3 to about 30. The pendent perfluoropolyether can
comprise, for example, a PFPE-K or a PFPE-Y. The composition can
further comprise a solvent comprising a fluorinated solvent.
Compositions of the present teachings can comprise a wide range of
additives and co-agents, including but not limited to, nano-sized
and micro-sized objects of all shapes and properties, such as
particles, fibers, nano-tubes and other natural, manufactured and
engineered components, said objects can have dimensions which are
smaller than the wavelengths of visible, ultraviolet and infrared
light or selected ranges therein. In some embodiments, one or more
of said objects may comprise a volume which is greater or less than
the total volume of the composition, substantially greater than the
total volume, and may be present at or on the surface of coatings
comprising the composition. In some embodiments, the composition
can comprise non-volatile fluids, for example, fluorinated fluids,
which can be present in the composition, dispersed in the
composition, at the surface of the composition, or combinations
thereof. In some embodiments, the composition can comprise
solvents, such a fluorinated and/or halogenated solvents,
initiators, catalysts, resins, reactants having more than one
reactive functionality, monomers, polymers, organic and inorganic
substances. In some embodiments, the composition itself can be
formed into articles, films, powders, and objects as described
herein. In some embodiments, the surface of the composition can be
formed to have a continuous or discontinuous, repeating or random
topography, shape, relief, impression, texture, a roughness,
pattern, design, feature, a height to width aspect ratio of a
feature, a volume of a feature, or combinations thereof. In some
embodiments, surfaces formed by or of the composition can be
superhydrophobic, with contact angles to water that are greater
than about 120 degrees to greater than about 170 degrees. In some
embodiments, surfaces formed by or of the composition can be
exceptionally resistant to adhesion by stains, marks, snow, ice,
organic oils, common household and industrial substances, and
pollutants. In some embodiments, surfaces formed by or of the
composition can be exceptionally slippery, lubricious, and have an
exceptionally low coefficient of friction. In some cases a touch
screen device is provided comprising a touch screen and a coating
on the touch screen, wherein the coating comprises the composition.
In some cases a 3D imaging device is provided comprising a screen
and a coating on the screen, wherein the coating comprises the
composition. In some cases an electrowetting display device is
provided comprising a screen and a coating on the screen. More
generally, any article can be coated with the composition, for
example, smooth, rough, patterned, lithographed, micro and/or nano
featured, superhydrophobic, textured, designed, printed, imprinted,
porous, tubular, sintered, striated, reliefed, impressioned,
hollowed, foamed edged, powdered, powder-coated, etched,
selectively-located, embossed, woven, non-woven, molded or formed
surfaces, lotus-effect surfaces, electrowetting surfaces,
laboratory vessels, fluidic devices, medical devices, powders,
fibers, optical fibers, optical or electrical components, 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, electrowetting displays, 3D
displays, and video displays.
[0058] All publications, patents, and patent applications mentioned
in this specification are herein incorporated by reference to the
same extent as if each individual publication, patent, or patent
application was specifically and individually indicated to be
incorporated by reference.
[0059] While embodiments of the present disclosure have been shown
and described herein, it will be obvious to those skilled in the
art that such embodiments are provided by way of example only.
Numerous variations, changes, and substitutions will now occur to
those skilled in the art without departing from the disclosure. It
should be understood that various alternatives to the embodiments
of the disclosure described herein may be employed in practicing
the disclosure. The alternative embodiments disclosed in various
paragraphs and sections of the disclosure should be construed to
apply, where appropriate, in all paragraphs and sections of the
disclosure. It is intended that the following claims define the
scope of the disclosure and that methods and structures within the
scope of these claims and their equivalents be covered thereby.
* * * * *