U.S. patent application number 14/640078 was filed with the patent office on 2015-06-25 for antimicrobial coatings.
The applicant listed for this patent is 3M INNOVATIVE PROPERTIES COMPANY. Invention is credited to MAHFUZA B. ALI, NAIYONG JING, NANCY S. LENNHOFF, VALERI LIRINE, PRADNA V. NAGARKAR, NARINA Y. STEPANOVA, CAROLINE M. YLITALO.
Application Number | 20150175812 14/640078 |
Document ID | / |
Family ID | 45004738 |
Filed Date | 2015-06-25 |
United States Patent
Application |
20150175812 |
Kind Code |
A1 |
ALI; MAHFUZA B. ; et
al. |
June 25, 2015 |
ANTIMICROBIAL COATINGS
Abstract
The disclosure provides polymers having antimicrobial activity
and articles with the polymers coated thereon. The polymers include
a first pendant group comprising a first quaternary ammonium
component, a second pendant group comprising a nonpolar component,
and a third pendant group comprising an organosilane component. The
disclosure also includes methods of coating articles with the
antimicrobial polymers. The methods further include the use of
adhesion-promoting reagents.
Inventors: |
ALI; MAHFUZA B.; (MENDOTA
HEIGHTS, MN) ; JING; NAIYONG; (WOODBURY, MN) ;
LIRINE; VALERI; (BROOKLINE, MA) ; NAGARKAR; PRADNA
V.; (WESTON, MA) ; YLITALO; CAROLINE M.;
(STILLWATER, MN) ; LENNHOFF; NANCY S.; (NORTH
ANDOVER, MA) ; STEPANOVA; NARINA Y.; (INVER GROVE
HEIGHTS, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
3M INNOVATIVE PROPERTIES COMPANY |
St. Paul |
MN |
US |
|
|
Family ID: |
45004738 |
Appl. No.: |
14/640078 |
Filed: |
March 6, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13115146 |
May 25, 2011 |
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14640078 |
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61348044 |
May 25, 2010 |
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61348157 |
May 25, 2010 |
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Current U.S.
Class: |
428/447 ;
424/78.35 |
Current CPC
Class: |
A61L 29/16 20130101;
A61L 2300/216 20130101; C09D 183/10 20130101; A61L 29/085 20130101;
C08F 230/08 20130101; G06F 3/041 20130101; A61L 2420/02 20130101;
B05D 3/06 20130101; C09D 5/1693 20130101; C08F 220/06 20130101;
A61L 2300/404 20130101; G06F 3/047 20130101; C08F 220/18 20130101;
Y10T 428/31663 20150401; B05D 3/02 20130101; C03C 17/42 20130101;
C03C 17/30 20130101; C08G 77/26 20130101; C08F 220/34 20130101;
C09D 5/1675 20130101; C09D 5/1637 20130101 |
International
Class: |
C09D 5/16 20060101
C09D005/16; G06F 3/047 20060101 G06F003/047 |
Claims
1. An article, comprising: a touch-sensitive substrate comprising a
surface; a first layer coated on the surface, the first layer
comprising an adhesion-promoting reagent; and a second layer coated
on the first layer, the second layer comprising an organic polymer
having a plurality of pendant groups comprising a first pendant
group comprising a first quaternary ammonium component; a second
pendant group comprising a nonpolar component; a third pendant
group comprising a first organosilane component.
2. The article of claim 1, wherein the adhesion-promoting reagent
is selected from the group consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
3. An article made by the process of: forming a first composition
of an organic polymer in organic solvent, the polymer having a
plurality of pendant groups comprising, a first pendant group
comprising a first quaternary ammonium component, a second pendant
group comprising a nonpolar component, and a third pendant group
comprising a first organosilane component; mixing a second
quaternary ammonium component with the first composition to form a
first mixture; and contacting the first mixture with a substrate
under conditions suitable to form covalent linkages between the
organic polymer, the substrate, and the second quaternary ammonium
component.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. patent application
Ser. No. 13/115,146, filed May 25, 2011, which claims the benefit
of U.S. Provisional Patent Application Nos. 61/348,044 and
61/348,157, both filed on May 25, 2010, which are incorporated
herein by reference in their entirety.
BACKGROUND
[0002] Surfaces that are intended to be touched by human operators,
accordingly, will be exposed to the microorganisms either typically
or incidentally found on skin. Touch panels, for example, can be
found in applications from ATM's to casinos to point of sale
terminals and portable computers. Since the data entry is based on
contact, touch panels are inherently susceptible to scratches and
to microbial contamination. Other surfaces that may be prone to
contamination include countertops, bedrails, writing utensils, and
keypads, for example.
[0003] These surfaces provide a suitable home for bacteria, fungi,
algae, and other one celled organisms which thrive and propagate
based on the availability of appropriate amounts of moisture,
temperature, nutrients, and receptive surfaces. As these organisms
metabolize, they produce chemical by-products. These chemicals are
known to damage (e.g., etch) certain surfaces (e.g., touch
sensitive panels). Further, the biomass of such colonies fog or
obscure the optical properties of the surfaces, irreparably
damaging them. Cleaning and disinfection with chemicals which leach
and poison the organisms and environmental controls which minimize
moisture have, to date, been the response to this problem. Although
cleaning and disinfection is common practice, it is done with the
knowledge of the risks of sub-lethal dose levels, ineffective
doses, resistant organisms, environmental exposure, human exposure,
and the limited duration of such cleaners after the initial
treatment.
[0004] Typical touch screen panels, e.g., capacitive touch screen
panels, require direct contact with the skin of the user's finger.
Thus, these panels are directly contacted by many different users.
As these organisms thrive, the variety of chemicals that these
organisms produce are also known to affect the human user. Thus,
these microorganisms, as well as their metabolic products can pose
serious health risks to users ranging from minor skin irritation to
more serious toxic response and disease.
[0005] The foregoing concerns demonstrate growing detrimental
effects of microorganisms on computer touch panels and a need for
controlling microorganisms that may be disposed on such touch
sensitive panels. The use of environmental controls has limited
effectiveness on microorganism prevention in part because of the
wide variety of environmental conditions under which various
microorganisms can survive and in part because of the costs and
difficulty of actually keeping moisture levels sufficiently low to
minimize microbial growth.
[0006] There exists a need for simple means to prevent the
colonization of articles by microorganisms and/or a means to reduce
the number of living microorganisms that become disposed on a
surface.
SUMMARY
[0007] In view of the general need to control the number of viable
microorganisms on a surface that is intentionally touched by its
user, the present disclosure provides an antimicrobial polymer that
can be used, in some embodiments, to form a coating that is bonded
to a touch-sensitive surface. The antimicrobial polymer may include
chemical components that impart other desirable properties (e.g.,
adhesive properties, scratch resistance properties, antistatic
properties) for the article on which it is applied. In some
embodiments, the components of the polymer may be selected for
their optically-transparent properties.
[0008] Thus, in one aspect, the present disclosure provides an
article. The article can comprise a touch-sensitive substrate
comprising a surface. The article further can comprise an organic
polymer having a plurality of pendant groups. The organic polymer
can be coupled to the surface. The plurality of pendant groups can
comprise a first pendant group comprising a first quaternary
ammonium component. The plurality of pendant groups further can
comprise a second pendant group comprising a nonpolar component.
The plurality of pendant groups further can comprise a third
pendant group comprising a first organosilane or organic silane
ester component. In some embodiments, the article further can
comprise a siliceous substrate that includes a first side and a
second side. In these embodiments, the organic polymer can be
coupled to the first side of the siliceous substrate and the
touch-sensitive substrate can be coupled to the second side of the
siliceous substrate.
[0009] In any of the above embodiments, the article does not
comprise a conductive layer.
[0010] In any of the above embodiments, the organic polymer further
can comprise a second quaternary ammonium component.
[0011] In any of the above embodiments, the organic polymer further
can comprise a second organosilane or organic silane ester
component. In any of the above embodiments, at least one of the
pendant components can comprise a fluorochemical.
[0012] In any of the above embodiments, in the organic polymer, the
ratio of the number of N atoms associated with the first quaternary
ammonium component and second quaternary ammonium component, if
present, and the number of Si atoms associated with the first
organosilane component and second organosilane component, if
present, is about 0.1:1 to about 10:1.
[0013] In any of the above embodiments, the surface to which the
organic polymer is coupled can be a glass or a polymeric surface.
In any of the above embodiments, the siliceous substrate can be
covalently coupled to the touch-sensitive substrate.
[0014] In another aspect, the present disclosure provides a method
of making a coated article. The method can comprise forming a first
composition of an organic polymer in a solvent. The polymer can
have a plurality of pendant groups comprising: a first pendant
group that includes a first quaternary ammonium component; a second
pendant group that includes a nonpolar component; and a third
pendant group that includes an organosilane or organic silane ester
component. The method further can comprise mixing a second
quaternary ammonium component with the first composition to form a
first mixture. The method further can comprise contacting the first
mixture with a substrate under conditions suitable to form covalent
linkages between the organic polymer, the substrate, and the second
quaternary ammonium compound. In some embodiments, the method
further can comprise, after contacting the first mixture with the
substrate, rinsing the coated article. In any of the above
embodiments, the method further can comprise coupling the substrate
to a touch-sensitive substrate. In any of the above embodiments,
the method further can comprise providing a second composition
comprising an adhesion-promoting reagent in a solvent and
contacting the second composition with the substrate, wherein
contacting the second composition with the substrate occurs prior
to contacting the first mixture with the substrate.
[0015] In yet another aspect, the present disclosure provides a
method of making a coated article. The method can comprise forming
a first composition of an organic polymer in a solvent, mixing an
adhesion-promoting reagent with the first composition to form a
second mixture, and contacting the second mixture with a siliceous
substrate under conditions suitable to form covalent linkages
between organic polymer and the siliceous substrate. The polymer
can have a plurality of pendant groups, including a first pendant
group comprising a first quaternary ammonium component, a second
pendant group comprising a nonpolar component, and a third pendant
group comprising a first organosilane component. In any embodiment
of the method, forming a second mixture further can comprise mixing
a second quaternary ammonium component with the adhesion-promoting
reagent and the first composition. In any embodiment of the method,
the adhesion-promoting reagent can be selected from the group
consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane. In any embodiment, the method
further can comprise providing a second composition comprising an
adhesion-promoting reagent in organic solvent and contacting the
second composition with the substrate, wherein contacting the
second composition with the substrate occurs prior to contacting
the second mixture with the substrate.
[0016] In yet another aspect, the present disclosure provides a
method of making a coated article. The method can comprise forming
a first composition of an organic polymer in organic solvent. The
polymer can have a plurality of pendant groups comprising a first
pendant group that includes a first quaternary ammonium component a
second pendant group that includes a nonpolar component, and a
third pendant group that includes an organosilane or organic silane
ester component. The method further can comprise mixing a second
quaternary ammonium compound with the first composition to form a
first mixture. The method further can comprise contacting the first
mixture with a touch-sensitive substrate under conditions suitable
to form covalent linkages between organic polymer and the
touch-sensitive substrate. In some embodiments, the method further
can comprise, after contacting the first mixture with the
touch-sensitive substrate, rinsing the coated article. In any of
the above embodiments, the method further can comprise providing a
second composition comprising an adhesion-promoting reagent in
organic solvent and contacting the second composition with the
touch-sensitive substrate, wherein contacting the second
composition with the touch-sensitive substrate occurs prior to
contacting the first mixture with the touch-sensitive
substrate.
[0017] In yet another aspect, the present disclosure provides a
method of making a coated article. The method can comprise forming
a first composition of an organic polymer in organic solvent,
mixing an adhesion-promoting reagent with the first composition to
form a second mixture, and contacting the second mixture with a
touch-sensitive substrate under conditions suitable to form
covalent linkages between organic polymer and the touch-sensitive
substrate. The polymer can have a plurality of pendant groups,
including a first pendant group comprising a first quaternary
ammonium component, a second pendant group comprising a nonpolar
component, and a third pendant group comprising a first
organosilane component. In any embodiment of the method, forming a
second mixture further can comprise mixing a second quaternary
ammonium component with the adhesion-promoting reagent and the
first composition. In any embodiment of the method, the
adhesion-promoting reagent can be selected from the group
consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane. In any embodiment, the method
further can comprise providing a second composition comprising an
adhesion-promoting reagent in organic solvent and contacting the
second composition with the touch-sensitive substrate, wherein
contacting the second composition with the touch-sensitive
substrate occurs prior to contacting the second mixture with the
touch-sensitive substrate.
[0018] In yet another aspect, the present disclosure provides an
antimicrobial polymer composition. The composition can comprise an
organic polymer having a plurality of pendant groups with the
proviso that the polymer does not comprise a pendant group that
includes a carboxylate or alkoxylate chemical group. The pendant
groups can include a first pendant group comprising a first
quaternary ammonium component. The pendant groups further can
include a second pendant group comprising a perfluorinated nonpolar
component. The pendant groups further can include a third pendant
group comprising a first organosilane component. In some
embodiments, the antimicrobial composition further can include a
fourth pendant component, wherein the fourth pendant component
comprises a polar chemical group.
[0019] The words "preferred" and "preferably" refer to embodiments
of the invention that may afford certain benefits, under certain
circumstances. However, other embodiments may also be preferred,
under the same or other circumstances. Furthermore, the recitation
of one or more preferred embodiments does not imply that other
embodiments are not useful, and is not intended to exclude other
embodiments from the scope of the invention.
[0020] As used herein, "a," "an," "the," "at least one," and "one
or more" are used interchangeably. Thus, for example, an article
comprising "a" siliceous substrate can be interpreted to mean that
the article can include "one or more" siliceous substrates.
[0021] The term "and/or" means one or all of the listed elements or
a combination of any two or more of the listed elements.
[0022] Also herein, the recitations of numerical ranges by
endpoints include all numbers subsumed within that range (e.g., 1
to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
[0023] The above summary of the present invention is not intended
to describe each disclosed embodiment or every implementation of
the present invention. The description that follows more
particularly exemplifies illustrative embodiments. In several
places throughout the application, guidance is provided through
lists of examples, which examples can be used in various
combinations. In each instance, the recited list serves only as a
representative group and should not be interpreted as an exclusive
list.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The invention will be further explained with reference to
the drawing figures listed below, where like structure is
referenced by like numerals throughout the several views.
[0025] FIG. 1a is a top perspective view of an embodiment of an
antimicrobial touch screen article, with a capacitive layer,
according to the present disclosure.
[0026] FIG. 1b is a top perspective view of an embodiment of an
antimicrobial touch screen article, without a capacitive layer,
according to the present disclosure.
[0027] FIG. 2 is a top perspective view of another embodiment of an
antimicrobial touch screen article according to the present
disclosure.
[0028] FIG. 3 is a top perspective view of another embodiment of an
antimicrobial touch screen article according to the present
disclosure.
[0029] FIG. 4 is a block diagram of one embodiment of a method of
making a coated article according to the present disclosure.
[0030] FIG. 5 is a bar graph showing the log reduction of
Staphylococcus aureus bacteria according to one test method after
exposure to several embodiments of an article comprising an
antimicrobial polymer of the present disclosure.
DETAILED DESCRIPTION
[0031] Polymeric materials are provided that can contain a
plurality of different pendant groups. Methods of making the
polymeric material and compositions that contain the polymeric
material are also provided. Additionally, articles with coatings
that contain the polymeric material are provided. The polymeric
material in the coatings is often crosslinked. The coatings can be
antimicrobial, scratch-resistant, or both.
[0032] Before any embodiments of the invention are explained in
detail, it is to be understood that the invention is not limited in
its application to the details of construction and the arrangement
of components set forth in the following description or illustrated
in the accompanying drawings. The invention is capable of other
embodiments and of being practiced or of being carried out in
various ways. Also, it is to be understood that the phraseology and
terminology used herein is for the purpose of description and
should not be regarded as limiting. The use of "including,"
"comprising," "containing," or "having" and variations thereof
herein is meant to encompass the items listed thereafter and
equivalents thereof as well as additional items. Unless specified
or limited otherwise, the terms "supported," and "coupled" and
variations thereof are used broadly and encompass both direct and
indirect supports and couplings. It is to be understood that other
embodiments may be utilized and structural or logical changes may
be made without departing from the scope of the present disclosure.
Furthermore, terms such as "front," "rear," "top," "bottom," and
the like are only used to describe elements as they relate to one
another, but are in no way meant to recite specific orientations of
the apparatus, to indicate or imply necessary or required
orientations of the apparatus, or to specify how the invention
described herein will be used, mounted, displayed, or positioned in
use.
[0033] The term "antimicrobial" refers to material that kills
microorganisms or inhibits their growth.
[0034] The term "silane" refers to a compound having four groups
attached to a silicon atom. That is, the silane has a
silicon-containing group.
[0035] The term "alkoxysilyl" refers to a silicon-containing group
having an alkoxy group bonded directly to the silicon atom. The
alkoxysilyl can be, for example, of formula --Si(OR)(Rx).sub.2
where R is an alkyl and each Rx is independently a hydroxyl,
alkoxy, alkyl, perfluoroalkyl, aryl, aralkyl, or part of a
silicone.
[0036] The term "ester equivalent" means groups such as silane
amides (RNR'Si), silane alkanoates (RC(O)OSi), Si--O--Si,
SiN(R)--Si, SiSR and RCONR'Si that are thermally and/or
catalytically displaceable by R''OH. R and R' are independently
chosen and can include hydrogen, alkyl, arylalkyl, alkenyl,
alkynyl, cycloalkyl, and substituted analogs such as alkoxyalkyl,
aminoalkyl, and alkylaminoalkyl. R'' may be the same as R and R'
except it may not be H.
[0037] The term "hydroxysilyl" refers to a silicon-containing group
having a hydroxyl group bonded directly to the silicon atom. The
hydroxysilyl can be, for example, of formula --Si(OH)(Rx).sub.2
where Rx is an alkyl, perfluoralkyl, aryl, aralkyl, alkoxy,
hydroxyl, or part of a silicone. A compound having a hydroxysilyl
group is often referred to as a "silanol". Silanols are a subset of
silanes.
[0038] The term "silicone" refers to a moiety that contains a
silicon-oxygen-silicon linkage group. Any other suitable groups can
be attached to the silicon atoms. Such a linkage can result from
the reaction of a first silane (e.g., a first silicon-containing
group such as a first alkoxysilyl group or hydroxysilyl group) with
a second silane (e.g., a second silicon-containing group such as a
second alkoxysilyl group or hydroxysilyl group). In some
embodiments, the silicone is part of a "silicone network". A
silicone network results when a first silane (i.e., a first
silicon-containing group) reacts with a second silane (e.g., a
second silicon-containing group) plus a third silane (e.g., a third
silicon-containing group such as a third alkoxysilyl group or
hydroxysilyl group) or when a first silane (e.g., a first
silicon-containing group) reacts with a second silane (e.g., a
second silicon-containing group) plus a third silane (e.g., a third
silicon-containing group) and a fourth silane (e.g., a fourth
silicon-containing group such as a fourth alkoxysilyl group or
hydroxysilyl group).
[0039] As used herein, the phrases "polymeric material with a
plurality of pendant groups", "polymeric material with multiple
pendant groups", or similar phrases are used interchangeably to
refer to a polymeric material that has at least three different
types of pendant groups. The multiple pendant groups include (1) a
first pendant group containing a quaternary amino group; (2) a
second pendant group containing a nonpolar group; and (3) a third
pendant group having an organosilane group. The polymeric material
with multiple pendant groups can be crosslinked through a
condensation reaction of multiple organosilane groups. Furthermore,
the polymeric material can be covalently coupled to a surface
comprising a silanol group or, preferably, a plurality of silanol
groups.
[0040] The present disclosure is generally directed to articles
comprising an antimicrobial coating and methods of making said
articles comprising an antimicrobial coating. The articles further
comprise a substrate. In some embodiments, the substrate comprises
a touch-sensitive substrate (e.g., a computer display touch panel).
The touch-sensitive substrate may comprise an active portion. The
active portion of the substrate includes a surface configured to be
touched (e.g., by a finger, a stylus, or the like). "Active
portion" is used herein in the broadest sense and refers to a
region of the substrate that can transduce a tactile stimulus into
an electrical signal. Nonlimiting examples of devices that comprise
a substrate with an "active portion" include touch screens (e.g.,
computer touch screens, personal digital assistant touch screens,
telephone touch screens, card reader touch screens, casino gaming
devices, touch-enabled industrial equipment controls, touch-enabled
vehicle accessory controls, and the like) Exemplary touch screens
are disclosed in U.S. Pat. Nos. 6,504,582; 6,504,583; 7,157,649;
and U.S. Patent Application Publication No. 2005/0259378.
[0041] Turning to the Figures, FIG. 1a shows one embodiment of an
antimicrobial touch sensor 110 according to the present invention.
The touch sensor 110 may be a touch sensitive panel such as, for
example, a "surface capacitive" computer touch panel, available
from 3M Touch Systems, Methuen, Mass., made up of several different
layers. The touch sensor 110 features an antimicrobial touch panel
112.
[0042] Touch panel 112 includes electrically insulative substrate
114. Insulative substrate 114 may be constructed from glass,
plastic or another transparent medium, for example. The touch panel
112 further comprises a touch-sensitive active portion 115 on the
insulative substrate 114. Active portion 115 includes a
transparent, electrically conductive layer 116 deposited directly
on substrate 114. Conductive layer 116, for example, can be a tin
oxide layer having a thickness of twenty to sixty nanometers and
may be deposited by sputtering, vacuum deposition and other
techniques known in the art. The thickness of the layers is
exaggerated in FIG. 1a for illustrative purposes only and is not
intended to represent the layers to scale. Conductive layer 116 may
also include a conductive polymeric material or a conductive
organic-inorganic composite.
[0043] A conductive pattern, not shown, can be disposed about the
perimeter of conductive layer 116 to provide a uniform electric
field throughout the layer 116 in order to establish the point of
contact between the panel 112 and a finger or stylus.
[0044] Active portion 115 may also include protective layer 118
deposited over conductive layer 116 to provide abrasion resistance
to protect conductive layer 116. Protective layer 118 may be a
layer of an organosiloxane formed by applying to the article a
composition (e.g., a solution) comprising methyltriethoxysilane,
tetraethylorthosilicate, isopropanol and water. Additionally, or
alternatively, the protective layer may comprise a hardcoat
material (e.g., the glare-resistant hardcoat described in Example 1
of U.S. Pat. No. 7,294,405).
[0045] Second conductive layer 120 may be provided to shield touch
sensor 110 from noise which may result from the electric circuits
of a display unit, not shown, to which display 110 may be attached
and may similarly include a tin oxide layer deposited in a similar
manner as discussed with reference to conductive layer 116.
However, conductive layer 120 is not a necessary limitation of the
invention as touch sensor 110 can function without it.
[0046] Antimicrobial polymer layer 122 in accordance with this
disclosure is coupled to active portion 115, usually on protective
layer 118 or even directly to conductive layer 116 if protective
layer 118 is not present or to the outermost layer, if additional
layers (not shown) are present to reduce energy dissipation of an
object contacting touch sensor 110. In this configuration,
antimicrobial polymer layer 122 can minimize or prevent damage to
touch sensor 110, providing an easy glide experience to the touch
screen user, as well as inhibit the survival and growth of
microorganisms which come to rest on touch sensor 110.
[0047] FIG. 1b shows one embodiment of another antimicrobial touch
sensor 110 according to the present invention. The touch sensor 110
may be a touch sensitive panel such as, for example, a "projected
capacitive" computer touch panel in a projected capacitive touch
screen, made up of several different layers. The touch sensor 110
features an antimicrobial touch panel 112.
[0048] Touch panel 112 includes electrically insulative substrate
114. Insulative substrate 114 may be constructed from glass,
plastic or another transparent medium, for example.
[0049] A conductive layer 124 can be disposed beneath the substrate
114 in order to establish the point of contact between the panel
112 and a finger or stylus. In some embodiments (not shown),
conductive layer 124 may be a plurality of conductive layers (e.g.
arrays of electrodes) with dielectric layers disposed there
between. Touch sensors with this configuration are disclosed in
U.S. Pat. No. 8,411,066.
[0050] Touch panel 112 may also include protective layer 118
deposited over insulative substrate 114 to provide abrasion
resistance to protect insulative substrate 114. Protective layer
118 may be a layer of an organosiloxane formed by applying to the
article a composition (e.g., a solution) comprising
methyltriethoxysilane, tetraethylorthosilicate, isopropanol and
water. Additionally, or alternatively, the protective layer may
comprise a hardcoat material (e.g., the glare-resistant hardcoat
described in Example 1 of U.S. Pat. No. 7,294,405).
[0051] Antimicrobial polymer layer 122 in accordance with this
disclosure is coupled to protective layer 118 or even directly to
insulative substrate 114 if protective layer 118 is not present or
to the outermost layer, if additional layers (not shown) are
present to reduce energy dissipation of an object contacting touch
sensor 110. In this configuration, antimicrobial polymer layer 122
can minimize or prevent damage to touch sensor 110, providing an
easy glide experience to the touch screen user, as well as inhibit
the survival and growth of microorganisms which come to rest on
touch sensor 110.
[0052] FIG. 2 shows another embodiment of a touch sensor 210. The
touch sensor 210 may include, for example, a resistive computer
touch panel 212, available from Elo TouchSystems, Freemont, Calif.,
which includes insulative substrate 214 and conductive layer 216,
similar to FIG. 1a. Protective layer 218 may include a hard coating
which protects and supports deformable conductive layer 224
interposed between conductive layer 216 and protective layer 218. A
nonlimiting example of a suitable hard coating includes the
glare-resistant hardcoat described in Example 1 of U.S. Pat. No.
7,294,405. As touch sensor 210 is contacted by a finger or stylus
deformable conductive layer 224 compresses and makes contact with
conductive layer 216 to indicate the position of the contact.
Antimicrobial polymer layer 222 is applied to protective layer
218.
[0053] FIG. 3 shows one embodiment of a vibration-sensing touch
sensor 350 that includes a rectangular touch plate 370 and
vibration sensors 360, 362, 364, and 366 located at the corners and
coupled to the touch plate. When integrated into a system, for
example overlaying an electronic display, the border portion 375 of
touch sensor 350 may be covered by a bezel, leaving an intended
touch area 380 exposed to a user. Dashed line 390 is used to
indicate a separation between the border area 375 and the intended
touch area 380. Dashed line 390 is an arbitrary designator, and
does not necessarily indicate that touches outside of its inscribed
area cannot be detected. To the contrary, dashed line 390 merely
inscribes an area where touch inputs are intended or expected to
occur, which may include the entire touch plate or some portion or
portions thereof. When dashed lines are used in this document to
designate intended touch areas, they are used in this manner.
Antimicrobial polymers (not shown) of the present disclosure can be
applied directly or indirectly to the surface of the touch area 380
of the vibration-sensing touch sensor 350. An example of indirect
application includes applying the antimicrobial polymer to one side
of a polymer film and a pressure-sensitive adhesive to the other
side of the film; then applying the adhesive side of the film to
the touch area of the vibration-sensing touch sensor.
[0054] While the touch plate is shown as rectangular in FIG. 3, it
can be of any arbitrary shape. The touch plate can be glass,
acrylic, polycarbonate, metal, wood, or any other material cable of
propagating vibrations that can be caused or altered by a touch
input to the touch plate and that can be sensed by the vibration
sensors. To detect the touch position in two dimensions on the
touch plate, at least three vibrations sensors can be used, and are
generally located at peripheral portions of the touch plate,
although other locations can be used. For convenience, redundancy,
or other reasons, it may be desirable to use at least four
vibration sensors, for example one at each corner of a rectangular
touch plate, as shown in FIG. 3. The vibration sensors can be any
sensors capable of detecting vibrations in the touch plate that are
caused or affected by a touch, for example bending wave
vibrations.
[0055] Piezoelectric materials may provide exemplary vibrations
sensors. The vibration sensors can be mechanically coupled to the
touch plate by use of an adhesive, solder, or other suitable
material. Conductive traces or wires (not shown) can be connected
to each of the vibration sensors for communication with controller
electronics (not shown). Exemplary vibration-sensing touch sensors,
their operation, their components, and their layout on a sensor are
disclosed in co-assigned U.S. Patent Application Publication No.
2004/0233174 and U.S. Patent Application Publication No.
2005/0134574.
Antimicrobial Polymers:
[0056] The present disclosure provides antimicrobial polymers. The
antimicrobial polymers are formed by reacting, in suitable organic
solvent, monomers that comprise a chemical group that serves one or
more functional purposes in the polymer.
[0057] In some embodiments, the antimicrobial polymers can be
coated (e.g., as a film or layer) onto a substrate as described
herein. The polymers have antimicrobial activity that can kill or
inhibit microorganisms that come into contact with the polymer
(e.g., on the surface of a touch panel). The antimicrobial activity
can be tested using a standardized antimicrobial resistance test
such as, for example, JIS-Z 2801 (Japanese Industrial Standards;
Japanese Standards Association; Tokyo, Japan). The polymers further
have scratch-resistant properties. The scratch-resistant property
of the polymer can be tested using the ASTM test method D
7027.26676.
[0058] Polymers of the present disclosure are formed in any
suitable solvent (e.g., an organic solvent) that will solubilize or
make a dispersion of the resultant polymer. Suitable organic
solvents have a boiling point about 200.degree. C. or lower and can
be mixed with small portions (<10%, w/w) of acidified water
without substantially degrading the solvent properties. Adding the
acidified water to the solvent facilitates complete hydrolysis of
silane groups which, in turn optimizes the formation of
--Si--O--Si-- bonds within the polymer and between the polymer and
the substrate. This can result in improved durability of
antimicrobial coating on the substrate. Preferably, the solvent
flashpoint is 100.degree. C. or lower. Nonlimiting examples of
suitable organic solvents include an alcohol (e.g., isopropyl
alcohol, methanol), MEK, acetone, DMF, DMAC (dimethyl acetamide)
ethyl acetate, THF, etc. The monomers are mixed with the solvent
and reacted to form an antimicrobial polymer. Suitable monomers
include derivatives of acrylate monomers, methacrylate monomers,
vinyl monomers, and olefinic monomers. The monomers comprise
chemical groups that are pendant from the polymer after the
polymerization reaction. The pendant groups include a first
quaternary ammonium group, a nonpolar group, and a first
organosilane group (e.g., trimethoxysilylpropane).
[0059] The polymer shown in Structure (I) shows a representation of
a portion of an antimicrobial polymer made from acrylate or
olefinic monomers according to the present disclosure.
##STR00001##
[0060] Polymers of the present disclosure include pendant groups
with antimicrobial activity. The groups with antimicrobial activity
can be selected for properties that are desirable in the articles
on which the polymer is coated. For example, the antimicrobial
group can be selected because it provides a polymer having
substantial optical clarity (i.e. high optical transmission
throughout a narrow or broad spectrum of wavelengths, low haze).
These properties easily can be measured by a person of ordinary
skill in the art, for example, by methods disclosed herein. In the
exemplary polymer of Structure (I), the first quaternary ammonium
pendant group includes the quaternary ammonium moiety R.sup.3 and
can be derived from a monomer where: [0061] R.sup.1=H or CH.sub.3,
[0062] R.sup.2.dbd.COO, CO, C.sub.1-C.sub.12 alkyl, aryl [0063]
R.sup.3=a quaternary ammonium having the formula
--(CH.sub.2).sub.n--N(R.sup.7)(R.sup.8)(R.sup.9)(X.sup.-) where
[0064] n=1-3 (i.e., an alkyl group from C.sub.1-C.sub.3) [0065]
R.sup.7, R.sup.8, and R.sup.9 are independently an alkyl
(C.sub.1-C.sub.22), aryl, or a combination of chemical groups
forming a ring structure; and [0066] X=Cl, Br,
N(SO.sub.2CF.sub.3).sub.2, BF.sub.4, OSO.sub.2C.sub.4F.sub.9,
OSO.sub.2CF.sub.3, OSO.sub.3CH.sub.3.
[0067] The first quaternary ammonium pendant groups are coupled
(e.g., covalently coupled) to the polymer such that, the antibiotic
activity of the antimicrobial coupled to the polymer is insoluble
in water (i.e., the antimicrobial is non-leaching when the polymer
is contacted with an aqueous solution). Nonlimiting examples of
suitable antimicrobial quaternary ammonium components include the
hexadecyldimethylethylamine, octadecyldimethylethylamine,
hexadecyldimethylpropylamine and octadecyldimethylpropylamine.
[0068] In the exemplary polymer of Structure (I), the nonpolar
pendant group includes the nonpolar moiety R.sup.4 and can be
derived from a monomer where R.sup.4 is an unsubstituted or
substituted alkyl group (C.sub.4 to C.sub.22), an aryl group,
perfluoroalkyl sulfonamide, perfluoroalkyl sulfone, perfluoroalkyl
carboxamide, a class of free-radically reactive fluoroalkyl or
fluoroalkylene group-containing compatibilizers of the respective
chemical formulas: R.sub.ffQ.sub.3(X.sub.1).sub.n1 and
(X.sub.1).sub.n1Q.sub.3R.sub.ff2Q.sub.3(X.sub.1).sub.n1), where
R.sub.ff is a fluoroalkyl, R.sub.ff2 is a fluoroalkylene, Q.sub.3
is a connecting group of valency at least 2 and is selected from
the group consisting of a covalent bond, an alkylene, an arylene,
an aralkylene, an alkarylene group, a straight or branched chain or
cycle-containing connecting group optionally containing heteroatoms
such as O, N, and S and optionally a heteroatom-containing
functional group such as carbonyl or sulfonyl, and combinations
thereof; X.sub.1 is a free-radically reactive group selected from
(meth)acryl, --SH, allyl, or vinyl groups and n1 is independently 1
to 3. Typical Q.sub.3 groups include:
--SO.sub.2N(R)CH.sub.2CH.sub.2--;
--SO.sub.2N(CH.sub.2CH.sub.2).sub.2--; --(CH.sub.2).sub.m--;
--CH.sub.2--O--(CH.sub.2).sub.3--; and --C(O)NRCH.sub.2CH.sub.2--,
where R is H or lower alkyl of 1 to 4 carbon atoms and m is 1 to 6.
Preferably the fluoroalkyl or fluoroalkylene group is a
perfluoroalkyl or perfluoroalkylene group. Exemplary, non-limiting
perfluorobutyl-substituted acrylate compatibilizers meeting these
criteria and useful in the present invention include one or more of
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2,
C.sub.4F.sub.9SO.sub.2N(CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2,
or
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.-
sub.2. One non-limiting example of a preferred
fluoroalkyl-substituted monomers that may be utilized in the
composition of the coat layer is: (1H,1H,2H,2H)-perfluorodecyl
acrylate, available from Lancaster Synthesis of Windham, N.H.
Numerous other (meth)acryl compounds with perfluoroalkyl moieties
that may also be utilized in the composition of the coat layer are
mentioned in U.S. Pat. No. 4,968,116, to Hulme-Lowe et al., and in
U.S. Pat. No. 5,239,026 (including perfluorocyclohexylmethyl
methacrylate), to Babirad et al. Other fluorochemical
(meth)acrylates that meet these criteria and may be utilized
include, for example, 2,2,3,3,4,4,5,5-octafluorohexanediol
diacrylate and .omega.-hydro 2,2,3,3,4,4,5,5-octafluoropentyl
acrylate (H--C.sub.4F.sub.8--CH.sub.2O--C(O)--CH.dbd.CH.sub.2).
Other fluorochemical (meth)acrylates that may be used alone, or as
mixtures, are described in U.S. Pat. No. 6,238,798, to Kang et
al.
[0069] Another monomer that may be used is a fluoroalkyl- or
fluoroalkylene-substituted thiol or polythiol. Non-limiting
examples of this type of monomers includes one or more of the
following:
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.sub.2SH,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.sub.2CH.sub.2SH,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2SH, and
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH(OC(O)CH.sub.2SH)CH.sub.2OC(O)CH.sub.2-
SH.
[0070] In another preferred embodiment, the coating composition
adds one or more multi-olefinic compounds bearing at least one
monovalent poly(hexafluoropropylene oxide) (HFPO) moiety and
optionally a compatibilizer such as a fluoroalkyl- or
fluoroalkylene-substituted mono or multi-acrylate such as
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2,
C.sub.4F.sub.9SO.sub.2N(CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2).sub.2,
or
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.-
sub.2, alcohol, olefin, thiol or polythiol to fluoropolymer curing
composition. Non-limiting examples of thiol or polythiol type of
compatibilizer includes one or more of the following:
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.sub.2SH,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OC(O)CH.sub.2CH.sub.2SH,
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2SH, and
C.sub.4F.sub.9SO.sub.2N(CH.sub.3)CH(OC(O)CH.sub.2SH)CH.sub.2OC(O)CH.sub.2-
SH.
[0071] As used in the examples, unless otherwise noted, "HFPO--"
refers to the end group
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- of the methyl ester
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)C(O)OCH.sub.3, wherein
"a" averages about 6.8, and the methyl ester has an average
molecular weight of 1,211 g/mol, and which can be prepared
according to the method reported in U.S. Pat. No. 3,250,808 (Moore
et al.) with purification by fractional distillation.
[0072] The mono- or multi-olefinic compound bearing at least one
monovalent poly(hexafluoropropylene oxide) (HFPO) moiety preferably
is in the form of a multiacrylate. These materials are of the
formula: R.sub.fpeQ(X).sub.n wherein Rfpe is the residue of a
monovalent HFPO moiety, Q is a connecting group comprising an
alkylene, arylene, arylene-alkylene, or alkylene-arylene group and
may comprise a straight or branched chain connecting group which
may contain heteroatoms such as O, N, and S, X is a free-radically
reactive group selected from meth(acryl), allyl, or vinyl groups
and n is 2 to 3. Typical Q group include: --(CH.sub.2).sub.m--;
--CH.sub.2O(CH.sub.2).sub.3--; and --C(O)NRCH.sub.2CH.sub.2--,
where R is H or lower alkyl of 1 to 4 carbon atoms and m is 1 to
6.
[0073] One class of multi-(meth)acryl compound bearing at least one
monovalent poly(hexafluoropropylene oxide) (HFPO) moiety comprises
compounds described in International Publication WO
2005/113641.
[0074] Other mono- and multi-(meth)acryl compounds bearing at least
one monovalent poly(hexafluoropropylene oxide) (HFPO) moiety
comprise compounds which are Michael adducts of HFPO amine
derivatives with multiacrylates described in International
Publication WO 2005/113642.
[0075] The nonpolar pendant group is a chemical group that
increases the relative hydrophobicity of the antimicrobial polymer.
The nonpolar pendant groups are selected for their ability to
influence the surface energy of the polymer. In particular, the
nonpolar pendant groups are selected to impart a low surface energy
polymer. Nonpolar pendant groups can also increase the scratch
resistance of the polymer, when the polymer is coated onto a hard
surface (e.g., glass). Nonlimiting example of suitable nonpolar
groups include linear or branched alkanes (e.g., isooctane,
isobutane) and aromatic groups.
[0076] In the exemplary polymer of Structure (I), the first
organosilane pendant group includes the siloxane moiety R.sup.5 and
can be derived from a monomer where: [0077]
R.sup.5.dbd.(CH.sub.2)m--Si(OR.sup.10).sub.3, [0078] m=1-6 (i.e.,
an alkyl group from C.sub.1-C.sub.6) and [0079] R.sup.10=an alkyl
group from C.sub.1-C.sub.3.
[0080] The first organosilane pendant group includes a
silicon-containing group. This pendant group can crosslink the
antimicrobial polymeric material, bond the antimicrobial polymeric
material to a substrate, bond a second organosilane to the
antimicrobial polymer, or it can confer the ability of the polymer
to perform any combination of the foregoing bonding configurations.
A nonlimiting example of a suitable organosilane pendant group is
the propyl trimethoxysilane group found in methacryloylpropyl
trimethoxysilane.
[0081] Although Structure (I) shows a portion of an exemplary
antimicrobial polymer comprising three sequential monomers with
different pendant groups, it will be recognized that the
antimicrobial polymer of the present disclosure is a random
copolymer, with the number and order of monomeric subunits (a, b,
c, and, optionally, d) influenced by the respective ratios of
monomeric units in the polymerization reaction and/or the
polymerization reaction conditions.
[0082] Antimicrobial polymers of the present disclosure optionally
can include, in addition to the quaternary ammonium, nonpolar, and
organosilane pendant groups, a fourth pendant group that includes a
polar component. The polar pendant group can confer adhesive
properties that allow the antimicrobial polymer to adhere to
certain substrates. Because the polar pendant groups promote
adhesion of the antimicrobial polymer to the substrate,
advantageously, this can result in an improved durability of the
polymer on the substrate. In some embodiments, the polar pendant
group may enhance the antimicrobial activity of the polymer.
Suitable polar pendant groups include, for example,
N-hydroxymethylacrylamide, dimethylacrylamide, and alcohol
groups.
[0083] In some embodiments, the antimicrobial polymer of the
present disclosure does not comprise a pendant group that includes
a carboxylate or alkoxylate chemical group.
[0084] Antimicrobial polymers of the present disclosure can be
synthesized by reacting, in an organic solvent, monomers comprising
the pendant groups. Suitable monomers for the reaction include, for
example, acrylate monomers, methacrylate monomers, and combinations
thereof. Other suitable monomers for the reaction include vinyl
monomers and olefinic monomers.
[0085] The monomers can be combined, on a weight percent basis, in
various ratios in the reaction. In some embodiments, the monomer
comprising the quaternary ammonium pendant group can comprise from
about 20% to about 80% of the monomers reacted to form a polymer.
In some embodiments, the monomer comprising the quaternary ammonium
pendant group can comprise greater than 20% of the monomers reacted
to form a polymer. In some embodiments, the monomer comprising the
quaternary ammonium pendant group can comprise greater than 30% of
the monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise greater than 40% of the monomers reacted to form a
polymer. In some embodiments, the monomer comprising the quaternary
ammonium pendant group can comprise greater than 50% of the
monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise greater than 60% of the monomers reacted to form a
polymer. In some embodiments, the monomer comprising the quaternary
ammonium pendant group can comprise greater than 70% of the
monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise 70% to 80% of the monomers reacted to form a polymer.
[0086] In some embodiments, the monomer comprising the nonpolar
pendant group can comprise from about 20% to about 60% of the
monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise greater than 20% of the monomers reacted to form a
polymer. In some embodiments, the monomer comprising the quaternary
ammonium pendant group can comprise greater than 30% of the
monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise 30% to 40% of the monomers reacted to form a polymer.
[0087] In some embodiments, the monomer comprising the organosilane
pendant group can comprise from about 1% to about 20% of the
monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise greater than 2% of the monomers reacted to form a polymer.
In some embodiments, the monomer comprising the quaternary ammonium
pendant group can comprise greater than 5% of the monomers reacted
to form a polymer. In some embodiments, the monomer comprising the
quaternary ammonium pendant group can comprise greater than 10% of
the monomers reacted to form a polymer. In some embodiments, the
monomer comprising the quaternary ammonium pendant group can
comprise greater than 15% of the monomers reacted to form a
polymer. In some embodiments, the monomer comprising the quaternary
ammonium pendant group can comprise 15% to 20% of the monomers
reacted to form a polymer.
[0088] In some embodiments, the reaction mixture used to make the
antimicrobial polymer comprises at least 20% monomers comprising a
quaternary ammonium pendant group, at least 20% monomers comprising
a nonpolar pendant group, and at least 2% monomers comprising an
organosilane pendant group.
[0089] The monomers are mixed in an organic solvent and are reacted
under conditions suitable to form a polymer. For example, the
reaction mixture can be purged with nitrogen to remove other
dissolved gasses. In some embodiments, the reaction mixture can be
sealed, heated, and mixed (e.g., mixed at 65.degree. C.) for a
period of time sufficient to allow polymerization of, for example,
at least 99.5% of the monomers. In some embodiments, an additional
initiator (e.g., 2,2-Azobis(2-methylbutyronitrile), available from
DuPont of Wilmington, Del., USA, under the trade name Vazo-67) can
be added to the mixture to react with any unreacted monomers from
the original mixture. The extent of the reaction of monomers can be
determined by, for example, a calculation of the percent solids in
the mixture. The antimicrobial polymer typically comprises about 25
weight percent (wt %) of the solution in which it is made.
Adhesion-Promoting Reagents:
[0090] In any embodiment the method of making an antimicrobial
coating according the present disclosure, one or more
adhesion-promoting reagent can be used in the process. Suitable
adhesion-promoting reagents include organosilane compounds having a
silane group that can react to form Si--O--Si linkages and a
leaving group (e.g. an alkoxy group).
[0091] The adhesion-promoting reagent can form Si--O--Si linkages
with another organosilane compound (e.g., an unreacted organosilane
compound of the present disclosure), an organosilane-containing
polymer (e.g., the antimicrobial polymers of the present
disclosure), and/or a siliceous substrate (e.g., glass).
Advantageously, the adhesion-promoting reagents promote improved
adhesion of the antimicrobial coatings by increasing the number of
attachment points (to the substrate) per antimicrobial molecule.
Furthermore, the adhesion-promoting reagents promote improved
durability of the antimicrobial coatings by increasing the number
of intramolecular linkages per antimicrobial polymer molecule
and/or the number of linkages between the antimicrobial polymer and
the substrate.
[0092] In addition to promoting the formation of Si--O--Si bonds
between the organosilane compounds in the coating compositions of
the present disclosure, the preferred adhesion-promoting reagents
can also be used as an adhesion promoter to increase the
interfacial adhesion between the substrate and the antimicrobial
polymer composition of the present disclosure.
[0093] Nonlimiting examples of suitable adhesion-promoting reagents
include N-2(aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine, and
N-phenyl-3-aminopropyltrimethoxysilane. In view of the present
disclosure, other suitable adhesion-promoting reagents will be
apparent to a person having ordinary skill in the art.
[0094] Other suitable adhesion-promoting reagents are disclosed in
U.S. Patent Application Publication No. US 2008/0064825. For
example, amino-substituted organosilane esters (e.g., alkoxy
silanes) are preferred adhesion-promoting reagents. The
antimicrobial articles of the present disclosure may be made by
reacting an amino-substituted organosilane ester or ester
equivalent and an antimicrobial polymer that has a plurality of
polar functionalities combinatively reactive with the silane ester
or ester equivalent. The amino-substituted organosilane ester or
ester equivalent bears on the silicon atom at least one ester or
ester equivalent group, preferably 2, or more preferably 3 groups.
Ester equivalents are well known to those skilled in the art and
include compounds such as silane amides (RNR'Si), silane alkanoates
(RC(O)OSi), Si--O--Si, SiN(R)--Si, SiSR and RCONR'Si. These ester
equivalents may also be cyclic such as those derived from ethylene
glycol, ethanolamine, ethylenediamine and their amides. R and R'
are defined as in the "ester equivalent" definition herein.
[0095] 3-aminopropyl alkoxysilanes are well known to cyclize on
heating and these RNHSi compounds would be useful in this
invention. Preferably, the amino-substituted organosilane ester or
ester equivalent has ester groups such as methoxy that are easily
volatilized as methanol so as to avoid leaving residue at the
interface which may interfere with bonding. The amino-substituted
organosilane must have at least one ester equivalent; for example,
it may be a trialkoxysilane.
[0096] For example, the amino-substituted organosilane may have the
formula: ZNH-L-SiX'X''X''', where Z is hydrogen, alkyl, or
substituted alkyl including amino-substituted alkyl; where L is a
divalent straight chain C1-12 alkylene or may comprise a C3-8
cycloalkylene, 3-8 membered ring heterocycloalkylene, C2-12
alkenylene, C4-8 cycloalkenylene, 3-8 membered ring
heterocycloalkenylene or heteroarylene unit. L may be interrupted
by one or more divalent aromatic groups or heteroatomic groups. The
aromatic group may include a heteroaromatic. The heteroatom is
preferably nitrogen, sulfur or oxygen. L is optionally substituted
with C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, amino,
C3-6 cycloalkyl, 3-6 membered heterocycloalkyl, monocyclic aryl,
5-6 membered ring heteroaryl, C1-4 alkylcarbonyloxy, C1-4
alkyloxycarbonyl, C1-4 alkylcarbonyl, formyl, C1-4
alkylcarbonylamino, or C1-4 aminocarbonyl. L is further optionally
interrupted by --O--, --S--, --N(Rc)-, --N(Rc)-C(O)--,
--N(Rc)--C(O)--O--, --O--C(O)--N(Rc)-, --N(Rc)--C(O)--N(Rd)-,
--O--C(O)--, --C(O)--O--, or --O--C(O)--O--. Each of Rc and Rd,
independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl,
aminoalkyl (primary, secondary or tertiary), or haloalkyl; and each
of X', X'' and X''' is a C1-18 alkyl, halogen, C1-8 alkoxy, C1-8
alkylcarbonyloxy, or amino group, with the proviso that at least
one of X', X'', and X''' is a labile group. Further, any two or all
of X', X'' and X''' may be joined through a covalent bond. The
amino group may be an alkylamino group. Examples of
amino-substituted organosilanes include
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane (SILQUEST A-1110),
3-aminopropyltriethoxysilane (SILQUEST A-1100),
3-(2-aminoethyl)aminopropyltrimethoxysilane (SILQUEST A-1120),
SILQUEST A-1130, (aminoethylaminomethyl)phenethyltrimethoxysilane,
(amino ethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (SILQ UEST
A-2120), bis-(.gamma.-triethoxysilylpropyl)amine (SILQUEST A-1170),
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, oligomeric
aminosilanes such as DYNASYLAN 1146,
3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
[0097] Additional "precursor" compounds such as a bis-silyl urea
[RO).sub.3Si(CH.sub.2)NR].sub.2C.dbd.O are also examples of
amino-substituted organosilane ester or ester equivalent that
liberate amine by first dissociating thermally. The amount of
aminosilane is between 0.01% and 10% by weight relative to the
functional polymer, preferably between 0.03% and 3%, and more
preferably between 0.1% and 1%.
[0098] In some embodiments, the adhesion-promoting reagents can be
added to a coating mixture comprising a first organosilane and a
liquid crystal silane, as disclosed herein, and contacted with a
substrate (e.g., a glass substrate) under conditions that
facilitate the formation of Si--O--Si linkages, as described
herein. The coating mixture can be contacted with a suitable
substrate, as described herein. Accordingly, the silane group in
the adhesion-promoting reagent can link a first organosilane
molecule to another first organosilane molecule (which may
optionally be a component of a polymeric structure), a quaternary
ammonium organosilane (e.g., the liquid crystal silane disclosed in
U.S. Pat. No. 6,504,582) molecule (which may optionally be a
component of a polymeric structure); or the substrate; or the
silane group in the adhesion-promoting reagent can link a liquid
crystal silane molecule to another liquid crystal silane molecule
(which may optionally be a component of a polymeric structure) or
to the substrate.
[0099] In some embodiments, the adhesion-promoting reagents can be
added to a coating mixture comprising a polymer having a plurality
of pendant groups that include a first pendant group that includes
a first quaternary ammonium component, a second pendant group that
includes a nonpolar component, and subsequently a third pendant
group that includes an organosilane or organic silane ester
component. Optionally, the coating mixture further can comprise a
first organosilane, as described herein. The coating mixture can be
contacted with a suitable substrate and heated as described herein
to facilitate the formation of Si--O--Si bonds.
[0100] In an alternative embodiment, one or more adhesion-promoting
reagent can be dissolved in an organic solvent and coated onto a
suitable substrate (e.g., glass) as described herein to form a
first coating. After removal of the solvent by evaporation, the
substrate comprises a layer (i.e., a "primer layer" or
"adhesion-promoting" layer) of the adhesion-promoting reagent
coated thereon. Subsequently, a composition (e.g., a solution)
comprising any antimicrobial polymer of the present disclosure in
organic solvent can be coated onto the primer layer. After removal
of the solvent by evaporation, the substrate now comprises two
layers, the "primer layer" and the antimicrobial polymer layer. The
substrate, now comprising two coated layers, can be heated (e.g.,
to about 120 degrees C. for about 3 minutes to about 15 minutes) to
facilitate the formation of Si--O--Si bonds and, thereby,
covalently couple the polymer to the substrate.
Catalysts:
[0101] In any embodiment the method of making an antimicrobial
coating according the present disclosure, one or more catalyst can
be used in the process. Suitable catalysts include any compound
that promotes the formation of Si--O--Si bonds. Nonlimiting
examples of suitable catalysts include an acid (e.g., an organic
acid), a base (e.g., an organic base), tin octoate and
1,8-Diazabicycloundecene (DBU). In any embodiment, the catalyst can
be added with the antimicrobial component and the
adhesion-promoting reagent, if present, to the first composition
described herein.
[0102] In use, the catalyst can be dissolved in the first
composition, second composition, first mixture and/or second
mixture described herein. Typically, the final concentration of the
catalyst in any coating composition is relatively low (e.g., about
0.04 weight percent). A person of ordinary skill in the art will
recognize that the concentration of the catalyst should be
sufficiently high enough to catalyze the cross-linking reaction,
while avoiding substantial interference with the optical properties
(e.g., color) of the coating and/or interference with the
shelf-life of the coating mixture.
Substrates and Articles:
[0103] Antimicrobial polymers of the present disclosure can be
applied as a coating to a variety of substrates. Useful substrates
include, for example, non-siliceous ceramic materials, siliceous
materials such as glasses and siliceous ceramic materials, metals,
metal oxides, natural and man-made stones, woven and non-woven
fabrics, wood, and polymeric materials that are either
thermoplastic polymers or thermoset polymers. Exemplary polymeric
substrates include, but are not limited to, rayon polyester,
polyethylene terephthalate (PET), poly(meth)acrylates,
polycarbonates, polystyrenes, polystyrene copolymers such as
styrene acrylonitrile copolymers, polyesters, polyethersulfone,
acrylics and acrylic copolymers, polyacrylamides, and
polyurethanes, and combinations thereof. Suitable natural polymer
substrates include, for example, polylactic acid (PLA),
polyglycolic acid (PGA), wood pulp, cotton, cellulose, rayon, and
combinations thereof.
[0104] The substrates can be used to fabricate a variety of useful
articles (e.g., as a part, a portion, or the entirety of the
article). The articles comprise a variety of surfaces that may be
deliberately or incidentally contacted with
microbiologically-contaminated items during routine use. The
articles include, for example, electronic displays (e.g., computer
touch screens). Suitable articles may be found in food-processing
environments (e.g., food-processing rooms, equipment, countertops)
and health care environments (e.g., patient care rooms,
countertops, bedrails, patient care equipment such as instruments
and stethoscopes, and in-dwelling medical devices such as urinary
catheters and endotracheal tubes).
Methods of Preparing Antimicrobial Coated Articles:
[0105] The present disclosure provides methods for coating the
antimicrobial polymer of the present disclosure onto a substrate.
The composition (e.g., a reaction mixture in a solution) comprising
the antimicrobial polymer in solvent (e.g., an aqueous solvent, an
organic solvent) can be contacted with a substrate. The solvent can
be evaporated to leave the antimicrobial polymer in the form of a
coating on the substrate. In some embodiments, the substrate can be
heated before and/or during the contacting step to accelerate the
evaporation of the solvent. Preferably, the substrate is heated to
a temperature that does not degrade the function of the polymer or
a component of the substrate onto which the polymer is coated. A
suitable temperature for contacting the polymer solution on a glass
substrate is from room temperature to about 120.degree. C. A person
of ordinary skill in the art will recognize that higher
temperatures will facilitate faster removal of organic solvent from
the polymer solution.
[0106] In some embodiments, the antimicrobial polymer can be
diluted to a final concentration of 1 wt. % to about 20 wt % in the
organic solvent before using the diluted solution to coat the
antimicrobial polymer onto a substrate. In some embodiments, the
antimicrobial polymer is diluted to a final concentration of 1 wt %
to about 5 wt % in the organic solvent before using the diluted
solution to coat the antimicrobial polymer onto a substrate.
Suitable organic solvents to dilute the polymer have a flashpoint
below 150.degree. C. and include ethers, ketones esters and
alcohols, for example, isopropyl alcohol.
[0107] Turning back to the drawings, FIG. 4 shows one embodiment of
a method of preparing a coated article according to the present
disclosure. The method includes the step 454 of forming a first
composition comprising an antimicrobial polymer in a solvent. The
polymer can be formed by mixing a plurality of monomers in a
suitable solvent (e.g., an organic solvent such as isopropyl
alcohol, for example) as disclosed herein. Preferably, a relatively
small portion (e.g., 3%) of the solvent comprises acidified water.
Acidified water in the reaction mixture can facilitate bonding
between silane groups. Optionally, after forming the antimicrobial
polymer, the polymer composition can be diluted (not shown) in a
solvent, as described above, before contacting it with a
substrate.
[0108] The method may include optional step 456 of mixing the first
composition with a second quaternary ammonium compound and/or a
second organosilane compound to form a first mixture. Suitable
second quaternary ammonium compounds are described in U.S. Pat. No.
6,504,583; and include antimicrobial silanated quaternary amine
compounds such as
N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-1-octadecanaminium
chloride (CAS Number 27668-52-6), for example. Suitable second
organosilane compounds comprise hydrolyzable groups and can
facilitate the formation of crosslinks between silanated compounds
and/or crosslinks between silanated compounds and a siliceous
substrate. Examples of suitable second organosilane compounds
include alkyl halide organosilane compounds and trimethoxysilyl
compounds (e.g., 3-chloropropyltrimethoxysilane).
[0109] The method further comprises the step 458 of contacting the
first composition with the first substrate under conditions
suitable to permit bonding between the antimicrobial polymer and
the first substrate. Initially, the first composition, which may
optionally include an antimicrobial monomer, is applied to a first
substrate. The first substrate may be any of the suitable
substrates disclosed herein. In some embodiments, the first
substrate may be a coating (e.g., a siliceous coating) on a second
substrate (e.g., a polymer or glass substrate). In some
embodiments, the first substrate may be glass, a polymer film, or a
diamond-like glass material. Suitable diamond-like glass materials
are described in U.S. Pat. Nos. 6,696,157; 6,015,597; and
6,795,636; and U.S. Patent Application Publication No. US
2008/196664. The first composition may be applied by a variety of
processes known in the art such as, for example, wiping, brushing,
dip coating, curtain coating, gravure coating, kiss coating, spin
coating, and spraying.
[0110] Contacting the first composition with the substrate further
comprises contacting the first composition under conditions that
facilitate the formation of Si--O--Si bonds. A person having
ordinary skill in the art will appreciate that during and after the
period which solvent of the first composition evaporates,
components of the first composition will begin reacting with each
other and/or with the siliceous substrate to form Si--O--Si bonds.
This reaction will proceed relatively slowly at ambient temperature
(circa 23.degree. C.). Heating the substrate can facilitate the
formation of cross-linking covalent bonds between the silane groups
in the antimicrobial coating composition and the silane groups on
the surface of the first substrate. Thus, in certain preferred
embodiments, the formation of the Si--O--Si bonds can be
accelerated by the optional step 460 of exposing the coated
substrate to an elevated temperature. Without being bound by
theory, other forces (e.g., hydrophobic interaction, electrostatic
forces, hydrogen bonding, and/or adhesion) also may facilitate
coupling of components of the antimicrobial coating composition to
the first substrate.
[0111] In general, exposing the first substrate to higher
temperatures while contacting it with the polymer composition will
require shorter times for the solvent to evaporate and for the
polymer to bond to the first substrate. However, the contacting
step should be performed at temperatures below which the siloxane
bonds dissociate. For example, in some embodiments, the contacting
step can be conducted at about ambient temperature (20-25.degree.
C.) for about 10 minutes to about 24 hours. In some embodiments,
the contacting step can be conducted at about 130.degree. C. for
about 30 seconds to about 3 minutes. The conditions for the
contacting step can have a significant impact on the properties of
the polymer coating on the substrate. For example, a polymer
contacted ("cured") at room temperature for 24 hours can be
measurably more hydrophobic than a polymer cured at about
130.degree. C. for about 3 minutes. In some embodiments, the
hydrophobicity of the coating correlates with the durability of the
polymer coating on the substrate.
[0112] In some embodiments (not shown), the method optionally
includes pre-treatments of the substrates by priming, plasma
etching, corona for interfacial adhesion of the coating to
substrates.
[0113] In some embodiments (not shown), the method optionally
includes post treatments of the coating by heating or irradiations
including UV, IR plasma, E-beam for further improvement of
interfacial adhesion of the coating to substrates. These treatments
can promote inter-polymer crosslinking, as well as increase the
number of covalent linkages between the polymer and the substrate,
thereby improving the durability of the coating on the surface of
the substrate. If the first substrate is exposed to an elevated
temperature (step 460), the method may include cooling the
substrate. Typically, the substrate is cooled to room
temperature.
[0114] In some embodiments, the method optionally includes the step
462 of coupling the first substrate to a second substrate. The
first substrate may be coupled to the second substrate before or
after the step 458 of contacting the first composition or first
mixture with the first substrate. The second substrate may be any
suitable substrate described herein. For example, the second
substrate may be a glass layer or particle and the first substrate
may be a glass or diamond-like coating and the polymer may be
applied to the first substrate after the first substrate is coated
onto the second substrate. In an alternative embodiment, the first
substrate may be a polymer film with adhesive on one major surface
of the film. In the alternative embodiment, the polymer composition
may be applied to the major surface of the film opposite the
adhesive and the polymer-coated adhesive film may subsequently be
coupled via the adhesive to a second substrate such as a glass or
polymer layer, for example.
[0115] In some embodiments, the method further comprises a step of
applying a siliceous layer to the first substrate. The first
substrate may be any suitable substrate described herein to which a
siliceous layer may be applied. The siliceous layer may be applied
by methods that are known to a person of ordinary skill in the art.
A nonlimiting example of applying a siliceous layer to a substrate
is described in Example 1 of U.S. Pat. No. 7,294,405; wherein an
antiglare hard coat siliceous layer is applied to a glass
substrate. In these embodiments, the method further includes
forming a first composition comprising the antimicrobial polymer in
a solvent, as described above, for example. Optionally, the these
embodiments may include the step of mixing the first composition
with a second quaternary ammonium compound to form a first mixture,
as described above, for example. The method further includes
contacting the first composition or first mixture to the siliceous
layer. The first composition or first mixture can be applied by any
suitable coating method, such as the coating methods described
herein, for example. Contacting the first composition with the
siliceous layer further comprises contacting the first composition
with the siliceous layer under conditions suitable to facilitate
the formation of Si--O--Si bonds, as described herein. Optionally,
contacting the first composition with the first substrate may
further comprise treating the polymer-coated substrate with actinic
and/or ionizing radiation (e.g., ultraviolet light, e-beam, plasma,
or the like). This treatment can promote inter-polymer
crosslinking, as well as increase the number of covalent linkages
between the polymer and the substrate, thereby improving the
durability of the coating on the surface of the substrate.
[0116] It should be noted that, in any embodiment of the methods
disclosed herein, pretreatment of siliceous layers or substrates
prior to applying antimicrobial polymer compositions of the present
disclosure can improve the bonding between the polymer and the
substrate (e.g., siliceous material). Pretreatment of the siliceous
layer or the substrate may include, for example, soaking the layer
or the substrate in a volatile solvent (e.g., water, isopropyl
alcohol) and/or wiping the layer or the substrate with the volatile
solvent. Optionally, the solvent may further comprise a solution of
a basic compound such as potassium hydroxide, for example. In some
embodiments, the solvent may be saturated with the solution of the
basic compound.
[0117] In particular, pretreatments that include heating the
siliceous layer or the substrate from about 100 degrees to about
150 degrees for 20 minutes to 60 minutes can improve the bonding
between the polymer and the substrate. Other suitable heat
treatments include exposing the siliceous substrate to a
temperature from about 475 to about 550 degrees C. for a duration
of at least about 3 minutes or longer; preferably, for about 3
minutes to about 10 minutes; more preferably, for about 6 minutes
to about 10 minutes. In some embodiments, pretreatment by heating
the substrate shortly before the antimicrobial coating is applied
results in improved bonding (e.g., as measured by the durability of
the coating) between the coating and the substrate. The improved
bonding can result in significantly greater durability of the
polymer layer on the substrate. This can be demonstrated, for
example, using the Eraser Test described herein. Without being
bound by theory, it is believed that pretreatment of the substrate
by heating removes excess moisture and other impurities (e.g.,
organic residues) present on the surface of the substrate (e.g.,
siliceous material) and provides greater ability of the surface
silane groups to react with the silanated polymers and/or compounds
in the coating compositions disclosed herein.
Embodiments
[0118] Embodiment A is an article, comprising:
[0119] an organic polymer having a plurality of pendant groups
comprising [0120] a first pendant group comprising a first
quaternary ammonium component; [0121] a second pendant group
comprising a nonpolar component; [0122] a third pendant group
comprising a first organosilane component; and
[0123] a touch-sensitive substrate comprising a surface;
[0124] wherein the organic polymer is coupled to the surface.
[0125] Embodiment B is the article of embodiment A, further
comprising a siliceous substrate that includes a first side and a
second side, wherein the organic polymer is coupled to the first
side of the siliceous substrate, and wherein the touch-sensitive
substrate is coupled to the second side of the siliceous
substrate.
[0126] Embodiment C is the article of embodiment A or embodiment B,
wherein the article does not comprise a conductive layer.
[0127] Embodiment D is the article of any one of the preceding
embodiments, wherein the organic polymer further comprises a second
quaternary ammonium component.
[0128] Embodiment E is the article of any one of the preceding
embodiments, wherein the organic polymer further comprises a second
organosilane component.
[0129] Embodiment F is the article of embodiment E, wherein the
second organosilane component comprises an alkyl halide.
[0130] Embodiment G is the article of any one of the preceding
embodiments wherein, in the organic polymer, the ratio of the
number of N atoms associated with the first quaternary ammonium
component and second quaternary ammonium component, if present, and
the number of Si atoms associated with the first organosilane
component and second organosilane component, if present, is about
0.1:1 to about 10:1.
[0131] Embodiment H is the article of any one of the preceding
embodiments, wherein at least one of the pendant components
comprises a fluorochemical.
[0132] Embodiment I is the article of embodiment H, wherein the
second pendant group comprises a fluorochemical.
[0133] Embodiment J is the article of any one of the preceding
embodiments, wherein the contact angle of deionized water deposited
on the cured polymer is about 80.degree. to about 120.degree.,
using the ASTM D 7334.7606-1 test method.
[0134] Embodiment K is the article of embodiment J, wherein the
contact angle of deionized water deposited on the cured polymer is
about 85.degree. to about 110.degree., as measured by ASTM test
method number D 7334.7606-1.
[0135] Embodiment L is the article of any one of the preceding
embodiments, wherein the scratch resistance of the cured polymer is
about #5 to about #8 Moh's hardness, as measured by ASTM test
method number D 7027.26676.
[0136] Embodiment M is the article of any one of the preceding
embodiments, wherein the surface to which the organic polymer is
coupled is a glass or a polymeric surface.
[0137] Embodiment N is the article of any one of the preceding
embodiments, wherein the siliceous substrate is covalently coupled
to the touch-sensitive substrate.
[0138] Embodiment O is the article of any one of embodiments A
through P, wherein the substrate further comprises an antiglare
component.
[0139] Embodiment P is a method of making a coated article, the
method comprising:
[0140] forming a first composition of an organic polymer in organic
solvent, the polymer having a plurality of pendant groups
comprising, [0141] a first pendant group comprising a first
quaternary ammonium component, [0142] a second pendant group
comprising a nonpolar component, and [0143] a third pendant group
comprising a first organosilane component;
[0144] mixing a second quaternary ammonium component with the first
composition to form a first mixture; and
[0145] contacting the first mixture with a substrate under
conditions suitable to form covalent linkages between the organic
polymer, the substrate, and the second quaternary ammonium
component.
[0146] Embodiment Q is the method of embodiment P, wherein forming
a first mixture further comprises forming a first mixture that
includes a catalyst compound.
[0147] Embodiment R is the method of embodiment P or embodiment Q,
wherein forming a first mixture further comprises forming a first
mixture comprising a second organosilane component.
[0148] Embodiment S is the method of any one of embodiments P
through R, further comprising coupling the substrate to a
touch-sensitive substrate.
[0149] Embodiment T is the method of embodiment S, wherein coupling
the siliceous substrate to the touch-sensitive substrate comprises
covalently coupling the siliceous substrate to the touch-sensitive
substrate.
[0150] Embodiment U is a method of making a coated article, the
method comprising:
[0151] forming a first composition of an organic polymer in organic
solvent, the polymer having a plurality of pendant groups
comprising, [0152] a first pendant group comprising a first
quaternary ammonium component, [0153] a second pendant group
comprising a nonpolar component, and [0154] a third pendant group
comprising a first organosilane component;
[0155] mixing an adhesion-promoting reagent with the first
composition to form a second mixture; and
[0156] contacting the second mixture with a substrate under
conditions suitable to form covalent linkages between the organic
polymer and the substrate.
[0157] Embodiment V is the method of embodiment U, wherein forming
a second mixture further comprises forming a first composition that
includes a catalyst compound.
[0158] Embodiment W is the method of embodiment U or embodiment V,
wherein forming a second mixture further comprises forming a second
mixture comprising a second quaternary ammonium component.
[0159] Embodiment X is the method of any one of embodiments U
through W, wherein forming a second mixture further comprises
forming a second mixture comprising a second organosilane
component.
[0160] Embodiment Y is the method of any one of embodiments U
through X, wherein the adhesion-promoting reagent is selected from
the group consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
[0161] Embodiment Z is The method of any one of embodiments P
through Y, further comprising:
[0162] contacting a second composition comprising an
adhesion-promoting reagent in organic solvent with the siliceous
substrate under conditions suitable to form covalent linkages
between the adhesion-promoting reagent and the siliceous
substrate;
[0163] wherein contacting the second composition with the siliceous
substrate occurs prior to contacting the first or second mixture
with the siliceous substrate.
[0164] Embodiment AA is the method of embodiment Z, wherein
contacting the second composition with the siliceous substrate
further comprises contacting the second composition with the
siliceous substrate at a temperature higher than 25.degree. C.
[0165] Embodiment BB is a method of making a coated article, the
method comprising:
[0166] forming a first composition of an organic polymer in organic
solvent, the polymer having a plurality of pendant groups
comprising, [0167] a first pendant group comprising a first
quaternary ammonium component, [0168] a second pendant group
comprising a nonpolar component, and [0169] a third pendant group
comprising a first organosilane component;
[0170] mixing a second quaternary ammonium component with the first
composition to form a first mixture; and
[0171] contacting the first mixture with a touch-sensitive
substrate under conditions suitable to form covalent linkages
between organic polymer and the touch-sensitive substrate.
[0172] Embodiment CC is the method of embodiment BB, wherein
forming a first mixture further comprises forming a first mixture
that includes a catalyst compound.
[0173] Embodiment DD is the method of embodiment BB or embodiment
CC, wherein mixing a second quaternary ammonium component with the
first composition further comprises mixing a second organosilane
component with the first composition.
[0174] Embodiment EE is the method of any one of embodiments BB
through DD, further comprising, after the contacting step, rinsing
the coated article.
[0175] Embodiment FF is a method of making a coated article, the
method comprising:
[0176] forming a first composition of an organic polymer in organic
solvent, the polymer having a plurality of pendant groups
comprising, [0177] a first pendant group comprising a first
quaternary ammonium component, [0178] a second pendant group
comprising a nonpolar component, and [0179] a third pendant group
comprising a first organosilane component;
[0180] mixing an adhesion-promoting reagent with the first
composition to form a second mixture; and
[0181] contacting the second mixture with a touch-sensitive
substrate under conditions suitable to form covalent linkages
between organic polymer, the touch-sensitive substrate, and the
second quaternary ammonium component.
[0182] Embodiment GG is the method of embodiment FF, wherein
forming a second mixture further comprises mixing a second
quaternary ammonium component with the adhesion-promoting reagent
and the first composition.
[0183] Embodiment HH is the method of embodiment FF or embodiment
GG, wherein the adhesion-promoting reagent is selected from the
group consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
[0184] Embodiment II is the method of any one of embodiments BB
through HH, further comprising:
[0185] providing a second composition comprising a
adhesion-promoting reagent in organic solvent;
[0186] contacting the second composition with the touch-sensitive
substrate;
[0187] wherein contacting a second composition with the
touch-sensitive substrate occurs prior to contacting the first or
second mixture with the siliceous substrate.
[0188] Embodiment JJ is an antimicrobial composition,
comprising:
[0189] an organic polymer having a plurality of pendant groups
comprising [0190] a first pendant group comprising a first
quaternary ammonium component; [0191] optionally, a second pendant
group comprising a perfluorinated nonpolar component; and [0192] a
third pendant group comprising a first organosilane component;
[0193] with the proviso that the polymer does not comprise a
pendant group that includes a carboxylate or alkoxylate chemical
group.
[0194] Embodiment KK is the antimicrobial composition of embodiment
JJ, further comprising a fourth pendant component, wherein the
fourth pendant component comprises a polar chemical group.
[0195] Embodiment LL is a composition, comprising:
[0196] a solvent;
[0197] a polymer having a plurality of pendant groups
comprising,
a first pendant group comprising a first quaternary ammonium
component, [0198] a second pendant group comprising a nonpolar
component, and [0199] a third pendant group comprising a first
organosilane component; and
[0200] an adhesion-promoting reagent.
[0201] Embodiment MM is the composition of embodiment LL, wherein
the adhesion-promoting reagent is selected from the group
consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl) phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
[0202] Embodiment NN is an article, comprising:
[0203] a touch-sensitive substrate comprising a surface;
[0204] a first layer coated on the surface, the first layer
comprising an adhesion-promoting reagent; and
[0205] a second layer coated on the first layer, the second layer
comprising an organic polymer having a plurality of pendant groups
comprising [0206] a first pendant group comprising a first
quaternary ammonium component; [0207] a second pendant group
comprising a nonpolar component; [0208] a third pendant group
comprising a first organosilane component.
[0209] Embodiment OO is the article of embodiment NN, wherein the
adhesion-promoting reagent is selected from the group consisting of
3-triethoxysilyl-N-(1,3-dimethyl-butyliden)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, and
3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-(2-aminoethyl)aminopropyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
(aminoethylaminomethyl)phenethyltriethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
bis-(.gamma.-triethoxysilylpropyl)amine,
N-(2-aminoethyl)-3-aminopropyltributoxysilane,
6-(aminohexylaminopropyl)trimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane,
p-(2-aminoethyl)phenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropylmethyldiethoxysilane, tetraethoxysilane and oligomers
thereof, methyltriethoxysilane and oligomers thereof, an oligomeric
aminosilane, 6,3-(N-methylamino)propyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane, and
3-aminopropyldimethylethoxysilane.
[0210] The invention will be further illustrated by reference to
the following non-limiting Examples. All parts and percentages are
expressed as parts by weight unless otherwise indicated.
EXAMPLES
[0211] The present invention is more particularly described in the
following examples that are intended as illustrations only, since
numerous modifications and variations within the scope of the
present invention will be apparent to those skilled in the art.
Unless otherwise noted, all parts, percentages, and ratios reported
in the following examples are on a weight basis, and all reagents
used in the examples were obtained, or are available, from the
chemical suppliers described below, or may be synthesized by
conventional techniques.
[0212] A list of reagents used in the following examples in shown
in Table 1.
TABLE-US-00001 TABLE 1 Abbreviation Chemical Name Source 2EHA
2-Ethylhexyl acrylate Dow; Midland, MI A-174 Methacryloylpropyl
trimethoxy silane Aldrich; Milwaukee, WI AA Acrylic acid BASF;
Florham, NJ A1120 N(beta-aminoethyl) gamma- ShinEtsu; Akron, OH
aminopropyltrimethoxysilane AEM5700 3-(trimethoxysilyl)- Aegis
Environmental, propyldimethyloctadecyl ammonium Midland, MI
chloride BHT 2,6-Di-tert-4-methyl phenol Aldrich; Milwaukee, WI
C.sub.16H.sub.33Br 1-bromohexyl decane Chemtura Corporation, Bay
Minette, AL C4FA Perfluorobutyl sulfonamide n-methyl ethyl Made as
described in acrylate U.S. Pat. No. 6,852,781 DMAc Dimethyl
acrylamide Jarchem Industries, Inc. Newark, NJ DMAEA
Dimethylaminoethyl acrylate CIBA; Marietta, GA DMAEA-
Dimethylaminoethyl acrylate C16 bromide See Example 2 C16Br
DMAEA-MCl Dimethylaminoethyl acrylate methyl CIBA; Marietta, GA
chloride DMAEMA Dimethylaminoethyl methacrylate CIBA; Marietta, GA
DMAEMA- Dimethylaminoethyl methacrylate C16 See Example 1 C16Br
bromide DMAEMA- Dimethylaminoethyl methacrylate methyl CIBA;
Marietta, GA MCl chloride EOA Methoxy polyethylene glycol acrylate
Shin Nakamura Chemicals; Wakayama, JP EOMA polyethyleneglycol
monomethacrylate Nippon Nyukazai Co; Tokyo, JP EtOAc Ethyl acetate
J.T. Baker; Austin, TX EtOH Ethanol J.T. Baker; Austin, TX HEMA
Hydoxyethyl methacrylate Cyro Industries; Parsippany, NJ HFPOA
Hexafluoropropylene oxide oligomer U.S. Patent Application amidol
acrylate Publication No. 2004/0077775 HFPOMA Hexafluoropropylene
oxide oligomer U.S. Patent Application amidol methacrylate
Publication No. 2004/0077775 IBMA Isobutyl methacrylate Lucite
International, Inc. Cordova, TN IOA Iso-octyl acrylate Sartomer
USA, LLC; Exton, PA IPA Isopropyl alcohol VWR; Houston, TX MEHQ
4-Methoxyphenol Alfa Aesar, Ward Hill, MA NHMAc
N-(hydroxymethyl)-acrylamide Aldrich; Milwaukee, WI NVP
N-Vinylpyrrolidinone ISP Chemicals, Inc.; Calvary City, KY SnOA
Tin-octoate Alfa Aesar, Ward Hill, MA Vazo-67
2,2-Azobis(2-methylbutyronitrile) Dupont; Wilmington, DE
Example 1
Synthesis of DMAEMA-C.sub.16Br Monomer
[0213] In a clean reactor; fitted with an overhead condenser,
mechanical stirrer, and a temperature probe; were charged 918 parts
by weight of acetone, 807 parts of C.sub.16H.sub.33Br) 415.5 parts
of DMAEMA, 2.0 parts of BHT and 2.0 parts of MEHQ. The batch was
stirred at 150 rpm and a mixed gas (90/10 O.sub.2/N.sub.2) was
purged through the solution throughout the reaction scheme. The
mixture was heated to 74.degree. C. for 18 hours. A sample was
taken out for analysis by gas chromatography (GC) and which
revealed the conversion of >98% of the reactants to the desired
product. At this point 918 parts of EtOAc was added slowly with
stirring at very high speed. A white solid started to precipitate
out. The heating was stopped and the mixture was cooled to room
temperature. The reaction precipitate was recovered by filtration
and the white solid material was washed with 200 parts of cold
EtOAc. The solid material was dried in a vacuum oven at 40.degree.
C. for 8 hours. The dried product was analyzed by nuclear magnetic
resonance (NMR) spectroscopy, which revealed the presence of
>99.9% pure DMAEMA-C.sub.16Br monomer.
Example 2
Synthesis of DMAEA-C.sub.16Br Monomer
[0214] In a clean reactor; fitted with an overhead condenser,
mechanical stirrer, and a temperature probe; were charged 546 parts
of acetone, 488 parts of C.sub.16H.sub.33Br, 225 parts of DMAEA,
1.0 parts of BHT and 1.0 parts of MEHQ. The batch was stirred at
150 rpm and a mixed gas (90/10 O.sub.2/N.sub.2) was purged through
the solution throughout the reaction scheme. The mixture was heated
to 74.degree. C. for 18 hours. A sample was taken out for analysis
by GC and it revealed the conversion of >98% of the reactants to
the desired product. At this point the reaction mixture heating was
stopped and 1,000 parts of EtOAc was added slowly with stirring at
very high speed. A white solid started to precipitate out. The
mixture was allowed to cool to room temperature. The precipitate
accumulated in the solution upon standing for couple of hours at
room temperature. The reaction mixture was filtered and the white
solid filtrate was washed with 1,000 parts of cold EtOAc. The white
solid filtrate was dried in a vacuum oven at 40.degree. C. for 8
hours. The solid material was analyzed by NMR spectroscopy, which
revealed the presence of >99.9% pure DMAEA-C.sub.16Br
monomer.
Examples 3-39
Synthesis of Antimicrobial Polymers
[0215] In a clean reaction bottle, the monomers (e.g., in Example
6, 50 parts of DMAEMA-C.sub.16Br monomer, 10 parts of A-174
monomer, and 40 parts of IOA monomer) were combined with 0.5 parts
of Vazo-67 and 300 parts of IPA. The mixture was purged with dry
nitrogen for 3 minutes. The reaction bottle was sealed and placed
in a 65.degree. C. preheated water bath with mixing. The reaction
mixture was heated for 17 hours at 65.degree. C. with mixing. The
viscous reaction mixture was analyzed for % solids. To drive the
reaction of the residual monomer to >99.5% completion, an
additional 0.1 parts of Vazo-67 was added to the mixture, the
solution was purged and sealed. The bottle was placed in the
65.degree. C. water bath with mixing and heated for 8 hours. A
conversion of (>99.5%) of the monomers was achieved, as evident
by % solids calculation.
[0216] The polymers shown in Table 2 each were made according to
this process. Table 2 lists the polymers that were synthesized in
each Example. Comparative examples, which do not comprise an
organosilane pendant group, are so designated in Table 2.
TABLE-US-00002 TABLE 2 Antimicrobial polymers. The polymer
designation (e.g., "p(DMAEMA- C16Br/A-174/IBMA)" in Example 4)
refers to the combination of monomers used in the reaction mixture.
Comparative examples, which do not comprise an organosilane pendant
group, are designated with the notation "comparative". Example #
Polymer Designation Monomer Ratio 3 comparative
p(DMAEMA-C.sub.16Br/AA/IOA) 50/20/30 4 p(DMAEMA-C16Br/A-174/IBMA)
50/10/40 5 p(DMAEA-MCl/A-174/IBMA) 50/10/40 6
p(DMAEMA-C16Br/A-174/IOA) 50/10/40 7 comparative
p(DMAEMA-C.sub.16Br/AA/IOA) 50/20/30 8
p(DMAEMA-C16Br/A-174/NHMAc/IOA 50/10/10/30 9 comparative
p(DMAEMA-C16Br/HEMA/NHMAc/IOA 50/10/10/30 10
p(DMAEMA-C16Br/A-174/DMAc/IOA 50/10/10/30 11 comparative
p(DMAEMA-C16Br/HEMA/DMAc/IOA 50/10/10/30 12 comparative
p(DMAEMA-C16Br/AA/IBMA 50/20/30 13 comparative
p(DMAEMA-C16Br/AA/2EHA 50/20/30 14 comparative
p(DMAEMA-C16Br/HFPOMA/AA) 50/20/30 15 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 50/20/10/20 16 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA) 50/20/10/20 17 comparative
p(DMAEMA-C16Br/HFPOMA/DMAc/AA) 50/20/10/20 18 comparative
p(DMAEMA-C16Br/HFPOA/AA) 50/20/30 19 comparative
p(DMAEMA-C16Br/HFPOA/HEMA/AA) 50/20/10/20 20 comparative
p(DMAEMA-C16Br/HFPOA/DMAc/AA) 50/20/10/20 21 comparative
p(DMAEMA-C16Br/HFPOA/EOA/AA) 50/20/10/20 22 comparative
p(DMAEMA-C16Br/HFPOA/IOA/AA) 50/20/20/10 23
p(DMAEA-C16Br/A-174/AA/IBMA) 50/5/5/40 24
p(DMAEA-C16-Br/A-174/AA/IOA) 50/5/5/40 25
p(DMAEMA-C16Br/EOMA/A-174/HFPOMA) 50/20/10/20 26
p(DMAEMA-C16Br/HEMA/A-174/HFPOMA) 50/20/10/20 27
p(DMAEMA-C16Br/A-174/NHMAc/IOA) 50/10/10/30 28
p(DMAEMA-C16Br/A-174/NVP/IOA) 50/5/15/30 29
p(DMAEMA-C16Br/A-174/NHMAc/IOA/EOA) 50/5/10/10/25 30
p(DMAEA-C16Br/A-174/NHMAc/IOA) 50/10/10/30 31
p(DMAEA-MCl/A-174/EOA/IOA) 50/5/20/25 32 p(DMAEMA-C16Br/A-174/IOA)
50/10/40 33 comparative p(DMAEMA-C16Br/HFPOMA/HEMA/AA) 50/20/10/20
34 p(DMAEMA-C16Br/A-174/IOA/AA) 50/10/30/10 35
p(DMAEMA-C16Br/C4FA/A-174/AA 50/20/10/20 36
p(DMAEA-C16Br/A-174/IOA) 50/10/40 37 p(DMAEA-C16Br/A-174/IOA/AA
50/10/30/10 38 p(DMAEA-C16Br/DMAEA-MC1/A-174/IOA 25/25/10/40 39
p(DMAEA-C16Br/A-174/NVP/IOA 50/5/15/30
Examples 40-62
Method of Coating Antimicrobial Polymers onto Conductive Surface
Capacitive Touch (SCT) Sensor Glass Substrates
[0217] Conductively-coated glass (part number 29617) was obtained
from Pilkington North America, Inc. (Toledo, Ohio). A
glare-resistant hardcoat was applied to the glass according to the
method described in Example 1 of U.S. Pat. No. 7,294,405. The
coated glass was cut into coupons, approximately 4'' by 4'' (10.2
cm by 10.2 cm), for coating and testing purposes.
[0218] Polymer solutions from the Examples shown in Table 3 were
diluted in isopropyl alcohol to 5 wt % polymer. Approximately 5
milliliters of the diluted polymer solution were applied to a wipe
(Sealed Edge Wiper 6259HC; Coventry, Kennesaw, Ga.), which was used
immediately to manually distribute the polymer solution evenly over
the surface of the glass coupon. The solvent was removed by heating
the sample at 120.degree. C. in a convection oven for 3-4 minutes.
After completely removing the solvent, the glass coupons were
washed with soap (Optisolve OP7153-LF detergent; available from
Kyzen North America (Manchester, N.H.) and deionized water in a
36'' Billco Versa Clean Washer (Billco Manufacturing, Inc.,
Zelienople, Pa.) with attached fluid head and roller wash pan and
dried. The dried samples were tested as described below.
TABLE-US-00003 TABLE 3 Polymer-coated SCT glass substrates.
Comparative examples, which do not comprise an organosilane pendant
group, are designated with the notation "comparative". Polymer
Example Example No. Polymer Designation No. 40
p(DMAEMA-C16Br/A-174/IBMA) 4 41 p(DMAEA-MCl/A-174/IBMA) 5 42
p(DMAEMA-C16Br/A-174/IOA) 6 43 comparative p(DMAEMA-C16Br/AA/IOA) 7
44 p(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 45 comparative
p(DMAEMA-C16Br/HEMA/NHMAc/IOA) 9 46 p(DMAEMA-C16Br/A-174/DMAc/IOA)
10 47 comparative p(DMAEMA-C16Br/HEMA/DMAc/IOA) 11 48 comparative
p(DMAEMA-C16Br/AA/IBMA) 12 49 comparative p(DMAEMA-C16Br/AA/2EHA)
13 50 comparative p(DMAEMA-C16Br/HFPOMA/AA) 14 51 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 52 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 53 comparative
p(DMAEMA-C16Br/HFPOMA/DMAc/AA) 17 54 comparative
p(DMAEMA-C16Br/HFPOA/AA) 18 55 comparative
p(DMAEMA-C16Br/HFPOA/HEMA/AA) 19 56 comparative
p(DMAEMA-C16Br/HFPOA/DMAc/AA) 20 57 comparative
p(DMAEMA-C16Br/HFPOA/EOA/AA) 21 58 comparative
p(DMAEMA-C16Br/HFPOA/IOA/AA) 22 59 p(DMAEA-C16BrA-174/AA/IBMA) 23
60 p(DMAEA-C16-Br/A-174/AA/IOA) 24 61 p(DMAEMA-C16Br/EOMA/A-174/ 25
HFPOMA) 62 p(DMAEMA-C16Br/HEMA/A-174/ 26 HFPOMA)
Examples 63-86
Method of Coating Hybrid Antimicrobial Polymers onto Conductive
Touch (SCT) Glass Substrates
[0219] AEM5700 antimicrobial solution was obtained from Aegis
Environmental (Midland, Mich.). The AEM5700 was diluted to 1 wt %
into IPA to make the working solution. Conductively-coated glass
coupons were prepared as described in Examples 40-62. Polymer
solutions from the Examples shown in Table 2 were diluted in IPA to
5 wt %. The diluted polymer solutions were mixed 1:1 with the
working solution of AEM5700. The resulting mixtures (listed in
Table 4) were applied to the glass coupons and the hybrid
antimicrobial polymer-coated coupons were treated, cleaned, and
dried as described in Examples 40-62.
[0220] A control (Example 86) consisted of applying 5 milliliters
of the AEM5700 working solution directly to a glass coupon and
treating, cleaning, and drying the coupon as described for Examples
59-62.
TABLE-US-00004 TABLE 4 Hybrid antimicrobial polymer-coated SCT
glass substrates. Comparative examples, which do not comprise an
organosilane pendant group, are designated with the notation
"comparative". Example No. Hybrid Polymer Designation Polymer
Example No. 63 p(DMAEMA-C16Br/A-174/IBMA/AEM) 4 64
p(DMAEA-MCl/A-174/IBMA/AEM) 5 65 p(DMAEMA-C16Br/A-174/IOA/AEM) 6 66
comparative p(DMAEMA-C16Br/AA/IOA/AEM) 7 67
p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8 68 comparative
p(DMAEMA-C16Br/HEMA/NHMAc/IOA/AEM) 9 69
p(DMAEMA-C16Br/A-174/DMAc/IOA/AEM) 10 70 comparative
p(DMAEMA-C16Br/HEMA/DMAc/IOA/AEM) 11 71 comparative
p(DMAEMA-C16Br/AA/IBMA/AEM) 12 72 comparative
p(DMAEMA-C16Br/AA/2EHA/AEM) 13 73 comparative
p(DMAEMA-C16Br/HFPOMA/AA/AEM) 14 74 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 75 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 76 comparative
p(DMAEMA-C16Br/HFPOMA/DMAc/AA/AEM) 17 77 comparative
p(DMAEMA-C16Br/HFPOA/AA/AEM) 18 78 comparative
p(DMAEMA-C16Br/HFPOA/HEMA/AA/AEM) 19 79 comparative
p(DMAEMA-C16Br/HFPOA/DMAc/AA/AEM) 20 80 comparative
p(DMAEMA-C16Br/HFPOA/EOA/AA/AEM) 21 81 comparative
p(DMAEMA-C16Br/HFPOA/IOA/AA/AEM) 22 82
p(DMAEA-C16BrA-174/AA/IBMA/AEM) 23 83
p(DMAEA-C16-Br/A-174/AA/IOA/AEM) 24 84 p(DMAEMA-C16Br/EOMA/A- 25
174/HFPOMA/AEM) 85 P(DMAEMA-C16Br/HEMA/A- 26 174/HFPOMA/AEM) 86 No
Polymer - AEM5700 Control --
Examples 87-109
Method of Coating Antimicrobial Polymers onto Dispersive Signal
Technology (DST) Glass Substrates
[0221] Chemstrengthened glass (2.2 mm flowed glass; part no.
37373.2) was obtained from EuropTec USA, Inc. (Clarksburg, W. Va.).
The glass was cut into coupons, approximately 4'' by 4'' (10.2 cm
by 10.2 cm), for coating and testing purposes.
[0222] Polymer solutions from the Examples shown in Table 3 were
diluted in isopropyl alcohol to 5 wt % polymer. Approximately 5
milliliters of the diluted polymer solution were applied to a wipe
(Sealed Edge Wiper 6259HC; Coventry, Kennesaw, Ga.), which was used
immediately to manually distribute the polymer solution evenly over
the surface of the glass coupon. The solvent was removed by heating
the sample at 120.degree. C. in a convection oven for 3-4 minutes.
After completely removing the solvent, the glass coupons were
washed with soap (Optisolve OP7153-LF detergent; available from
Kyzen North America (Manchester, N.H.) and deionized water in a
36'' Billco Versa Clean Washer (Billco Manufacturing, Inc.,
Zelienople, Pa.) with attached fluid head and roller wash pan and
dried. The dried samples were tested as described below.
TABLE-US-00005 TABLE 5 Polymer-coated DST glass substrates.
Comparative examples, which do not comprise an organosilane pendant
group, are designated with the notation "comparative". Polymer
Exam- Example No. Polymer Designation ple No. 87
p(DMAEMA-C16Br/A-174/IBMA) 4 88 p(DMAEA-MCl/A-174/IBMA) 5 89
p(DMAEMA-C16Br/A-174/IOA) 6 90 comparative p(DMAEMA-C16Br/AA/IOA) 7
91 P(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 92 comparative
P(DMAEMA-C16Br/HEMA/NHMAc/IOA) 9 93 p(DMAEMA-C16Br/A-174/DMAc/IOA)
10 94 comparative p(DMAEMA-C16Br/HEMA/DMAc/IOA) 11 95 comparative
p(DMAEMA-C16Br/AA/IBMA) 12 96 comparative p(DMAEMA-C16Br/AA/2EHA)
13 97 comparative p(DMAEMA-C16Br/HFPOMA/AA) 14 98 comparative
P(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 99 comparative
P(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 100 comparative
P(DMAEMA-C16Br/HFPOMA/DMAc/AA) 17 101 comparative
p(DMAEMA-C16Br/HFPOA/AA) 18 102 comparative
p(DMAEMA-C16Br/HFPOA/HEMA/AA) 19 103 comparative
p(DMAEMA-C16Br/HFPOA/DMAc/AA) 20 104 comparative
p(DMAEMA-C16Br/HFPOA/EOA/AA) 21 105 comparative
p(DMAEMA-C16Br/HFPOA/IOA/AA) 22 106 p(DMAEA-C16BrA-174/AA/IBMA) 23
107 p(DMAEA-C16-Br/A-174/AA/IOA) 24 108 p(DMAEMA-C16Br/EOMA/A-174/
25 HFPOMA) 109 p(DMAEMA-C16Br/HEMA/A-174/ 26 HFPOMA)
Examples 110-133
Method of Coating Hybrid Antimicrobial Polymers onto Dispersive
Signal Technology (DST) Glass Substrates
[0223] AEM5700 antimicrobial solution was obtained from Aegis
Environmental (Midland, Mich.). The AEM5700 was diluted to 1 wt %
into IPA to make the working solution. DST glass coupons were
prepared as described in Examples 87-109. Polymer solutions from
the Examples shown in Table 2 were diluted in IPA to 5 wt %. The
diluted polymer solutions were mixed 1:1 with the working solution
of AEM5700. The resulting mixtures (shown in Table 6) were applied
to the glass coupons and the hybrid antimicrobial polymer-coated
coupons were treated, cleaned, and dried as described in Examples
87-109 and were tested as described below.
[0224] A control (Example 133) consisted of applying 5 milliliters
of the AEM5700 working solution directly to a glass coupon and
treating, cleaning, and drying the coupon as described for Examples
87-109.
TABLE-US-00006 TABLE 6 Hybrid antimicrobial polymer-coated DST
glass substrates. Comparative examples, which do not comprise an
organosilane pendant group, are designated with the notation
"comparative". Polymer Example No. Hybrid Polymer Designation
Example No. 110 p(DMAEMA-C16Br/A-174/IBMA/AEM) 4 111
p(DMAEA-MCl/A-174/IBMA/AEM) 5 112 p(DMAEMA-C16Br/A-174/IOA/AEM) 6
113 comparative p(DMAEMA-C16Br/AA/IOA/AEM) 7 114
p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8 115 comparative
p(DMAEMA-C16Br/HEMA/NHMAc/IOA/AEM) 9 116
p(DMAEMA-C16Br/A-174/DMAc/IOA/AEM) 10 117 comparative
p(DMAEMA-C16Br/HEMA/DMAc/IOA/AEM) 11 118 comparative
p(DMAEMA-C16Br/AA/IBMA/AEM) 12 119 comparative
p(DMAEMA-C16Br/AA/2EHA/AEM) 13 120 comparative
p(DMAEMA-C16Br/HFPOMA/AA/AEM) 14 121 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 122 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 123 comparative
p(DMAEMA-C16Br/HFPOMA/DMAc/AA/AEM) 17 124 comparative
p(DMAEMA-C16Br/HFPOA/AA/AEM) 18 125 comparative
p(DMAEMA-C16Br/HFPOA/HEMA/AA/AEM) 19 126 comparative
p(DMAEMA-C16Br/HFPOA/DMAc/AA/AEM) 20 127 comparative
p(DMAEMA-C16Br/HFPOA/EOA/AA/AEM) 21 128 comparative
p(DMAEMA-C16Br/HFPOA/IOA/AA/AEM) 22 129
p(DMAEA-C16BrA-174/AA/IBMA/AEM) 23 130
p(DMAEA-C16-Br/A-174/AA/IOA/AEM) 24 131
p(DMAEMA-C16Br/EOMA/A-174/HFPOMA/AEM) 25 132 p(DMAEMA-C16Br/HEMA/A-
26 174/HFPOMA/AEM) 133 No Polymer - AEM5700 Control --
Examples 134-143
Method of Coating Antimicrobial Polymers onto Projected Capacitive
Touch (PCT) Sensor Glass Substrates
[0225] TPK antiglare top glass (1.1 mm thick; part no. AG-90) was
obtained from TPK Touch Solutions (Xiamen Headquarters, Fujian,
China)). The glass was cut into coupons, approximately 4'' by 4''
(10.2 cm by 10.2 cm), for coating and testing purposes. Just prior
to coating with the antimicrobial polymer solutions, the glass
coupons were heated to 130.degree. C. in a convection oven for 30
minutes.
[0226] Polymer solutions from the Examples shown in Table 3 were
diluted in isopropyl alcohol to 5 wt % polymer. Approximately 5
milliliters of the diluted polymer solution were applied to a wipe
(Sealed Edge Wiper 6259HC; Coventry, Kennesaw, Ga.), which was used
immediately to manually distribute the polymer solution evenly over
the surface of the PCT glass coupon. In Examples 134-138, the
solvent was removed by allowing the samples to air-dry at
20.degree. C. for 24 hours. In Examples 139-143, the solvent was
removed by heating the sample at 120.degree. C. in a convection
oven for 3 minutes. After completely removing the solvent, the
glass coupons were wiped with a clean, dry wipe that was identical
to the wipe that was used to coat the polymers onto the glass. The
dried samples were tested as described below.
TABLE-US-00007 TABLE 7 Polymer-coated PCT glass substrates.
Comparative examples, which do not comprise an organosilane pendant
group, are designated with the notation "comparative". Polymer
Exam- Example No. Polymer Designation ple No. 134
p(DMAEMA-C16Br/A-174/IOA) 6 135 comparative p(DMAEMA-C16Br/AA/IOA)
7 136 p(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 137 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 138 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16 139 p(DMAEMA-C16Br/A-174/IOA) 6
140 comparative p(DMAEMA-C16Br/AA/IOA) 7 141
p(DMAEMA-C16Br/A-174/NHMAc/IOA) 8 142 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA) 15 143 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA) 16
Examples 144-155
Method of Coating Hybrid Antimicrobial Polymers onto Projected
Capacitive Touch (PCT) Sensor Glass Substrates
[0227] AEM5700 antimicrobial solution was obtained from Aegis
Environmental (Midland, Mich.). The AEM5700 was diluted to 1 wt %
into IPA to make the working solution. PCT glass coupons were
prepared as described in Examples 134-143. Polymer solutions from
the Examples shown in Table 2 were diluted in IPA to 5 wt %. The
diluted polymer solutions were mixed 1:1 with the working solution
of AEM5700. The resulting mixtures (shown in Table 8) were applied
to the glass coupons and the hybrid antimicrobial polymer-coated
coupons were treated, dried, and cleaned as described in Examples
134-143 and were tested as described below.
[0228] Controls (Examples 149 and 155) consisted of applying 5
milliliters of the AEM5700 working solution directly to a glass
coupon and treating, cleaning, and drying the coupon as described
for Examples 134-143.
TABLE-US-00008 TABLE 8 Hybrid antimicrobial polymer-coated PCT
glass substrates. Comparative examples, which do not comprise an
organosilane pendant group, are designated with the notation
"comparative". Example No. Polymer Designation Polymer Example No.
144 P(DMAEMA-C16Br/A-174/IOA/AEM) 6 145 comparative
p(DMAEMA-C16Br/AA/IOA/AEM) 7 146
p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8 147 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 148 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 149 No Polymer - AEM5700
Control -- 150 p(DMAEMA-C16Br/A-174/IOA/AEM) 6 151 comparative
p(DMAEMA-C16Br/AA/IOA/AEM) 7 152
p(DMAEMA-C16Br/A-174/NHMAc/IOA/AEM) 8 153 comparative
p(DMAEMA-C16Br/HFPOMA/EOMA/AA/AEM) 15 154 comparative
p(DMAEMA-C16Br/HFPOMA/HEMA/AA/AEM) 16 155 No Polymer - AEM5700
Control --
Example 156
Physical Testing for Antimicrobial Polymer-Coated Glass Substrates
and Hybrid Antimicrobial Polymer-Coated Glass Substrates
[0229] ASTM test methods are published by ASTM International (West
Conshohocken, Pa.). The coated glass substrates were tested for a
variety of physical properties. The hydrophobicity of the
polymer-coated surface was tested by measuring the contact angle of
a drop of deionized water using the ASTM D7334.7606 test method.
The scratch resistance of the polymer-coated surface was tested
using the ASTM D7027-05 test ("Scratch test") with a constant load
of 1000 g using Moh's hardness pens. The result is reported as the
hardest pen that did not cause a scratch with the 1000 g load. The
transmitted haze and transmittance of the polymer-coated glass
substrates were measured using the ASTM D 1003 on the Haze Gard
Plus meter, from BYK-Gardner GmbH, Geretsried, Germany, and
transmission is reported as the percent of light transmitted
through the sample. The clarity was measured using a BYK-Gardner
Haze Gard Plus instrument, calibrated using 0% (Black cover)
standard and a clarity standard of 77.8% provided by BYK-Garner
(catalog #4732). Reflected Haze is measured according to test
method ASTM E430. Gloss at 20.degree. and 60.degree. was measured
on a BYK Gloss meter using ASTM D523 test method.
[0230] The eraser rub test, which is a measurement of the
durability of the coating, was performed according to the United
States Military Specification for the Coating of Optical Glass
Elements (MIL-C-675C) dated 22 Aug. 1980. The value reported is the
number of eraser rubs required to remove the coating from the
glass.
[0231] Tables 9-11 show the results of screening a variety of
antimicrobial polymer and hybrid antimicrobial polymer compositions
for their physical properties on each respective type of glass
substrate.
TABLE-US-00009 TABLE 9 Physical properties of antimicrobial-coated
SCT glass substrates. "NR" denotes that the specified data were not
collected. All data reported in the table are the average of ten
independent determinations of the physical characteristic for each
coupon of coated glass. The data for Example 86 is the average (and
standard deviation) for ten independent determinations of the
physical characteristic for ten separate coupons of glass that were
coated on separate days with the same working solution of AEM5700.
Comparative examples, which do not comprise an organosilane pendant
group, are designated with the notation "comp.". Coated Substrate
Contact Scratch % Ref 20.degree. 60.degree. (Example No.) Angle
Test % T Haze Clarity Haze gloss gloss 40 89.56 NR 91.20 8.70 89.60
475.00 70.20 81.50 41 58.85 NR 92.00 6.30 89.80 413.00 73.00 83.60
42 88.45 NR 91.80 5.80 88.50 431.00 75.50 85.50 43 comp. 108.25 NR
91.80 8.90 88.50 418.70 66.80 77.80 44 87.54 Pencil #7 91.00 7.44
88.97 454.00 76.90 83.90 45 comp. 85.46 Pencil #7 91.00 6.57 87.70
441.00 80.17 86.00 46 84.85 Pencil #7 90.77 6.73 87.03 426.00 80.57
86.03 47 comp. 80.72 Pencil #7 90.97 6.68 87.27 451.00 79.03 85.10
48 comp. 72.06 Pencil #7 90.87 7.06 88.60 440.00 78.10 85.90 49
comp. 76.59 Pencil #7 90.93 7.51 88.47 446.00 76.30 82.80 50 comp.
53.17 Pencil #7 91.73 7.56 88.23 439.67 71.87 83.33 51 comp. 67.11
Pencil #6 91.77 7.28 88.17 429.67 71.97 83.80 52 comp. 53.04 Pencil
#6 91.73 8.29 89.33 423.67 68.07 77.67 53 comp. 53.34 Pencil #6
91.77 7.83 88.20 433.67 66.13 74.53 54 comp. 49.67 Pencil #6 91.63
7.66 88.90 430.33 71.90 81.47 55 comp. 49.24 Pencil #7 91.60 8.08
89.13 432.00 71.57 79.03 56 comp. 58.68 Pencil #7 91.73 6.71 89.33
437.33 71.90 83.93 57 comp. 58.68 Pencil #7 91.77 6.35 91.03 401.33
78.80 86.73 58 comp. 58.84 Pencil #8 91.57 12.57 89.37 393.00 66.03
69.83 59 67.26 Pencil #7 91.30 10.08 89.53 416.33 70.80 78.37 60
63.31 Pencil #7 91.50 9.26 89.63 423.00 71.13 80.17 61 67.98 Pencil
#6 91.80 6.62 89.57 435.33 73.87 84.40 62 72.61 Pencil #7 91.80
6.41 89.80 436.67 74.50 85.03 63 85.00 NR 90.80 6.98 89.30 477.00
72.30 87.80 64 75.00 NR 91.90 5.80 87.80 440.00 74.50 85.80 65
89.00 NR 91.90 6.10 89.50 418.00 73.10 84.60 66 comp. 81.00 NR
91.80 6.80 89.20 422.00 70.80 83.80 67 88.16 Pencil #7 91.10 6.76
87.80 460.00 77.97 84.93 68 comp. 88.24 Pencil #7 90.90 7.39 88.90
455.00 78.87 85.73 69 86.81 Pencil #7 91.03 7.04 87.60 420.00 79.03
86.70 70 comp. 85.48 Pencil #7 90.97 7.56 88.70 453.00 75.30 83.53
71 comp. 75.26 Pencil #7 90.87 7.08 88.10 438.00 78.10 85.23 72
comp. 81.08 Pencil #7 90.97 8.31 88.80 451.00 76.27 82.17 73 comp.
67.17 Pencil #7 91.57 7.68 89.57 421.00 71.17 80.47 74 comp. 77.47
Pencil #8 91.70 7.03 89.43 432.00 76.27 87.67 75 comp. 65.68 Pencil
#6 91.63 7.28 88.20 434.33 76.83 86.70 76 comp. 67.11 Pencil #7
91.80 7.49 88.50 463.00 73.60 84.30 77 comp. 66.72 Pencil #6 91.63
8.36 89.17 437.33 74.17 84.50 78 comp. 71.04 Pencil #7 91.33 7.95
88.57 439.67 75.07 86.13 79 comp. 64.77 Pencil #7 91.77 7.35 89.63
428.00 75.43 86.13 80 comp. 75.25 Pencil #7 91.53 6.74 90.00 435.00
78.50 88.27 81 comp. 70.76 Pencil #7 91.70 8.95 89.50 407.67 70.27
76.57 82 62.54 Pencil #5 91.60 9.10 90.20 413.33 70.90 76.77 83
67.52 Pencil #6 91.53 8.20 90.50 404.33 72.13 79.93 84 69.72 Pencil
#6 91.90 6.29 90.53 418.33 75.60 85.07 85 69.79 Pencil #6 91.87
6.40 90.73 417.67 75.37 84.50 86 comp. 81.02 .+-. 10.50 Pencil #7
91.63 .+-. 0.35 7.00 .+-. 0.93 89.20 .+-. 0.60 431.40 .+-. 19.40
74.70 .+-. 2.96 84.60 .+-. 2.77
TABLE-US-00010 TABLE 10 Physical properties of antimicrobial-coated
DST glass substrates. All data reported in the table are the
average of ten independent determinations of the physical
characteristic for each coupon of coated glass. The data for
Example 133 is the average (and standard deviation) for ten
independent determinations of the physical characteristic for ten
separate coupons of glass that were coated on separate days with
the same working solution of AEM5700. Comparative examples, which
do not comprise an organosilane pendant group, are designated with
the notation "comp.". Scratch Test Coated with hardness Substrate
Contact pens loaded % Ref 20.degree. 60.degree. (Example No.) Angle
1000 g % T Haze Clarity Haze gloss gloss 87 85.21 pencil 6 visible
92.3 4.79 78.3 564 22.4 75.4 88 67.42 pencil 6 visible 92.3 4.52
77.9 578 22 75.4 89 89.7 pencil 7 visible 92.4 4.55 77.47 571 21
74.4 90 comp. 83.79 pencil 8 visible 92 10.77 77.3 513 17.5 58.23
91 94.09 Pencil #5 visible 91.9 10.45 72.9 487 14.7 55.4 92 comp.
82.26 Pencil #5 visible 92.2 5.6 74.1 533.7 17.1 68.2 93 88.13
Pencil #5 visible 92.1 5.8 73.2 532 16.7 67.6 94 comp. 76.39 Pencil
#4 visible 92.2 5.8 73 529.7 16.7 67.7 95 comp. 79.14 Pencil #4
visible 92 6.1 72.9 528.7 16.7 67.3 96 comp. 83.58 Pencil #4
visible 91.8 9.8 72.6 493.3 14.8 58.1 97 comp. 58.81 Pencil
#7-Visible 92.30 5.91 76.90 547.33 19.13 70.80 98 comp. 67.00
Pencil #7-Visible 92.33 5.66 77.63 560.00 20.17 73.20 99 comp.
71.33 Pencil #8-Visible 92.43 6.87 78.73 508.33 17.90 68.43 100
comp. 58.56 Pencil #7 visible 92.17 6.83 71.60 520.67 15.70 65.97
101 comp. 64.58 Pencil #8-Visible 92.30 6.77 74.83 489.33 17.47
65.63 102 comp. 60.30 Pencil #7 visible 92.13 7.72 72.73 477.33
14.67 62.37 103 comp. 54.51 Pencil #7 visible 92.10 6.17 74.90
551.33 18.70 69.77 104 comp. 62.70 Pencil #7 visible 92.13 6.23
74.67 549.67 18.27 68.67 105 comp. 67.55 Pencil #8-Visible 91.67
15.00 72.47 486.33 15.13 51.60 106 61.35 Pencil #6 visible 92.47
9.31 74.57 506.00 16.43 59.03 107 54.38 Pencil #6 visible 92.50
6.69 76.95 537.50 18.00 66.55 108 44.63 Pencil #7 visible 92.67
5.51 75.70 536.67 17.53 68.33 109 58.18 Pencil #7 visible 92.53
8.12 74.73 503.00 15.60 58.90 110 88.88 pencil 7 visible 92.1 10.33
67.3 470 13.1 56 111 64.24 pencil 7 visible 92.3 5.98 69.7 518 15.2
65.3 112 90.44 pencil 7 visible 92.3 5.93 70.1 520 15.6 65.9 113
comp. 86.34 pencil 7 visible 92 9.67 70.6 500 14.8 60.3 114 94.46
Pencil #4 visible 92.10 6.92 72.97 516.00 16.10 63.80 115 comp.
89.31 Pencil #4 visible 92.10 6.17 72.93 522.67 16.23 66.30 116
89.77 Pencil #4 visible 92.10 5.94 71.40 523.67 15.87 66.37 117
comp. 84.88 Pencil #6 visible 92.07 6.19 70.37 513.00 15.20 65.07
118 comp. 82.01 Pencil #6 visible 92.03 6.16 71.83 520.67 16.00
66.67 119 comp. 86.04 Pencil #7 visible 92.00 6.62 76.13 541.00
17.80 67.07 120 comp. 69.72 Pencil #6-Visible 92.40 6.17 78.50
536.00 20.90 71.13 121 comp. 94.94 Pencil #5-Visible 92.63 4.49
77.37 558.67 21.87 74.53 122 comp. 96.19 Pencil #5-Visible 92.47
5.22 78.47 539.00 20.07 71.23 123 comp. 69.78 Pencil #6 visible
92.13 5.22 74.20 540.33 18.40 69.53 124 comp. 66.84 Pencil #7
visible 92.10 5.37 73.67 547.33 18.20 69.20 125 comp. 67.10 Pencil
#7 visible 91.97 5.35 73.77 551.00 18.03 69.70 126 comp. 68.12
Pencil #7 visible 92.00 5.62 74.27 546.00 17.50 68.17 127 comp.
66.43 Pencil #7 visible 92.03 5.52 74.13 554.33 18.77 70.43 128
comp. 70.32 Pencil #7 visible 91.97 6.45 74.10 549.33 18.17 66.80
129 56.55 Pencil #7 visible 92.40 10.17 75.27 516.00 16.67 59.87
130 52.83 Pencil #7 visible 92.43 8.36 74.90 512.67 16.27 62.00 131
73.09 Pencil #6 visible 92.57 7.02 72.87 514.67 15.37 62.03 132
65.94 Pencil #6 visible 92.57 6.73 71.83 526.33 15.90 63.97 133
comp. 75.29 .+-. 18.64 Pencil #6 visible 92.32 .+-. 0.21 5.43 .+-.
0.48 73.30 .+-. 2.87 537.80 .+-. 19.25 17.23 .+-. 1.78 68.48 .+-.
3.08
TABLE-US-00011 TABLE 11 Physical properties of antimicrobial-coated
PCT glass substrates. All data reported in the table are the
average often independent determinations of the physical
characteristic for each coupon of coated glass. The data for
Examples 149 and 150 are the averages (and standard deviations) for
ten independent determinations of the physical characteristic for
two separate coupons of glass that were coated on separate days
with the same working solution of AEM5700. Comparative examples,
which do not comprise an organosilane pendant group, are designated
with the notation "comp.". Coated Substrate Advancing (Example
Contact Eraser % Ref 20.degree. 60.degree. No.) Angle Rub Test % T
Haze Clarity Haze gloss gloss 134 98.38 18.50 93.60 5.75 91.43
468.33 62.67 78.07 135 comp. 92.69 27.00 93.27 5.74 91.23 482.67
67.10 80.10 136 82.05 10.00 93.57 6.33 90.93 465.67 59.87 74.90 137
comp. 77.65 16.00 93.1 7.3 90.3 483.3 61.2 73.6 138 comp. 94.60
15.50 93.6 5.0 92.7 461.3 67.1 81.8 139 88.72 13.50 93.2 5.4 92.7
471.7 70.6 82.7 140 comp. 86.10 12.50 93.5 5.9 92.0 440.0 64.9 79.0
141 80.52 15.50 93.2 5.2 91.8 477.3 68.9 82.7 142 comp. 86.89 17.50
93.6 5.3 93.2 453.0 68.7 82.7 143 comp. 80.81 15.50 93.2 5.4 92.2
475.7 71.2 83.7 144 94.09 20.00 93.53 5.69 93.17 446.33 66.90 80.93
145 comp. 93.71 37.50 93.20 5.17 91.77 483.00 70.40 83.73 146 87.01
15.00 92.90 4.34 90.47 518.67 68.17 79.60 147 comp. 85.82 26.50
93.20 5.47 92.23 473.33 69.90 82.37 148 comp. 95.14 27.50 93.50
4.79 92.30 471.67 67.73 84.03 150 92.55 36.50 93.07 6.35 90.97
475.67 65.53 77.90 151 comp. 86.94 15.50 92.9 4.9 88.4 526.7 62.6
74.7 152 84.87 22.50 93.1 6.8 90.3 478.0 63.4 75.5 153 comp. 84.96
15.00 92.9 4.6 88.2 529.7 62.9 75.1 154 comp. 87.33 21.50 93.2 6.7
91.3 468.0 65.5 78.1 149 88.34 .+-. 1.39 25.50 .+-. 4.24 93.2 .+-.
0.6 5.0 .+-. 0.1 90.6 .+-. 1.7 526.05.2.+-. 64.2 .+-. 0.9 78.1 .+-.
1.1 155 90.62 .+-. 2.43 36.00 .+-. 6.36 93.3 .+-. 0.0 4.8 .+-. 0.1
92.2 .+-. 1.3 452.4 .+-. 22.1 71.9 .+-. 1.3 85.6 .+-. 2.0
Example 157
Antimicrobial Activity Testing for Antimicrobial Polymer-Coated
Glass Substrates and Hybrid Antimicrobial Polymer-Coated Glass
Substrates
[0232] Antimicrobial activity of the coated glass substrates was
tested using three standard methods. The ASTM 2149 test method
(ASTM International; West Conshohocken, Pa.) was used to evaluate
the effectiveness of the non-leaching antimicrobial polymer-coated
surfaces of the glass coupons. Overnight cultures of Staphylococcus
aureus (ATCC 6538) and Staphylococcus. epidermidis (ATCC 12228)
were diluted in phosphate buffer to a concentration of
approximately 1.times.10.sup.6 CFU/ml. A 1.times.1-inch (2.54
cm.times.2.54 cm) square of glass sample was placed into a tube
containing 50 ml of dilute bacterial suspensions. The samples were
incubated with constant agitation for 24 hours at 28+/-1.degree. C.
Immediately after the samples were placed into the tubes (T=0 hr)
and after 24 hours (T=24 hr), a small aliquot of the suspension was
serially-diluted and the diluted samples were inoculated onto
Petrifilm Aerobic Count (AC) Plates (3M Company, St. Paul, Minn.)
according to the manufacturer's instructions. The plates were
incubated for 48 hours at 35.degree. C.+1.degree. C. Bacterial
colonies from appropriate dilution were counted according to the
manufacturer's instructions and recorded as colony-forming units
(CFU) per ml.
[0233] The JIS Z 2801 test method (Japan Industrial Standards;
Japanese Standards Association; Tokyo, JP) was used to evaluate the
antibacterial activity of antibacterial polymer-coated glass
substrates. The bacterial inoculum was prepared in a solution of 1
part Nutrient Broth (NB) and 499 parts phosphate buffer. A portion
of the inoculum was used to determine the number of viable bacteria
in the inoculum. Another portion of the bacterial suspension (150
.mu.L) was placed onto the surface of the glass sample and the
inoculated glass sample was incubated for the specified contact
time at 28+/-1.degree. C. (see FIG. 5). After incubation, the glass
sample was placed into 20 ml of D/E Neutralizing Broth. The number
of surviving bacteria in the Neutralizing broth was determined by
inoculating the broth onto nutrient agar using a Spiral Plater WASP
II, DW Scientific, Shipley, West Yorkshire, UK, incubating the
plates for 24 hours at 35.degree. C.+1.degree. C. and counting the
colonies using a colony reader (ProtoCol colony Counter;
Microbiology International; Frederick, Md.). FIG. 6 shows a
comparison of the results from 5 different coated samples that were
tested using the ASTM 2149 test method and the JIS Z 2801 test
method. This experimental data from the JIS test method showed a
greater than 3-log reduction of the microorganisms after a two hour
contact time with the antimicrobial polymer-treated glass samples.
In this experiment, the control was SCT glass that was not treated
with an antimicrobial polymer.
[0234] Test method ASTM E2180-01 was designed to evaluate
quantitatively the antimicrobial effectiveness of antimicrobial
coatings on the coated surfaces. Overnight cultures of
Staphylococcus aureus (ATCC 6538) were used to inoculate the agar
slurry, which was applied to the antimicrobial polymer-coated
surface of the glass samples. The microorganisms were recovered
from inoculated agar slurry using Dey/Engley (D/E) Neutralizing
Broth. Bacterial plate counts were performed using 3M Petrifilm
Aerobic Count (AC) Plates (3M Company, St. Paul, Minn., USA)
according to the manufacturer's instructions. The colony counts
were recorded as colony-forming unit (CFU) per cm.sup.2. The
difference between bacterial count in a slurry when the inoculum is
immediately applied to the surface (T=0 hr) and the bacterial count
in the slurry after 24 hours of contact with the antimicrobial
surface is recorded as the log 10 reduction. The polymer-treated
glass samples were compared to an untreated sample of PET film
(Acrylate-primer coated polyethylene terephthalate film, 4 mil
(0.10 mm) thick, obtained from Mitsubishi Polyester Film, Greer,
S.C.). The results (not shown) indicate that each of the
antimicrobial polymer-treated glass samples had a log 10 reduction
of about 0.5 to about 0.8 using this test method.
Comparative Example 158
Synthesis of Comparative Antimicrobial Polymer
[0235] A comparative antimicrobial polymer was synthesized
according to Example No. 2 of PCT Patent Application Publication
No. WO2010/036465. The polymer was diluted in IPA to 5 wt % and was
coated onto conductively-coated glass (part number 29617), obtained
from Pilkington North America, Inc. (Toledo, Ohio), as described in
Examples 40-62 above. The surface hydrophobicity of the resulting
coated substrate was compared to the coated sample of Example 65 by
measuring the contact angle of a drop of deionized water on each
coated substrate using ASTM test method D7334.7606. The results are
shown in Table 12. The results indicate that the antimicrobial
polymer of Example 65 was more hydrophobic than the polymer of
comparative Example 158.
TABLE-US-00012 TABLE 12 Comparison of surface hydrophobicity of
coated substrates. Advancing Coated Substrate Contact Angle
Comparative Example 158 30.6 Example 65 96.12
Examples 159-162
Synthesis of Comparative Antimicrobial Polymer
[0236] Samples of SCT glass were prepared and coated using the
procedures described in Examples 40-62. Samples of PCT glass were
prepared and coated using the procedures described in Examples
134-143. The respective coating formulations are listed in Table
13. A1120 (N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane)
was added to the coating solutions as an adhesion-promoting
reagent. Tin-octoate was added to the coating solutions as a
catalyst to promote cross-linking reactions. After applying the
coating formulations to the glass and allowing evaporation of the
solvent, the coated substrates in Examples 159, 161, and 162 were
placed in a convection oven (138.degree. C.) for 4 minutes and then
cooled to room temperature. After applying the coating formulations
to the glass and allowing evaporation of the solvent, the coated
substrates in Example 160 was placed in a convection oven
(120.degree. C.) for 3 minutes and then cooled to room temperature.
After cooling, all substrates were immediately washed in a Billco
washer as described in Examples 40-62.
TABLE-US-00013 TABLE 13 Coating solutions for Examples 159-162.
Example Substrate Coating Formulation 159 SCT A 1:1 blend of 3 Wt %
(in IPA) AEM5700 and 5 Wt % (in IPA) of the polymer of Example 6,
to which 2 Wt % tin-octoate and 0.04 Wt % A1120 were added. 160 PCT
A 1:1 blend of 3 Wt % (in IPA) AEM5700 and 5 Wt % (in IPA) of the
polymer of Example 6, to which 2 Wt % tin-octoate and 0.04 Wt %
A1120 were added. 161 SCT 5 Wt % (in IPA) of the polymer of Example
6, to which 2 Wt % tin-octoate was added 162 PCT 5 Wt % (in IPA) of
the polymer of Example 6, to which 2 Wt % tin-octoate was added
[0237] The samples were tested for antimicrobial activity using the
JIS Z 2801 test procedure described in Example 157. Uncoated
samples of each type of glass were used as controls. The bacterial
inoculum was prepared in a solution of 1 part Nutrient Broth (NB)
and 499 parts phosphate buffer. A portion of the inoculum was used
to determine the number of viable bacteria in the inoculum. Another
portion of the bacterial suspension (150 .mu.L) was placed onto the
surface of the glass sample and the inoculated glass sample was
incubated for the specified contact time at 28.degree..+-.1.degree.
C. After incubation, the glass sample was placed into 20 ml of D/E
Neutralizing Broth. The number of surviving bacteria in the
Neutralizing broth was determined by inoculating the broth onto
nutrient agar using a Spiral Plater WASP, incubating the plates for
24 hours at 35.degree. C.+1.degree. C. and counting the colonies
using a colony reader (ProtoCol colony Counter; Microbiology
International; Frederick, Md.). The results are shown in Tables 14
and 15, which show data from experiments conducted on separate
days.
Comparative Examples 163-164
Synthesis of Comparative Antimicrobial Polymer
[0238] Samples of SCT glass were prepared and coated using the
procedures described in Examples 40-62. Samples of PCT glass were
prepared and coated using the procedures described in Examples
134-143. The respective coating formulations are listed in Table
14. A1120 (N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane)
was added to the coating solutions as an adhesion-promoting
reagent. Tin-octoate was added to the coating solutions as a
catalyst to promote cross-linking reactions. After applying the
coating formulations to the glass and allowing evaporation of the
solvent, the coated substrates in Comparative Example 161 was
placed in a convection oven (138.degree. C.) for 4 minutes and then
cooled to room temperature. After applying the coating formulations
to the glass and allowing evaporation of the solvent, the coated
substrates in Comparative Example 162 was placed in a convection
oven (120.degree. C.) for 3 minutes and then cooled to room
temperature. After cooling, all substrates were immediately washed
in a Billco washer as described in Examples 40-62.
TABLE-US-00014 TABLE 14 Coating solutions for Comparative Example
163-164. Comparative Example Substrate Coating Formulation 163 SCT
A mixture of 3 Wt % AEM5700 in IPA with 2 Wt % tin-octoate and
0.04% A1120. 164 PCT A mixture of 3 Wt % AEM5700 in IPA with 2 Wt %
tin-octoate and 0.04% A1120.
[0239] The samples were tested for antimicrobial activity using the
JIS Z 2801 test procedure described for Examples 159-160. Uncoated
samples of each type of glass were used as controls. The results
are shown in Tables 15 and 16, which show data from experiments
conducted on separate days.
TABLE-US-00015 TABLE 15 Tests for antibacterial properties of
coated-glass samples. Bacterial suspensions were tested for viable
cells after 15 minutes and 2 hours contact time with the coated
glass surfaces, respectively. All results are the average of three
samples tested for each type. Log.sub.10 Log.sub.10 Reduction
Reduction of viable of viable Log.sub.10 Log.sub.10 bacteria
bacteria cfu cfu after 15-min. after 2-hour Sample (15-min) (2 hr)
contact time contact time Control (SCT glass) 5.56 5.58 0 0 Control
(PCT glass) 5.53 5.65 0 0 Example 159 3.95 1.48 1.61 4.1 Example
160 3.44 1.05 2.09 4.6 Comp. Example 163 5.37 4.27 0.19 1.31 Comp.
Example 164 5.42 4.12 0.11 1.53 cfu = colony-forming unit.
TABLE-US-00016 TABLE 16 Tests for antibacterial properties of
coated-glass samples. Bacterial suspensions were tested for viable
cells after 15 minutes and 2 hours contact time with the coated
glass surfaces, respectively. All results are the average of three
samples tested for each type. Log.sub.10 Log.sub.10 Reduction
Reduction of viable of viable Log.sub.10 Log.sub.10 bacteria
bacteria cfu cfu after 15-min. after 2-hour Sample (15-min) (2 hr)
contact time contact time Control (SCT glass) 5.51 5.64 0 0 Control
(PCT glass) 5.53 5.65 0 0 Example 159 3.38 0.90 2.13 4.61 Example
160 4.32 1.07 1.2 4.43 Example 161 4.35 0.99 1.16 4.52 Example 162
4.48 1.45 1.04 4.05 Comp. Example 163 5.14 3.69 0.37 1.82 Comp.
Example 164 5.37 4.21 0.15 1.29 cfu = colony-forming unit.
[0240] The present invention has now been described with reference
to several specific embodiments foreseen by the inventor for which
enabling descriptions are available. Insubstantial modifications of
the invention, including modifications not presently foreseen, may
nonetheless constitute equivalents thereto. Thus, the scope of the
present invention should not be limited by the details and
structures described herein, but rather solely by the following
claims, and equivalents thereto.
* * * * *