Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 2022/240633
PCT/US2022/027616
STABILIZATION OF ANTIMICROBIAL COATINGS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a PCT International Application of United States
Provisional Patent
Application No. 63/188,582 filed on May 14, 2021. The disclosure of the above
application is
incorporated herein by reference.
BACKGROUND
[0002] The presence of bacteria, fungus, and/or viruses on surfaces is a major
concern today
affecting home, work, and recreational environments. Exposure to certain
bacteria, fungi (or
their spores), and/or viruses can seriously impact the health of humans, pets
and other animals.
Previous attempts at imparting protective properties to a building panel
included applying an
antibacterial and/or antifungal coating to a surface of a building material.
However, such
antimicrobial coatings may have been formulated at the expense of coating
performance ¨ such
as uniformity, agglomeration, storage stability ¨ thus, the need exists for a
coating that can
exhibit adequate protective performance without sacrificing necessary coating
performance.
BRIEF SUMMARY
[0003] Described herein is a coated building panel comprising: a substrate
comprising a first
major surface opposite a second major surface; a coating atop at least one of
the first major
surface or the second major surface, the coating comprising: a binder
composition; an
antimicrobial composition comprising a cationic compound; a stabilization
composition
comprising: a silicate compound; and a surfactant having an HLB value between
about 10 and
about 14.
[0004] Other embodiments of the present invention include a coating
composition comprising: a
liquid carrier; a solid blend comprising: a binder composition; an
antimicrobial composition
comprising a cationic compound; a stabilization composition comprising: a
silicate compound;
and a surfactant having an HLB value between about 10 and about 14.
[0005] Other embodiments of the present invention include a method of forming
a coated
building panel comprising a) applying the coating composition according to the
aforementioned
coating composition to a substrate; and b) drying the coating composition so
that substantially all
liquid carrier is removed to form the coated building panel.
1
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
[0006] Further areas of applicability of the present invention will become
apparent from the
detailed description provided hereinafter. It should be understood that the
detailed description
and specific examples, while indicating the preferred embodiment of the
invention, are intended
for purposes of illustration only and are not intended to limit the scope of
the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The present invention will become more fully understood from the
detailed description
and the accompanying drawings, wherein:
[0008] FIG. 1 is top perspective view of a building panel according to the
present invention;
[0009] FIG. 2 is a cross-sectional view of the building panel according to the
present invention,
the cross-sectional view being along the II line set forth in FIG. 1; and
[0010] FIG. 3 is a ceiling system comprising the building panel of the present
invention.
DETAILED DESCRIPTION
[0011] The following description of the preferred embodiment(s) is merely
exemplary in nature
and is in no way intended to limit the invention, its application, or uses.
[0012] As used throughout, ranges are used as shorthand for describing each
and every value
that is within the range. Any value within the range can be selected as the
terminus of the range.
In addition, all references cited herein are hereby incorporated by referenced
in their entireties.
In the event of a conflict in a definition in the present disclosure and that
of a cited reference, the
present disclosure controls.
[0013] Unless otherwise specified, all percentages and amounts expressed
herein and elsewhere
in the specification should be understood to refer to percentages by weight.
The amounts given
are based on the active weight of the material.
[0014] The description of illustrative embodiments according to principles of
the present
invention is intended to be read in connection with the accompanying drawings,
which arc to be
considered part of the entire written description. In the description of
embodiments of the
invention disclosed herein, any reference to direction or orientation is
merely intended for
convenience of description and is not intended in any way to limit the scope
of the present
invention. Relative terms such as "lower," "upper," "horizontal," "vertical,"
"above," "below,"
"up," "down," "top," and "bottom" as well as derivatives thereof (e.g..
"horizontally,"
2
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
"downwardly," "upwardly." etc.) should be construed to refer to the
orientation as then described
or as shown in the drawing under discussion. These relative terms are for
convenience of
description only and do not require that the apparatus be constructed or
operated in a particular
orientation unless explicitly indicated as such.
[0015] Terms such as -attached," -affixed," -connected," -coupled," -
interconnected," and
similar refer to a relationship wherein structures are secured or attached to
one another either
directly or indirectly through intervening structures, as well as both movable
or rigid attachments
or relationships, unless expressly described otherwise. Moreover, the features
and benefits of the
invention are illustrated by reference to the exemplified embodiments.
Accordingly, the
invention expressly should not be limited to such exemplary embodiments
illustrating some
possible non-limiting combination of features that may exist alone or in other
combinations of
features; the scope of the invention being defined by the claims appended
hereto.
[0016] Unless otherwise specified, all percentages and amounts expressed
herein and elsewhere
in the specification should be understood to refer to percentages by weight.
The amounts given
are based on the active weight of the material. According to the present
application, the term
"about" means +1- 5% of the reference value. According to the present
application, the term
"substantially free" less than about 0.1 wt. % based on the total of the
referenced value.
[0017] Referring to FIG. 1, the present invention includes a building panel 10
comprising a first
major exposed surface 11 opposite a second major exposed surface 12 and a side
exposed
surface 13 that extends between the first major exposed surface 11 and the
second major exposed
surface 12, thereby defining a perimeter of the ceiling panel 10.
[0018] Referring to FIG. 3, the present invention may further include a
ceiling system 1
comprising one or more of the building panels 10 installed in an interior
space, whereby the
interior space comprises a plenum space 3 and an active room environment 2. In
such
embodiments, the building panel 10 may be referenced as a ceiling panel 10.
The plenum space
3 provides space for mechanical lines within a building (e.g., HVAC, plumbing,
etc.). The active
space 2 provides room for the building occupants during normal intended use of
the building
(e.g., in an office building, the active space would be occupied by offices
containing computers,
lamps, etc.).
[0019] In the installed state, the building panels 10 may be supported in the
interior space by one
or more parallel support struts 5. Each of the support struts 5 may comprise
an inverted T-bar
3
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
having a horizontal flange 31 and a vertical web 32. The ceiling system 1 may
further comprise
a plurality of first struts that are substantially parallel to each other and
a plurality of second
struts that are substantially perpendicular to the first struts (not
pictured). In some embodiments,
the plurality of second struts intersects the plurality of first struts to
create an intersecting ceiling
support grid. The plenum space 3 exists above the ceiling support grid 6 and
the active room
environment 2 exists below the ceiling support grid 6. In the installed state,
the first major
exposed surface 11 of the building panel 10 may face the active room
environment 2 and the
second major exposed surface 12 of the building panel 10 may face the plenum
space 3. .
[0020] Referring now to FIGS. 1 and 2, the building panel 10 of the present
invention may have
a panel thickness to as measured from the first major exposed surface 11 to
the second major
exposed surface 12. The panel thickness to may range from about 12 mm to about
40 mm ¨
including all values and sub-ranges there-between. The building panel 10 may
have a length Lp
ranging from about 30 cm to about 310 cm ¨ including all values and sub-ranges
there-between.
The building panel 100 may have a width Wp ranging from about 10 cm to about
125 cm ¨
including all values and sub-ranges there-between.
[0021] The building panel 10 may comprise a body 100 and a surface coating 200
applied
thereto ¨ as discussed further herein. The body 100 comprises an upper surface
111 opposite a
lower surface 112 and a body side surface 113 that extends between the upper
surface 111 and
the lower surface 112, thereby defining a perimeter of the body 100. The body
100 may have a
body thickness ti that as measured by the distance between the upper surface
111 to the lower
surface 112 of the body 100. The body thickness ti may range from about 12 mm
to about 40
mm ¨ including all values and sub-ranges there-between.
[0022] The body 100 may be porous, thereby allowing airflow through the body
100 between the
upper surface 111 and the lower surface 122 ¨ as discussed further herein. The
body 100 may be
comprised of a binder and fibers. In some embodiments, the body 100 may
further comprise a
filler and/or additive.
[0023] Non-limiting examples of binder may include a starch-based polymer,
polyvinyl alcohol
(PVOH), a latex, polysaccharide polymers, cellulosic polymers, protein
solution polymers, an
acrylic polymer, polymaleic anhydride, epoxy resins, or a combination of two
or more thereof.
Non-limiting examples of filler may include powders of calcium carbonate,
limestone, titanium
dioxide, sand, barium sulfate, clay, mica, dolomite, silica, talc, perlite,
polymers, gypsum,
4
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
wollastonite, expanded-perlite, calcite, aluminum trihydrate, pigments, zinc
oxide, or zinc
sulfate.
[0024] The fibers may be organic fibers, inorganic fibers, or a blend thereof.
Non-limiting
examples of inorganic fibers mineral wool (also referred to as slag wool),
rock wool, stone wool,
and glass fibers. Non-limiting examples of organic fiber include fiberglass,
cellulosic fibers (e.g.
paper fiber ¨ such as newspaper, hemp fiber, jute fiber, flax fiber, wood
fiber, or other natural
fibers), polymer fibers (including polyester, polyethylene, aramid ¨ i.e.,
aromatic polyamide,
and/or polypropylene), protein fibers (e.g., sheep wool), and combinations
thereof.
[0025] The porosity of the body 100 may allow for airflow through the body 100
under
atmospheric conditions such that the building panel 10 may function as an
acoustic building
panel ¨ specifically, an acoustic ceiling panel 10, which requires properties
related to noise
reduction and sound attenuation properties ¨ as discussed further herein.
[0026] Specifically, the body 100 of the present invention may have a porosity
ranging from
about 60% to about 98% - including all values and sub-ranges there between. In
a preferred
embodiment, the body 100 has a porosity ranging from about 75% to 95% -
including all values
and sub-ranges there between. According to the present invention, porosity
refers to the
following:
% Porosity = [VTotal (VBinder VF VFiller)] VTotal
[0027] Where VTotai refers to the total volume of the body 100 defined by the
upper surface 111,
the lower surface 112, and the body side surfaces 113. VBillder refers to the
total volume occupied
by the binder in the body 100. VF refers to the total volume occupied by the
fibers in the body
100. VIllter refers to the total volume occupied by the filler in the body
100. Viit, refers to the
total volume occupied by the hydrophobic component in the body 100. Thus, the
% porosity
represents the amount of free volume within the body 100.
[0028] The building panel 10 of the present invention comprising the body 100
may exhibit
sufficient airflow for the building panel 10 to have the ability to reduce the
amount of reflected
sound in a room. The reduction in amount of reflected sound in a room is
expressed by a Noise
Reduction Coefficient (NRC) rating as described in American Society for
Testing and Materials
(ASTM) test method C423. This rating is the average of sound absorption
coefficients at four 1/3
octave bands (250, 500, 1000, and 2000 Hz), where, for example, a system
having an NRC of
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
0.90 has about 90% of the absorbing ability of an ideal absorber. A higher NRC
value indicates
that the material provides better sound absorption and reduced sound
reflection.
[0029] The building panel 10 of the present invention exhibits an NRC of at
least about 0.5. In a
preferred embodiment, the building panel 10 of the present invention may have
an NRC ranging
from about 0.60 to about 0.99 ¨ including all value and sub-ranges there-
between.
[0030] The surface coating 200 of the present invention may be applied to at
least one of the
upper surface 111 and/or the body side surface 113 of the body 100. In some
embodiments, the
surface coating 200 of the present invention may he applied directly to at
least one of the upper
surface 111 and/or the body side surface 113 of the body 100. Although not
pictured, in some
embodiments, the building panel 10 may further comprise a scrim that is
immediately adjacent to
the upper surface 111 of the body 100. The scrim may comprise a first major
surface opposite a
second major surface, whereby the second major surface contacts the upper
surface 111 of the
body 100. In such embodiments, the surface coating 200 may be applied to the
first major
surface of the scrim.
[0031] he surface coating 200 may comprise an outer surface 201 opposite an
inner surface 202.
The inner surface 202 of the surface coating 200 faces toward the body 100
while the outer
surface 201 of the surface coating 200 faces away from the body 100. The
surface coating 200
may comprise a topcoat 210. The topcoat 21.() may comprise an outer surface
211 opposite an
inner surface 212. The topcoat 210 may have a topcoat thickness t3 as measured
between the
inner surface 212 and the outer surface 211 of the topcoat 210.
[0032] The topcoat 210 may be applied to the upper surface 111 of the body 100
or the first
major surface of the scrim_ Once applied, the inner surface 212 of the topcoat
210 faces the
upper surface 111 of the body 100 or the first major surface of the scrim, and
the outer surface
211 of the topcoat 210 forms the first major exposed surface 11 of the
building panel 10. Stated
otherwise, the first major exposed surface 11 of the building panel 10 may
comprises the outer
surface 211 of the topcoat 210.
[0033] The surface coating 200 may comprise an edge-coat 230. The edge-coat
230 may
comprise an outer surface 231 opposite an inner surface 232. The edge-coat 230
may be applied
to the body side surface 113 of the body 100. Once applied, the inner surface
232 of the edge-
coat 230 faces the body side surface 113 of the body 100 and the outer surface
231. of the edge-
coat 230 forms the side exposed surface 13 of the building panel 10. Stated
otherwise, the side
6
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
exposed surface 13 of the building panel 10 may comprise the outer surface 231
of the edge-coat
230.
[0034] Although the building panel 10 shown in FIGS. 1 and 2 include both the
topcoat 210 and
the edge-coat 230, the present invention is not limited to surface coatings
200 that include both
the topcoat 210 and the edge-coat 230. In some embodiments, the building panel
10 may
comprise a surface coating 200 that includes only the topcoat 210 ¨ whereby
the side exposed
surface 13 of the building panel 10 is formed by the body side surface 113 of
the body 100. In
other embodiments, the building panel 10 may comprise a surface coating 200
that includes only
the edge-coat 230 ¨ whereby first major exposed surface 11 of the building
panel 10 is formed
by either the upper surface 111 of the body 100, the first major surface of
the scrim, or a coating
applied thereto that is different from the surface coating 200 of the present
invention.
[0035] The surface coating 200 is formed from a coating composition that may
comprise a
binder composition, an antimicrobial composition, and a stabilization
composition. The surface
coating may further comprise a pigment composition. The coating composition
may further
comprise one or more additives. The coating may be pigmented or non-pigmented
¨ whereby
non-pigmented coatings may be referred to as "clear coat" or "clear coating."
[0036] The surface coating 200 is present in a dry-state. According to the
present invention, the
phrase "dry-state" refers to the coating composition being substantially free
of a liquid carrier
(e.g., liquid water). Thus, the surface coating 200, which is in the dry-
state, may comprise the
binder composition, antimicrobial composition, the stabilization composition,
and additives
while having less than about 0.1 wt. % of liquid carrier based on the total
weight of the surface
coating 200. In a preferred embodiment, the surface coating 200 in the dry-
state has a solid's
content of about 100 wt. % based on the total weight of the surface coating
200.
[0037] Conversely, the coating composition may be applied to either the body
100 or a scrim in
a "wet-state," which refers to the coating composition containing various
amounts of liquid
carrier ¨ as discussed further herein. Therefore, in the wet-state, the
coating composition may
comprise at least the binder composition, the antimicrobial composition, the
stabilization
composition. In some embodiments, the coating composition in the wet-state may
further
comprise the additives. The liquid carrier may be selected from water, VOC
solvent ¨ such as
acetone, toluene, methyl acetate ¨ or combinations thereof. In a preferred
embodiment, the
7
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
liquid carrier is water and comprises less than 1 wt. % of VOC solvent based
on the total weight
of the liquid carrier.
[0038] In the wet-state, the coating composition may generally have a solids
content ranging
from about 5 wt. % to about 80 wt. % ¨ including all percentages and sub-
ranges there-between,
[0039] The solid's content is calculated as the fraction of materials present
in the coating
composition that is not the liquid carrier. Specifically, the solid's content
of the coating
composition in the wet-state may be calculated as the total amount of the
coating composition in
the dry-state (i.e., the amount of the binder composition, the antimicrobial
composition, and the
stabilization composition) and dividing it by the total weight of the coating
composition in the
wet-state, including liquid carrier.
[0040] According to the embodiments where the coating composition forms a
clear coating (i.e.,
no pigment), the coating composition in the wet-state may have a solids
content ranging from
about 19 wt. % to about 35 wt. % -- including all percentages and sub--ranges
there-between,
According to the embodiments where the coating composition forms a topcoat
2.10, the coating
composition in the wet-state may have a solids content ranging from about 50
wt. % to about 75
wt. % ¨ including all amounts and sub-ranges there-between. The topcoat 210
may comprise a
pigment. According to the embodiments where the coating composition forms an
edge-coat 230,
the coating composition in the wet-state may have a solids content ranging
from about 65 wt. %
to about 85 wt. % including all amounts and sub-ranges there-between.
[0041] The coating composition may comprise the binder composition in an
amount ranging
from about 4.0 wt. % to about 85.0 wt. % ¨ based on the total weight of
coating composition in
the dry-state ¨ i.e., as the surface coating 200 ¨ including all weight
percentages and sub-ranges
there-between.
[0042] According to the embodiments where the coating composition forms a
clear coating (i.e.,
no pigment), the coating composition may comprise the binder composition in an
amount
ranging from about 65 wt. % to about 88 wt. %
based on the total weight of coating
composition in the dry-state ¨ i.e., as the surface coating 200 ¨ including
all weight percentages
and sub-ranges there-between. According to the embodiments where the coating
composition
forms a pigmented coating topcoat 210, the coating composition may comprise
the binder
composition in an amount ranging from about 8 wt. % to about 18 wt. % ¨ based
on the total
weight of coating composition in the dry-state ¨ i.e., as the surface coating
200 ¨ including all
8
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
weight percentages and sub-ranges there-between. According to the embodiments
where the
coating composition forms a pigmented edge-coat 230, the coating composition
may comprise
the binder composition in an amount ranging from about 10 wt. % to about 20
wt. % --- based on
the total weight of coating composition in the dry-state ¨ i.e., as the
surface coating 200 ¨
including all weight percentages and sub-ranges there-between.
[0043] The binder composition may comprise a blend of one or more polymers.
The polymers
may be ionic. The polymers may be anionic. The polymers may exhibit a pH
ranging from
about 5.0 to about 9.0 ¨ including all pH values and sub-ranges there-between.
[0044] The polymeric binder may be one or more of a polyurethane, an acrylic
polymer, an
alkyd emulsion, and blends thereof.
[0045] Non-limiting examples of acrylic polymer, polymaleic anhydride, or a
combination of
two or more thereof. Non-limiting examples of polymeric binder may include a
homopolymer
or copolymer formed from the following monomers: vinyl acetate (i.e.,
polyvinyl acetate), vinyl
propinoate, vinyl butyrate, ethylene, vinyl chloride, vinylidene chloride,
vinyl fluoride,
vinylidene fluoride, ethyl acrylate, methyl acrylate, propyl acrylate, butyl
acrylate, ethyl
methacrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl
methacrylate, hydroxyethyl
acrylate, styrene, butadiene, urethane, epoxy, melamine, and an ester. The
polymeric binder may
include one or more of aqueous lattices of polyvinyl acetate, polyvinyl
acrylic, polyurethane,
polyurethane acrylic, polystyrene acrylic, epoxy, polyethylene vinyl chloride,
polyvinylidene
chloride, and polyvinyl chloride.
[0046] In a non-liming embodiment, the binder may be a polymeric composition
that is formed
by curing an alkyd resin (also referred to as an alkyd emulsion). Non-limiting
examples of alkyd
emulsion include polyester resins which include residues of polybasic, usually
di-basic, acid(s)
and polyhydroxy, usually tri- or higher hydroxy alcohols and further including
monobasic fatty
acid residues. The monobasic residues may be derived (directly or indirectly)
from oils (fatty
acid triglycerides) and alkyd resins are also referred to as oil modified
polyester resins.
[0047] The alkyd resins may be cured from residual carboxyl and hydroxyl
functionality or by
unsaturation (often multiple unsaturation) in the monobasic fatty acid
residues. Alkyd resins
may include other residues and/or additives to provide specific functionality
for the intended end
use e.g. sources of additional carboxyl groups may be included to improve
water compatibility.
One or more catalyst may be blended with an alkyd resin to help accelerate
curing.
9
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
[0048] Alkyd resins may be prepared by reacting a monobasic fatty acid, fatty
ester or naturally
occurring, partially saponified oil with a glycol or polyol and/or a
polycarboxylic acid.
[0049] Non-limiting examples of monobasic fatty acid, fatty ester or naturally
occuiTing-
partially saponified oil may be prepared by reacting a fatty acid or oil with
a polyol. Examples of
suitable oils include sunflower oil, canola oil, dehydrated castor oil,
coconut oil, corn oil,
cottonseed oil, fish oil, linseed oil, oiticica oil, soya oil, and lung oil,
animal grease, castor oil,
lard, palm kernel oil, peanut oil, perilla oil, safflower, tallow oil, walnut
oil. Suitable examples of
the fatty acid components of oil or fatty acids by themselves are selected
from the following oil
derived fatty acids; tallow acid, linoleic acid, linolenic acid, oleic acid,
soya acid, myristic acid,
linseed acid, crotonic acid, versatic acid, coconut acid, tall oil fatty acid,
rosin acid, neodecanoic,
neopcntanoic, isostcaric, 12-hydroxystearic, cottonseed acid with linolcic,
linolcnic and oleic
being more preferred
[0050] Non-limiting examples of suitable glycol or polyol include aliphatic,
alicyclic, and aryl
alkyl glycols. Suitable examples of glycols include: ethylene glycol;
propylene glycol; diethylene
glycol; triethylene glycol; tetraethylene glycol; pentaethylene glycol;
hexaethylene glycol;
heptaethylene glycol; octacthylenc glycol; nonacthylenc glycol; decaethylene
glycol; 1,3-
prop anediol ; 2,4-dimethy1-2-ethyl-hexane-1,3-diol; 2,2-dimethy1-1,2-
propanediol; 2-ethyl-2-
butyl- 1,3-prop anediol ; 2-ethyl-2-i s obutyl- 1,3 -prop anediol ; 1,3-
butanediol; 1,4-butanediol; 1,5-
pentanediol ; 1,6-hexanediol; 2,2,4-tetramethy1-1,6-hexanediol;
thiodiethanol; 1,2-
cyclohexanedimethanol; 1,3 -cyclohex anedimethanol ;
1 .4-cyclohex anedimethanol ; 2 ,2,4-
trimethyl-1,3 -p entanediol ; 2,2,4-tetra methy1-1,3-cy clobutanediol ; p-
xylenediol hydroxypiv a ly1
hydroxypivalate; 1.10-decanediol; hydrogenated bisphenol A;
trimethylolpropane;
trimethylolethane; pentaerythritol; erythritol; threitol; dipentaerythritol;
sorbitol; glycerine;
trimellitic anhydride; pyromellitic dianhydride; dimethylolpropicnic acid and
the like.
[0051] Non-limiting examples of polycarboxylic acid include isophthalic acid,
terephthalic acid,
phthalic anhydride(acid), adipic acid, tetrachlorophthalic anhydride,
dodecanedioic acid, sebacic
acid, azclaic acid, 1,4-cyclohcxancdicarboxylic acid, 1,3-
cyclohcxanedicarboxylic acid, malcic
anhydride, fumaric acid, succinic anhydride(acid), 2,6-naphthalenedicarboxylic
acid, glutaric
acid and esters thereof.
[0052] The coating composition may comprise the antimicrobial composition in
an amount
ranging from about 0.1 wt. % to about 10.0 wt. % - based on the total weight
of coating
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
composition in the dry-state ¨ i.e., the surface coating 200 ¨ including all
weight percentages and
sub-ranges there-between. According to the embodiments where the coating
composition forms
a clear coat, the coating composition may comprise the antimicrobial
composition in an amount
ranging from about 3.0 wt. % to about 10.0 wt. % - based on the total weight
of coating
composition in the dry-state ¨ i.e., the surface coating 200 ¨ including all
weight percentages and
sub-ranges there-between. According to the embodiments where the coating
composition forms
a pigmented top coat 210, the coating composition may comprise the
antimicrobial composition
in an amount ranging from about 0.1 wt. % to about 0.5 wt. % - based on the
total weight of
coating composition in the dry-state ¨ i.e., the surface coating 200 ¨
including all weight
percentages and sub-ranges there-between. According to the embodiments where
the coating
composition forms an edge coat 230, the coating composition may comprise the
antimicrobial
composition in an amount ranging from about 0.3 wt. % to about 1.0 wt. % -
based on the total
weight of coating composition in the dry-state ¨ i.e., the surface coating 200
¨ including all
weight percentages and sub-ranges there-between.
[0053] The antimicrobial composition may comprise one or more cationic
compounds. The
cationic compound may be a quaternary ammonium compound. The quaternary
ammonium
compound may have the following structure:
R
N +,
R4 R2
[0054] The groups R. R2, R3 and l;t4can vary within wide iirnits and examples
of quaternary
ammonium compounds that have anti-microbial properties will he well known to
the person of
ordinary skill in the art.
[0055] Each group 1.{1, R2, 1?,; and R4. may, for example, independently he a
substituted or
unsubstituted and/or straight chain or branched and/or interrupted or
uninterrupted alkyl, aryl,
alkylaryl, aryl alkyl, cycle alkyl, (aromatic or non-aromatic) heterocycly1 or
alkenyl group.
Alternatively, two or more of R1, RI, R3 and Ri.may together with the nitrogen
atom form a
substituted or unsubstituted heterocyclic ring. The total number of carbon
atoms in the groups
R;,, kJ and Ri must be at least 4. Typically the sum of the carbon atoms in
the groups R1.
R3 and R4 is 10 or more. In a preferred aspect of the invention at least one
of the groups RI, R2,
11
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
R3 and R4 contains from 8 to 18 carbon atoms, For example, 1, 2, 3 or 4 of RI,
R2, R3 and R4 can
contain from 8 to 18 carbon atoms or 10 to 16 carbon atoms.
[0056] Suitable substituents for the groups R1, R2. R3 and R.4 may be selected
from the group
consisting of alkyl, substituted alkyl, aikenyl, substituted alkenyl,
heterocyelyi, substituted
beterocyclyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,
alkylaryl, substituted
alkylaryl, arylalkyl, substituted arylalkyl, F, CI, Br, 1, .. OR, .. NR'R",
...... CF3, CN, NO2,
C1R.', ---------- SR', ---- C(=0)NR.R", ------------- NR.`C(,))R",
OCA=0)Rr, ---------- 0(CP. "R"),C1,---..--0)R ?õ ........ 0(C R "),NR
"C(=0)R. --- ("f RR),NR "S 02R
OC(=0)NR'R", __________ NR'C'.(=0)0R", __ SO2R`, __________ SO2NR`R", and
_________ NR'S 02R", where R and R"
are individually hydrogen, CI-Cs alkyl, cycloalkyl. heteroeyely1õ aryl, or
arylalkyl, and r is an
integer from I_ to 6, or R' and R" together form a cyclic functionality,
wherein the term "substituted" as applied to alkyl, alkenyl, hete,rocyclyi,
cycloalkyl, aryl,
alkylaryl and arylalkyi refers to the substituents described above, starting
with F and ending with
NR'S07.R.".
[0057] When one or more of RI, R2, R3 and R4is interrupted, suitable
interrupting groups include
hut are not limited to hetematoms such as oxygen, nitrogen, sulphur, and
phosphorus-containing
moieties (e.g. phosphinate). A preferred interrupting group is oxygen.
[0058] Suitable anions for the gnats include but are not limited to halide
anions such as the
chloride, fluoride, bromide or iodide and the non halide suluhonate,
[0059] In some embodiments, the quaternary ammonium compound may be those
having the
formula:
(CII3)fi(A),,,N+X-
[0060] wherein A may be as defined above in relation to 1-,11, R. R1 and R. X-
is selected from
chloride, fluoride, bromide or iodide and sulphonate (preferably chloride or
bromide), n is from 1
to 3 (preferably 2 or 3) and mis from 1 to 3 (preferably I or 2) provided that
the sum of n and M.
is 4, Preferably, A is a C&20 (e.g. Cs-I8, i.e. having 8,9. 10, 11, 12,
13,1.4. 15, 16, 17 or 18 carbon
atoms or C8_12) substituted or unsubstituted and/or straight chain or branched
and/or interrupted
or uninterrupted alkyl, aryl, alkylaryl, arylalkyl or cycloalkyl group
(wherein suitable
substituents are as defined above in relation to RI, R2, R3 and R4). Each
group A may be the same
or different.
12
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
[0061] In some embodiments, the quaternary ammonium compound may be of the
formula
(013),(A),,,N+X- are those wherein st..,,3 and m=1, In such compounds A may be
as defined
above and is preferably a C6.10 substituted or unsubstituted and/or straight
chain or branched
and/or interrupted or uninterrupted alkyl., aryl, or alkylaryl. group.
Examples of this type of
quaternary ammonium compound include Cetrimide (which is predominately
trimethyltetradecylanimoniUM bromide), dod.ecyhrimethylaannordum
bromide,
trimethy itetradec yl ammonium bromide, hex adecy I trimetli y i ammonium
bromide.
[0062] In other embodiments, the quaternary ammonium compound may be of the
formula
(C113),(A)N+X- are those wherein n=2 and irc2. In such compounds A may be as
defined
above in relation to R1. R2, R3 and R.4. Preferably A is a C61) substituted or
unsubstituted and/or
straight chain or branched and/or interrupted or unintermmed alkyl, aryl, or
alkylaryl group. For
exampleõk may represent a straight chain, unsubstituted and uninterrupted Cs-
12 alkyl group or a
benzyl group. In these compounds, the groups A may be the same or different.
Examples of this
type of compound include dideryl &methyl anunoniwn chloride and dioctyl
ditnethyl
ammonium chloride.
[0063] Non-limiting examples of quaternary ammonium compounds described above
include the
group of compounds which are generally called benzlkonium halides and aryl
ring substituted
derivatives thereof, Examples of compounds of this type include benzalkonium
chloride, which
has the structural formula:
N
Cl-
[0064] wherein R may be as defined above in relation to R1, R2, R3 and R.
Preferably, R is a Cs-.
is alkyl group or the betrialkonium chloride is prmided and/or used as a
mixture of Ca-is alkyl
groups, particularly a mixture of straight chain, unsubstituted and
uninterrupted alkyl groups n-
C81-117 to n-C18H37, mainly h-Ci?FV5(dodecyl), n-C14F-129(tetradecyl), and n-C
(hexadecyl).
[0065] Other preferred quaternary ammonium compounds include those in which
the benzene
ring, is substituted, for example alkyldimedlyi ethylbenzyl ammonium chloride.
As an example, a
13
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
mixture containing, for example, equal Inoiar amounts of alk-yl dirnethyl
benzyi ammonium
chloride and alkyldimealy1 ethylbenzyl ammonium chloride may be used.
[0066] Mixtures of, for example, one or more alkyl dimethyl benzyl ammonium
chlorides and
one or more compounds of formula (CF13)2(A)2N+X-, such as dide.µ.-,y1
dimetb.y1 aninionium
chloride may be used.
[0067] The coating composition may comprise the stabilization composition in
an amount
ranging from about 0.5 wt. % to about 15.0 wt. % - based on the total weight
of coating
composition in the dry-state ¨ i.e., the surface coating 200 ¨ including all
weight percentages and
sub-ranges there-between. According to the embodiments where the coating
composition forms
the clear coat, the stabilization composition may he present in an amount
ranging from about 8.0
wt. % to about 15.0 wt. % - based on the total weight of coating composition
in the dry-state ¨
i.e., the surface coating 200 ¨ including all weight percentages and sub-
ranges there-between.
According to the embodiments where the coating composition forms the pigmented
top coat 210,
the stabilization composition may be present in an amount ranging from about
0.5 wt. % to about
1.2 wt. % - based on the total weight of coating composition in the dry-state
¨ i.e., the surface
coating 200 ¨ including all weight percentages and sub-ranges there-between.
According to the
embodiments where the coating composition forms the edge coat 230, the
stabilization
composition may be present in an amount ranging from about 0.8 wt. % to about
2.0 wt. % -
based on the total weight of coating composition in the dry-state ¨ i.e., the
surface coating 200 ¨
including all weight percentages and sub-ranges there-between.
[0068] The stabilization composition may comprise a surfactant. The coating
composition may
comprise the surfactant composition in an amount ranging from about 0.2 wt. %
to about 14.0
wt. % - based on the total weight of coating composition in the dry-state ¨
i.e., the surface
coating 200 ¨ including all weight percentages and sub-ranges there-between.
According to the
embodiments where the coating composition forms the clear coat, the coating
composition may
comprise the surfactant composition in an amount ranging from about 6.0 wt. %
to about 14.0
wt. % - based on the total weight of coating composition in the dry-state ¨
i.e., the surface
coating 200 ¨ including all weight percentages and sub-ranges there-between.
According to the
embodiments where the coating composition forms the pigmented top coat 210,
the coating
composition may comprise the surfactant composition in an amount ranging from
about 0.2 wt.
14
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
% to about 0.8 wt. % - based on the total weight of coating composition in the
dry-state - i.e., the
surface coating 200 - including all weight percentages and sub-ranges there-
between.
[0069] The term "surfactant" refers to synthetic and naturally occurring
amphiphilic molecules
that have hydrophobic portion(s) and hydrophilic portion(s). Due to the
amphiphille
(amphipathic) nature, the surfactants and co-surfactants typically can reduce
the surface tension
between two immiscible liquids, for example, the oil and water phases in an
emulsion, stabilizing
the emulsion.
[0070] The amphiphilic (amphipathic) nature may result in a "hydrophilic-
lipophilic balance" or
otherwise referred to as a "hydrophile-lipophile balance" or "111.13" - which
refers
synonymously to a value that is used to index and describe a surfactant
according to its relative
hydrophobicitythydrophilicity, relative to other surfactants. A surfactant's
fILB value is an
indication of the molecular balance of the hydrophobic and lipophilic portions
of the surfactant,
which is an amphipathic molecule. Each surfactant and mixture of surfactants
(and/or co-
surfactants) has an .FILI3 value that is a numerical representation of the
relative weight percent of
hydrophobic and hydrophilic portions of the surfactant molecule(s). 141_,B
values are derived
from a semi-empirical formula. The -relative weight percentages of the
hydrophobic and
hydrophilic groups are indicative of surfactant properties, including the
molecular structure, for
example, the types of aggregates the surfactant will form and the solubility
of the surfactant.
[0071] HLB values may be a rough guide, hydrophilic surfactants are generally
considered to be
those compounds having an HLB value greater than about 10, as well as anionic,
cationic, or
zwitterionic compounds for which the H1_13 scale is not generally applicable.
Similarly,
hydrophobic surfactants are compounds having an IlLfl value less than about
10. Stated
otherwise, surfactants with 111-.13 values greater than 10 or greater than
about 10 are more soluble
in aqueous compositions, for example, water, and are called "hydrophilic
surfactants," while
surfactants having FILB values less than 10 or less than about 10 are more
soluble in fats, oils
and waxes, and are referred to as "hydrophobic, surfactants" or "lipophilic
surfactants."
Relatively amphiphilic surfactants are soluble in oil and water based liquids
and typically
have FILE values close to 10 or about 10.
[0072] Surfactant HLB values range from 1-45, while the range for non-ionic
surfactants
typically is from 1-20. The more lipophilic a surfactant is, the lower its HLB
value. Conversely,
the inure hydrophilic a surfactant is, the higher its HLB value, The
surfactant composition of the
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
present invention may comprise one or more surfactants having an FILE value
ranging from
about 10 to about 14 --- including all HUB values and sub-ranges there-
between. In some
embodiments, the surfactant composition of the present invention may comprise
one or more
surfactants having an FMB value ranging from about 10 to about 12 ¨ including
all HUB values
and sub-ranges there-between.
[0073] Non-limiting examples of surfactants having an HLB value between about
10 and about
14 include polysorbate 81 (HLB 10); PEG-40 Sorbitan Hexaoleate (HLB 10); PEG-
40 Sorbitan
Perisostearate (HLB 10); PEG-10VC Glycerides WEB 10); PEG sorbitol hexaoleate
(1-11_11
10.2); Polysorbate 65 (11LB 10.5); PEG-25 Hydrogenated Castor Oil (HUB 10.8);
Polysorbate 85
(HUB 11); PEG-7 Glyceryl Cocoate (HUB 11); PEG-8 &carafe (HUB 11.1); PEG
sorhitan
tetraoleate (HUB, 12); PEG-35 Almond Glycerides (HLB 121; PEG-10 ley]. ether
(HLB 12.4.);
PEG-8 isooctylphenyl ether (HLB 12.4); PEG-10 stearyi ether (HUB 12.41; PEG-35
Castor Oil
(HUB 12.5); PEG--10 c.!etyl ether (HUB 12.9); Nonoxyno1-9 (HUB 12.9): PEG-40
Castor Oil
(HUB 131; PEG-10 isooctylphenyl ether fli[LB 13.5); PEG-40 Hydrogenated Castor
Oil (HUB
14)
[0074] The stabilization composition may comprise a silicate compound. The
silicate compound
may be thixotropic.
[0075] The coating composition may comprise the silicate compound in an amount
ranging from
about 0.1 wt. % to about 1.0 wt. % - based on the total weight of coating
composition in the dry-
state ¨ i.e., the surface coating 200 ¨ including all weight percentages and
sub-ranges there-
between. According to the embodiments when the coating composition forms a
clear coat, the
silicate compound may be present in an amount ranging from about 0.6 wt. % to
about 1.0 wt. %
- based on the total weight of coating composition in the dry-state ¨ i.e.,
the surface coating 200
¨ including all weight percentages and sub-ranges there-between.
According to the
embodiments when the coating composition forms a pigment top coat 210, the
silicate compound
may be present in an amount ranging from about 0.1 wt. % to about 0.5 wt. % -
based on the
total weight of coating composition in the dry-state ¨ i.e., the surface
coating 200 ¨ including all
weight percentages and sub-ranges there-between. According to the embodiments
when the
coating composition forms an edge coat, the silicate compound may be present
in an amount
ranging from about 0.1 wt. % to about 0.4 wt. % - based on the total weight of
coating
16
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
composition in the dry-state ¨ i.e., the surface coating 200 ¨ including all
weight percentages and
sub-ranges there-between.
[0076] A weight ratio of the surfactant composition to the silicate compound
may range from
about 3.0:1.0 to about 1.0:1.0 ¨ including all ratios and sub-ranges there-
between. In some
embodiments, the weight ratio of the surfactant composition to the silicate
compound may be
about 3.0:1Ø In some embodiments, the weight ratio of the surfactant
composition to the
silicate compound may be about 2.5:1Ø In some embodiments, the weight ratio
of the
surfactant composition to the silicate compound may be about 2.0:1Ø In some
embodiments,
the weight ratio of the surfactant composition to the silicate compound may be
about 3.0:2Ø In
some embodiments, the weight ratio of the surfactant composition to the
silicate compound may
be about 1.0:1Ø
[0077] The silicate compound may be a lithium magnesium silicate. The silicate
compound may
be a synthetic clay. In one embodiment, the lithium magnesium silicate may
have the formula:
[Mg,Li,,Sis0200W-Tyr
[0078] wherein w=3 to 6, x=0 to 3, y=0 to 4, z=12-2w¨x, and the overall
negative lattice charge
is balanced by counter-ions; and wherein the counter-ions are selected from
the group consisting
of selected Nal., Kit NH4 Cs, Li1, Mg', Ca41, Ba, N(CH3)4 and mixtures
thereof. In some
embodiments, the silicate compound may be lithium sodium magnesium silicate.
[0079] It has been discovered that the combination of the silicate compound
and surfactant
composition imparts a surprising stabilization effect to the coating when the
coating comprises
an hinder composition comprising an anionic component and an antimicrobial
composition
comprising a cationic compound. The surprising stabilization effect results in
the form of the
coating composition not forming agglomeration
coagulation in the wet-state while also
allowing for superior application characteristics (measured by drawdown),
[0080] The surface coating 200 may further comprise a pigment composition. The
pigment
composition may comprise one or more of titanium dioxide, alkaline metal
carbonates, and
combinations thereof.
[0081] The pigment composition may be present in an amount ranging from about
50 wt. % to
about 90 wt. % based on the total weight of the pigment composition ¨
including all weight
percentages and sub-ranges there-between. According to the embodiments where
the coating
composition may form a pigmented top coat 210, the pigment composition may be
present in an
17
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
amount ranging from about 65 wt. % to about 90 wt. % based on the total weight
of the pigment
composition ¨ including all weight percentages and sub-ranges there-between.
According to the
embodiments where the coating composition may form a pigmented edge coat 230,
the pigment
composition may be present in an amount ranging from about 70 wt. % to about
90 wt. % based
on the total weight of the pigment composition ¨ including all weight
percentages and sub-ranges
there-between.
[0082] The surface coating 200 may comprise one or more additives. Additives
may be present
in the coating composition in an amount ranging from about 0.05 to about 2.5
wt. % - based on
the total weight of the coating composition in the wet-state. Non-limiting
examples of additives
include, other biocides, defoamers, and the like.
[0083] Defoamers may include polyether siloxane. Defoamers may be present in
an amount
ranging from about 0.01 wt. % to about 0.05 wt. % based on the weight of the
surface coating
200 in the dry-state.
[0084] The building panel. 10 according to the present invention may be formed
by applying the
coating composition in the wet-state to either the body 100 or the scrim. Once
applied, the
coating composition in the wet-state may be dried at a temperature ranging
from about 85 C to
about 135 C including all temperatures and sub-ranges there-between.
[0085] The coating composition may be applied by spray, roll, or vacuum
coating.
[0086] After drying, all liquid carrier is driven off thereby leaving the
surface coating 200 i.e.,
the coating composition in the dry-state. The surface coating 200 may be
present in an amount
ranging from about in an amount ranging from about 55 g/m2 to about 1500 g/m2
¨ including all
amounts and sub-ranges there-between. According to the embodiments where the
coating
composition forms the face coating 210, the coating may be present in an
amount ranging from
55 g/m2 to about 360 g/m2 including all amounts and sub-ranges there-between,
According to
the embodiments where the coating composition forms the edge coating 230, the
coating may be
present in an amount ranging from 750 gini2 to about 1500 g/m2 --- including
all amounts and sub--
ranges there-between,
EXAMPLES
[0087] Experiment 1
[0088] A first series of experiments were performed to test the impact of
combining the
antimicrobial composition and stabilization composition of the present
invention in a coating
18
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
comprising a binder composition. Below is a list of components with relevant
values and/or
compositional information.
[0089] Liquid Carrier - including water
[0090] Binder - anionic emulsion polymer
[0091] Antimicrobial composition (-AC-) - quaternary ammonium compound
[0092] Silicate compound ("SC") - lithium sodium magnesium silicate
[0093] Surfactant 1 - HLB 8
[0094] Surfactant 2 - HLB 10
[0095] Surfactant 3 - HLB 12
[0096] Surfactant 4 - HLB 14
Table 1
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8
134E 134E 134E 134E 134E 134E 134E 134E
Liquid Carrier 94.7 91.7 89.0 86.7 84.8
83.1 80.4 78.2
Binder 4.2 7.3 10.1 12.5 14.4 16.1 19.0 21.2
AC 0.2 0.2 0.2 0.2 0.2 0.2 0.1
0.1
SC 0.4 0.4 0.3 0.3 0.3 0.3 0.2
0.2
Surfactant 1 -
Surfactant 2 0.5 0.4 0.4 0.4 0.3 0.3 0.3
0.3
Surfactant 3 -
Surfactant 4 -
Agglomeration No No No No No No No No
Draw Down Pass Pass Pass Pass Pass Pass Pass Pass
Dry Time Pass Pass Pass Pass Pass Pass Pass Pass
Table 1 (continued)
Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15
134F 134F 134F 134F 134F 135C 135B
Liquid Carrier 94.9 89.1 84.8 81.9 79.4 92.7
78.5
Binder 4.1 10.0 14.4 17.4 20.0 6.4
20.9
AC 0.2 0.2 0.2 0.2 0.1 0.2 0.1
SC 0.4 0.3 0.3 0.3 0.2 0.4 0.2
Surfactant 1 - 0.4
Surfactant 2 -
Surfactant 3 0.5 0.4 0.3 0.3 0.3
Surfactant 4 - 0.2
Agglomeration No No No No No Yes No
19
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
Draw Down Pass Pass Pass Pass Pass Fail
Pass
Dry Time Pass Pass Pass Pass Pass Pass
Fail
[0097] Table 1 demonstrates that the coating formulation comprising the
antimicrobial
composition of a quaternary ammonium compound exhibits superior stability in
the presence of a
surfactant having an HLB between 10 and 14 as well as a silicate compound ¨
whereby Example
14 demonstrates failing stability in the presence of a surfactant having an
HLB less than 10 (i.e.,
an HLB value of 8).
[0098] An additional set of experiments were performed to test the impact of
silicate compound
with antimicrobial component.
Table 2
Ex. 16 Ex. 17 Ex. 18 Ex. 19
133A Page 132 Page 132 Page 132
Liquid Carrier 83.5 80.8 89.3 81.0
Binder 15.6 18.8 10.1 18.8
AC 0.3 0.2 0.3 0.2
SC 0.7 0.2 0.3
Surfactant 1
Surfactant 2
Surfactant 3
Surfactant 4
Agglomeration Yes Yes Yes Yes
Agglomeration
Small Small Small Large
Size
Draw Down Fail Fail Fail Fail
[0099] As demonstrated by Table 2, the presence of the silicate compound alone
is not enough to
impart coating stability when the antimicrobial component is combined with an
anionic polymer
¨ further supporting the presence of the surfactant having an HLB value
between 10 and 14
imparting an unexpected improvement in coating stability.
[01001 Experiment 2
[0101] A second experiment was performed to test the antimicrobial performance
of the coating
of the present invention. Two coating compositions were prepared ¨ each
comprising an anionic
binder and liquid carrier. The first coating composition (Ex. 20) further
comprising an
antimicrobial composition comprising quaternary ammonium and a stabilization
composition
CA 03218901 2023- 11- 13
WO 2022/240633
PCT/US2022/027616
according to the present invention. The second coating composition (Ex. 21)
further comprising
an antimicrobial composition comprising a silver-based compound.
[0102] A first, second, and third Petri dish were inoculated with identical
concentrations of
Staphylococcus auereus ATCC 6538P and incubated for a period of 2 hours ¨
whereby the initial
bacteria concentration for each of the first, second, and third Petri dishes
were recorded. After
the initial incubation, a first amount of the first coating composition was
applied to the first Petri
dish (Ex. 20). a second amount of the second coating composition was applied
to the second
Petri dish (Ex. 21), and the third Petri dish was kept untreated (Control).
After a second
incubation period of 24-28 hours, a second bacteria concentration for each of
the first, second,
and third Petri dishes were records. The results are set forth below in Table
3.
Table 3
Ex. 20 Ex. 21
Control
Coating Amount 2.0 g/ft2
2.5 g/ft2 0.0 g/ft2
Second Bacterial
-0.2 1.89 4.34
Concentration
Bacterial Concentration
99.997 99.6
Percent Reduction
Value of Antimicrobial
2.45 4.54
Activity (R)
[0103] As demonstrated by Table 3, the coating composition of the present
invention (Ex. 20)
surprisingly exhibits a superior antimicrobial activity as compared to a
standard silver-based
antimicrobial composition at even a lower application amount. The 0.397
percent improvement
in bacterial concentration reduction (i.e., 99.997 vs. 99.6) is substantial as
reflected by over 2.0
value improvement in Antimicrobial Activity Value (R).
21
CA 03218901 2023- 11- 13
