USOO9265248B2

(12) United States Patent (10) Patent No.: US 9,265,248 B2

Gentle et al. (45) Date of Patent: Feb. 23, 2016

(54) WATER SOLUBLE ANTIMICROBIAL A01N 31/14: A01N33/12: A01N 55/02:

COMPOSITION A01N 43/80: A01N 47/40: A01N 25/22:
AO1N 55/OO
(75) Inventors: Thomas M. Gentle, St. Michael, MN See application file for complete search history.
(US); John J. Matta, Shoreview, MN
(US); Adam W. Hauser, Minneapolis,
MN (US); Wil Goetsch, Maple Grove, (56) References Cited
MN (US); Joshua Erickson, Champlin,
MN (US) U.S. PATENT DOCUMENTS
5,505,953 A 4/1996 Chowhan
(73) Assignee: Medivators Inc., Minneapolis, MN (US) 6,221.944 B1 ck 4, 2001 Liebeskind et al. . . . . . . . . . 524/386
2005, 0008534 A1 1/2005 Hodge et al.
(*) Notice: Subject to any disclaimer, the term of this 2007/O104766 A1* 5, 2007 WE al . . . . . . . . . . . . . . . . . . 424/443
patent is extended or adjusted under 35 2008/0275230 A1 11/2008 Liu et al.
U.S.C. 154(b) by 0 days.
FOREIGN PATENT DOCUMENTS
(21) Appl. No.: 14/238,930
CN 101.461368 A 6, 2009
1-1. EP 0356264 A2 2/1990
(22) PCT Filed: Aug. 15, 2012 EP O492843 A2 7, 1992
(86). PCT No.: PCT/US2012/050908 S. w89.23A, 8,8.
WO WO-01 01994 A1 1/2001
S371 (c)(1), WO WO-01/97851 A2 12/2001
(2), (4) Date: Jun. 13, 2014 WO WO-02/30469 A2 4, 2002
WO WO-02/069954 A2 9, 2002
(87) PCT Pub. No.: WO2013/025783 WO WO-03/070008 A1 8, 2003
WO WO-2006/076334 A1 T 2006
PCT Pub. Date: Feb. 21, 2013 WO WO-2006/081617 A1 8, 2006
WO WO-2007/004O67 A2 1/2007
(65) Prior Publication Data WO WO-2007/027859 A1 3/2007
WO WO-2008.002434 A2 1/2008
US 2014/O294749 A1 Oct. 2, 2014 WO WO-2009/108407 A1 9, 2009
WO WO-2013/025783 A2 2, 2013
Related U.S. Application Data WO WO-2013/025783 A3 2, 2013
(60) Provisional application No. 61/523,701, filed on Aug. OTHER PUBLICATIONS
15, 2011, provisional application No. 61/558,045,
filed on Nov. 10, 2011. “International Application Serial No. PCT/US2012/050908, Interna
tional Search Report mailed May 10, 2013”.9 pgs.
(51) Int. Cl. “International Application Serial No. PCT/US2012/050908, Invita
AOIN 25/22 (2006.01) tion to Pay Additional Fees mailed Nov. 3, 2012, 11 pgs.
AOIN 47/40 (2006.01) “International Application Serial No. PCT/US2012/050908, Written
AOIN 43/16 (2006.01) Opinion mailed May 10, 2013”, 13 pgs.
AOIN3L/08 (2006.01) Canadian Application Serial No. 2,844,791, Office Action mailed
AOIN3L/4 (2006.01) May 11, 2015, 3 pgs.
AOIN3L/6 (2006.01)
AOIN 43/80 (2006.01) (Continued)
AOIN 55/02 (2006.01)
AOIN 55/00 (2006.01)
AOIN33/12 (2006.01) Primary Examiner — Anoop Singh
AOIN 25/10 (2006.01) Assistant Examiner — Doan Phan
AOIN 25/34 (2006.01) riva
D06M I3/463 (2006.01) WCSX Agent, or Firm — Schwegman Lundberg &
D06M 16/00 (2006.01) s u 81. x•
(52) U.S. Cl.
CPC ................ A0IN 25/22 (2013.01); A0IN 25/10 (57) ABSTRACT
(2013.01); A0IN 25/34 (2013.01); A0IN31/08
(2013.01); A0IN 31/14 (2013.01); A0IN 31/16 The present invention provides for antimicrobial composi
(2013.01); A0IN33/12 (2013.01); A0IN 43/16 tions, methods of preparing the antimicrobial compositions,
(2013.01); A0IN 43/80 (2013.01); A0IN 47/40 methods of using the antimicrobial compositions, and/or kits
(2013.01); A0IN 55/00 (2013.01); A0IN 55/02 that include the antimicrobial compositions. The antimicro
(2013.01): D06M 13/463 (2013.01): D06M bial compositions can be in a dry, Solid (e.g., powdered) form,
16/00 (2013.01) or can be in a liquid (e.g., aqueous) form.
(58) Field of Classification Search
CPC. D06M 13/463: D06M 16/00; A01N 43/16;
A01N 25/10; A01N 25/34: A01N31/08; 18 Claims, 8 Drawing Sheets
 US 9,265.248 B2
Page 2

(56) References Cited International Application Serial No. PCT/US2012/050908, Interna

tional Preliminary Report on Patentability mailed Feb. 27, 2014, 15
OTHER PUBLICATIONS pg.S.

Europeam Application Serial No. 12754132.4, Office Action mailed

Apr. 4, 2014, 2 pgs. * cited by examiner
U.S. Patent Feb. 23, 2016 Sheet 1 of 8 US 9,265.248 B2

VERTICAL FABRIC FLUD DISPERSION

-0- UA HEAT (EAE WASHED WITH SPORTSENSE

3.0 -HUA HEAT (EAE WASHED WITH SPORT

DAY OF STUDY

/W/
U.S. Patent Feb. 23, 2016 Sheet 2 of 8 US 9,265.248 B2

HORIZONTAL FABRIC FLUID DSPERSION

-0- UA HEAT CAE WASHED WITH SPORTSENSE

14
12
1.0
0.8
0.6
0.4
O2
0.0
4. 7
DAY OF STUDY

AW.”
U.S. Patent Feb. 23, 2016 Sheet 3 of 8 US 9,265.248 B2

VERTICAL FABRC FUD DISPERSION

--UA HEAT CEA CONTROL
--UA HEAT CEASPRAYED WITHSPORISENSE
-A-UA HEAT CEAFSOAKED WITHSPORISENSE

1 2 5 4. 5 6

DAY OF STUDY

AW.f
U.S. Patent Feb. 23, 2016 Sheet 4 of 8 US 9,265.248 B2

HORIZONTAL FABRIC FLUID DISPERSION

--JA HEAT CEA CONTROL
--JA HEATGEASPRAYED WHSPORISENSE
-A-UA HEAT CEASOKED WITHSPORISENSE

DAY OF STUDY

A/
U.S. Patent Feb. 23, 2016 Sheet 5 of 8 US 9,265.248 B2

MOISTURE RELEASE (EVAPORATION)

-0- UA HEAT CA WASHED WITH SPORTSENSE
-s-UA HEAT CEAFWASHED WITHSPOR-WASH"
40
3.5
S.O2.5 N 4N 2
2.0
15
O
O5
OO
4. 7 O

DAY OF STUDY
U.S. Patent Feb. 23, 2016 Sheet 6 of 8 US 9,265.248 B2

MOISTURE RELEASE (EVAPORATION)

--UA HEAT GEAR CONTROL
--UA HEAT GFA 'SPRAYED WITHSPORISENSE
-a-UA HEATGEARSOKED WHSPORISENSE
50

0.5
O.O
2 3. 4. 5 6

DAY OF STUDY

Aiz (f
U.S. Patent Feb. 23, 2016 Sheet 7 of 8 US 9,265.248 B2

SIMULATED PERSPRATION TEST

-0- UA HEAT CAE WASHED WITH SPORTSENSE

4.5
40
5.5
5.0
2.5
2.0
15
10
O.5
O.O
O 5 10 15 2O

TIME (HOURS)
AZ 7
U.S. Patent Feb. 23, 2016 Sheet 8 of 8 US 9,265.248 B2

SIMULATED PERSPRATION TEST

--UA HEAT CEA CONTROL

--UA HEAT GEA'SPRAYED WITHSPORISENSE

O 5 O 15 2O

TIME (HOURS)
/W4
 US 9,265,248 B2
1. 2
WATER SOLUBLE ANTIMICROBAL afford an oil or solid that is not readily soluble in water, and
COMPOSITION can degrade over time when exposed to ambient conditions.
The polymerized version of the AEM 5700 (BiosafetM) is
CLAIM OF PRIORITY a powder that is difficult to work with and leaves particulates
behind upon dissolving in water. The BiosafetM, upon formu
This application is a national stage application under 35 lation into a sprayable liquid, includes an appreciable amount
U.S.C. S371 of PCT/US2012/050908, filed Aug. 15, 2012, ofundissolved solid particulates that should be removed (e.g.,
and published as WO 2013/025783 on Feb. 21, 2013, which by filtering), or the sprayer can become clogged from the
claims the benefit of priority of U.S. Provisional Application Solid particulates. This can lead to costly and time-consuming
No. 61/523,701, filed Aug. 15, 2011, entitled “WATER
10 steps in the production of liquid, sprayable commercial prod
ucts manufactured from BiosafetM.
SOLUBLE ANTIMICROBAL POWDER, and claims the
benefit of priority of U.S. Provisional Application No. Consequently, there exists a need for antimicrobial com
61/558,045, filed Nov. 10, 2011, entitled “WATER
positions (e.g., ones that includes 3-(trimethoxysilyl)propy
SOLUBLE ANTIMICROBAL POWDER,” which applica ldimethyl octadecyl ammonium chloride), as well as methods
tions and publication are incorporated by reference as if
15 of manufacturing the same in a convenient, reliable, and
cost-effective manner.
reproduced herein and made a parthereof in their entirety, and
the benefit of priority of each of which is claimed herein. SUMMARY OF THE INVENTION
BACKGROUND OF THE INVENTION The present invention provides for antimicrobial composi
tions, methods of preparing the antimicrobial compositions,
A variety of industries are Subject to problems occurring methods of using the antimicrobial compositions, and/or kits
with the growth of microorganisms. Such industries include, that include the antimicrobial compositions. The antimicro
for example, the sporting equipment industry, the sporting bial compositions can be in a dry, Solid (e.g., powdered) form,
apparel industry, the construction industry, medical health 25 or can be in a liquid (e.g., aqueous) form.
care institutions, the medical device industry, the lumber In specific embodiments, the antimicrobial compositions
industry, and the textile industry. As such, reduction or elimi described herein can effectively reduce the number of
nation of microorganisms on Surfaces is important in a broad microbes located upon a Substrate. In additional specific
variety of applications. One approach to interfere with the embodiments, the antimicrobial compositions described
ability of microorganisms to Survive on various materials is to 30 herein can effectively kill or inhibit a microorganism. In
modify the surface of those materials by attachment of anti additional specific embodiments, the antimicrobial composi
microbial agents. tions described herein can effectively eliminate or lower the
Deciding how best to attach an antimicrobial agent to a malodor associated with the growth of a microorganism. In
material is guided, at least in part, by the planned end-use of additional specific embodiments, the antimicrobial composi
the material. One important and useful consideration is that 35 tions described herein can effectively eliminate or lower
the antimicrobial activity be persistent. This may beachieved staining or discoloration of a Substrate, which is associated
by permanently attaching the antimicrobial agent to the Sur with the growth of a microorganism. In additional specific
face, so that it is unable to migrate or leach away from the embodiments, the antimicrobial compositions described
modified material surface when the modified material is herein are long-lasting, exhibiting antimicrobial activities for
exposed to fluids. For example, for applications in which the 40 extended periods of time. This includes those embodiments in
modified material will come into contact with aqueous fluids, which the antimicrobial composition is formulated as a film
it is important that the antimicrobial agent is not rinsed away or a coating on a Substrate. In additional specific embodi
when the modified material comes into contact with aqueous ments, the antimicrobial compositions described can employ
fluids. For applications in which the modified material will antimicrobial agents that are relatively inexpensive, safe,
come into contact with aqueous biological fluids, it is impor 45 non-toxic, and/or convenient to use. For example, the antimi
tant that the antimicrobial agent is not rinsed away, or other crobial compositions can be applied to a Substrate by spray
wise inactivated, when the modified material is exposed to ing, dipping, laundering, soaking, brushing, and/or rolling the
aqueous biological fluids. For applications in which the modi substrate with the antimicrobial composition.
fied material is to be used repeatedly, it is important that the In specific embodiments, the antimicrobial compositions
antimicrobial agent is not washed or rinsed away when the 50 described herein can effectively treat a textile, such as a
modified material is washed or rinsed in fluids in between moisture wicking performance fabric, without inhibiting the
repeated uses. ability of the textile to wick away moisture from the user of
One approach employs methods that attach silane-based the textile. In treating the textile, the antimicrobial composi
quaternary ammonium compounds to particular Substrates tion can quickly kill microbes (e.g., bacteria, fungi, viruses,
via a siloxane bond. For example, the AEGISR) product line 55 etc.) located on/in the textile, employing an alcohol (e.g.,
includes products that utilize 3-(trimethoxysilyl)propyldim ethanol). Additionally, in specific embodiments, the antimi
ethyl octadecyl ammonium chloride. According to product crobial composition can effectively prevent (or minimize)
literature, AEM 5700 includes 43% 3-trimethoxysilylpropy microbes from colonizing/growing on/in the textile, for
loctadecyl ammonium chloride in methanol, which can be extended periods of time (e.g., up to about 90 days).
used, e.g., to coat the Surface of textiles. This is not a poly 60 In preventing (or minimizing) the microbes from coloniz
meric compound, although some interlinking of the applied ing/growing, the antimicrobial composition includes a poly
silane may occur after application to the Substrate. The meric carrier (e.g., polyvinyl alcohol) coated with an antimi
methanol present in the commercial product AEM 5700 can crobial (e.g., 3-(trimethoxysilyl)propyl dimethyl octadecyl
be toxic, hazardous and therefore undesirable for some con ammonium chloride), which effectively binds to the textile,
Sumers. Another problem with the AEM liquid is the insta 65 providing the microbe protection without significantly reduc
bility to pH change or temp/pressure changes. The product ing the effectiveness of wicking moisture. In not significantly
AEM 5700, upon removal of the methanol, will typically reducing the effectiveness of wicking moisture, the treated
 US 9,265,248 B2
3 4
textile will not be especially sensitive to detergents, cleaners, (a) contacting an antimicrobial agent, a polymeric carrier and
and antimicrobial products. As such, with use of the antimi a solvent to form a slurry, and (b) removing the solvent from
crobial composition to treat a textile, the antimicrobial com the slurry to form the antimicrobial composition. The antimi
position can improve the ability of the textile to wick away crobial agent is relatively water Soluble (e.g., has a solubility
moisture from the user, while maintaining the antimicrobial in water of at least about 0.05 g/mL at 80° C. and 1 atm). The
properties. The antimicrobial composition will therefore have polymeric carrier is also relatively water Soluble (e.g., has a
little or no negative impact on the wicking process for the solubility in water of at least about 0.05 g/mL at 80° C. and 1
treated textile, and in Some instances will improve the mois atm). In specific embodiments, the antimicrobial composi
ture wicking performance, along with lasting antimicrobial tion can be in the form of a dry, powdered composition. In
effectiveness (e.g., up to about 90 days). 10 additional specific embodiments, the antimicrobial agent can
Suitable textiles include, e.g., polyester fabrics, synthetic be a solid. In additional specific embodiments, the polymeric
polyester fabrics, non-engineered polyester fabrics, perfor carrier can be a Solid.
mance apparels, moisture wicking performance fabrics, deli The present invention also provides for a method of pre
cate moisture wicking performance fabrics, and moisture paring an antimicrobial composition. The method includes:
wicking performance apparel. 15 (a) contacting an antimicrobial agent that includes 3-(tri
The antimicrobial compositions described herein can be methoxysilyl)propyl dimethyl octadecyl ammonium chlo
manufactured in a dry, Solid (e.g., powdered) form, or can be ride, a polymeric carrier that includes polyvinyl alcohol
manufactured in a liquid (e.g., aqueous) form. Manufacturers (PVA) and a solvent that includes hexanes, to form a slurry,
and consumers may prefer the Solid form, as use of organic and (b) removing in vacuum, at a temperature above about
Solvents such as methanol (which can be toxic, hazardous and 25°C., the hexanes from the slurry to form the antimicrobial
therefore undesirable), are avoided. When manufactured in composition. The antimicrobial composition is essentially
the solid form, the antimicrobial compositions described free of organic solvent (e.g., the antimicrobial composition
herein are relatively water-soluble. includes less than about 0.1 wt.% organic solvent). A signifi
Upon dissolving in water, the antimicrobial compositions cant portion of the 3-(trimethoxysilyl)propyl dimethyl octa
described hereincan include a relatively low amount ofundis 25 decyl ammonium chloride is complexed with the polyvinyl
solved solid particulates. This will avoid the necessity of alcohol (PVA) (e.g., at least about 90 mol.% of the 3-(tri
removing those solid particulates (e.g., by filtering) when methoxysilyl)propyl dimethyl octadecyl ammonium chloride
formulating into a liquid, sprayable product. This will mini is complexed with the polyvinyl alcohol (PVA). Additionally,
mize the likelihood that the sprayer will become clogged from upon dissolving in water, the composition is essentially free
the Solid particulates. The antimicrobial compositions 30 of undissolved solid particulates (e.g., upon dissolving in
described herein, bothin a dry, Solid (e.g., powdered) form, as water at 80°C. and 1 atm, the composition includes less than
well as the liquid (e.g., aqueous) form, are relatively stable to about 0.1 wt.% ofundissolved solid particulates). In specific
ambient conditions, and will undergo a relatively minimal embodiments, the antimicrobial composition can be in the
amount of degradation over extended periods of time. The form of a dry, powdered composition. In additional specific
antimicrobial compositions will also retain the antimicrobial 35 embodiments, the antimicrobial agent can be a solid. In addi
properties over extended periods of time. As such, the anti tional specific embodiments, the polymeric carrier can be a
microbial compositions can have a relatively extended shelf solid.
life. Additionally, the antimicrobial compositions can avoid The present invention also provides for a method of pre
the necessity of being sealed in glass ampoules, which are paring an aqueous antimicrobial composition. The method
typically employed for the extended periods of time related to 40 includes: (a) preparing an antimicrobial composition as
the shipping and storage of Some liquid antimicrobial com described herein, and (b) dissolving the antimicrobial com
positions. position in an aqueous Solution to provide the aqueous anti
The present invention provides for an antimicrobial com microbial composition.
position. The antimicrobial composition includes: (a) an anti The present invention also provides for a liquid, aqueous
microbial agent, and (b) a polymeric carrier. The antimicro 45 antimicrobial composition. The composition includes: (a) an
bial agent is relatively water soluble (e.g., has a solubility in antimicrobial agent, (b) a polymeric carrier, and (c) water.
water of at least about 0.05 g/mL at 80° C. and 1 atm). The The antimicrobial agent is relatively water soluble (e.g., has a
polymeric carrier is also relatively water Soluble (e.g., has a solubility in water of at least about 0.05 g/mL at 80° C. and 1
solubility in water of at least about 0.05 g/mL at 80° C. and 1 atm). The polymeric carrier is also relatively water soluble
atm). Additionally, a significant portion of the antimicrobial 50 (e.g., has a solubility in water of at least about 0.05 g/mL at
agent is complexed with the polymeric carrier (e.g., at least 80° C. and 1 atm). Additionally, upon dissolving in water, the
about 20 mol.% of the antimicrobial agent is complexed with composition is essentially free of undissolved solid particu
the polymeric carrier). lates (e.g., upon dissolving in water at 80° C. and 1 atm, the
The present invention also provides for an antimicrobial composition includes less than about 0.1 wt.% ofundissolved
composition that includes: (a) an antimicrobial agent that 55 Solid particulates).
includes 3-(trimethoxysilyl)propyl dimethyl octadecyl The present invention also provides for a liquid, aqueous
ammonium chloride, and (b) a polymeric carrier that includes antimicrobial composition. The liquid, aqueous antimicro
polyvinyl alcohol (PVA). The antimicrobial composition is bial composition includes: (a) an antimicrobial agent that
essentially free of organic solvent (e.g., the antimicrobial includes 3-(trimethoxysilyl)propyl dimethyl octadecyl
composition includes less than about 0.1 wt.% organic Sol 60 ammonium chloride, (b) a polymeric carrier that includes
Vent). In specific embodiments, the antimicrobial composi polyvinyl alcohol (PVA), (c) water, (d) alcohol, and (e) fra
tion can be in the form of a dry, powdered composition. In grance. Upon dissolving in water, the composition is essen
additional specific embodiments, the antimicrobial agent can tially free of undissolved solid particulates (e.g., upon dis
be a solid. In additional specific embodiments, the polymeric solving in water at 80°C. and 1 atm, the composition includes
carrier can be a solid. 65 less than about 0.1 wt.% of undissolved solid particulates).
The present invention also provides for a method of pre The present invention also provides for a liquid, aqueous
paring an antimicrobial composition. The method includes: antimicrobial composition. The liquid, aqueous antimicro
 US 9,265,248 B2
5 6
bial composition includes: (a) about 0.01 to about 4.0 wt.% of closed subject matter will be described in conjunction with
3-(trimethoxysilyl)propyl dimethyl octadecyl ammonium the enumerated claims, it will be understood that the dis
chloride (TPAC), (b) about 0.1 to about 4.0 wt.% of polyvinyl closed subject matter is not intended to limit those claims. On
alcohol (PVA), (c) about 18 to about 99.9 wt.% water, (d)0 to the contrary, the disclosed subject matter is intended to cover
about 80.0 wt.% of ethanol, (e)0 to about 2.0 wt.% fragrance, all alternatives, modifications, and equivalents, which can be
and (f) 0 to about 0.004 wt.% of an anti-foaming agent. Upon included within the scope of the present invention, as defined
dissolving in water, the composition is essentially free of by the claims.
undissolved solid particulates (e.g., upon dissolving in water References in the specification to “one embodiment,” “an
at 80°C. and 1 atm, the composition includes less than about embodiment,” “an example embodiment.” etc., indicate that
0.1 wt.% of undissolved solid particulates). 10 the embodiment described may include a particular feature,
The present invention also provides for a liquid, aqueous structure, or characteristic, but every embodiment may not
antimicrobial composition. The liquid, aqueous antimicro necessarily include the particular feature, structure, or char
bial composition includes: (a) about 0.5 wt.% of 3-(tri acteristic. Moreover, Such phrases are not necessarily refer
methoxysilyl)propyl dimethyl octadecyl ammonium chlo ring to the same embodiment. Further, when a particular
ride, (b) about 1.0 wt.% of polyvinyl alcohol (PVA), (c) about 15 feature, structure, or characteristic is described in connection
88.3 wt.% of water, (d) about 10.0 wt.% of ethanol, (e) about with an embodiment, it is submitted that it is within the
0.2 wt.% fragrance, and (f) about 0.002 wt.% of an anti knowledge of one skilled in the art to affect such feature,
foaming agent. Upon dissolving in water, the composition is structure, or characteristic in connection with other embodi
essentially free of undissolved solid particulates (e.g., upon ments whether or not explicitly described.
dissolving in water at 80° C. and 1 atm, the composition The present invention relates to antimicrobial composi
includes less than about 0.1 wt.% of undissolved solid par tions, methods of preparing the antimicrobial compositions,
ticulates). methods of using the antimicrobial compositions, and/or kits
The present invention also provides for a kit, that includes: that include the antimicrobial compositions. When describing
(a) an enclosed container that includes a removable closure, the present invention, the following terms have the following
(b) an antimicrobial composition described herein, located 25 meanings, unless otherwise indicated.
inside the enclosed container, and (c) printed indicia located Antimicrobial Composition
on the enclosed container. The antimicrobial composition described herein can be
The present invention also provides for methods of using manufactured in a dry, Solid (e.g., powdered) form, as well as
the antimicrobial compositions described herein. In specific the liquid (e.g., aqueous) form. When manufactured in the
embodiments, the antimicrobial compositions described 30 solid form, the antimicrobial compositions described herein
herein can be used to effectively reduce the number of be substantially free of liquid (e.g., can include less than
microbes located upon a substrate. In additional specific about 1 wt.% liquid), yet can be can be relatively water
embodiments, the antimicrobial compositions described soluble. Additionally, manufacturers and consumers may pre
herein can be used to effectively kill or inhibit a microorgan ferantimicrobial compositions in the Solid form, as the use of
ism. In additional specific embodiments, the antimicrobial 35 organic solvents such as methanol (which can be toxic, haz
compositions described herein can be used to effectively ardous and therefore undesirable), are avoided. Moreover,
eliminate or lower the malodor associated with the growth of avoidance of liquid carriers will typically decrease the pack
a microorganism. In additional specific embodiments, the aging, shipping and storage costs.
antimicrobial compositions described herein can also be used In specific embodiments, the dry, solid form antimicrobial
to effectively eliminate or lower staining or discoloration of a 40 composition car be used neat, in reducing the number of
Substrate, which is associated with the growth of a microor microbes located upon a Substrate. For example, the dry, Solid
ganism. form antimicrobial composition can be directly applied to a
Substrate (e.g., carpet, rug or textile) under ambient condi
BRIEF DESCRIPTION OF THE DRAWINGS tions, for an extended period of time, sufficient to reduce the
45 number of microbes located upon a Substrate. In doing so,
FIG. 1 illustrates a vertical fabric fluid dispersion for an moisture from the atmosphere can assist the antimicrobial
exemplary composition of the present invention. agent in Sufficiently contacting the Substrate. Alternatively,
FIG. 2 illustrates a horizontal fabric fluid dispersion for an the dry, Solid form antimicrobial composition can be used to
exemplary composition of the present invention. manufacture a liquid form antimicrobial composition, which
FIG. 3 illustrates a vertical fabric fluid dispersion for an 50 will itself reduce the number of microbes located upon a
exemplary composition of the present invention. Substrate. In Such an embodiment, the dry, Solid form antimi
FIG. 4 illustrates a horizontal fabric fluid dispersion for an crobial composition can be used and viewed as an antimicro
exemplary composition of the present invention. bial concentrate, or a concentrated form of antimicrobial
FIG. 5 illustrates a moisture release (evaporation) for an composition.
exemplary composition of the present invention. 55 In specific embodiments, the dry, solid form antimicrobial
FIG. 6 illustrates a moisture release (evaporation) for an composition can be relatively water-soluble. Water solubility
exemplary composition of the present invention. will help provide a suitable liquid composition in which the
FIG. 7 illustrates a simulated perspiration test for an exem antimicrobial can effectively be delivered to the substrate. For
plary composition of the present invention. example, the dry, Solid form antimicrobial composition car
FIG. 8 illustrates a simulated perspiration test for an exem 60 have a solubility in water of at least about 0.05 g/mL at 80°C.
plary composition of the present invention. and 1 atm, at least about 0075 g/mL at 80° C. and 1 atm, or at
least about 0.1 g/mL at 80° C. and 1 atm.
DETAILED DESCRIPTION OF THE INVENTION Upon dissolving in water, the Solid antimicrobial compo
sition can include a relatively low amount of undissolved
Reference will now be made in detail to certain claims of 65 solid particulates. This will avoid the necessity of removing
the disclosed invention, examples of which are illustrated in those solid particulates (e.g., by filtering) when formulating
the accompanying structures and formulas. While the dis into a liquid, sprayable product. This will minimize the like
 US 9,265,248 B2
7 8
lihood that the sprayer will become clogged from the solid “antimicrobial agent” refers to a substance that kills a micro
particulates. For example, the dry, solid form antimicrobial organism, inhibits the growth of a microorganism, or both.
composition, upon dissolving in water at 80° C. and 1 atm, Typically, an antimicrobial kills a microorganism or inhibits
can include less than about 1.0 wt.% of undissolved solid their growth by cell wall damage, inhibition of cell wall
particulates, can include less than about 0.5 wt.% of undis synthesis, alteration of cell wall permeability, inhibition of
solved solid particulates, can include less than about 0.1 wt. the synthesis of proteins and nucleic acids, and inhibition of
% of undissolved solid particulates, or can include less than enzyme action. In specific embodiments, the antimicrobial
about 0.01 wt.% of undissolved solid particulates. agent is relatively inexpensive, safe, non-toxic, and/or con
As stated herein, the presence in commercial products of Venient to use.
organic solvents such as methanol (which can be toxic and 10
The antimicrobial agent can be a solid. Alternatively, the
hazardous) are undesirable to some consumers. As such, the antimicrobial agent can be a liquid. Alternatively, the antimi
present invention provides for a dry, solid form antimicrobial crobial agent can be an oil.
composition that can be substantially free of organic Solvents. The antimicrobial agent can be relatively water-soluble.
For example, the dry, Solid form antimicrobial composition Water solubility will help provide a suitable liquid composi
can include less than about 1.0 wt.% organic Solvent, less 15
tion in which the antimicrobial agent can effectively be deliv
than about 0.5 wt.% organic solvent, less than about 0.1 wt.
% organic solvent, or less than about 0.01 wt.% organic ered to the Substrate. For example, the antimicrobial agent can
Solvent. Such solvents include, e.g., organic solvents such as have a solubility in water of at least about 0.05 g/mL at 80°C.
methanol. and 1 atm, at least about 0.075 g/mL at 80°C. and 1 atm, or at
The dry, Solid form antimicrobial composition can remain least about 10 g/L at 20° C. and 1 atm at least about 0.1 g/mL
relatively stable and retain the antimicrobial properties over at 80° C. and 1 atm.
extended periods of time. Such a stability and retention of The antimicrobial agent can be complexed with the poly
antimicrobial properties will allow the commercial product to meric carrier. For example, at least about 20 mol.% of the
be shipped and stored over periods of time and conditions antimicrobial agent is complexed with the polymeric carrier,
typically encountered with Such products. For example, at 25 at least about 40 mol.% of the antimicrobial agent is com
least about 75 mol. 9% of the dry, solid form antimicrobial plexed with the polymeric carrier, at least about 60 mol.% of
composition can remain stable and retain the antimicrobial the antimicrobial agent is complexed with the polymeric car
properties at about 20° C. and at about 50% relative humidity, rier, at least about 80 mol. 96 of the antimicrobial agent is
when exposed to the atmosphere, for at least about 9 months. complexed with the polymeric carrier, at least about 90 mol.
Specifically, at least about 90 mol.% of the dry, solid form 30 % of the antimicrobial agent is complexed with the polymeric
antimicrobial composition can remain stable and retain the carrier, or at least about 95 mol.% of the antimicrobial agent
antimicrobial properties at about 20° C. and at about 50% is complexed with the polymeric carrier.
relative humidity, when exposed to the atmosphere, for at Any Suitable antimicrobial agent can be employed, pro
least about 3 months. More specifically, at least about 98 mol. vided the antimicrobial agent effectively kills a microorgan
% of the dry, solid form antimicrobial composition can 35 ism, inhibits the growth of a microorganism, or both. Suitable
remain stable and retain the antimicrobial properties at about specific classes of antimicrobial agents include, e.g., quater
20° C. and at about 50% relative humidity, when exposed to nary ammonium compound, a silver-containing compound, a
the atmosphere, for at least about 9 months. phenol containing compound, a secondary or tertiary nitro
The dry, solid formantimicrobial composition can be rela gen containing compound, an aldehyde containing com
tively safe and non-toxic. Such a suitable safety profile will 40 pound, a peroxygen containing compound.
furnish a commercial product with a broader appeal to those Suitable specific antimicrobial agents include:
consumers desiring a relatively safe and non-toxic product, TPAC is 3-(trimethoxysilyl)propyl dimethyl octadecyl
when practical and feasible. For example, the dry, solid form ammonium chloride. TPAC is also known as Dow Corning
antimicrobial composition can have a LDso in rats of greater 5700 (DC 5700);
C
-O

No-1 W
Si
YN---~~~~
than about 2 g/kg of body mass. Specifically, the dry, Solid 55 poly(hexamethylene biguanide) hydrochloride (PHMB)
form antimicrobial composition can have a LDs in rats of
greater than about 5 g/kg of body mass. More specifically, the
dry, solid form antimicrobial composition can have a LDs in
rats of greater than about 10 g/kg of body mass.
NH NH
The dry, Solid form antimicrobial composition can be a 60
| |
powder. Alternatively, the dry, solid form antimicrobial com
position can be a film. Additionally, the dry, solid form anti
microbial composition can be relatively odorless and/or rela o HCI
tively colorless.
Antimicrobial Agent 65
The antimicrobial compositions described herein will sialic acid (N-acetyl-neuraminic acid, Neu5Ac, NAN,
include one or more antimicrobial agents. As used herein, an NANA)
 US 9,265,248 B2
10
time. Such a stability and retention of antimicrobial proper
ties will allow the commercial product to be shipped and
stored over periods of time and conditions typically encoun
tered with such products. For example, at least about 75
mol.% of the antimicrobial agent can remainstable and retain
the antimicrobial properties at about 20° C. and at about 50%
relative humidity, when exposed to the atmosphere, for at
poly(diallyldimethylammonium chloride) (poly DAD least about 3 months. Specifically, at least about 90 mol.% of
MAC) the antimicrobial agent can remain stable and retain the anti

Cl
V/
: 1-n-n-n-n-N-n-n-n

poly(vinyl benzyltrimethyl ammonium chloride) (PVBT microbial properties at about 20° C. and at about 50% relative
MAC); humidity, when exposed to the atmosphere, for at least about
5-chloro-2-(2,4-dichlorophenoxy)phenol; 3 months. More specifically, at least about 98 mol.% of the
alkyldimethylbenzylammonium chloride (ADBAC); antimicrobial agent can remain stable and retain the antimi
2,4,4-trichloro-2'-hydroxydiphenyl ether 25 crobial properties at about 20° C. and at about 50% relative
humidity, when exposed to the atmosphere, for at least about
3 months.
C OH
The antimicrobial agent can be selected based at least in

C CO
methylisothiazolinone
Cl;
30

35
part upon the safety and toxicity. Such a suitable safety profile
will furnish a commercial product with a broader appeal to
those consumers desiring a relatively safe and non-toxic
product, when practical and feasible. In Such embodiments,
the antimicrobial agent can be relatively safe and non-toxic.
For example, the antimicrobial agent can have a LDso in rats
of greater than about 2 g/kg of body mass. Specifically, the
antimicrobial agent can have a LDso in rats of greater than
about 5 g/kg of body mass. More specifically, the antimicro
bial agent can have a LDso in rats of greater than about 10 g/kg
40 of body mass.
Polymeric Carrier
The antimicrobial compositions described herein will
include one or more polymeric carriers. As used herein, a
N-(2-hydroxyl)propyl-3-trimethylammonium chitosan "polymeric carrier refers to a polymeric compound, or a
45 mixture of polymeric compounds, that does not effectively
chloride (HTCC); and dissolve in the solvent at 80° C. and 1 atm, does effectively
a silver complex of poly(amidoamine) (PAMAM); dissolve in water at 80°C. and 1 atm, and sufficiently com
2-isopropyl-5-methylphenol; and plexes a significant amount of antimicrobial agent when con
Poly-D-glucosamine. tacting with the solvent.
The antimicrobial agent can be employed in any Suitable 50 The polymeric carrier can be relatively water-soluble.
amount, provided the amount of antimicrobial agent is effec Water solubility will help provide a suitable liquid composi
tive to kill a microorganism, inhibit the growth of a microor tion in which the antimicrobial agent (which is complexed to
ganism, or both. For example, the antimicrobial agent can be the polymeric carrier) to be effectively be delivered to the
employed in up to about 10 wt.% of the liquid composition, Substrate. For example, the polymeric carrier can have a solu
in about 0.01 to about 10.0 wt.% of the liquid composition, in 55 bility in water of at least about 0.05 g/mL at 80°C. and 1 atm,
about 0.01 to about 5.0 wt.% of the liquid composition, or in at least about 0.075 g/mL at 80°C. and 1 atm, or at least about
about 0.1 to about 2.0 wt.% of the liquid composition. Spe 0.1 g/mL at 80° C. and 1 atm.
cifically, the antimicrobial agent can be employed in up to Any suitable polymeric carrier can be employed, provided
about 80 wt.% of the antimicrobial composition, in about 0.1 the polymeric carrier does not effectively dissolve in the
to about 80.0 wt.% of the antimicrobial composition, in about 60 solvent at 80°C. and 1 atm, does effectively dissolve in water
0.1 to about 50.0 wt.% of the antimicrobial composition, or in at 80° C. and 1 atm, and Sufficiently complexes a significant
about 1 to about 50.0 wt.% of the antimicrobial composition. amount of antimicrobial agent when contacting with the Sol
The weight ratio of antimicrobial agent to polymeric car vent. Suitable polymeric carriers include, e.g., polyvinyl
rier can be about 1:99 to about 99:1, about 1:10 to about 10:1, acetate (PVAc), polyvinyl alcohol (PVA), starch (and modi
about 1:5 to about 5:1, or about 1:3 to about 3:1. 65 fied/functionalized starches), polyethylene glycol (PEG),
The antimicrobial agent can remain relatively stable and ethylene vinyl alcohol (EVA), cellulose, cellulose acetate,
retain the antimicrobial properties over extended periods of and chitosan.
 US 9,265,248 B2
11 12
The polymeric carrier does not effectively dissolve in the will have a sufficiently low boiling point (i.e., it is relatively
solvent at 80° C. and 1 atm. In specific embodiments, the volatile) can be used. Alternatively, the solvent can be
polymeric carrier has a solubility in the solvent of less than removed via filtering or decanting the antimicrobial agent and
about 1.0 g/L at 80° C. and 1 atm. In additional specific polymeric carrier. In Such embodiments, employing a solvent
embodiments, the polymeric carrier has a solubility in the that will have a sufficiently low boiling point (i.e., it is rela
solvent of less than about 0.75 g/L at 80° C. and 1 atm. In tively volatile) may not be particularly necessary.
additional specific embodiments, the polymeric carrier has a The solvent can be employed in any suitable amount, pro
solubility in the solvent of less than about 0.5 g/L at 80°C. and vided the solvent does not effectively dissolve the polymeric
1 atm.
The polymeric carrier effectively dissolves in water at 80° 10
carrier at 80° C. and 1 atm, does effectively dissolve the
C. and 1 atm. In specific embodiments, the polymeric carrier antimicrobial agent at 80° C. and 1 atm, and the solvent can
has a solubility in water of at least about 0.05 g/mL at 80°C. subsequently be removed. For example, the solvent can be
and 1 atm. In additional specific embodiments, the polymeric employed in about 1 milliliter (mL) per kilogram (kg) of
carrier has a solubility in water of at least about 0.075 g/mL at polymeric carrier to about 10 liters (L) per gram (g) of poly
80° C. and 1 atm. In additional specific embodiments, the 15 meric carrier. Typically, the solvent can be employed in about
polymeric carrier has a solubility in water of at least about 0.1 50 milliliter (mL) per kilogram (kg) of polymeric carrier, to
g/mL at 80° C. and 1 atm. about 2 liters (L) per gram (g) of polymeric carrier.
The polymeric carrier can be employed in any Suitable In specific embodiments, the methods of preparing the
amount, provided the amount of polymeric carrier does not antimicrobial composition described herein can include: (a)
effectively dissolve in the solvent at 80° C. and 1 atm, does contacting an antimicrobial agent that includes 3-(trimethox
effectively dissolve in water at 80° C. and 1 atm, and suffi ysilyl)propyl dimethyl octadecyl ammonium chloride, a
ciently complexes a significantamount of antimicrobial agent polymeric carrier that includes polyvinyl alcohol (PVA), and
when contacting with the solvent. For example, the polymeric a solvent that includes hexanes, to form a slurry, and (h)
carrier can be employed in up to about 10 wt.% of the removing the hexanes in vacuum from the slurry, at a tem
antimicrobial composition, in about 0.01 to about 10.0 wt.% 25 perature above about 25°C., to form the antimicrobial com
of the antimicrobial composition, in about 0.1 to about 8.0 wt. position.
% of the antimicrobial composition, or in about 0.1 to about Additional specific embodiments include: (a) contacting
5.0 wt.% of the antimicrobial composition. Specifically, the antimicrobial agents that include alkyldimethylbeZyl ammo
polymeric carrier can be employed in up to about 80 wt.% of nium chloride and 3-(trimethoxysilyl)propyl dimethyl octa
the antimicrobial composition. More specifically, the poly 30 decyl ammonium chloride, a polymeric carrier that includes
meric carrier can be employed in about 0.1 to about 80.0 wt. polyvinyl alcohol (PVA), and a solvent that includes ethanol,
% of the antimicrobial composition. More specifically, the to form a slurry, and (h) removing the ethanol in vacuum from
polymeric carrier can be employed in about 0.1 to about 50.0 the slurry, at a temperature above about 25°C., to form the
wt.% of the antimicrobial composition. More specifically, the dry, powdered antimicrobial composition.
polymeric carrier can be employed in about 1 to about 50.0 35 Without being bound to any particular theory, it is believed
wt.% of the antimicrobial composition. that upon formation of the antimicrobial composition, at least
The weight ratio of polymeric carrier to antimicrobial a portion of the antimicrobial agent becomes trapped by the
agent can be, e.g., about 1:99 to about 99:1, about 1:10 to polymer. As such, the antimicrobial agent does not necessar
about 10:1, about 1:5 to about 5:1, or about 3:1 to about 1:3. ily adsorb or bind to the polymer, but is instead housed or
Method of Preparing an Antimicrobial Composition 40 trapped by the polymer.
The present invention provides for methods of preparing an Liquid, Aqueous Antimicrobial Composition
antimicrobial composition. The methods can include: (a) con The liquid, aqueous antimicrobial compositions described
tacting an antimicrobial agent, a polymeric carrier and a herein can be relatively odorless and/or relatively colorless.
solvent to form a slurry, and (b) removing the solvent from the Such physical properties can be desirable to Some consumers,
slurry to form the antimicrobial composition. In specific 45 as the antimicrobial compositions will not have an offensive
embodiments, the antimicrobial composition can be in the or unpleasant odor, nor will the antimicrobial compositions
form of a dry, powdered composition. In additional specific discolor or stain Substrates such as clothing apparel.
embodiments, the antimicrobial agent can be a solid. In addi The liquid, aqueous antimicrobial composition can
tional specific embodiments, the polymeric carrier can be a include: (a) an antimicrobial agent (or agents), (b) a poly
solid. 50 meric carrier (or carriers), and (c) water. In specific embodi
Any suitable solvent can be employed, provided the sol ments, the liquid, aqueous antimicrobial composition can
vent does not effectively dissolve the polymeric carrier at 80° include: (a) an antimicrobial agent that includes 3-(tri
C. and 1 atm, but does effectively dissolve the antimicrobial methoxysilyl)propyl dimethyl octadecyl ammonium chlo
agent at 80° C. and 1 atm. As such, the polymeric carrier can ride, (b) a polymeric carrier that includes polyvinyl alcohol
be immiscible in the suitable solvent, and the antimicrobial 55 (PVA), (c) water, (d) alcohol, and (e) fragrance. In further
agent can be miscible in the suitable solvent. One suitable specific embodiments, the liquid, aqueous antimicrobial
class of Suitable solvents includes non-polar aprotic organic composition can include: (a) 3-(trimethoxysilyl)propyl dim
Solvents, e.g., hexanes. Another Suitable class of Suitable ethyl octadecyl ammonium chloride, (b) polyvinyl alcohol
Solvents includes polar aprotic organic solvents (e.g., chloro (PVA), (c) water, (d) alcohol, and (e) fragrance.
form) and polar protic organic solvents (e.g., ethanol). Addi 60 In specific embodiments, the liquid, aqueous antimicrobial
tionally, the Suitable solvent can include a single compound, composition can include: (a) antimicrobial agents that
or a mixture of two or more compounds. include 3-(trimethoxysilyl)propyl dimethyl octadecyl ammo
The suitable solvent can also be selected based upon the nium chloride and, alkyldimethylbezyl ammonium chloride
ease, cost and efficiency of removing the Solvent from the (b) a polymeric carrier that includes polyvinyl alcohol (PVA),
mixture of antimicrobial agent and polymeric carrier. For 65 (c) water, (d) alcohol, and (e) fragrance.
example, when the solvent is removed in vacuum, for In specific embodiments, the liquid, aqueous antimicrobial
example, at a temperature above about 25°C., a solvent that composition can include: (a) an antimicrobial agent that
 US 9,265,248 B2
13 14
includes alkyldimethylbezyl ammonium chloride (b) a poly More specifically, at least about 98 mol. 9% of the liquid,
meric carrier that includes polyvinyl alcohol (PVA), (c) water, aqueous antimicrobial composition can remain stable and
(d) buffer (e) and surfactant. retain the antimicrobial properties at about 20° C. and at about
In further specific embodiments, the liquid, aqueous anti 50% relative humidity, when exposed to the atmosphere, for
microbial composition can include: (a) about 0.01 to about at least about 3 months.
4.0 wt.% of 3 (trimethoxysilyl)propyl dimethyl octadecyl The liquid, aqueous antimicrobial composition can be non
ammonium chloride, (b) about 0.1 to about 4.0 wt.% of leaching. Additionally, the liquid, aqueous antimicrobial
polyvinyl alcohol (PVA), (c) about 18 to about 99.9 wt.% composition can be relatively safe and non-toxic. For
water, (d) 0 to about 80.0 wt.% of ethanol, (e) 0 to about 2.0 example, the liquid, aqueous antimicrobial composition can
wt % fragrance, and (f) 0 to about 0.004 wt.% of an anti 10 have a LDso in rats of greater than about 1 ml/kg of body
foaming agent. In further specific embodiments, the liquid, mass. Specifically, the liquid, aqueous antimicrobial compo
aqueous antimicrobial composition can include: (a) about 0.5 sition can have a LDso in rats of greater than about 2 ml/kg of
wt. 9% of 3 (trimethoxysilyl)propyl dimethyl octadecyl body mass. More specifically, the liquid, aqueous antimicro
ammonium chloride, (b) about 1.0 wt.% of polyvinyl alcohol bial composition can have a LDs in rats of greater than about
(PVA), (c) about 88.3 wt.% of water, (d) about 10.0 wt.% of 15 5 ml/kg of body mass. More specifically, the liquid, aqueous
ethanol, (e) about 0.2 wt.% fragrance, and (f) about 0.002 wt. antimicrobial composition can have a LDs in rats of greater
% of an anti-foaming agent. than about 10 ml/kg of body mass.
The liquid, aqueous antimicrobial composition can be The liquid, aqueous antimicrobial composition can be con
essentially Free of undissolved solid particulates. For figured for use in a variety of types of liquid composition. For
example, the liquid, aqueous antimicrobial composition can example, the aqueous antimicrobial composition can be con
include less than about 1.0 wt.% of undissolved solid par figured for spraying, dipping, brushing, and/or rolling a Sub
ticulates, can include less than about 0.5 wt.% of undissolved strate with the liquid antimicrobial composition. Addition
solid particulates, can include less than about 0.1 wt.% of ally, the aqueous antimicrobial composition can be
undissolved solid particulates, or can include less than about configured for use in a wide-variety of compositions. For
0.01 wt.% of undissolved solid particulates. The inclusion of 25 example, the composition can be configured for use in manu
a minimal amount of undissolved solid particulates will avoid facturing a plastic or rubber composition. Alternatively, the
the necessity of removing those Solid particulates (e.g., by composition can be configured for use in manufacturing a
filtering) when formulating into a liquid, sprayable product, fabric or textile composition. Specifically, the aqueous anti
which in turn, will minimize the likelihood that the sprayer microbial composition can be configured for use in an athletic
will become clogged from the solid particulates. 30 equipment composition, an athletic gear composition, anath
The liquid, aqueous antimicrobial composition can be letic apparel composition, or an athletic footwear composi
essentially free of heavy metals. For example, the liquid, tion. More specifically, because the composition can readily
aqueous antimicrobial composition can include less than be configured for use in a sprayable composition, the aqueous
about 0.5 wt.% of heavy metals, can include less than about antimicrobial composition can be configured for use in a
0.1 wt.% of heavy metals, can include less than about 0.01 wt. 35 sprayable athletic equipment composition, a sprayable ath
% of heavy metals, or can include less than about 0.001 wt.% letic gear composition, a sprayable athletic apparel composi
of heavy metals. tion, or a sprayable athletic footwear composition.
The liquid, aqueous antimicrobial composition can be In specific embodiments, the liquid, aqueous antimicrobial
essentially free of poly-chlorinated phenols (PCPs). For compositions can improve the ability of specified textiles to
example, the liquid, aqueous antimicrobial composition can 40 wick away moisture from the user of the textile. For example,
include less than about 0.5 wt.% of poly-chlorinated phenols when applied to a textile that includes polyester, the liquid,
(PCPs), can include less than about 0.1 wt.% of poly-chlo aqueous antimicrobial compositions can improve the ability
rinated phenols (PCPs), can include less than about 0.01 wt. of the polyester to wick away moisture from the user.
% of poly-chlorinated phenols (PCPs), or can include less Method of Preparing an Aqueous Antimicrobial Composition
than about 0.001 wt.% of poly-chlorinated phenols (PCPs). 45 As stated herein, the dry, Solid form antimicrobial compo
The liquid, aqueous antimicrobial composition can be sition can be used to manufacture a liquid form antimicrobial
essentially free of methanol. For example, the liquid, aqueous composition. Methods of preparing the aqueous antimicro
antimicrobial composition can include less than about 0.5 wt. bial composition can include: (a) preparing a dry, Solid form
% of methanol, can include less than about 0.1 wt.% of antimicrobial composition as described herein, and (b) dis
methanol, can include less than about 0.01 wt.% of methanol, 50 Solving the dry, Solid form antimicrobial composition in an
or can include less than about 0.001 wt.% of methanol. The aqueous solution to provide the aqueous antimicrobial com
presence of organic solvents such as methanol (which can be position.
toxic and hazardous) in commercial products can be undesir The methods of preparing aqueous antimicrobial compo
able to both manufacturers and consumers. As such, the sitions described herein provide aqueous antimicrobial com
avoidance of methanol in commercial products is preferred 55 positions that can be essentially free of undissolved solid
by Some consumers and manufacturers. particulates. This will avoid the necessity of removing those
The liquid, aqueous antimicrobial composition can remain Solid particulates (e.g., by filtering) when formulating into a
relatively stable and retain the antimicrobial properties over liquid, sprayable product. This will minimize the likelihood
extended periods of time. For example, at least about 75 mol. that the sprayer will become clogged from the Solid particu
% of the liquid, aqueous antimicrobial composition can 60 lates.
remain stable and retain the antimicrobial properties at about Methods of Using the Aqueous Antimicrobial Composition
20° C. and at about 50% relative humidity, when exposed to The aqueous antimicrobial compositions can be used in a
the atmosphere, for at least about 3 months. Specifically, at wide-variety of applications or uses. Typically, the aqueous
least about 90 mol. 9% of the liquid, aqueous antimicrobial antimicrobial compositions will be used to reduce the number
composition can remain stable and retain the antimicrobial 65 of microbes located upon a Substrate. For example, the aque
properties at about 20° C. and at about 50% relative humidity, ous antimicrobial compositions can be used to kill or inhibit
when exposed to the atmosphere, for at least about 3 months. a microorganism, can be used to eliminate or lower malodor
 US 9,265,248 B2
15 16
associated with the growth of a microorganism, and/or can be ing or film can remain stable and retain the antimicrobial
used to eliminate or lower staining or discoloration of a Sub properties for about 1 to about 15 years. Depending on the
strate. The use of the aqueous antimicrobial compositions constituents and how the composition is made, the longevity
will typically include contacting a topical Surface of a Sub of the films can vary drastically.
strate with an effective amount of the aqueous antimicrobial As such, liquid antimicrobial compositions described
composition, for a Sufficient period of time. herein can be long-lasting, exhibiting antimicrobial activities
The aqueous antimicrobial compositions can be applied to for extended periods of time. This includes those embodi
a wide-variety of Substrates. For example, the aqueous anti ments in which the liquid antimicrobial composition is for
microbial compositions can be applied to a topical Surface of mulated as a film or a coating on a Substrate, as well as those
a mammal, non-woven fabric, woven fabric, natural textile, 10 in which the substrate is treated one or more times with the
synthetic textile, organic particulate, inorganic particulate, antimicrobial compositions.
fiber, agglomerate, foam, film, cellulosic material, metal, In specific embodiments, the microorganism can include at
plastic, natural rubber, synthetic rubber, glass, paint, stain, least one of a virus, fungus, mold, algae, yeast, mushroom and
adhesive, Stone, grout, fiberglass, medical device, clothing bacterium.
apparel, sporting equipment, wood, concrete, construction 15 As used herein, “fungi' or “fungus' refers to a large and
product, building product, and/or activated carbon. Suitable diverse group of eucaryotic microorganisms whose cells con
textiles include, e.g., polyester fabrics, synthetic polyester tain a nucleus, vacuoles, and mitochondria. Fungi include
fabrics, non-engineered polyester fabrics, performance algae, molds, yeasts, mushrooms, and slime molds. See, Biol
apparels, moisture wicking performance fabrics, delicate ogy of Microorganisms, T. Brock and M. Madigan, 6th Ed.,
moisture wicking performance fabrics, and moisture wicking 1991, Prentice Hill (Englewood Cliffs, N.J.). Exemplary
performance apparel. One Suitable line of performance appar fungi include Ascomycetes (e.g., Neurospora, Saccharomy
els is commercially sold under the Under Armour R label. ces, Morchella), Basidiomycetes (e.g., Amanita, Agaricus),
In specific embodiments, the aqueous antimicrobial com Zygomycetes (e.g., Mucor, Rhizopus), Oomycetes (e.g., Allo
position can be directly applied to a Substrate, such as a textile myces), and Deuteromycetes (e.g., Penicillium, Aspergillus).
(e.g., clothing apparel, such as a shirt or socks) or sporting 25 As used herein, "algae refers to a large and diverse assem
equipment (e.g., hockey gloves or pads). In Such embodi blage of eucaryotic organisms that contain chlorophyll and
ments, upon application, the liquid in the composition will carry out oxygenic photosynthesis. See, Biology of Microor
essentially evaporate, leaving the antimicrobial agent and ganisms, T. Brock and M. Madigan, 6th Ed., 1991, Prentice
polymeric carrier remaining on the Substrate. The antimicro Hill (Englewood Cliffs, N.J.). Exemplary algae include
bial agent can remain relatively stable and retain the antimi 30 Green Algae (e.g., Chlamydomonas), Euglenids (e.g.,
crobial properties over extended periods of time typically Euglena), Golden Brown Algae (e.g., Navicula), Brown
encountered with the specific use of the aqueous antimicro Algae (e.g., Laminaria), Dinoflagellates (e.g., Gonyaulax).
bial compositions. Factors such as frequency and duration of and Red Algae (e.g., polisiphonia).
using the Substrate, frequency and duration of Washing or As used herein, "mold refers to a filamentous fungus,
laundering the Substrate, as well as frequency and duration of 35 generally a circular colony that may be cottony, wooly, etc. or
exposure to sunlight and harsh chemicals will influence both glabrous, but with filaments not organized into large fruiting
the stability of the antimicrobial agent as well as the retention bodies, such as mushrooms. See, e.g., Stedman’s Medical
of the antimicrobial properties, over the extended periods of Dictionary, 25th Ed., Williams & Wilkins, 1990 (Baltimore,
time. Md.). One exemplary mold is the Basidiomycetes called
In specific embodiments, the aqueous antimicrobial com 40 wood-rotting fungi. Two types of wood-rotting fungi are the
positions can be applied to a substrate. Such as a moisture white rot and the brown rot. An ecological activity of many
wicking performance fabric. After exposing the fabric to the fungi, especially members of the Basidiomycetes is the
aqueous antimicrobial composition, the alcohol (e.g., etha decomposition of wood, paper, cloth, and other products
nol) will quickly kill odor causing bacteria and will typically derived from natural Sources. Basidiomycetes that attack
evaporate along with water. During the evaporation of fluid, 45 these products are able to utilize cellulose or lignin as carbon
the polymeric carrier (e.g., polyvinyl alcohol), being rela and energy sources. Lignin is a complex polymer in which the
tively vapor permeable, will allow moisture to pass through building blocks are phenolic compounds. It is an important
the fabric without being significantly hindered. constituent of woody plants. The decomposition of lignin in
In specific embodiments, the aqueous antimicrobial com nature occurs almost exclusively through the agency of these
positions can be applied to a Substrate, thereby providing a 50 wood-rotting fungi. Brown rot attacks and decomposes the
coating or film on the Substrate. The coating or film can cellulose and the lignin is left unchanged. White rot attacks
provide antimicrobial properties to the Substrate (e.g., can and decomposes both cellulose and lignin. See, Biology of
effectively kill or inhibit a microorganism, can effectively Microorganisms, T. Brock and M. Madigan, 6th Ed., 1991,
eliminate or lower malodor associated with the growth of a Prentice Hill (Englewood Cliffs, N.J.).
microorganism, and/or can effectively eliminate or lower 55 As used herein, “yeast” refers to unicellular fungi, most of
staining or discoloration of a Substrate). When the aqueous which are classified with the Ascomytes. See, Biology of
antimicrobial compositions are applied to a Substrate to pro Microorganisms, T. Brock and M. Madigan, 6th Ed., 1991,
vide a coating or film on the Substrate, the resulting film or Prentice Hill (Englewood Cliffs, N.J.).
coating can remain relatively stable and retain the antimicro As used herein, "mushrooms' refer to filamentous fungi
bial properties over extended periods of time. For example, 60 that are typically from large structures called fruiting bodies,
the coating or film can remain stable and retain the antimi the edible part of the mushroom. See, Biology of Microor
crobial properties for at least about 1 year. In specific embodi ganisms, T. Brock and M. Madigan, 6th Ed., 1991, Prentice
ments, the coating or film can remain stable and retain the Hill (Englewood Cliffs, N.J.).
antimicrobial properties for about 1 to about 5 years. In addi As used herein, “slime molds’ refers to nonphototrophic
tional specific embodiments, the coating or film can remain 65 eucaryotic microorganisms that have some similarity to both
stable and retain the antimicrobial properties for about 1 to fungi and protozoa. The slime molds can be divided into two
about 10 years. In additional specific embodiments, the coat groups, the cellular slime molds, whose vegetative forms are
 US 9,265,248 B2
17 18
composed of single amoeba-like cells, and the acellular slime at least about 20 mol. 9% of the antimicrobial agent is
molds, whose vegetative forms are naked masses of proto complexed with the polymeric carrier.
plasms of indefinite size and shape called plasmodia. Slime 2. The present invention also provides for the antimicrobial
molds live primarily on decaying plant matter, Such as wood, composition of embodiment 1, having a solubility in water of
paper, and cloth. See, Biology of Microorganisms, T. Brock at least about 0.05 g/mL at 80°C. and 1 atm.
and M. Madigan, 6th Ed., 1991, Prentice Hill (Englewood 3. The present invention also provides for the antimicrobial
Cliffs, N.J.). composition of embodiment 1, wherein upon dissolving in
As used herein, a “virus' refers to a small infectious agent water at 80° C. and 1 atm, includes less than about 0.1 wt.%
that can replicate only inside the living cells of organisms. 10
ofundissolved solid particulates.
Virus particles (known as virions) consist of two or three 4. The present invention also provides for the antimicrobial
composition of any one of embodiments 1-3, including less
parts: the genetic material made from either DNA or RNA, than about 0.1 wt.% organic solvent.
long molecules that carry genetic information; a protein coat 5. The present invention also provides for the antimicrobial
that protects these genes; and in Some cases an envelope of 15 composition of any one of embodiments 1-3, including less
lipids that Surrounds the protein coat when they are outside a than about 0.1 wt.% methanol.
cell. The shapes of viruses range from simple helical and 6. The present invention also provides for the antimicrobial
icosahedral forms to more complex structures. The average composition of any one of embodiments 1-5, wherein at least
virus is about one one-hundredth the size of the average about 95 mol.% of the antimicrobial agent is complexed with
bacterium. An enormous variety of genomic structures can be the polymeric carrier.
seen among viral species; as a group they contain more struc 7. The present invention also provides for the antimicrobial
tural genomic diversity than plants, animals, archaea, or bac composition of any one of embodiments 1-6, wherein at least
about 90 mol. 9% of antimicrobial composition will remain
teria. There are millions of different types of viruses, although stable at about 20° C. and at about 50% relative humidity,
only about 5,000 of them have been described in detail. A 25 when exposed to the atmosphere, for at least about 3 months.
virus has either DNA or RNA genes and is called a DNA virus 8. The present invention also provides for the antimicrobial
or a RNA virus respectively. The vast majority of viruses have composition of any one of embodiments 1-7, that is relatively
RNA genomes. Plant viruses tend to have single-stranded non-toxic, such that the LDso in rats is greater than about 2
RNA genomes and bacteriophages tend to have double g/kg of body mass.
stranded DNA genomes.
30 9. The present invention also provides for the antimicrobial
composition of any one of embodiments 1-8, wherein the
Kits antimicrobial agent is a solid.
The present invention provides for a kit that includes: (a) an 10. The present invention also provides for the antimicro
enclosed container that includes a removable closure, (h) an bial composition of any one of embodiments 1-8, wherein the
antimicrobial composition as described herein, located inside 35 antimicrobial agent is a liquid.
the enclosed container, and (c) printed indicia located on the 11. The present invention also provides for the antimicro
enclosed container. bial composition of any one of embodiments 1-10, wherein
the antimicrobial agent includes at least one of a quaternary
The kit can include a liquid applicator that includes at least ammonium compound; a silver-containing compound, a phe
one of a spray bottle, wipe, cloth, sponge, non-woven fabric, 40 nol containing compound, a secondary or tertiary nitrogen
and woven fabric. containing compound, an aldehyde containing compound,
Specific enumerated embodiments 1 to 66 provided and a peroxygen containing compound.
below are for illustration purposes only, and do not otherwise 12. The present invention also provides for the antimicro
limit the scope of the disclosed subject matter, as defined by bial composition of any one of embodiments 1-10, wherein
the claims. These enumerated embodiments encompass all 45 the antimicrobial agent includes at least one of
combinations, Sub-combinations, and multiply referenced 3-(trimethoxysilyl)propyl dimethyl octadecyl ammonium
(e.g., multiply dependent) combinations described therein. chloride

Enumerated Embodiments poly(hexamethylene biguanide) hydrochloride (PHMB)

1. The present invention provides for an antimicrobial com
position that includes: 60
(a) an antimicrobial agent, and
(b) a polymeric carrier,
wherein,
the antimicrobial agent has a solubility in water of at least
about 0.05 g/mL at 80°C. and 1 atm, 65
the polymeric carrier has a solubility in water of at least poly(dialyldimethylammonium chloride) (poly DAD
about 0.05 g/mL at 80°C. and 1 atm, and MAC)
 US 9,265,248 B2
19 20

C V/
1--1a1a1a1n-N-1-1-1-
10
poly(vinyl benzyltrimethyl ammonium chloride) (PVBT 19. The present invention also provides for the antimicro
MAC); bial composition of any one of embodiments 1-15, wherein
5-chloro-2-(2,4-dichlorophenoxy)phenol; the antimicrobial composition is an antimicrobial concen
alkyldimethylbenzylammonium chloride (ADBAC); trate.
2,4,4-trichloro-2'-hydroxydiphenyl ether 15
20. The present invention also provides for the antimicro
bial composition of any one of embodiments 1-19, wherein
C OH the antimicrobial composition is relatively odorless.
21. The present invention also provides for the antimicro

C Cro
methylisothiazolinone
Cl;

25
bial composition of any one of embodiments 1-20, wherein
the antimicrobial composition is relatively colorless.
22. The present invention also provides for an antimicrobial
composition including:
(a) an antimicrobial agent including 3-(trimethoxysilyl)
propyl dimethyl octadecyl ammonium chloride, and
(b) a polymeric carrier including polyvinyl alcohol (PVA),
wherein the antimicrobial composition includes less than
about 0.1 wt.% organic solvent.
23. The present invention also provides for the antimicro
N-CH:
30 bial composition of embodiment 22, which is powdered and
S
M wherein upon dissolving in water at 80° C. and 1 atm, the
composition includes less than about 0.1 wt.% ofundissolved
Solid particulates,
24. The present invention also provides for the antimicro
pix
35 bial composition of and one of embodiments 22-23, wherein
ex HC at least about 90 mol. 96 of the 3-(trimethoxysilyl)propyl
dimethyl octadecyl ammonium chloride is complexed with
sialic acid (N-acetyl-neuraminic acid, Neu5Ac, NAN, the polyvinyl alcohol (PVA).
NANA); 25. The present invention also provides for a method of
N-(2-hydroxyl)propyl-3-trimethylammonium chitosan 40 preparing an antimicrobial composition of any one of
chloride (HTCC); and embodiments 1-24, the method including:
a silver complex of poly(amidoamine) (PAMAM); (a) contacting an antimicrobial agent, a polymeric carrier
2-isopropyl-5-methylphenol; and a solvent to form a slurry, and
Chitosan and (b) removing the solvent from the slurry to form the anti
poly-D-glucosamine. 45 microbial composition,
13. The present invention also provides for the antimicro wherein,
bial composition of any one of embodiments 1-12, wherein the antimicrobial agent has a solubility in water of at least
the polymeric carrier is a Solid. about 0.05 g/mL at 80° C. and 1 atm, and a solubility in the
14. The present invention also provides for the antimicro solvent of at least about 0.1 g/L at 80° C. and 1 atm, and
bial composition of any one of embodiments 1-12, wherein 50 the polymeric carrier has a solubility in water of at least
the polymeric carrier includes at least one of polyvinyl acetate about 0.05 g/mL at 80° C. and 1 atm, and a solubility in the
(PVAc), polyvinyl alcohol (PVA), starch, polyethylene glycol solvent of less than about 1.0 g/mL at 80° C. and 1 atm.
(PEG), ethylene vinyl alcohol (EVA), cellulose, cellulose 26. The present invention also provides for the method of
acetate, and chitosan. embodiment 25, wherein the solvent includes a non-polar
15. The present invention also provides for the antimicro 55 aprotic organic solvent.
bial composition of any one of embodiments 1-14, wherein 27. The present invention also provides for the method of
the weight ratio of antimicrobial agent to polymeric carrier is any one of embodiments 25-26, wherein the solvent includes
about 1:99 to about 99:1. hexanes.
16. The present invention also provides for the antimicro 28. The present invention also provides for the method of
bial composition of any one of embodiments 145, wherein the 60 any one of embodiments 25-27, wherein the solvent is
antimicrobial composition is in a dry, Solid form. removed in vacuum.
17. The present invention also provides for the antimicro 29. The present invention also provides for the method of
bial composition of any one of embodiments 1-15, wherein any one of embodiments 25-27, wherein the solvent is
the antimicrobial composition is a powder. removed by filtration.
18. The present invention also provides for the antimicro 65 30. The present invention also provides for the method of
bial composition of any one of embodiments 1-15, wherein any one of embodiments 25-29, wherein the solvent is
the antimicrobial composition is a film. removed at a temperature above about 25°C.
 US 9,265,248 B2
21 22
31. The present invention also provides for a method of least about 90 mol.% of aqueous antimicrobial composition
preparing an antimicrobial composition, the method includ will remain stable at about 20° C. and at about 50% relative
19.
humidity, when exposed to the atmosphere, for at least about
a) contacting an antimicrobial agent including 3-(tri 9 months.
methoxysilyl)propyl dimethyl octadecyl ammonium chlo
ride, a polymeric carrier including polyvinyl alcohol (PVA) 37. The present invention also provides for the liquid, aque
and a solvent including hexanes to form a slurry, and ous antimicrobial composition of any one of embodiments
(b) removing in vacuum, at a temperature above about 25° 35-36, including less than about 0.1 wt.% organic solvent.
C., the hexanes from the slurry to form the dry, powdered 10
38. The present invention also provides for the liquid, aque
antimicrobial composition, including less than about 0.1 wt. ous antimicrobial composition of any one of embodiments
% organic solvent, 35-36, including less than about 0.1 wt.% methanol.
wherein, 39. The present invention also provides for the liquid, aque
at least about 20 mol.% of the 3-(trimethoxysilyl)propyl ous antimicrobial composition of any one of embodiments
dimethyl octadecyl ammonium chloride is complexed with 15 35-38, that is relatively non-toxic, such that the LDs in rats is
the polyvinyl alcohol (PVA), and greater than about 2 ml/kg of body mass.
upon dissolving in water at 80° C. and 1 atm, the compo 40. The present invention also provides for the liquid, aque
sition includes less than about 0.1 wt.% of undissolved solid
particulates. ous antimicrobial composition of any one of embodiments
32. The present invention also provides for a method of 35-39, wherein the antimicrobial agent includes at least one
of a quaternary ammonium compound, a silver-containing
preparing an aqueous antimicrobial composition, the method compound, a phenol containing compound, a secondary or
including: tertiary nitrogen containing compound, an aldehyde contain
(a) preparing an antimicrobial composition of any one of ing compound, and a peroxygen containing compound.
embodiments 23-29, and 25
(b) dissolving the antimicrobial composition in an aqueous 41. The present invention also provides for the liquid, aque
Solution to provide the aqueous antimicrobial composition. ous antimicrobial composition of any one of embodiments
33. The present invention also provides for the method of 35-40, wherein the antimicrobial agent includes at least one
embodiment 32, wherein the aqueous antimicrobial compo of:
sition includes less than about 0.1 wt.% of undissolved solid 3-(trimethoxysilyl)propyl dimethyl octadecyl ammonium
particulates. chloride

34. The present invention also provides for the method of 45 poly(hexamethylene biguanide) hydrochloride (PHMB)
embodiment 32, wherein the aqueous antimicrobial compo
sition includes less than about 0.1 wt.% of undissolved solid
particulates, such that the method of preparing the aqueous NH NH
antimicrobial composition does not include filtering the aque | |
50 pis
ous antimicrobial composition to remove undissolved solid
particulates. ex HC
35. The present invention also provides for a liquid, aqueous
antimicrobial composition including: sialic acid (N-acetyl-neuraminic acid, Neu5Ac, NAN,
(a) an antimicrobial agent, 55
NANA)
(b) a polymeric carrier, and
(c) water,
which includes less than about 0.1 wt.% of undissolved solid
particulates,
60
wherein,
the antimicrobial agent has a solubility in water of at least
about 0.05 g/mL at 80°C. and 1 atm, and
the polymeric carrier has a solubility in water of at least
about 0.05 g/mL at 80°C. and 1 atm. 65
36. The present invention also provides for the liquid, aque poly(dialyldimethylammonium chloride) (poly DAD
ous antimicrobial composition of embodiment 35, wherein at MAC)
 US 9,265,248 B2
23 24

10
poly(vinyl benzyltrimethyl ammonium chloride) (PVBT (b) a polymeric carrier including polyvinyl alcohol (PVA),
MAC); (c) water,
5-chloro-2-(2,4-dichlorophenoxy)phenol; (d) alcohol, and
alkyldimethylbenzylammonium chloride (ADBAC); (e) fragrance.
2,4,4-trichloro-2'-hydroxydiphenyl ether 15 49. The present invention also provides for a liquid, aqueous
antimicrobial composition including:
C OH
(a) about 0.01 to about 4.0 wt.% of 3-(trimethoxysilyl)
propyl dimethyl octadecyl ammonium chloride,
(b) about 0.1 to about 4.0 wt.% of polyvinyl alcohol (PVA),
(c) about 18 to about 99.9 wt.% water,
C
oo Cl;
2O (d) 0 to about 80.0 wt.% of ethanol,
(e) 0 to about 2.0 wt.% fragrance, and
(f) 0 to about 0.004 wt.% of an anti-foaming agent.
methylisothiazolinone
50. The present invention also provides for a liquid, aqueous
25 antimicrobial composition including:
(a) about 0.5 wt.% of 3-(trimethoxysilyl)propyl dimethyl
O octadecyl ammonium chloride,
(b) about 1.0 wt.% of polyvinyl alcohol (PVA),
30 (c) about 88.3 wt.% of water,
M
N-CH: (d) about 10.0 wt.% of ethanol,
(e) about 0.2 wt.% fragrance, and
(f) about 0.002 wt.% of an anti-foaming agent.
N-(2-hydroxyl)propyl-3-trimethylammonium chitosan as 51. The present invention also provides for the antimicro
chloride (HTCC); and bial composition of any one of embodiments 1-24 and 35-50,
a silver complex of poly(amidoamine) (PAMAM); wherein the composition is configured for use in a sprayable
2-isopropyl-5-methylphenol; and composition.
poly-D-glucosamine. 52. The present invention also provides for the antimicro
42. The present invention also provides for the liquid, aque- 40 bial composition of any one of embodiments 1-24 and 35-50,
ous antimicrobial composition of any one of embodiments wherein the composition is configured for use in an athletic
35-41, wherein the polymeric carrier includes at least one of letic apparelcomposition,
equipment an athletic gear composition, anath
composition, or an athletic footwear composi
polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), starch, tion.
polyethylene glycol (PEG), ethylene vinyl alcohol (EVA),
cellulose, cellulose acetate, and chitosan. 45 53. The present invention also provides for the antimicro
43. The present invention also provides for the liquid, aque bial composition of any one of embodiments 1-24 and 35-50,
ous antimicrobial composition of any one of embodiments wherein the composition is configured for use in a sprayable
35-42, wherein the weight ratio of antimicrobial agent to athletic equipment composition, a sprayable athletic gear
polymeric carrier is about 1:99 to about 99:1. composition, a sprayable athletic apparel composition, or a
44. The present invention also provides for the liquid, aque 50 sprayable athletic footwear composition.
ous antimicrobial composition of any one of embodiments 54. The present invention also provides for the antimicro
35-43, which is relatively non-leaching. bial composition of any one of embodiments 1-24 and 35-50,
45. The present invention also provides for the liquid, aque wherein the composition is configured for use in manufactur
ous antimicrobial composition of any one of embodiments ing a plastic or rubber composition.
35-44, further including at least one (C-C)alkyl substituted 55 55. The present invention also provides for the antimicro
with one or more hydroxyl. bial composition of any one of embodiments 1-24 and 35-50,
46. The present invention also provides for the liquid, aque wherein the composition is configured for use in manufactur
ous antimicrobial composition of any one of embodiments ing a fabric or textile composition.
35-45, which includes less than about 0.1 wt.% heavy metals. 56. The present invention also provides for a method of
47. The present invention also provides for the liquid, aque 60 reducing the number of microbes located upona Substrate, the
ous antimicrobial composition of any one of embodiments method including contacting the Substrate with an antimicro
35-46, which includes less than about 0.1 wt.% poly-chlori bial composition of any one of embodiments 1-24 and 35-50,
nated phenols (PCPs). for a sufficient period of time to reduce the number of
48. The present invention also provides for a liquid, aqueous microbes located upon the Substrate.
antimicrobial composition including: 65 57. The present invention also provides for a method of
(a) an antimicrobial agent including 3-(trimethoxysilyl) killing or inhibiting a microorganism, the method including
propyl dimethyl octadecyl ammonium chloride, contacting the microorganism with an antimicrobial compo
 US 9,265,248 B2
25 26
sition of any one of embodiments 1-24 and 35-50, for a EXAMPLES
sufficient period of time to kill or inhibit the microorganism.
58. The present invention also provides for a method of Examples 1 and 2
eliminating or lowering malodor associated with the growth Examples 1 and 2 evaluated the adsorption of TPAC on
of a microorganism, the method including contacting the starch and polyvinyl alcohol (PVA) surfaces.
microorganism with an antimicrobial composition of any one
of embodiments 1-24 and 35-50, for a sufficient period of Example 1
time effective to eliminate or lower the malodor.
10 Into a 250 mL round bottomed flask were placed 50 mL of
59. The present invention also provides for a method of hexanes, 15 mL of 72% TPAC in methanol, and 15 g of
eliminating or lowering staining or discoloration of a Sub soluble starch.
strate, which is associated with the growth of a microorgan Example 2
ism, the method including contacting the Substrate with an
antimicrobial composition of any one of embodiments 1-24 15 into a 250 mL round bottomed flask were placed 50 mL of
and 35-50, for a sufficient period of time effective to eliminate hexanes, 15 mL of 72% TPAC in methanol, and 10g of fully
or lower the staining or discoloration. hydrolyzed polyvinyl alcohol (mol. wt. 89-90,000).
Each flask was attached to a condenser and stirred vigor
60. The present invention also provides for the method of ously in a water bathat approximately 40°C. for about 1 hour.
any one of embodiments 56-59, wherein the microbe or The samples were then allowed to stir overnight at room
microorganism includes at least one of a virus, fungus, mold, temperature (~18 hr.). Each flask was then placed on a rotary
slime mold, algae, yeast, mushroom and bacterium. evaporator and solvent was removed under vacuum until rela
tively dry to give a powder. Each powder was then dissolved
61. The present invention also provides for a substrate hav in waterata concentration of 1 wt %. The dissolution required
ing applied thereto a coating or film to provide antimicrobial 25 heating and stirring. Each powder went into solution.
properties, said coating or film formed from contacting the A portion of each clear Solution was pipetted into a white
weighing dish and sprayed with bromocresol purple to deter
Substrate with an antimicrobial composition of any one of mine the presence of TPAC. The bromocresol purple will
embodiments 1-24 and 35-50. complex with the quaternary ammonium portion of the TPAC
62. The present invention also provides for the substrate of 30
molecule to show a deep blue color. A failure will show either
a yellow, or at high pH, a purple color.
embodiment 61, wherein the contacting includes at least one The sample containing polyvinyl alcohol (PVA) showed a
of spraying, dipping, brushing, and rolling the Substrate with color change, but the sample containing starch did not. This
the antimicrobial composition. indicated that the sample containing polyvinyl alcohol was
63. The present invention also provides for the substrate of 35
successfully coated with TPAC while the sample containing
starch was not coated with TPAC.
any one of embodiments 61-62, wherein at least about 90 mol.
% of the antimicrobial located on the substrate will remain Examples 3, 4, and 5
stable on the substrate, at about 20° C. and at about 50%
relative humidity, when exposed to the atmosphere, for at 40
Examples 3 and 4 evaluated the amount of adsorption of
least about 3 months. TPAC on PVA (wit/wt) as a function of time and temperature.
Samples having the same weight ratios of TPAC to PVA were
64. The present invention also provides for the substrate of prepared but allowed to react for various periods of time and
any one of embodiments 61-63, which is at least one of a temperature.
topical Surface of a mammal, non-woven fabric, woven fab
ric, natural textile, synthetic textile, organic particulate, inor 45 Example 3
ganic particulate, fiber, agglomerate, foam, film, cellulosic
material, metal, plastic, natural rubber, synthetic rubber, Into a 250 mL round bottomed flask were placed 100 mL of
glass, paint, stain, adhesive, Stone, grout, fiberglass, medical hexanes, 15 mL of 72% TPAC in methanol, and 10g of fully
device, clothing apparel, sporting equipment, wood, con hydrolyzed polyvinyl alcohol (MW 89-90,000). The sample
50 was stirred for 4 hr at 60° C. The sample was worked up as
crete, construction product, building product, and activated described in Example 2. The sample was found to have about
carbon. 3 wt % of TPAC adsorbed onto the PVA powder
65. The present invention also provides for a kit including:
Example 4
(a) an enclosed container including a removable closure, 55
(b) an antimicrobial composition of any one of embodi Into a 250 mL round bottomed flask were placed 50 mL of
ments 1-24 and 35-50, located inside the enclosed container, hexanes, 15 mL of 72% TPAC in methanol, and 10g of fully
and hydrolyzed polyvinyl alcohol (MW 89-90,000). The sample
was stirred for 18 hr at room temperature. The sample was
(c) printed indicia located on the enclosed container. 60 worked up as described in Example 2. The sample was found
66. The present invention also provides for the kit of to have about 10 wt % of TPAC adsorbed onto the PVA
embodiment 65, further including a liquid applicator includ powder
ing at least one of a spray bottle, wipe, cloth, sponge, non Example 5
woven fabric, and woven fabric. 65
The invention will now be described by the following non Into a 250 mL round bottomed flask were placed 50 mL of
limiting examples. hexanes, 15 mL of 72% DC5700 in methanol, and 10 g of
 US 9,265,248 B2
27 28
fully hydrolyzed polyvinyl alcohol (MW 89-90,000). The Example 10 showed an adsorption of about 6% g/g, had some
sample was stirred for 4 days at room temperature. The solubility in methanol, but did not filter well. The partially
sample was worked up as described in Example 2. The sample hydrolyzed PVA swelled in some solvents (i.e., methanol), so
was found to have about 10 wt % of TPAC adsorbed onto PVA a nice dry powder could not be achieved.
powder Examples 11 and 12
Examples 6, 7, and 8 Example 11
The following examples demonstrate the use of other sol Into a 250 mL round bottomed flask were placed 50 mL of
10
vents to determine how they affect the adsorption of TPAC hexanes, followed by addition of 27 mL of 72% TPAC in
onto PVA powder methanol via syringe. 25 g of fully hydrolyzed polyvinyl
alcohol (MW 89-90,000) was then added with vigorous stir
Example 6 ring. Upon dissolution, the flask was placed on a rotary evapo
rator to remove the methanol and hexanes. As the Solvent was
15 removed, a powder formed.
A sample was prepared in a manner similar to that
described in Example 2 above. The sample contained 15 mL A portion of the powder 2 wt % was added to a solution of
water and heated at about 80° C. to form a clear 2 wt %
72%TPAC: 10 g of fully hydrolyzed PVA (MW 89-90,000); solution. The solution was then evaluated as described above
and 50 mL of 1.2-methoxypropanol. The sample was stirred to determine the content of TPAC. The sample was found to
at room temperature for 18 hours. have 0.94% DC5700, indicating the dry powder is nearly 1/1
Example 7 (g/g) TPAC/PVA.
Example 12
A sample was prepared in a manner similar to that
described in Example 2 above. The sample contained 15 mL 25 Example 11 was scaled up several times. The samples were
72%TPAC: 10 g of fully hydrolyzed PVA (MW 89-90,000); placed in glass baking pans and dried in a vacuum oven and
1.08 g of deionized water and 50 mL of 1.2-methoxypro then air dried. Samples were evaluated by preparing a 2 wt %
panol. The sample was prepared by first adding solvent, fol Solution in deionized water, heating to form a clear Solution.
lowed by water, then TPAC. These were stirred for 20 minutes Samples were found to contain a ratio of TPAC to PVA
prior to adding the PVA. The sample was stirred at room 30
ranging from of about 0.05/1 to 1.75/1.
temperature for 18 hours.
Example 12-01
Example 8
1.5 g of Thymol (2-isopropyl-5-methylphenol) was dis
A sample was prepared in a manner similar to that solved in 50 mL of ethyl alcohol in a 250 mL round bottom
described in Example 1 above. The sample contained 45 mL 35 flask. 30 g of fully hydrolyzed polyvinyl alcohol (MW
72%TPAC: 10 g of fully hydrolyzed PVA (MW 89-90,000); 89,000-90,000) was added to the flask with vigorous stirring.
and 50 mL of hexanes. The sample was stirred at room tem The flask was Subsequently placed on a rotary evaporator to
perature for 18 hours. remove all ethyl alcohol and create a fine, uniform powder. A
Samples prepared in Examples 6, 7, and 8 were evaluated clear aqueous solution of -0.05 wt % Thymol (1.05 wt %
to determine the amount of TPAC adsorbed onto the polyvi 40 resulting powder) was made from this powder by dissolving
nyl alcohol. The samples from Examples 6 and 7 showed less at ~80°C. Similar solutions with up to 10% alcohol were also
stable and clear.
adsorption onto PVA than those of Examples 1 and 2 above.
The sample prepared in Example 7 showed an increase in Example 12-02
adsorption from 10% to 12%. 45
Similarly to example 12-01, 3.0 g of Thymol was dissolved
Examples 9 and 10 in 50-60 mL of ethyl alcohol, then 30 g of PVA was added
with stirring, and the ethyl alcohol was pulled off via rotary
The following Examples demonstrate the use of ground evaporator. The resulting fine, white powder was dissolved in
PVA powders to prepare antimicrobial powders. PVA pow water at ~80° C. at 0.1 wt % Thymol (1.1 wt % resulting
ders were ground for 5 min. in a coffee grinder to decrease the 50 powder) to create a clear solution. Both examples 12-01 and
particle size and increase the available Surface area. 12-02 were dried onto polycarbonate squares to form clear
films.
Example 9
Example 12-03
Into a 250 mL round bottomed flask were placed 50 mL of 55
hexanes, 15 mL of 72% TPAC in methanol, and 10 g of A uniform powder was made similarly to examples 12-01
ground fully hydrolyzed polyvinyl alcohol (MW 89-90,000). and 12-02. In a 250 mL round bottom flask, 3 g of benzalko
nium chloride (alkyldimethylbenzylammonium chloride)
Example 10 was dissolved in 50-60 mL of ethyl alcohol. 30 g of PVA was
60 added with stirring, and then the flask was placed on a rotary
Into a 250 mL round bottomed flask were placed 50 mL of evaporator to pull off all of the ethyl alcohol and form a
hexanes, 15 mL of 72% DC5700 in methanol, and 10 g of powder.
ground partially hydrolyzed polyvinyl alcohol (MW ~31,
000). Example 12-04
Samples from Examples 9 and 10 were evaluated as 65
described above. The sample from Example 9 showed an A uniform powder was made similarly to examples 12.03.
adsorption of less than 0.3 g/g, TPAC/PVA. The sample from In a 250 mL round bottom flask, 9 g of benzalkonium chloride
 US 9,265,248 B2
29 30
(alkyldimethylbenzylammonium chloride) was dissolved in oft (via vacuum) the ethanol. The result was dried further in a
50-60 mL of ethyl alcohol. 30 g of PVA was added with vacuum oven to obtain a dry, white, uniform powder of small
stirring, and then the flask was placed on a rotary evaporatorgranules. This powder was then dissolved into water at ~80°
to pull off all of the ethyl alcohol and form a powder. Both C. and coated on polycarbonate carriers for residual antimi
examples 12-03 and 12-04 were dissolved in water at ~80° C. 5 crobial
Solutionstesting. Furthermore.Sprav
and antimicrobial 0-15%testing
alcohol
waswas added to the
performed
to form clear solutions (1.1 wt % powder and 1.3 wt % powder pray 9. p
respectively). Solutions contained from 0-10 wt % added Results
ethyl alcohol. Solutions were also dried onto polycarbonate
squares to create clear films. 10 Examples 12-01 to 12-05
Example 12-05 Solutions of examples 12-01 to 12-05 were used to coat
polycarbonate or glass carriers. Once dried, bacteria were
3.9 g of Alkyldimethylbenzy ammonium chloride and 20.8 inoculated on top of the coating and a log reduction of bac
g of 72%TPAC were dissolved in 60-80 mL of ethanol. 30 g teria was obtained after a certain contact time. CFU-Colony
of fully hydrolyzed PVA was added with stirring to form a Forming Units, TNTC=Too numerous to count,
slurry. The flask was then placed on a rotary evaporator to pull BCP-benzalkonium chloride powder, ThP-thymol powder
Avg. total
number of
# of CFU recovered Positive CFU

Sample Organism 10 min 30 min 60 min Controls inoculated

1.3 wt % SA O 1 O Staph. 530

Benzalkonium SA O O O (iiietS
Powder PA O O O Psued. 1200
Example(12-04) PA O O O aeruginosa
1.1 wt % SA TNTC -3OO 89
thymol SA TNTC -3OO O
Powder PA TNTC 11 1
Example(12-02) PA 270 12 na

Test Samples (1 hr. contact time)

Total # of CFU
Recovered

Staph. Psued. Positive Avg. total number

Sample (iiietis Aeriginosa Controls of CFU inoculated

1.1 wt % BCP O O Staph. aureus 1700

O O Psued. 1SOOO
1.3 wt % BCP O TNTC Aeruginosa
O O
1.05 wt %. ThP 8O O
O 5
1.1 wt %. ThP 45 O
O 145
O.OS wt % 485 25
Chitosan, 1 wt % 2.5 10
PVA
O.1 wt % na 5
Chitosan, 1 wt.% 30 30
PVA

Staphylococcusatiretts
# of CFU CFU Recovered

Sample inoculated 1 min 5 min 10 min

1.3 wt % BCP 2OOOOO O O O

(Example 12-04) 2OOOOO O O O
2OOOOO 11 O O
2OOOOO O O O

10 minute contact time

Average CFU # CFU Average Log 10

Sample inoculated Recovered Reduction

1 wt % PVA 5.95 x 106 TNTC None

control TNTC
112
TNTC
TNTC
 US 9,265,248 B2
31 32
-continued
126
TNTC
TNTC
NA
O3 wt % 1.8 x 106 TNTC O.S
benzalkonium >300-appx. 360
chloride 2.0 x 106 TNTC
control >300-appx. 400
1.9 x 106 TNTC
>300-appx. 375
1.3 wt % BCP 2.05 x 105 >300-appx. 350 2.88
(Example 12-04) 45
5.0 x 103 10
1
5.0 x 102 10
2
O

A film formed on polycarbonate surfaces from a 1.5% solu- -continued

tion of powder, Example 12 (TPAC/PVA=0.5/1), was used to 20
obtain the results below. 0.13% BZK, 5 minutes A. 6.OOE-05 O 5.78
196 PVA B O
C O
CFU CFU Log 10 minutes A. S.1OE--OS O 5.71
Sample Inoculated Recovered Reduction B O
25 C O
Pseudomonas aeruginosa 0.5% TPAC, 5 minutes A. 6.OOE-05 O 5.78
0.3% BZK, B O
30 minutes A. 1700 1255 O.13 196 PVA C O
B 1700 1210 O.15 10 minutes A. S.1OE--OS O 5.71
C 1700 1155 O.17 B O
60 minutes A.B 1700
1700
96S
1OSO
"f
O.21
0.13% BZK.
1% PVA s
5 mile:S kB 6.OOE-05
X. X-
gO 5.78
C 1700 1160 O.17 0.
Staphylococcusatiretts C O
10 minutes A. S.1OE--OS O 5.71
30 minutes A. 2060 1455 O.15 B O
B 2060 68O O48 35 C O
C 2060 1085 O.28 0.5% TPAC, 5 minutes A. 6.OOE-05 TNTC NA
60 minutes A. 2060 NA NA 196 PVA B TNTC
B 2060 O 3.31 10 minutes A. S.1OE--OS TNTC NA
C 2060 64 1.51 B TNTC
Candida albicans

30 minutes A. 700 2O 1.93 40

B 700 O 3.23 Test substances are described as wt % chemical of solution,
C 700 445 O.S8 with which films were made on polycarbonate surfaces. The
60 minutes A. 700 O 3.23 bacteria were then inoculated on the dried carriers to obtain
B 700 10 2.23 the results above
C 700 O 3.23 s
Brevibacterium epidermidis 45
30 minutes A. 330 120 1.04 Test Organism Contact time Sample CFU Inoculated (+0)
B 330 15 1.9S
C 330 O 3.12 E. coi 3 minutes 1 2. SOE-03 O
60 minutes A. 330 O 3.12 2 O
B 330 5 2.42 50 3 O
C 330 O 3.12 4 O
Staphylococci is epidermidis 5 O
5 minutes 1 2. SOE-03 O
30 minutes A. 220 2O 1.79 2 O
B 220 25 1.69 3 O
C 220 60 1.31 55 4 O
60 minutes A. 220 O 3.09 5 O
B 220 5 2.39 C. albicans 3 minutes 1 1.3OE--O3 O
C 220 O 3.09 2 O
3 O
Average 4 O
Test Contact CFU CFU Log 60 5 O
Substance time Sample Inoculated Recovered Reduction 6 minutes 1 1.3OE--O3 O
2 (+)
0.5% TPAC, 5 minutes A. 6.OOE--OS 9 3.87 3 O
0.13% BZK, B 35 4 O
196 PVA C 17 5 O
10 minutes A. S.1 OE--OS O 5.58 M. terrae 5 minutes 1 8.4OE-05 O
B 1 65 2 O
C O 3 O
 US 9,265,248 B2
33 34
-continued than 99% reduction of bacteria was seen on the coated poly
carbonate Squares when compared to an uncoated control.
Test Organism Contact time Sample CFU Inoculated (+0)
Example 14
10 minutes 8.4OE-05 A solution similar to that of Example 13 was prepared. This
solution was used to coat 3 inchx3 inch (7.6 cmx7.6 cm)
cotton Squares. The cotton Squares were soaked in a shallow
dish for approximately 18 hrs. The excess solution was
Note:
10 poured off, and the trays were placed in an oven for 4 hrs at
“+” indicates growth, “0” indicates no growth 60° C. The coated cotton, along with uncoated controls were
Test substance used: 1% PVA, 0.5% TPAC, 0.13% BAC, 15% ethanol tested against Staphylococcus aureus with a contact time of
The table above illustrates the efficacy of a certain solution created from example 12-05. 30 and 60 minutes. After both time points, a greater than 99%
Bacteria were inoculated on the carriers, then the solution was sprayed and allowed to sit for reduction of bacteria was seen on the coated cotton Squares
the indicated contact time,
15 compared to an uncoated control.
Example 15
Jan. 27, 2012 Germicidal Spray Test
Test S. airetts A aeruginosa S. enterica Evaluation of Samples
sample 5 min 10 min 5 min 10 min 5 min 10 min Each fabric sample was treated with product applied by
1 A. O O O O O O
spraying 1 ounce of product onto the fabric thoroughly or
B O O O O O O Submerging the fabric sample in each formulation for a period
C O O O O O O of five minutes, and allowing the sample to dry for 24 hours.
2 A.
B
--
--
--
--
O
O
O
O
O
O
O
O
25 All tests were performed under controlled parameters (i.e.,
C -- O O O O O
humidity, temperature, etc.) using artificial perspiration
3 A. -- -- O O O O obtained from the American Association of Textile Chemists
B -- O O O O O and Colorists (AATCC) test method 15. The absorption test
4
C
A.
--
--
--
--
O
O
O
O
O
O
O
O
followed the AATCC test method 79 protocol; all other stud
B -- -- O -- O O
30 ies were independently constructed.
Fluid Dispersion Test
NOTE: The Fluid Dispersion Test is designed to measure the fluid
+ means survivors were present, and 0 represents total kill, dispersion (i.e., wicking) properties of moisture wicking per
Test Articles Used formance apparel. Due to the construction of the fabric of
35 moisture wicking products, testing required the fabric to
remain flat throughout the testing process; within the fabric
Testarticles
there exist horizontal channels that allow fluid to wick more
rapidly towards the perimeter. A diameter of 6 cm was set
1
2
196
196
PVA-0.5%
PVA-0.5%
TPAC-15%.
TPAC-15%.
EtOH-0.13% BAC
EtOH-0.07% BAC
within the sample. A burette was used to deliver the artificial
3 196 PVA-0.5% TPAC-10% EtOH-0.13% BAC
40 perspiration to the center of the fabric sample until enough
4 196 PVA-0.5% TPAC-10% EtOH volume of fluid was applied for the fabric to disperse across
the premeasured diameter both horizontally and vertically.
Positive Controls
When saturated with artificial perspiration fluid, the origi
nally white moisture wicking fabric appears transparent and
45 darkens in color. The volume of artificial perspiration fluid to
Positive Controls—Inoculum Titer (CFU)
saturate the fabric was recorded. The ability of the fabric to
disperse artificial perspiration was evaluated in comparison
SA 3.75E-06 with a control sample and other product samples.
PA
SE
2.48E--O6
4.5OE-04
Moisture Evaporation Test
50 The Moisture Evaporation test is designed to analyze the
time required for samples saturated with artificial perspira
The three tables above represent another liquid spray test in tion to evaporate fluid to the point where discoloration of the
which the bacteria were inoculated on carriers, sprayed with fabric can no longer be seen. This test analyzes the time
the solution, then allowed to sit for the indicated contact required for moisture wicking fabrics to evaporate fluid. The
times. 55 experiment was setup with the fabric samples Submerged in
artificial perspiration for 30 seconds; samples were then
Example 13 immediately removed and placed on a level rack to evaluate
the evaporation of fluid. The point at which samples are
The powder prepared in Example 4 was used to prepare a deemed completely evaporated is when no saturated channel
solution of 352 g of deionized water; 8g of TPAC coated PVA 60 can be seen. All samples were examined under atmospheric
(0.1 g/1 g) and 40 g of isopropyl alcohol. The Solution was conditions at room temperature and ambient humidity.
clear and contained 0.21% TPAC. Although the humidity fluctuates during testing it all samples
This solution was used to soak 12 polycarbonate 1 inchx1 are exposed to the same humidity during testing.
inch (2.5 cmx2.5 cm) squares for approximately 4 hours. The Simulated Perspiration Test
coated squares were then placed in Petri dishes to dry over 65 The simulated perspiration test evaluates the three stages of
night. These squares were then used for the Staphylococcus wicking; drawing moisture from the skin, dispersing it
aureus residual test. After a period of 30 minutes, a greater throughout the fabric to the outer surface of the fabric, and
 US 9,265,248 B2
35 36
evaporating the moisture from the outer surface of the fabric 4. The method of claim 1 or 2, wherein the liquid, aqueous
to cool the wearer. The test provides insight on antimicrobial antimicrobial composition is applied to a Substrate by at least
agents and the impact they have on each phase of wicking. one of spraying, dipping, brushing, and rolling the Substrate
Because the percent influence for each stage on wicking with the antimicrobial composition.
cannot be determined this test provides a feasible and useful 5. The method of claim 1 or 2, wherein the liquid, aqueous
analysis of the total wicking performance for each fabric antimicrobial composition is formulated such that at least 90
sample and can be used to evaluate the wicking performance mol. 9% of the antimicrobial located on the substrate will
of apparel regardless of material. remain stable on the substrate, at 20° C. and at 50% relative
The Simulated Perspiration Test emulates moisture wick humidity, when exposed to the atmosphere, for at least 3
ing performance of apparel in direct contact with a moisture 10 months.
Source, thus accurately Summarizing all three stages of the 6. The method of claim 1 or 2, wherein the liquid, aqueous
wicking process accurately. Grouting sponges were selected antimicrobial composition is applied to a Substrate with a
as the moisture release agent for their Small pore size and high liquid applicator comprising at least one of a spray bottle,
water holding capacity. Sponges were cut into a 5.5 inch wipe, cloth, Sponge, non-woven fabric, and woven fabric.
diameter, having a thickness of 2.4 inches, and placed inside 15 7. The method of claim 1 or 2, wherein the liquid, aqueous
a 5.5 inch diameter container that is 2.25 inches tall. With the antimicrobial composition is formulated such that at least 90
sponge Saturated with artificial perspiration, the Sponge was mol. 96 of aqueous antimicrobial composition will remain
set inside the container and additional artificial perspiration stable at 20° C. and at 50% relative humidity, when exposed
fluid is added to have all samples equivalent in mass; the to the atmosphere, for at least 9 months.
fabric samples are included in the mass. The container includ 8. The method of claim 1 or 2, wherein the liquid, aqueous
ing fabric sample, sponge within the container, and artificial antimicrobial composition comprises less than 0.1 wt.%
perspiration were monitored for 24 hours. With the fabric methanol.
sample completely covering and contacting the sponge, all
loss in mass was attributed to fluid loss evaporated through 9. The method of claim 1 or 2, wherein the liquid, aqueous
the fabric. The loss in mass can be used to measure the rate at antimicrobial composition is non-toxic, such that the LDso in
which each fabric sample wicks moisture from the surface of 25
rats is greater than 2 ml/kg of body mass.
the Sponge. 10. The method of claim 1 or 2, wherein the liquid, aqueous
What is claimed is: antimicrobial composition comprises less than 0.1 wt.%
1. A method of eliminating or lowering malodor associated heavy metals.
with a microorganism, the method comprising contacting the 11. The method of claim 1 or 2, wherein the liquid, aqueous
microorganism with a liquid, aqueous antimicrobial compo 30
antimicrobial composition comprises less than 0.1 wt.%
sition comprising: poly-chlorinated phenols (PCPs).
(a) about 0.01 to about 4.0 wt.% of 3-(trimethoxysilyl) 12. The method of claim 1 or 2, wherein the liquid, aqueous
propyl dimethyl octadecyl ammonium chloride, antimicrobial composition is a sprayable composition.
(b) about 0.1 to about 4.0 wt.% of polyvinyl alcohol (PVA), 13. The method of claim 1 or 2, wherein the liquid, aqueous
(c) about 18 to about 99.9 wt.% water, antimicrobial composition is applied to a substrate selected
(d) 0 to about 80.0 wt.% of ethanol, 35
from the group consisting of athletic equipment, athletic gear,
(e) 0 to about 2.0 wt.% fragrance, and athletic apparel, and athletic footwear.
(f) 0 to about 0.004 wt.% of an anti-foaming agent 14. The method of claim 1 or 2, wherein the liquid, aqueous
which comprises less than 0.1 wt.% of undissolved solid antimicrobial composition is applied to a topical Surface of at
particulates, least one of a mammal, non-woven fabric, woven fabric,
for a sufficient period of time effective to eliminate or lower 40 natural textile, synthetic textile, organic particulate, inorganic
the malodor; particulate, fiber, agglomerate, foam, film, cellulosic mate
wherein at least 95 mol.% of the 3-(trimethoxysilyl)propyl rial, metal, plastic, natural rubber, synthetic rubber, glass,
dimethyl octadecyl ammonium chloride is complexed paint, stain, adhesive, stone, grout, fiberglass, medical device,
with the polyvinyl alcohol (PVA). clothing apparel, sporting equipment, wood, concrete, con
2. A method of eliminating or lowering malodor associated 45 struction product, building product, and activated carbon.
with a microorganism, the method comprising contacting the 15. The method of claim 1 or 2, wherein the liquid, aqueous
microorganism with a liquid, aqueous antimicrobial compo antimicrobial composition is applied to a topical Surface of at
sition comprising: least one of polyester fabric, synthetic polyester fabric, non
(a) about 0.5 wt.% of 3-(trimethoxysilyl)propyl dimethyl engineered polyester fabric, performance apparel, moisture
octadecyl ammonium chloride, wicking performance fabric, delicate moisture wicking per
(b) about 1.0 wt.% of polyvinyl alcohol (PVA), 50
formance fabric, and moisture wicking performance apparel.
(c) about 88.3 wt.% of water, 16. The method of claim 1 or 2, wherein a substrate is
(d) about 10.0 wt.% of ethanol, treated one or more times with the liquid, aqueous antimicro
(e) about 0.2 wt.% fragrance, and bial composition.
(f) about 0.002 wt.% of an anti-foaming agent 17. The method of claim 1 or 2, wherein a substrate is
which comprises less than 0.1 wt.% of undissolved solid 55 treated one or more times with the liquid, aqueous antimicro
particulates, bial composition, to provide a coating or film on the Substrate,
for a sufficient period of time effective to eliminate or lower and the resulting film or coating remains stable and retains the
the malodor; antimicrobial properties for at least 1 year.
wherein at least 95 mol.% of the 3-(trimethoxysilyl)propyl 18. The method of claim 1 or 2, wherein a substrate is
dimethyl octadecyl ammonium chloride is complexed treated one or more times with the liquid, aqueous antimicro
with the polyvinyl alcohol (PVA). 60
3. The method of claim 1 or 2, wherein the microbe or bial composition, to provide a coating or film on the Substrate,
microorganism is selected from the group consisting of a and the resulting film or coating remains stable and retains the
virus, fungus, mold, slime mold, algae, yeast, mushroom and antimicrobial properties for 1 to 5 years.
bacterium. k k k k k