MAIMUUTTUNUT DIHUTTUURIHIN US009999226B2

(12) United States Patent ( 10) Patent No.: US 9,999,226 B2

Toreki et al. (45) Date of Patent: Jun . 19 , 2018
(54 ) WATER -BORNE ANTIMICROBIAL ( 2013 .01); A61L 31/ 146 (2013.01); A61L
FORMULATIONS WITH HYDROGEN 31/ 16 (2013 .01) ; C09D 5 / 14 ( 2013 .01); C09D
PEROXIDE 7761 (2018 . 01 ); C09D 7762 (2018 .01); C09D
(71 ) Applicant: Quick -Med Technologies , Inc ., 7767 (2018 .01); C09D 131/04 ( 2013 . 01) ;
Gainesville , FL (US ) C09D 133 /00 (2013 . 01 ); C09D 175 /04
( 2013 .01) ; A61L 2202/ 24 (2013 .01 ); A61L
(72 ) Inventors: William Toreki, Gainesville , FL (US ); 2300 / 11 (2013.01) ; A61L 2300 / 404 ( 2013.01);
Rustom S. Kanga , Kennesaw ,GA (US) A61L 2420 /04 (2013 .01 ) ; COOK 2003 /2217
( 2013 .01); C08K 2003/ 2237 ( 2013 .01 ); C08K
(73 ) Assignee : QUICK -MED TECHNOLOGIES, 2003 /2244 (2013 .01); C08K 2003/2296
INC ., Gainesville, FL (US) ( 2013 .01) ; C09D 11/ 00 ( 2013 .01)
( * ) Notice : Subject to any disclaimer, the term of this (58 ) Field of Classification Search
None
patent is extended or adjusted under 35 See application file for complete search history .
U .S . C . 154 (b ) by 0 days. days.
(56 ) References Cited
(21) Appl. No.: 15/413,258 U . S . PATENT DOCUMENTS
(22 ) Filed : Jan . 23, 2017 740 ,832 A 10 / 1903 Elias
2 ,563,442 A 8 /1951 Wood et al.
(65 ) Prior Publication Data 4 , 172, 841 A 10 / 1979 Danna et al.
US 2017/0156339 A1 Jun . 8, 2017 4 , 174 ,418 A 11/ 1979 Welch et al.
5 ,656 ,0378 /1997
A Vigo et al.
Related U . S. Application Data 8 ,124 , 169 B2
2 /2012 Ylitalo et al .
2002 /0185199 Al 12 /2002 Myers et al.
(63 ) Continuation of application No. 14 /396 , 033, filed as 2007/0243237 A1 10 /2007 Khaled et al.
application No . PCT/US2013/077333 on Dec. 21 , 2010 / 0247615 AL 9 /2010 Toreki et al.
2013 , now Pat. No . 9 ,549,547 . 2011/0171280 A1* 7 / 2011 Toreki ......... DOOM 11/ 155
424 /411
(60 ) Provisional application No. 61/740 ,075 , filed on Dec . (Continued )
20 , 2012 .
FOREIGN PATENT DOCUMENTS
(51) Int. Ci.
AOIN 59 / 00 ( 2006 .01) WO 2009018009 A1 2 /2009
B05D 3/00 ( 2006 .01) OTHER PUBLICATIONS
A01N 59 / 16 ( 2006 .01 )
A61L 2 /00 ( 2006 .01 ) Xie , Yanping; He, Yiping; Irwin , Peter L .; Jin, Tony ; and Shi,
A61L 9700 ( 2006 .01 ) Xianming; “ Antimicrobial Activity and Mechanism of Action of
AOIN 25 / 10 ( 2006 .01) Zinc Oxide Nanoparticles Against Camylobacter jejuni” , Applied
A61L 27744
and Environmental Microbiology 77 ( 7 ), p . 2325 - 2331, ( 2011) .
( 2006 .01) Yousef, Jehad M .; and Danial, Enas N .; “ In Vitro Antibacterial
A6IL 27 /56 ( 2006 .01) Activity and Minimum Inhibitory Concentration of Zinc Oxide and
A61L 28 / 00 (2006 .01) Nano -particle Zinc Oxide Against Pathogenic Strains” , Journal of
A61L 29/ 12 (2006 .01) Health Sciences 2 ( 4 ), p . 38 -42 , ( 2012 ) .
Wang, Chao ; Liu , Lian -Long ; Zhang, Ai- Ting; Xie , Peng ; Lu ,
A61L 29/ 14 (2006 .01) Jian - Jun ; and Zou , Ziao - Ting; “ Antimicrobial Effects of Zinc Oxide
A61L 31/ 12 (2006 .01) Nanoparticles on Escherichia coli K88” , African Journal of Bio
A61L 31/ 14 ( 2006 .01) technology 11( 44 ), p . 10248 - 10254 , (2012 ).
A61L 2 /20 ( 2006 .01) Sevinc , Berdan , Aydin , and Hanley, Luke; “ Antimicrobial Activity
of Dental Composites Containing Zinc Oxide Nanoparticles ” , Jour
A61L 2 /232 ( 2006 .01 ) nal of BiomedicalMaterials Research , Part B , Applied Biomaterials
A61L 2 /238 ( 2006 .01) 94 ( 1 ), p . 22 - 31 (2011).
C09D 5 / 14 ( 2006 .01) Seil, Justin T., and Webster, Thomas J.; “ Zinc Oxide Nanoparticle
and Polymer Antimicrobial Biomaterial Composites " , MRS Pro
A61L 27/54 ( 2006 .01) ceedings 1316 , (2010 ) [Abstract ].
AOIL 31/ 16 (2006 .01) (Continued )
C09D 131/04 (2006 .01)
C09D 133 / 00 ( 2006 .01 ) Primary Examiner — Cachet I Sellman
C09D 175 / 04 ( 2006 .01) (74 ) Attorney, Agent, or Firm — Gerry J. Elman ; Elman
C09D 11/ 00 ( 2014 .01) Technology Law , P .C .
C08K 3 /22 ( 2006 .01 ) (57) ABSTRACT
(52 ) U . S . CI. This invention relates to regenerable antimicrobial coatings
??? ......... ... AOIN 59 / 16 (2013 .01); AOIN 25 / 10 with long - lasting efficacy for use in medical applications
( 2013 .01) ; A01N 59/00 ( 2013 .01); A61L 2 /00 including implants, medical instruments or devices , and
( 2013.01 ); A6IL 2 / 208 ( 2013.01) ; A6IL 2 /232 hospital equipment. The same coatings would also have
(2013 .01); A6IL 2 /238 (2013. 01 ); A61L 9/ 00 broad utility in the consumer, industrial, and institutional
( 2013.01 ); A61L 27/ 446 (2013 . 01 ); A61L markets . The coating technology would be based on seques
27 /54 (2013 .01); A61L 27/56 (2013 .01); AGIL tration of hydrogen peroxide (HP ) by zinc oxide binders
28 / 0092 ( 2013 .01); A61L 29 / 126 ( 2013 .01); incorporated into the coatings .
A61L 29 / 146 (2013 .01 ); A6IL 31/ 128 20 Claims, No Drawings
 US 9 ,999 ,226 B2
Page 2

( 56 ) References Cited tional Journal of Engineering, Science and Technology 2 ( 1 ), p .

202 - 208, ( 2010 ) .
U . S . PATENT DOCUMENTS Gittard , Shaun D .; Perfect, John R .; Montiero -Riviere , Nancy A ;
Wei, Wei; Jin , Chunming; and Narayan , Robert, J.; “ Assessing the
2011/0206578 A1 8/2011 Foster et al. Antimicrobial Activity of Zinc Oxide Thin Films Using Disk
2013 /0183495 A1 * 7/ 2013 Rock . .. .. .. .. ... DO6M 11/50 Diffusion and Biofilm Reactor” , Applied Surface Science 255 ( 11),
428 / 156 p . 5806 -5811 , (2009 ) [Abstract ].
Zhang, Lingling; Jiang , Yunhong ; Ding, Yulong ; Daskalakis,
OTHER PUBLICATIONS Nikolaos; Jeuken , Lars; Povey , Malcolm ; O 'Neill , Alex J.; and
Chang , B . P.; Akil, H . Md., Nasir , R . Md.; and Nurdijati, S .; York , David W .; "Mechanistic Investigation into Antimicrobial
Behavior of Suspensions of ZnO Nanoparticles against E . coli” ,
“ Mechanical and Antimicrobial Properties of Treated and Untreated Journal of Nanoparticle Research 12 ( 5 ), p . 1625 - 1636 , ( 2010 ).
Zinc Oxide Filled UHMWPE Composites” , Journal of Thermoplas Rosenthal- Toib , Liora ; Zohar, Keren ; Alagem , Meital; and Tsur,
tic Composite Materials 24 (5 ), p . 653 -667 , ( 2011) [ Abstract ]. Yoed ; " Synthesis of Stabilized Nanoparticles of Zinc Peroxide” ,
Singh , Gagandeep ; Joyce, Eadaoin M .; Beddow , James ; and Mason , Chemical Engineering Journal 136 , p . 425 - 429 , ( 2008, Singh ,
Timothy J.; “ Evaluation of Antimicrobial Activity of ZnO Nahar; Mittal, Shelly ; Sood, K .N ., Rashmi; and Gupta , Prabat K .;
Nanoparticles Coated Sonochemically onto Textile Fabrics” , Bio “ Controlling the Flow of Nascent Oxygen Using Hydrogen Perox
technology and Food Sciences 2 ( 1 ), p . 106 - 120, (2012 ). ide Results in Controlling the Synthesis of ZnO /ZnO2” ,
Rajendran , R .; Balakumar, C .; Ahammed , Hasabo A ., Mohammed , Chalcogenide Letters 7 ( 4 ), p . 275 -281, (2010 ) [Abstract ].
Jayakumar S .; Vaideki, K ; and Rajesh , E .M .; “ Use of Zinc Oxide
Nano Particles for Production of Antimicrobial Textiles ” , Interna * cited by examiner
 US 9,999,226 B2
WATER - BORNE ANTIMICROBIAL spreading of microbes from one group to the other. In an
FORMULATIONS WITH HYDROGEN extensive contamination study based in a southern Ontario
PEROXIDE hospital, 11. 8 % of surfaces sampled were positive for
MRSA (n = 612 ) while 2 .4 ( n = 552 ) of surfaces were positive
CROSS -REFERENCE TO RELATED 5 for C . difficile ( Faires , Meredith C .; Pearl, David L .; Cicco
APPLICATIONS telli, William A .; Straus, Karen ; Zinken , Giovanna ; Berke ,
Olaf; Reid - Smith , Richard J.; and Weese , J. Scott ; “ A
This non -provisional application is a continuation of U .S . Prospective Study to Examine the Epidemiology of Methi
Non -Provisional patent application Ser . No. 14 /396 ,033 cillin -Resistant Staphylococcus aureus and Clostridium dif
which is a national stage entry of International Patent 10 ficile Contamination in the General Environment of Three
Application , Serial Number PCT/US2013 /077333 , filed Community Hospitals in Southern Ontario , Canada” , BMC
Dec . 21 . 2013 , which claims benefit of priority to U .S . Infectious Diseases 12 (290 ) , ( 2012 ). Furthermore, a study
Provisional Patent Application 61/740,075 filed Dec. 20 , from as far back as 1997 discovered that 42 % of medical
2012 . The entire disclosures of each of the aforementioned personnel who had no direct contact with actual infected
applications are incorporated herein by reference . 15 patients, had MRSA contaminated gloves acquired directly
from hospital room surfaces (Boyce , John M .; Potter -Bynoe,
TECHNICAL FIELD Gail; Chenevert, Claire ; and King , Thomas ; “ Environmental
Contamination Due to Methicillin -Resistant Staphylococcus
This invention pertains to regenerable coatings with aureus: Possible Infection Control Implications ” , Infection
durable antimicrobial properties . 20 Control and Hospital Epidemiology 18 (9 ), p 622 -627 ,
(1997 ) . Other studies indicated that certain Gram -positive
BACKGROUND ART species such as Staph . aureus can survive up to 7 months on
dry surfaces, while certain Gram -negative organisms such as
Healthcare facilities are known to be a breeding ground E . coli and Pseudomonas aeruginosa can last up to 16
for a variety of infectious diseases. The pathogens that cause 25 months on dry surfaces (Kramer, Axel; Schwebke , Ingeborg ;
these diseases can reside in many places in the hospital and Kampf, Günter; “ How Long Do Nosocomial Pathogens
environment — not just in devices and equipment used in Persist on Inanimate Surfaces ? A Systematic Review ” , BMC
medical procedures , but also from common surfaces such as infectious Diseases 6 ( 1 ) , p 130 , (2006 ).
floors, telephones, bed rails, bathroom fixtures, hand rails, Contaminated surfaces such as these are leading to
and computer keyboards. Microbes living on these contami- 30 increased incidences of hospital acquired infections (HAIS )
nated surfaces are touched by multiple people leading to and it has been estimated that 1 in 20 hospital patients will
increased spread ofhospital acquired infections (HAIS ), and be infected with an HAI as a direct result of the care they
it has been estimated that 1 in 20 hospital patients will be receive at hospital institutions (Scott II, R . Douglas; “ The
infected with an HAI as a direct result of the care they Direct Costs of Healthcare -Associated Infections in U .S .
receive at hospital. 35 Hospitals and the Benefits of Prevention " , Division of
Hydrogen peroxide (HP ) is currently receiving renewed Healthcare Quality Promotion : National Center for Pre
attention as a safe , environmentally - friendly, and cost- effec - paredness , Detection , and Control of Infectious Diseases,
tive antimicrobial, as evidenced by the recent introduction of Centers for Disease Control and Prevention , (2009). One
several commercially -available cleaning products based on study estimates that 1.7 million HAIs occurred in U . S .
HP. 40 hospitals in 2002, leading to approximately 99 ,000 deaths,
Casual contact with everyday objects is a leading cause exceeding the number of cases of any currently notifiable
for the spread of infection , and disease . One dirty hand can disease , and also exceeding the number attributable to
infect multiple surfaces . Rubbing one 's eye or eating a several of the top ten leading causes of death reported in
sandwich then becomes a vector for infection . Even surfaces U . S . vital statistics (Klevens , R . Monina ; Edwards, Johna
are cleaned and sanitized frequently can quickly become 45 than R .; Richards Jr., Chesley L ., Horan , Teresa C .; Gaynes ,
recontaminated after the applied disinfectant has evaporated . Robert P .; Pollock , Daniel A .; Cardo , Denise M .; “ Estimat
Antimicrobial cleaning products based on hydrogen per - ing Health Care - Associated Infections and Deaths in U . S .
oxide have recently been commercialized for hospital and Hospitals, 2002 ” , Public Health Reports 1 22 (2 ), p 160 - 166 ,
home use by several leading brands , including Clorox and (2007 ) . Not only are these increased numbers of infections
Lysol. Unfortunately, since HP is volatile , surfaces cleaned 50 contributing to the decline of the health of U . S . citizens; the
with these products ( or even with alcohol, bleach , etc .) lose direct costs of these HAIs to hospitals are estimated to be
the antimicrobial effect immediately after drying. between $ 28 . 4 and $ 45 billion per year in the U . S . (Scott
Hospitals, nursing homes , and other healthcare facilities 2009 ). These increased costs result from longer hospitaliza
are known to be a breeding ground for a variety of infectious tions, increased use of diagnostic imaging, increased use of
diseases. The pathogens that cause these diseases can reside 55 intensive care , and increased use of newer more expensive
in many places in the hospital environment including floors , antibiotics . Assuming a 20 % -70 % HAI prevention range ,
curtains, telephones, bedding , bed rails, chairs and chair preventing HAIs can have cost benefits from $ 5 .7 billion to
backs , hand rails, and computer keyboards . In a surface $ 31.5 billion .
contamination targeting study conducted in a Welsh hospi Further compounding the issue , new legislation and
tal, 2 , 573 touch actions were examined . The results showed 60 national government programs are making serious adjust
that 1 ,489 touch actions were by nurses , 519 were by ments in response to the increase of HAIs . In 2008 , the
patients , 380 were by visitors, and 185 were by physicians United States Centers for Medicare and Medicaid Services
(Obee , Peter; PhD Thesis: “ Hospital Surfaces and their halted reimbursements to hospitals for certain “ reasonably
Importance in Cross Contamination and the Spread and preventable ” HAIs as a result of the 2005 Deficit Reduction
Transmission of Bacteria” , Accessed : University of Wales, 65 Act (Graves , Nicholas ; and McGowan , John E .; “Nosoco
Institute Cardiff Repository URI: < http ://hdl.handle .net/ mial Infection , the Deficit Reduction Act, and Incentives for
10369/844 > ). This demonstrates the high potential for Hospitals ” , JAMA: The Journal of the American Medical
 US 9 ,999 ,226 B2
Association , 300 ( 13 ) p 1577 -1579, (2008 ). Starting Jul. 1, “ fixed ” onto devices or surfaces such as coatings or com
2012 , states were required to implement non -payment posites , the level of antimicrobial performance is greatly
polices for healthcare - associated conditions and public diminished . There have been numerous attempts to incor
reporting of these infections is now mandatory . Additionally, porate ZnO into useful antimicrobial products, and even
as of Oct. 1 , 2012, hospitals with HAI-associated readmis - 5 though antimicrobial effects are claimed , they are most often
sion rates surpassing the predicted level will be punished trivial. For instance , dental implants containing 10 % Zno
with a 1 % decrease of all Medicare payments and the nanoparticles showed only a 80 % (< 1 log) reduction of
penalty will rise to 3 % by 2015 (UMF Corporation, “ Doing bacteria (Sevinc , Berdan , Aydin , and Hanley, Luke; “ Anti
Everything: Multimodal Intervention to Prevent Healthcare microbial Activity of Dental Composites Containing Zinc
Associated Infections” , White Paper: UMF Corporation , 10 Oxide Nanoparticles” , Journal of Biomedical Materials
( 2012). Research , Part B , Applied Biomaterials 94 ( 1 ), p 22- 31
Hydrogen peroxide is a favored antimicrobial in many ( 2011 ) . One study reported " significant” reductions of bac
applications because its breakdown products , water and teria by incorporating ZnO nanoparticles into PVC compos
oxygen , are innocuous, and it tends to have broad spectrum ites ; however, the actual measured reduction was less than
antimicrobial activity , meaning that it is not only effective 15 50 % , even when the composites contained 75 % ZnO ( Seil,
against bacteria , but it also kills viral and fungal organisms. Justin T.; and Webster, Thomas J.; “ Zinc Oxide Nanoparticle
Broad spectrum activity is important in situations where and Polymer Antimicrobial Biomaterial Composites” , MRS
harmful organisms are present but their identity is not Proceedings 1316 , (2010 ). Zinc oxide - filled UHMWPE
known. Hydrogen peroxide is a well -known antiseptic composites showed only “ slight inhibition ” of Staph . aureus
which has been extensively employed in aqueous solution 20 (Chang , B . P .; Akil, H . Md.; Nasir , R . Md.; and Nurdijati, S .;
for the treatment of infectious processes in both human and “Mechanical and Antimicrobial Properties of Treated and
veterinary topical therapy . Both HP and zinc oxide (ZnO ) Untreated Zinc Oxide Filled UHMWPE Composites” , Jour
have received GRAS (Generally Recognized as Safe) des - nal of Thermoplastic Composite Materials 24 (5 ), p 653-667,
ignations from the U . S . Food and Drug Administration (2011 ). ZnO nanoparticles coated onto textile fabrics gave
(FDA ). Both are also widely -available and relatively - inex - 25 only a 97 % reduction of Staph . aureus (SA ), and 87 %
pensive commodity materials . reduction of E . coli , prior to any laundering (Singh, Gagan
The designation of compounds, formulations and devices deep ; Joyce, Eadaoin M .; Beddow , James; and Mason ,
as “ antimicrobial” is often misused . To a layman , a 90 % Timothy J.; “ Evaluation of Antimicrobial Activity of ZnO
reduction of bacteria on a surface may seem great; however , Nanoparticles Coated Sonochemically onto Textile Fabrics” ,
onemust remember that bacteria multiply exponentially and 30 Biotechnology and Food Sciences 2 ( 1 ), p 106 - 120 , (2012 ).
quickly . For instance , it is said that a single E . coli (EC ) cell A similar textile study found almost identical low reduction
under favorable conditions can multiply into over ten mil levels , and efficacy against EC dropped to just 40 % after
lion cells within 12 hours ! Thus , it is imperative that a useful only one laundering (Rajendran , R .; Balakumar, C .; Aha
antimicrobial product give an extremely high level ofmicro mmed , Hasabo A .; Mohammed , Jayakumar S .; Vaideki, K .;
bial kill . For this reason , the efficacy of antimicrobial 35 and Rajesh , E . M .; “ Use of Zinc Oxide Nano Particles for
products is commonly described in terms of “ log reduction.” Production of Antimicrobial Textiles ” , International Journal
This means that a 90 % kill equals 1- log reduction , and 99 % of Engineering, Science and Technology 2 ( 1), p 202 - 208 ,
kill equals a 2 - log reduction . Killing 99 . 9999 % of the (2010 ). Silicon wafers coated with ZnO showed only a 10 %
bacteria equals a 6 - log reduction . Regulatory agencies such reduction in 24-hour biofilm formation (Gittard , Shaun D .;
as the FDA and U . S . Environmental Protection Agency 40 Perfect, John R .;Montiero -Riviere , Nancy A ; Wei, Wei; Jin ,
(EPA ) historically have required a minimum of 3 - log per - Chunming; and Narayan , Robert, J.; “ Assessing the Anti
formance for a product to be classified as “ antimicrobial” ; microbial Activity of Zinc Oxide Thin Films Using Disk
however, today a 4 -log to 6 -log requirement is becoming Diffusion and Biofilm Reactor” , Applied Surface Science
more common . For this reason , testing of bactericidal activ - 255 ( 11), p 5806 -5811, ( 2009). The point here is that
ity is commonly done using challenge levels of at least 106 45 although ZnO , even in nanoparticulate form , is widely
cfu /mL (colony forming units per milliliter ). touted as having antimicrobial properties, it is relatively
Zinc oxide (ZnO ) has received much attention in recent ineffective when incorporated into coatings or composites.
years as an antimicrobial agent. It has been found that Zno The current invention will increase the antimicrobial effi
nanoparticles show a higher efficacy than conventional Zno c acy of coatings containing ZnO by a few orders of mag
powders in the micron size range . This is to be expected , 50 nitude (to at least the 3 -log to 6 -log level) via reacting the
based on the higher surface area of the nanoparticles. coatings with cleaning agents comprising HP.
Indeed , high antimicrobial efficacy is realized for ZnO The exact mechanism for the antimicrobial effect of ZnO
nanoparticles in suspension (i.e. as liquid antimicrobial is still somewhat of a mystery (Xie 2011 , Zhang , Lingling ;
products ) for various pathogenic bacteria [Xie , Yanping; He, Jiang, Yunhong; Ding , Yulong ; Daskalakis, Nikolaos; Jeu
Yiping ; Irwin , Peter L .; Jin , Tony ; and Shi, Xianming ; 55 ken , Lars; Povey, Malcolm ; O 'Neill, Alex J.; and York ,
“ Antimicrobial Activity and Mechanism of Action of Zinc David W .; “Mechanistic Investigation into Antimicrobial
Oxide Nanoparticles Against Camylobacter jejuni” , Applied Behavior of Suspensions of ZnO Nanoparticles against E .
and Environmental Microbiology 77(7 ), p 2325 - 2331, coli ”, Journal of Nanoparticle Research 12 (5 ), p 1625
(2011); Yousef, Jehad M .; and Danial, Enas N .; “ In Vitro 1636 , (2010 ); however, it is widely known that ZnO can
Antibacterial Activity and Minimum Inhibitory Concentra - 60 generate hydrogen peroxide and other reactive oxygen spe
tion of Zinc Oxide and Nano - particle Zinc Oxide Against cies upon exposure to UV light (Xie 2011, Wang 2012).
Pathogenic Strains " , Journal of Health Sciences 2 (4 ), p There is also evidence that ZnO can interact with , and cause
38 -42, ( 2012 ); Wang, Chao ; Liu , Lian -Long ; Zhang , Ai- disruption of, the bacterial cell walls .
Ting ; Xie , Peng; Lu , Jian - Jun ; and Zou , Ziao - Ting; “ Anti- Zinc oxide and hydrogen peroxide are known to react
microbial Effects of Zinc Oxide Nanoparticles on Escheri- 65 with each other to form “ zinc peroxide” . Zinc peroxide (ZP )
chia coli K88 ”, African Journal of Biotechnology 11( 44 ), p is used as an oxidant, an antimicrobial , a blowing agent, and
10248 - 10254 , ( 2012 ) . However, when these particles are in the vulcanization of rubber, and its synthesis was patented
 US 9 ,999 ,226 B2
5
in 1903 (U .S . Pat. No. 740 ,832 ). In 1951, Wood patented an sufficient to permit an antimicrobially -enhancing
improved method of producing zinc peroxide, which amount of hydrogen peroxide to be sequestered
involved using sulfuric acid to essentially hydrolyze and thereon , and thereafter ,
“ soften ” the ZnO for improved yield (U . S . Pat . No . 2 ,563 , c . removing the source of aqueous hydrogen peroxide ,
442). Later, Dana (U .S . Pat. No . 4 , 172, 841) found that a 5 wherein said metal derivative comprises 1 % to 50 %
solution of zinc acetate mixed with HP was useful for (w / w ) of the weight of the doped polymer, wherein said
producing antimicrobial textiles . This chemistry essentially metal derivative is a hydroxide, an oxide , or a peroxide of a
amounted to an in -situ deposition of ZP on the textile fabric . metal selected from the group consisting of zinc , magne
Similar results were found using both zirconium and mag sium , titanium , and zirconium ,
nesium salts ( U . S . Pat. Nos. 4 , 174 ,418 and 5 ,656 ,037 ). 10 wherein the water absorbency of said polymer is between
Reaction of zinc oxide and /or zinc hydroxide with HP has 0 .5 % and 20 % ( w /w ), wherein said polymer doped with said
been used to synthesize nanoparticles of ZP (Rosenthal metal derivative has been determined to be capable of
Toib , Liora ; Zohar, Keren ; Alagem , Meital; and Tsur, Yoed ; sequestering hydrogen peroxide when exposed to said
“ Synthesis
inesis of
Or Stabilized Nanoparticles of Zinc Peroxide” , 15 source of aqueous hydrogen peroxide ;
Chemical Engineering Journal 136 , p 425 -429, (2008 , whereby said antimicrobial activity , when tested using
Singh , Nahar; Mittal, Shelly ; Sood, K . N .; Rashmi; and ASTM Standard Method E2180 at least 24 hours after said
Gupta , Prabat K .; “ Controlling the Flow ofNascent Oxygen removal of the source of hydrogen peroxide , provides at
Using Hydrogen peroxide Results in Controlling the Syn - least a 3 - log reduction of viable Escherichia coli bacteria
thesis of ZnO /ZnO2” , Chalcogenide Letters 7 (4 ), p 275 - 20 greater than that of a corresponding surface of said polymer
281, (2010 ). Zinc hydroxide (ZH ) is easily formed in doped with said metal derivative which has not been
solution by reaction of zinc salts with sodium hydroxide, but exposed to hydrogen peroxide .
is difficult or impossible to isolate in the dry state due to Optionally the above method may further comprise the
conversion to ZnO as it dries . ZnO on the other hand , can step of;
also be hydrolyzed back to ZH , and either ZnO or ZH can 25 conducting an assay to confirm durable antimicrobial
react with HP to form ZP, which can undergo a slow activity of the surface of said polymer doped with said metal
hydrolysis releasing HP in the presence of water. In other derivative after said step c .
words, the ZH / ZnO /HP /ZP system essentially involves the Preferably the metal derivative is selected from the group
sequestration of HP in a reversible manner. This slow release consisting of zinc hydroxide , zinc peroxide , zinc oxide , zinc
of HP is responsible for observed antimicrobial effect of 30 oxide nanoparticles , and zinc oxide micron particles. More
ZP -based materials . Herein lies the key element of the preferably the metal derivative is selected from the group
current invention — it is a sequestration system for storage consisting ofzinc oxide nanoparticles and zinc oxidemicron
particles .
(sequestration ) and controlled release of antimicrobially The metal derivative comprises 10 % to 30 % (w / w ) of the
effective amounts of hydrogen peroxide.
Several major companies have recently introduced HP 35 weight of the doped polymer.
Suitable polymers of the invention are selected from the
based cleaning products . Lysol (Reckitt Benckiser ) has group consisting of polyacrylonitrile, acrylonitrile butadiene
come out with an entire product line of household cleaning styrene (ABS) polymer, acrylic (PMMA ), celluloid , cellu
products based on hydrogen peroxide: “ Guided by our lose acetate , ethylene -vinyl acetate (EVA ), ethylene vinyl
LYSOL® Mission for Health , we are proud to introduce the 40 alcohol (EVOH ), fluoropolymers (PTFE , FEP, PFA , CTFE ,
innovative LYSOL® Power & FreeTM product line to con - ECTFE , ETFE ), ionomers, acrylic /PVC alloy, liquid crystal
sumers who are in search of trusted , powerful cleaning polymer (LCP ), polyacetal (POM or Acetal), polyacrylates
agents that help to maintain a healthy home by using the (acrylic ), polyacrylonitrile (PAN or acrylonitrile ), poly
very common , yet very effective household staple of hydro - amide (PA or Nylon ), polyamide- imide (PAI), polyarylether
gen peroxide ,” (see http ://www .prnewswire . com /news- re - 45 ketone (PAEK or Ketone ), polybutadiene (PBD ), polybuty
leases/lysol-launches -line -of-hydrogen - peroxide - products - lene (PB ), polybutylene terephthalate (PBT) ,
that-marks -a- new -era - in -household - cleaning polycaprolactone (PCL ), polychlorotrifluoroethylene
165569576 .html). The label on Lysol's general purpose (PCTFE ), polyethylene terephthalate (PET ), polycyclohex
cleaner lists 0.9 % HP as the active ingredient. Clorox has ylene dimethylene terephthalate (PCT), polycarbonate (PC ),
recently introduced a line of HP-based cleaners and wipes 50 polyhydroxyalkanoates (PHAs), polyketone (PK ), polyester,
for hospital use — “ Clorox HealthcareTM Hydrogen Peroxide polyethylene (PE), polyetheretherketone (PEEK ), polyether
Cleaner Disinfectants ” (see http ://www . cloroxprofessional- ketoneketone (PEKK ), polyetherimide (PEI), polyethersul
. com /products /clorox - healthcare -hydrogen - peroxide fone (PES), polyethylenechlorinates (PEC ), polyimide (PI),
cleaner-disinfectants/at-a - glance /). The Clorox Material polylactic acid (PLA ), polymethylpentene (PMP), polyphe
Safety Data Sheet lists “ 1 to 5 % ” as the concentration of HP. 55 nylene oxide (PPO ), polyphenylene sulfide (PPS ),
polyphthalamide (PPA ), polypropylene (PP ), polystyrene
SUMMARY (PS ), polysulfone (PSU ), polytrimethylene terephthalate
(PTT), polyurethane (PU ), polyvinyl acetate (PVA ), poly
An embodiment of the present invention is a method of vinyl chloride (PVC ), polyvinylidene chloride (PVDC );
enhancing and regenerating durable antimicrobial activity of 60 styrene -acrylonitrile (SAN ), silicone polymers, thermoplas
the surface of an article, wherein said method comprises the tics, thermosets, elastomers; and copolymers, blends, and
steps in sequence of: mixtures thereof.
a . providing, on the surface of an article on which durable A preferred polymer of the invention is selected from the
antimicrobial activity is desired , a polymer doped with group of polyurethanes, polyacrylates, and polyvinyl
a metal derivative , 65 acetate .
b . exposing the polymer doped with a metal derivative to Optionally , the doped polymer is a mixture that further
a source of aqueous hydrogen peroxide for a time comprises a hydrophilic acrylic polymer.
 US 9 ,999,226 B2
The source of aqueous hydrogen peroxide for the process A typical regenerable antimicrobial coating comprising a
desirably has a concentration of hydrogen peroxide between UV -curable coating may further comprise a binder ; curing
0 .5 % and 10 % . Preferably the concentration of hydrogen agents ; stabilizers ; an acrylate oligomer ; a urethane oli
peroxide is between 1 % and 5 % . The hydrogen peroxide gomer, a crosslinking agent such as tris (2 -hydroxy ethyl)
source may be a commercial cleaner containing at least 0 .5 % 5 isocyanurate triacrylate and /or hexane diol diacrylate , a
hydrogen peroxide . defoamer, a thermal stabilizer, a non - blocking slip additive,
Typically the doped polymer is exposed to hydrogen a photoinitiator, a near-UV photoinitiator, or mixtures
peroxide for 1 minute to 30 minutes. Longer exposure times thereof.
are acceptable . A typical regenerable antimicrobial coating comprising a
A preferred method to assay the level of sequestered 10 water-borne coating may further comprise a self-crosslink
hydrogen peroxide is a colorimetric spot test. ing linking acrylic dispersion , a UV curable polyurethane
It is an embodiment of the invention to provide a regen - dispersion , or a self-crosslinking polyurethane dispersion,
erable antimicrobial coating comprising, and further comprise an alcohol, a glycol, defoamers , pho
a . a metal derivative , wherein said metal derivative is a toinitiators, thermal stabilizers , anti- oxidants, surfactants or
hydroxide, an oxide, or a peroxide of a metal selected 15 mixtures thereof.
from the group consisting of zinc, magnesium , tita - A typical regenerable antimicrobial coating comprising a
nium , and zirconium , solvent-borne coating may further comprise a solvent
b . a polymer , wherein said polymer is doped with 1 % to selected from the group ofmethylethylketone , ethanol, and
50 % ( w /w ) of said metal derivative , mixtures thereof; and a coating polymer selected from the
c . sequestered hydrogen peroxide , 20 group consisting of polyvinyl acetate and polyvinyl acetate
wherein the water absorbency of said polymer is between crotonic acid copolymer; and further comprise defoamers,
0 .5 % and 20 % (w / w ), wherein said polymer doped with said photoinitiators , thermal stabilizers , anti-oxidants, surfac
metal derivative has been determined to be capable of tants or mixtures thereof.
sequestering hydrogen peroxide when exposed to said The article may be selected from the group consisting of
source of aqueous hydrogen peroxide ; wherein the antimi- 25 medical implants ; medical instruments or devices ; hospital
crobial activity of said doped polymer can be regenerated on equipment; bed rails ; table tops; bedpans ; i.v. stands; lamp
subsequent exposure to aqueous hydrogen peroxide, handles; blood pressure cuffs; dental equipment; surgical
whereby said antimicrobial coating, when tested using instruments ; orthopedic devices; hot/cold packs; wheelchair
ASTM Standard Method E2180 at least 24 hours after cushions; doorknobs ; bathroom fixtures ; food preparation
preparation , provides at least a 3 -log reduction of viable 30 surfaces ; equipment touch -screens; floor waxes; paints;
Escherichia coli bacteria greater than that of a correspond - inks; clear coats ; varnish ; kitchen equipment and tables in
ing coating which has not been exposed to hydrogen per restaurants, schools , and other institutions; home appliances ;
oxide. and seats, armrests, railings , and tray tables for airlines and
The regenerable antimicrobial coating comprises a poly other public transportation .
mer selected from the group consisting of polyacrylonitrile , 35
acrylonitrile butadiene styrene (ABS) polymer, acrylic DEFINITIONS
(PMMA), celluloid , cellulose acetate , ethylene -vinyl acetate
(EVA ), ethylene vinyl alcohol (EVOH ), fluoropolymers “ Doping” as used herein refers the process of infusing ,
(PTFE , FEP, PFA , CTFE , ECTFE , ETFE ), ionomers, mixing , or otherwise adding a metal derivative to a polymer,
acrylic/PVC alloy, liquid crystal polymer (LCP), polyacetal 40 which aids in changing the physical and chemical properties
(POM or Acetal), polyacrylates (acrylic ), polyacrylonitrile of the overall mixture .
(PAN or acrylonitrile ), polyamide (PA or Nylon ), poly - “ Antimicrobial” refers to the microbicidal or microbi
amide- imide (PAI), polyaryletherketone (PAEK or Ketone ), static properties of a compound , composition , formulation ,
polybutadiene (PBD ), polybutylene (PB ), polybutylene article, or material that enables it to kill, destroy , inactivate ,
terephthalate (PBT), polycaprolactone ( PCL ), polychlorotri- 45 or neutralize a microorganism ; or to prevent or reduce the
fluoroethylene (PCTFE ), polyethylene terephthalate (PET), growth , ability to survive, or propagation of a microorgan
polycyclohexylene dimethylene terephthalate (PCT), poly ism .
carbonate (PC ),polyhydroxyalkanoates (PHAS), polyketone “ Article ” refers to a solid which may be rigid or flexible.
( PK ), polyester, polyethylene (PE ), polyetheretherketone In the context of the present invention , an article having a
(PEEK ), polyetherketoneketone (PEKK ), polyetherimide 50 surface with durable antimicrobial activity is either capable
(PEI), polyethersulfone (PES ), polyethylenechlorinates of being coated with doped polymer or is comprised of such
(PEC ), polyimide (PI), polylactic acid (PLA ), polymethyl- a doped polymer .
pentene (PMP), polyphenylene oxide (PPO ), polyphenylene “ Surface” refers to the common outside surface of the
sulfide (PPS ), polyphthalamide (PPA ), polypropylene ( PP ), article including any coating thereon .
polystyrene (PS ), polysulfone (PSU ), polytrimethylene 55 “ Durable” means that the antimicrobial activity of an
terephthalate (PTT ), polyurethane (PU ), polyvinyl acetate article remains after the article is treated . is washed or
(PVA ), polyvinyl chloride (PVC ), polyvinylidene chloride laundered one or more times, or that the antimicrobial
(PVDC ); styrene- acrylonitrile (SAN ) , silicone polymers , activity persists for a significant portion of the expected
thermoplastics , thermosets , elastomers ; and copolymers, useful lifetime of the treated substrate under normal use
blends, and mixtures thereof. 60 conditions.
Preferably the polymer is selected from the group of “Metal Derivative ” means an ion , salt, complex , hydrated
polyurethanes, polyacrylates, and polyvinyl acetate. The ion, an ionic complex , a complex of an ion with hydrogen
doped polymer may be a mixture that further comprises a peroxide , a metal hydroxide species, a metal oxide species ,
hydrophilic acrylic polymer. or a metal peroxide species , or mixtures thereof, derived
The regenerable antimicrobial coating may be a UV - 65 from one or more metallic elements for use in the invention .
curable coating, water -borne coating, or solvent -borne coat-
Preferred for use in this invention are metal derivatives of
ing. zinc , magnesium , or zirconium . For the purposes of this
 US 9 ,999,226 B2
10
invention , the alkali metals (lithium , sodium , potassium , “ green ” HP technology would help to overcome the public 's
rubidium , cesium , and francium ) are not included in the perception of antimicrobials as “ toxic chemicals ” .
definition of “metal” ; however, those elements also may be Another embodiment of this invention is a method to
present in the formulations described herein . fabricate polymeric coatings or polymeric objects or articles
5 which contain zinc oxide particles capable of binding and
DETAILED DESCRIPTION sequestering hydrogen peroxide in order to impart durable
antimicrobial properties to the coatings, objects or articles
This invention relates to regenerable antimicrobial coat - even after the HP -based cleaning solution has dried or
ings with durable antimicrobial efficacy for use in medical evaporated . The method comprises the steps of incorporat
applications including implants . medical instruments or 10 ing candidate particles into a model coating system , and then
devices, and hospital equipment. The same coatings have evaluating the antimicrobial efficacy of the coating after
exposure to hydrogen peroxide. One may vary relevant
broad utility in the consumer, industrial , and institutional parameters
markets for example for the preparation of floor waxes and loading , andsuch as particle composition and size , particle
paints having regenerable antimicrobial activity. The coating 15 optimize antimicrobialcomposition
polymer
performance
will be varied in order to
. Polymer composition
technology is based on sequestration of hydrogen peroxide may be varied by adjusting parameters such as hydrophilic
(HP) by binders based on metal derivatives such as zinc ity , crosslink density, or water -absorbing capacity .
oxide incorporated into the coatings . Coatings could be The “ self -sterilizing ” surfaces resulting from the above
applied to key “ frequent touch ” areas where microbial outlined method would be broadly applicable in a wide
contamination occurs particularly those areas that can ( or 20 range of places and applications , and widespread use would
need to ) be periodically cleaned . This includes, for example, contribute significantly to the reduction of contaminated
countertops, bathroom fixtures, doorknobs, railings , and surfaces. The spread of disease and infection could be
appliances. Materials to be coated would include , for significantly reduced , leading to better health for all seg
example , metal, plastic, fiberglass, porcelain , and stone . ments of the population , as well as a significant reduction in
These coated surfaces would be cleaned regularly with a 25 healthcare costs .
cleaner containing HP. With each cleaning, the antimicrobial Potentially useful zinc oxide particles and nanoparticles
properties of the coated surfaces would be regenerated . The are available from commercial suppliers . The zinc oxide
same polymers used for coatings can also be fabricated into particles vary not only in size , but also in shape , and
polymer articles or device with durable antimicrobial activ - crystallinity . Many are available in dry or suspended form .
ity , such as by casting , molding, extrusion , etc . 30 There are many different forms of ZnO that may be useful
In accordance with the invention , zinc oxide particulates for the invention .
or fillers may be incorporated into coatings as binders for HP For example , the zinc oxide particlesmay be incorporated
for use in applications where durable and regenerable anti- into either one or both of two model coating systems, a
microbial protection is needed . Exposure of coated surfaces UV -curable 100 % -solids acrylate coating system , or alter
to HP solutions, or commercially -available HP- containing 35 natively , a water -borne , UV -curable polyurethane ( PU ) dis
cleaning products can cause binding of HP to the zinc oxide persion system . These coatings may be in the form of inks ,
particles ; allowing HP to be sequestered within the coating paint, varnish , clear - coats , or similar materials , and could be
after the surface has dried . This imparts a durable and applied during manufacture of a device , or sold as post
long - lasting antimicrobial effect to the surface sufficient to treatments . Appropriate methods for evenly dispersing par
reduce or eliminate the proliferation and spread of patho - 40 ticulates into these coatings systems include processes such
genic organisms in -between cleaning cycles. Additionally , as simple mixing, media milling , high pressure homogeni
the antimicrobial effect is regenerated each time the surface zation , and the use of ultrasonics .
is cleaned with an HP -containing solution . Test coatings may be fabricated on Mylar sheets or other
An embodiment of the invention is a novel polymer substrates which are easily handled for testing. A coating on
coating which sequesters HP into a coated surface, keeping 45 thin transparent Mylar (polyester ) film is convenient for
it there in active form even after the applied HP solution or testing because it allows for easy cutting and testing of the
cleaning product has long since dried or evaporated . This coated material. Mixtures of zinc oxide particles and coating
allows the surface to maintain long - lasting antimicrobial formulations found to have acceptable dispersion properties
effects between cleanings. Data is presented herein to dem - can readily be fabricated into coatings having approximately
onstrate that these coated and HP -exposed surfaces can kill 505 to 20 microns in thickness .
greater than 99 . 9999 % ofmicrobes which contact the sur - Since ZnO is known to exhibit some level of antimicro
face , even weeks after the HP exposure . bial activity on its own , it is helpful to evaluate baseline
The polymer coatings bind hydrogen peroxide (HP ), even antimicrobial performance of coatings prior to HP exposure .
after the surface has dried, thus maintaining sanitized sur- The comparative antimicrobial performance of the as-pro
faces and preventing microbial growth and the spread of 55 duced coatings can be evaluated using two standard ASTM
disease . Although the coatings were developed with medical antimicrobial performance methods (Agar Slurry and Shake
and hospital applications in mind, the potential for use in Flask methods ) using both Gram + and Gram - organisms
other areas are enormous, with broad utility in the consumer , (such as Staph . aureus and E . coli). The comparative testing
industrial, and institutional markets . Examples of places of the coating after exposure to commercially -available
where such coatings would have particularly helpful impact 60 HP -based cleaning products , or after prolonged exposure to
include bathroom fixtures in public restrooms; kitchen higher concentrations of HP, provides a measure of the
equipment and tables in restaurants , schools and other enhanced antimicrobial efficacy of the HP treated coatings .
institutions; home appliances ; or seats, armrests , railings, Combinations of particles and coatings can be character
and tray tables for airlines and other public transportation . ized by instrumental methods to determine the surface
Such coatings could be easily implemented into existing 65 properties of the coatings . Coating characteristics (such as
manufacturing processes, retrofitted to existing equipment, hydrophobicity and degree of crosslinking ) can also be
or even sold as paints for DIY use . Widespread use of safe modified to enhance antimicrobial performance .
 US 9 , 999, 226 B2
12
The general concept of this invention is to incorporate coating formulation is designated as SS1. For the purpose of
active metal oxide particulates such as zinc oxide into our study the 100 % solids UV curable coating solution was
coatings for substrates such as medical devices such as doped with the required amount of ZnO using a commer
implants, medical instruments or devices, and hospital cially available pre - dispersed Nano ZnO in a monomer such
equipment, or for manufacture of such articles from the 5 as TRPGDA .
polymers described herein . Examples of such substrates and Coatings from water -borne dispersions can be used
devices include , for example : bed rails ; table tops; bedpans ; advantageously for the design of a regenerable antimicrobial
i. v . stands; lamp handles ; blood pressure cuffs , dental equip - coating because of the variety of dispersions available , as
ment; surgical instruments ; orthopedic devices, hot/cold well as ease of incorporation of metal oxide particles in the
packs , wheelchair cushions , Additionally , the invention is 10 final coating . Water -borne dispersions have a superior envi
applicable for use on other common surfaces such as door - ronmental edge since there is very little VOC . Other advan
knobs, bathroom fixtures , food preparation surfaces, and tages include : control of surface characteristics such as
equipment touch - screensnot just in hospitals , but also for hydrophobic /hydrophilic balance ; scratch and abrasion
institutional use (schools, prisons, restaurants , etc .), as well resistant coating upon crosslinking ; ease of incorporation of
as in common household applications. Coatings can be 15 inorganic oxides , high productivity ; adhesion to wide vari
applied at the time of manufacture of specific articles, ety of substrates; low or no shrinkage upon cure .
devices, or surfaces . Alternatively , the required coatings can There are many types of commercially -available water
be applied at the point of use (much like paint, varnish , or borne dispersions that can be used advantageously in a
floor wax ). regenerable antimicrobial coating application . UV - curable
The general concept of a regenerable ZnO binder for 20 acrylic dispersions or UV -curable polyurethane dispersions
hydrogen peroxide locked into a polymer matrix can be are particularly effective as matrixes for ZnO particulates .
widely applicable to almost any kind of existing coating These types of systems show dry , non -tacky films before UV
system . Examples include 100 % solidsUV curable coatings, cure, and develop solvent-resistant and tough coatings after
water -borne dispersions, solvent-borne coatings, extrusion UV cure .
coatings , and powder coatings . The invention is also appli - 25 Another type of water-borne dispersion that can be used
cable for use with all types of composites , or thermoplastics, advantageously is a self -cros slinking acrylic or polyure
and in virtually anymolded , extruded , or melt blown type of thane dispersion (designated ee ). The EE dispersions start
application , such as thermoplastic polyurethanes, rubber , the oxidative crosslinking process immediately upon
and silicone . removal of water . Using heat accelerates the process but
Regenerable antimicrobial coatings comprising 100 % sol- 30 room temperature crosslinking would proceed over a period
ids UV radiation curable coatings readily incorporate metal of time and form tough , solvent-resistant coatings . The Nano
oxide particles using well known and studied milling pro - ZnO dispersions can be incorporated quite easily in the EE
cesses. Additionally, the UV curable coatings allow greater systems. Alternately , micro ZnO powders can also be dis
flexibility in terms of targeting specific physical property persed in using various techniques described above.
attributes required for such a coating [ Idacavage, Mike J; 35 A third type of polyurethane dispersion used are " physi
" Introduction to the Basics of UV /EB Chemistry and For- cally
day
drying” thermoplastic polyurethanes . The physically
mulations” , SUNY ESF, Institute for Sustainable Materials drying polyurethanes are fairly high MW polyurethane
and Manufacturing Webinar, Es stech , Inc . (2012 )]. Someof particles dispersed in water and form excellent films upon
those attributes are : control of surface characteristics such as water removal. They attain their final property immediately
hydrophobic/hydrophilic balance, scratch and abrasion 40 upon drying . Similar to the UV curable and EE systems
resistance ; speed of cure ; weatherability ; flexibility ; ease of above the ZnO dispersions can be easily incorporated in the
incorporation of inorganic oxides ; high productivity ; envi- physically drying PD systems as well. The physically drying
ronmentally -friendly, low volatile organic compounds PDU can be further crosslinked if desired using a “ 2K ”
(VOC ) emission ; and adhesion to wide variety of substrates . system adding an external crosslinking compound right
UV curable coatings also have some shortcomings or areas 45 before coating, although that might lead to shelf life issues .
of improvements to be taken into account, including: sig . A typical water -borne acrylic baseline coating formula
nificant shrinkage upon cure leading to unacceptable adhe - tion comprises water, a co -solvent such as isopropyl alcohol
sion to some non -porous low surface energy substrates ; line or a glycol ether, a binder, and a self - crosslinking linking
of sight process which requires other strategies for dark cure acrylic dispersion . The acrylic dispersion is a polymerized
of 3 - dimensional parts ; thick coatings, opaque coatings, and 50 system that has self-crosslinking or UV curable groups.
highly pigmented coatings are difficult to cure . Upon water removal the dispersion would coalesce and form
A variety of 100 % solids UV - curable coating formula non - tacky film . Over time the properties improve for the
tions are particularly useful as coating matrixes for the Zno self-crosslinking. Upon UV curing , the properties improve
particulates. The coating formulations will typically com for the UV curable acrylic . The formulation may further
prise a blend of several acrylic monomers as well as curing 55 comprise additives such as defoamers, photoinitiators, ther
agents , stabilizers, and other additives. Properties such as mal stabilizers, anti -oxidants , and surfactants. All of the
hardness , surface texture , hydrophobicity , and permeability components may be combined in different ratios to effect
can be modified by adjusting the ratios of key components . different surface properties.
Typical components of the UV -curable coating include a A typical water-borne polyurethane baseline coating for
binder such as an inert polyester resin ; an acrylate oligomer 60 mulation comprises water, a co - solvent such as isopropyl
such as polyethylene glycol diacrylate ; a urethane oligomer alcohol or a glycol ether ; a binder, a UV -curable polyure
such as an aliphatic urethane hexaacrylate oligomer; a thane dispersion . The polyurethane dispersion is a high
crosslinking agent such as tris (2 -hydroxy ethyl) isocyanu11 molecular weight polyurethane in a stable dispersion that
rate triacrylate and/or hexane diol diacrylate . Typical addi- has self -crosslinking or UV curable groups. Upon water
tives include a defoamer, a thermal stabilizer, a non -block - 65 removal the dispersion would coalesce and form non -tacky
ing slip additive , a photoinitiator, and a near -UV film . Over time the properties improve for the self-cross
photoinitiator. In the example below , an acrylic UV -curable linking . Upon UV curing, the properties improve for the UV
 US 9 ,999,226 B2
13 14
curable polyurethane. The formulation may further comprise Pre-dispersed metal oxide nano - dispersions are commer
additives such as defoamers, photoinitiators , thermal stabi- cially available, including NanoArc? ZnO nanoparticles
lizers , anti-oxidants , and surfactants . All of the components from Nanophase Technologies, available as concentrated
may be combined in different ratios to effect different (30 wt % ) dispersions in low viscosity acrylate monomers
surface properties. 5 such as TPGDA (tripropyleneglycol diacrylate ) and
A third type ofbinder system shown as an example herein HDODA (1,6 -hexanediol diacrylate ). These can be directly
is solvent-borne coatings. Coatings based on a solid , ther- incorporated into the 100 % solids UV -curable coating sys
moplastic, ultrahigh molecular homopolymer polyvinylac tem . Pre -dispersed ZnO nano- dispersions in water are avail
etate resins gave clear, flexible films with good gloss and able in the market. These include Nano Arc® Zinc Oxide
resistant to oil and grease . Structure of ultrahigh molecular 10 nanoparticles from Nanophase Technologies, available as
homopolymer polyvinylacetate resins (called Vinnapas concentrated (50 wt % ) dispersions water. These pre - dis
UW4 FS ) is as shown in Formula 1. persed metal oxide nano -dispersions in water can be easily
incorporated , pH permitting , in most water- borne disper
sions described above. A variety of other pre -made aqueous
Formula 1 and non -aqueous dispersions, such as those modified with
silane coupling agents, or with various dispersing agents, are
also commercially available . Predispersed solvent-based
Nano ZO was available in methoxypropylacetate called
20 Nanobyk 3841.
CH3 CH3 – CH3 CH3 It is also an embodiment of the invention to incorporate
ZH directly into the coatings. HP is more reactive with zinc
hydroxide (ZH ) than with ZnO . However , zinc hydroxide is
The resin was dissolved in MEK at 30 % solids to give difficult to isolate in dry form since it converts to ZnO as
high viscosity liquid . It was further modified with a surface 25 water is taken away. Yet, ZH aqueous suspensions effec
active wetting agent (Byk3440 ). This stock solution was tively can be added to the water-borne coating system . The
XR -NSF - SB -F1 (SB -F1 for short ). SB -F1 was then doped process is as follows. ZH is synthesized by neutralization of
with a solvent-based Nano ZO in methoxypropylacetate . zinc chloride /nitrate with sodium hydroxide , and used after
However , for the purpose of the present invention we will washing to remove the salt by - products . As described above
exemplify water-borne UV -curable acrylics, UV -curable ble 3030 (U . S . Pat. No . 2 ,563,442), zinc oxide can be partially
polyurethane dispersions (PUD ). These types of systems hydrolyzed to produce a “ softer ” and more reactive surface .
show dry, non -tacky films before UV cure, and develop For instance, treatment of ZnO particles with sulfuric acid
solvent-resistant and tough coatings after UV cure. Two should produce a particle surface with higher reactivity
baseline coating systems (designated as WBF1 and WBF2 towards HP. For this purpose a larger ZnO powder (micron
were used as a matrix for the ZnO particulates. These BF2 )) 35 size range ) is used in order to facilitate handling and prevent
contain the acrylic or PU resins as well as co - solvents, and
complete dissolution of the particle . After washing with
water, these surface -modified ZnO particles can be com
other additives , which can be combined in different ratios to b ined with the water -borne coating system .
effect different surface properties. Polymerizable metal acrylates such as zinc acrylate
Coatings for both types of systems (UV -curable and 40 (available from Sartomer ) can be used as part of the formu
water -borne) can be applied to transparent Mylar film sub - lation to introduce metal ions into the coating system . These
strates for initial testing . Suitable coating thickness can can then be further reacted with hydrogen peroxide as
range from 10 to 25 microns . These two classes of base before . In fact, it is known that HP forms complexes with
coatings are merely representative of coatings, thermoplas zinc acetate ( similar in structure to zinc acrylate ) to give
tics , and polymer composites in general. These two classes 45 antimicrobial properties after drying (U . S . Pat. No . 4 , 172 ,
of coatings can be used for a variety of real -world coating 841). Metal acrylates; however, also create hydrophobic
applications . Furthermore , the invention should be transfer coatings , which may affect its efficacy .
able to many other commercially important coating and Another embodiment of the invention is to utilize ZnO as
fabrication systems. the inorganic binder for HP. It is known that other metal
Zinc oxide is commercially produced by oxidation of zinc 50 oxides (such as Zr, Mg, and Ti) can also form complexes
vapor in air. The zinc precursor may be zinc metal (direct with HP . Particulates comprising oxides of these other
process ), or zinc ores ( indirect process ). Zinc oxides with metals can be identified , screened for sequestration of HP,
special properties (such as nanoparticles ) have been made by and evaluated for antimicrobial efficacy .
chemical methods using zinc hydroxide intermediates ( see As described above , potentially useful ZnO particles can
for instance Rosenthal-Toib 2008 , wherein a zinc peroxide 55 be incorporated into coating systems such as UV 100 %
intermediate was used ). Because of the higher surface area solids, or water-borne PU /Acrylic , or other solvent -borne
of nanoparticles compared to micron -sized Zno , it is coatings systems. Depending on the type of particle , a given
expected that nanoparticles will provide higher antimicro - particle may be useful in either one or both systems. For
bial efficacy due to the increased area for reaction with HP. instance , premade dispersions in aqueous systems, labora
Many ZnO nanoparticle variations are available commer - 60 tory - synthesized ZH , or acid -modified ZnO particles or
cially . For example , the 2011 - 13 Alfa - Aesar catalog lists polymerizable acrylate monomers are typically components
approximately 30 different Zno particulate products. A in the water- borne system . Zinc acrylate monomers, or
selection of potentially useful ZnO particulates can be dispersions of ZnO in polymerizable acrylates are more
chosen based on structure , chemical properties, morphology , suited for the non aqueous UV -curable 100 % solids system .
and form . Someof these products are conveniently available 65 Similarly, the solvent-borne ZnO systems could be utilized
in forms that lend themselves to direct incorporation into for both the solvent-borne coatings as well as the 100 %
either of the two types of selected coating bases . solids UV coatings. Uniform homogenous incorporation and
 US 9 ,999,226 B2
15 16
thorough dispersion can be achieved with relatively simple using the relatively low HP concentration in a commercial
mixing , as from an overhead mixer . product ( such as Lysol 0 . 9 % HP active), it is also an
Many nano-based inorganic oxides can be incorporated embodiment to expose samples to higher concentrations of
into the water-borne dispersions solutions using high speed , HP and compare results . A typical testing protocol is to
high intensity mixing . In such instances a high shear homog - 5 expose samples of coatings to 10 % and 3 % HP solutions
enizer is desirable for this purpose . As much as 40 - 50 % of ( optionally , with surfactant to enhance wetting of surface ,
the oxides can be uniformly incorporated using these tech - and to mimic the effect of detergent in the commercial
niques , and stay suspended for a definite period of time; cleaning products ). The samples are immersed in HP solu
however, re -mixing may be required after a certain shelf life tions for from 5 to 60 minutes then removed and allowed to
period . Inorganic particulates can also be suitably dispersed 10 air dry .
using various dispersive aids. Milling or grinding ofmetal Coating/ particulate combination ( s ) showing the potential
oxides , organic and inorganic pigments and other solids for sequestering antimicrobial HP can be selected for further
have been routinely accomplished using various types of optimization . Characterization of the selected coating will
milling processes. Those include amongst others media (or provide information which may be valuable for learning
ball) milling , basket milling and 2 -Roll or 3 -Roll milling . 15 how to modify the coatings in a positive manner. The
Milling or grinding of metal oxides results in solutions coatings may be analyzed using optical microscopy, SEM ,
which have significantly longer shelf life since the metal and FTIR will show the distribution and orientation of ZnO
oxides are dispersed almost to the molecular state in the on the coating surface . Monitoring of dyne levels (hydro
binder or solvents. phobicity ) of the oxide doped coatings can be used to gage
In most cases the size of the metal oxide nanoparticles 20 the efficacy of HP incorporation . It is expected that a higher
allows UV - and visibly -transparent coatings , even for rela - surface of exposed ZnO will allow for more reaction with
tively high loadings . Thus, UV curing is as efficientwith the HP and thus higher efficacy. Back - scatter and EDX analysis
added metal oxides having particle size lower than the can also show more precisely the availability of ZnO on the
wavelength of light. In fact, even for highly pigmented surface ( as opposed to just the topography seen with SEM ) .
systems UV curing is efficient with the proper choice and 25 Light abrasion of the surface may cause ZnO particles that
range of photoinitiators . For initial screening, a particle are “ buried " under the coating polymer to become surface
loading of approximately 15 -20 weight percent in the final active and enhance efficacy . This effect can be investigated
coatings is preferred. Since the particles are relatively denser by checking for enhanced antimicrobial activity after
than the bulk coating , this represents a smaller volume repeated rubbing with a slightly abrasive applicator ( such as
fraction . 30 Scotch -Brite pad ) containing HP cleaning solution .
The coating/particle combinations can be prepared and Other ways the coatings or polymer articles or objects can
evaluated for homogeneity , uniformity, and stability by be enhanced include adding a higher level of particulates , or
making test coatings . Adjustments to formulations (such as by altering coating hardness , crosslinking, or hydrophobic
adding more crosslinking agent or UV initiator, or adjusting ity. Since the hydrogen peroxide needs to react with the
coating conditions ) can be made in order to ensure that 35 metal oxide in the cured coating the hydrophilic /hydropho
fully -cured , uniform and reproducible coatings are pro - bic balance may be critical. This can be suitably targeted by
duced. the choice of monomers or oligomers which are polar,
Test coatings can be prepared on clear, thin , flexible hydrophilic and even water soluble . Several oligomers based
Mylar sheets which are easily cut for testing. In general, on polyethylene glycol are used in UV curable systems to
coatings containing dispersed Zno particulate can be 40 create an anti - fog coating .
applied using a Byk coating bar or a Meyer rod to produce These function very well as a hydrophilic surface to allow
coatings in the 10 - 20 micron size range. 100 % solids coat- efficient absorption of hydrogen peroxide into the body of
ings can be UV cured in a conveyer lamp oven , water-borne the coating and to react with the high surface area nano
coatings can be air -dried prior to final UV crosslinking and metal oxides. The dyne level of the coating can thus be
the self crosslinking and physically drying systems can be 45 adjusted to target the hydrophilic /hydrophobic balance .
cured by simply removing the water and / or solvent. Samples Besides the hydrophilic/hydrophobic balance , the coating
of each coating system without any ZnO incorporated can be roughness can also play a key role . Many additives are
used as negative controls in efficacy testing . available such as flattening agents which impart matte
In order to provide a baseline for visualizing any enhance character to the UV cured coating. Other additives such as
ment of antimicrobial properties due to subsequent exposure 50 micronized polypropylene waxes provide a unique textur
to HP, it is necessary to first determine the baseline antimi- izing effect to the coating increasing the likelihood of
crobialproperties of the coatings. Two standard methods can efficacy of reaction between hydrogen peroxide and the
be used , and initial testing can be against both a Gram - metal oxide dopant.
organism and a Gram + organism . The 0 % Zno baseline The amount of HP sequestered onto the surface of coat
coatings are used as negative controls for comparison of 55 ings is measured directly by using known titration tech
measured bacterial reduction . A desirable target for antimi- niques . These methods involve titration of fluids in contact
crobial efficacy is a 3 to 6 -log reduction in viable bacteria with the coated surface using thiosulfate or permanganate, or
compared to an untreated control surface (i. e . a coating by a colorimetric " spot -test" using similar reagents . For
containing no ZnO , or a coating containing ZnO , but not example , a droplet of reagent containing permanganate or
exposed to HP ), after the coating has been exposed to a HP 60 iron ions is applied to a surface of the current invention after
solution or commercial cleaning product containing HP, it has been exposed to HP. A color change will occur based
tested at least 24 hours after the end of said exposure (i.e . a on the presence or sequestered HP.
durable antimicrobial activity ). Additional antimicrobial characterization can be per
The coatings can be exposed to HP solutions prior to formed utilizing test methods described herein , and can
retesting for antimicrobial activity using the same two 65 include a wide range of pathogenic bacteria, including
methods as described above . Although one embodiment of resistant strains such as MRSA and VRE . Other organisms
the invention is to show that coatings can be made active that could be tested include Enterococcus faecium , Escheri
 US 9 ,999,226 B2
17 18
chia coli, Pseudomonas aeruginosa , and Klebsiella pneu - different extents, it is convenient to use the actualmeasured
monia . A time- kill study using E . coli and S . aureus can also absorbance of the polymer to characterize these effects .
be performed to determine the rate of induction of the In general, a polymer which absorbs between 0 . 5 % and
antimicrobial effect. In addition , testing against selected 20 % ( w / w ) water will be useful in the practice of this
fungal organisms (such as Candida albicans and Aspergillus 5 invention , as this allows for penetration of HP, but does not
niger ) can be carried out using appropriate methods ( such as cause extensive swelling or degradation of the polymer. A
ASTM G21). preferred range is between 2 % and 10 % (w / w ) absorption of
In addition , the anti-viral efficacy of coated surfaces water. A method such as ASTM D570 may be used to
exposed to HP - based cleaning solutions can be measured determine water absorbance of the base polymer, or the
against selected types of viruses using appropriate methods . 1 polymer with metal derivative dispersed therein .
Preliminary life -cycle (extended use ) testing of coatings Many different polymers are useful in the practice of this
can be done by evaluating basic antimicrobial efficacy of invention . The following is a partial list of polymers that can
coatings subjected to repeated cleaning cycles (i.e . 25x and be used : Polyacrylonitrile , acrylonitrile butadiene styrene
50x with a scrubbing pad ). Observations on the physical 16 (ABS ) polymer, Acrylic ( PMMA ), Celluloid , Cellulose
appearance and integrity of the coatings can be made . acetate, Ethylene - Vinyl Acetate (EVA ), Ethylene vinyl alco
Many different polymers may be used in the practice of hol (EVOH ), Fluoropolymers (PTFE , FEP, PFA , CTFE ,
this invention ; however , it is necessary for the dispersed ECTFE , ETFE ), Ionomers , acrylic /PVC alloy, Liquid Crys
metal derivative to come into contact with the peroxide in tal Polymer (LCP ), Polyacetal (POM or Acetal), Polyacry
order for a complex of the metal derivative and peroxide to 20 lates ( Acrylic ), Polyacrylonitrile (PAN or Acrylonitrile),
form , thus sequestering the peroxide in the polymer so that Polyamide (PA or Nylon ), Polyamide -imide (PAI), Polyary
it may be released later to provide antimicrobial effect. One letherketone (PAEK or Ketone), Polybutadiene (PBD ),
skilled in the art will realize that the contact between metal Polybutylene (PB ), Polybutylene terephthalate (PBT ), Poly
derivative and peroxide will be maximized by using a higher caprolactone (PCL ), Polychlorotrifluoroethylene (PCTFE ),
concentration of peroxide and /or a longer contact time. The 25 Polyethylene terephthalate (PET) , Polycyclohexylene dim
contact between metal derivative and peroxide will also ethylene terephthalate (PCT), Polycarbonate (PC ), Polyhy
increase as the amount of metal derivative dispersed in the droxyalkanoates (PHAS), Polyketone (PK ), Polyester, Poly
polymer increases , and particularly as the amount of the ethylene (PE ), Polycarbonate (PC ), Polyetheretherketone
metal derivative particles exposed or near the surface of the (PEEK ), Polyetherketoneketone (PEKK ), Polyetherimide
polymer increases. In order for particles ofmetal derivative 30 (PEI), Polyethersulfone ( PES ), Polyethylenechlorinates
covered by polymer (I.e. those particles below the surface ) (PEC ), Polyimide (PI), Polylactic acid ( PLA ), Polymethyl
to come in contact with the peroxide, the peroxide must be pentene (PMP ), Polyphenylene oxide (PPO ), Polyphenylene
able to penetrate (diffuse ) into the polymer matrix . One sulfide (PPS ), Polyphthalamide (PPA ), Polypropylene (PP),
factor that controls the penetration of peroxide into the Polystyrene (PS ), Polysulfone (PSU ), Polytrimethylene
polymer matrix includes hydrophilic character, since HP is 35 terephthalate (PTT), Polyurethane (PU ), Polyvinyl acetate
a polar molecule like water. Another factor that controls the (PVA ), Polyvinyl chloride (PVC ), Polyvinylidene chloride
penetration of peroxide into the polymer matrix is crosslink (PVDC ); Styrene -acrylonitrile (SAN ), Silicone polymers,
density . Polymers with a lower crosslink density will allow Thermoplastics, Thermosets , and Elastomers ; as well as
better penetration of HP solution . These same factors will copolymers, blends, and mixtures of the above -listed poly
also allow release ofsequestered HP later when it is needed 40 mers .
for antimicrobial effect by allowing water back into the In light of the general disclosure provided herein above ,
polymer matrix in a reversible manner so that peroxide can with respect to the manner of practicing this inventive
be unsequestered and diffuse to the polymer surface in a method , those skilled in the art will appreciate that this
controlled manner. disclosure enables the practice of the inventive method as
However, extremely high hydrophilic character or low 45 defined in the attached claims. However, the following
crosslinking (either alone or in combination ) is undesirable , experimental details are provided to ensure a complete
as it could lead to a high absorption of water, and extensive written description of this invention , including the best
swelling (or even dissolution of ) the polymer and loss of mode thereof. However, it will be appreciated that the scope
desirable polymer properties such as hardness or structural of this invention should not be construed in terms of the
integrity . Thus , a balance of properties is required . Hydro - 50 specific examples provided . Rather, the scope of this inven
philic character can be increased by adding hydrophilic tion is to be apprehended with reference to the claims
agents or wetting agents, which may be either polymeric appended hereto , in light of the complete description of this
agents or low molecular weight agents. For example , the inventive method constituted by this entire disclosure .
water-borne formulations described in the examples herein
demonstrate the enhanced efficacy manifested by adding 55 EXAMPLES
hydrophilic polymers to a formulation . This can be seen by
comparing samples WB F1 and WBF2 to WBF3 and WBF4 The following examples are representative of the inven
at a constant ( 20 % ) ZnO content — the antimicrobial activity tion and exemplify experiments using a commercially -avail
of WBF3 and WBF4 is much higher due to increased able ZnO powder.
hydrophilic character from adding a hydrophilic modifier 60
(see for example data in Table 7 vs. Table 19). The amount Example 1. Preparation of Antimicrobial Zno
of hydrophilic agent needed will vary based on the exact Powder
chemical structure of a particular polymer system . The
overall effect of the incorporation of hydrophilic agent, or Commercially available ZnO powder was mixed with
degree of crosslinking , on absorption of water (or peroxide 65 water to make a 1 % aqueous dispersion and was treated with
solution ) will be the percentage of water absorbed by the 3 % hydrogen peroxide solution . The mixture was stirred for
polymer. Since these factors affect different polymers to 15 minutes and then dried to obtain the treated ZnO powder.
 US 9 , 999, 226 B2
19 20
The treated dried ZnO powder was found to have an zinc hydroxide mixture can be displaced using HDODA
antimicrobial effect which was approximately 2 -logs greater ( 1,6 -hexanediol diacrylate ) monomer. This could not be
than dried ZnO powder which had not been exposed to HP. done directly because water and HDODA are notmiscible.
The ethanol serves as an intermediate .
5
Example 2 . Preparation of 100 % Solids UV Stock
Solution Example 5 . Preparation and Use of Nano -ZnO in
100 % -Solids UV -Cured Coating Compositions
The 100 % solids UV stock solution , acrylic UV -curable
coating formulation designated as SS1, was mixed for 15 10 UVTwo different stock solutions were prepared XR -NSF
minutes until it is homogenous. The stock solution in the designed and
- F1
to
XR -NSF -UV- F2. Both stock solutions are
be hydrophilic due to the addition of a hydro
proper portion is then mixed with a dispersive aid and small philic (water soluble ) oligomer at 30 -40 % .
particle size ( in the nano range ) Zinc Oxide using a high
speed mixer to obtain a slurry comprising about 20 % ZnO .
The slurry is then incorporated into either a 2 -roll mill or XR -NSF -UV - F1 Formulation
media milling machine to grind the oxide particles until no Component Function Weight %
particles are seen in the Hegman grind gage. Alternately , the
milled solution may be dissolved in a solvent and particle Genomer 6083/HD Inert resin (polyurethane) in monomer. 50 .0
size analysis carried out. The above milled 100 % solids 20 Main binder for the coating.
Hydrophilic Oligomer
MIRAMER M280 41. 3
solutions are rod coated onto polyester substrates. The Tego Foamex N Defoamer 1.0
coated substrate are sent into an in -line UV curable unit at G16 stabilizer Oxidative Stabilizer 0 .5
20 ft./min using a 300 WPI power setting . If the surface is MP1200 Wax Detack 1. 1
slightly tacky the UV curing can be repeated (20 fpm /300 Esacure ONE Photoinitiator 3 .6
??? Photoinitiator 1. 2
wpi) to obtain a completely dry and non -tacky surface . A 25 Byk Silclean 3710 Surface Active Agent 1.2
similar control can also be coated and cured using just the
SS1 stock solution without Zno . Comparative antimicrobial Total 100 .0
studies can be then carried out on the control sample (w /o
ZnO ), an untreated sample (with ZnO ), and a sample (with
ZnO ) treated with hydrogen peroxide solution . 30
XR -NSF-UV- F2 Formulation
Example 3 . Preparation of Water -Borne UV Component Function Weight %
Curable Polyurethane Dispersion (PUD ) Genomer 6083 /HD Inert resin (polyurethane ) in monomer. 30 .0
35 Main binder for the coating.
The UV curable PDU stock solution designated as WBS1 Genomer 4690 Aliphatic urethane hexaacrylate 30 . 0
Higher Crosslinking
is mixed for 15 minutes until it is homogenous . The above MIRAMER M280 Hydrophilic Oligomer 31. 2
WBS1 stock solution in the proper portion is then mixed Tego Foamex N Defoamer 1 .0
0.5
with a pre -milled ZnO solution in water using a high speed G16 stabilizer Oxidative Stabilizer
MP1200 Wax Detack 1. 0
mixer to obtain a final solution having about 10 % nano ZnO 40 CPK Photoinitiator 5 .0
based on dry weight of the coating. The above UV PUD Byk Silclean 3710 Surface Active Agent 1 .2
solution doped with nano ZnO is rod coated onto polyester Total 100 .00
substrates . The coated substrate is dried at 110° C . for 2 -5
minutes until it is completely dry to touch . The dried coated
substrate is then sent into an in -line UV curable unit at 20 The respective Zinc Peroxide (ZP ), Zinc Hydroxide (ZH ),
ft./min using a 300 WPIpower setting to completely cure the and Zinc Oxide (ZO ) solutions (in 1 ,6 - hexanediol diacrylate
coating. A similar PDU control can be coated , dried , and (HDODA ) or tripropylene glycol diacrylate ( TRPGDA ))
cured using just the WBS1 stock solution without the nano were then added into the stock solutions targeting either
Zno . Comparative antimicrobial studies can be then carried so 10 % , 15 % or 20 % pigment loadings as shown in the Table
out on the control sample (wlo nano Zno ), an untreated 1 below (PHR added is amount of pigment solutions based
sample (with nano Zno ), and a sample (with nano Zno ) on 100 grams of stock solution to get the % loadings
treated with Hydrogen Peroxide solution . desired ). The ZH could only be added at 10 % due to the
lower concentration (18 .5 % ).
Example 4 . Preparation of Zinc Hydroxide in 55 TABLE 1
Ethanol
100 % Solids UV Curable Coating Compositions

The reaction product of a mixture of zinc chloride and Pigment

For
zinc nitrate with sodium hydroxide was dispersed in addi- 60 Coating
Stock PHR 20 g
Solution Zn Solution Loading % Pigment added stock
tional water and allowed to undergo several cycles of
settling and decanting. This process removes the salt (NaC1 UV -F1 UV- F1
and NaNO3) by - products present in the binder. A portion of UV - F2 UV - F2
this washed ZH aqueous suspension was saved for use in F1 - 15ZP UV - F1 30 % ZP
HDODA
15
15 30
30 100 20.0
experiments . Using another portion , the water was then 65 F2- 15ZP UV - F2 30 % ZP 15 30 100 20 .0
replaced with ethanol for several cycles in order to achieve HDODA
zinc hydroxide in dry ethanol. The ethanol of the resulting
 US 9, 999,226 B2
21 22
TABLE 1 -continued solution and allowed to dry for at least 72 hours at room
100 % Solids UV Curable Coating Compositions
temperature . The samples were tested for antimicrobial
efficacy against Staph. aureus using ASTM E2180 “ agar
For slurry ” method , with an overnight exposure time. This same
Stock Pigment PHR 20 g 5 method is used in all of the following examples. All samples
Coating Solution Zn Solution Loading % Pigment added stock showed a “ full kill ” of SA (5 .49 log reduction ), as indicated
F1 - 10ZH UV- F1 18.5 % ZH 10
10 18. 5 117 .6 23 . 5 in Table 2 below , in comparison to an untreated Mylar film
HDODA not exposed to HP. Note that the term “ Overnight” in the
F2 - 10ZH UV - F2 18 . 5 % ZH 5
18.5 117 . 6 23 . 5 antimicrobial results refers to the difference in bacterial
HDODA
F1 -2020 UV-F1 30TRPDA
% ZO 20 3 0 200 40.0 10 population between the sample and a negative control
sample inoculated with the same bacterial load after both
F2 - 20ZO UV - F2 30 % ZO 20 3 0 200 40 .0 have been incubated overnight. The term “ t= 0 ” refers to the
TRPDA difference between the bacterial population on the sample
F1 - 15ZO UV - F1 30 % ZO
TRPDA
?
30 100 20.0 after overnight incubation vs . the initial amount of inocula
F2 - 1520 UV - F2 30 % ZO ? Z 20.0 15 tition , as measured on a negative control sample at t= 0 .Unless
TRPDA otherwise noted , all average log reductions are the average
* ZO is NanoArc ® ZN - 2660 of three sample replicates .
For most of the above coatings two different rod sizes Rod TABLE 2
# 8 ( 8R ) and Rod # 16 ( 16R ) were used in order to see the 20 Antimicrobial Efficacy Against Staph . aureus
effect of coating thickness on sequestration ability . The
theoretical coating weight (CW ) would be around 18. 3 g/m² Avg Log Avg Log
for 8R and around 36 .6 g /m2 for 16R . This is very approxi Reduction Reduction
mate and would probably be 25 -50 % lower due to low Sample versus SA HP Exposure Overnight t=0
viscosities of all solutions. Assuming the density of the 25 081213
–
coating to be 1 .0 g/ cc , the coating thickness would be 1 ( F1 stock; Sample 5 , F1- 10ZH
loaded with
Exposure to 5.49* = 0 .00 5 .24 * = 0. 00
10 % HP
micron for CW of 1 g/m². However, since the density of the 10 % ZH )
coating is > > 1 .0 g / cc due to the pigment loading , the 081213; Sample 6 , F2- 10ZH Exposure to 5 .49* + 0 .00 5. 24 * $ 0 .00
conversion would be further affected to the low end of the 10 % HP
081213 7 , F1- 20ZO Exposure to 5 .49 * + 0 .00 5 . 24 * + 0 .00
coating thickness. Thus, we estimate the coating thickness to 30 (F1 stock loaded with 20 % 10 % HP
be around 10 - 15 microns for the 8R and 25 - 30 microns for nano -ZO )
16R . 081213 ; Sample 8 , F2- 20ZO Exposure to 5 .49 * + 0 .00 5 . 24 * + 0 .00
Observations from the UV Curable Coatings: 10 % HP
All coatings were done on a polyester substrate from SKC 081213; Sample 9, F1-1520 Exposure to 5 .49 * 0 .00 5.24 * = 0. 00
10 % HP
Films called SH41 35 081213; Sample 10, F2 -15ZO Exposure to 5 .49 * = 0 . 00 5. 24 * + 0.00
As expected the F2 formulation had higher crosslink 10 % HP
density than F1 as seen from the “ shrinkage ” upon cure Sample 1, -UV- F1 Control Exposure to 5 .49 * + 0 .00 5 . 24 * + 0 .00
leading to the polyester film curling up 10 % HP
Sample 2 , UV -F2 Control Exposure to 5 .49 * 0.00 5.24 * 0.00
All coatings were structured . This might be a function 10 % HP
either of the particle size or inadequate milling of the 40 Uncoated Mylar sheet, Exposure to 5 .49 * + 0 . 00 5 . 24 * + 0 . 00
additive with the UV solution . Milling results in Sample 11 10 % HP
molecular interaction between the nanoparticle and the Untreated Mylar sheet,
Sample 11
No HP
exposure
No kill No kill

UV resin
Not surprisingly , the ZP and ZH were particularly struc
tured since they had higher particle size . The ZO with 45 The samples ofExample 5 were then tested against E . coli
particle size around 20 - 40 NM was found to be less (EC ). Control samples and uncoated Mylar showed essen
structured tially no kill, as expected . Samples containing ZH and ZO
Even the structured coatings show good scratch resistance showed full-kill (6 .67 log -reduction ) of EC . Results are
and adhesion to the PET substrate shown in Table 3 below .
The structure may not necessarily be bad since it will have 50
higher ability to absorb HP on the surface due to TABLE 3
“ micro -roughness ” Antimicrobial Efficacy Against E . coli
The dosage used for UV curing of most coatings was
around 0 .9 J/Cm² (see exception below ) by using 2 Avg Log Avg Log
passes at 30 fpm at 300 WPI power 55
Sample versus EC
Reduction
HP Exposure Overnight
Reduction
t=0
The Zinc Oxide coating was very difficult to cure , espe
cially the 20 % loading at 0 .9 J/Cm². We had to use 5x 081213 ; Sample 5 , F1- 10ZH Exposure to 6 .67 * 1 0 .00 5. 18 * 1 0 .00
the dosage (~ 5 J/Cm -) to get decent cure . This was not ( F1 stock loaded with 10 % 10 % HP
surprising since ZnO are known UV attenuators and in ZH )
fact are used as weathering additives to prevent damage 60 081213; Sample 6 , F2- 1OZH Exposure to 6 .67 * = 0.00 5.18 * + 0 . 00
10 % HP
from sunlight ( see below ) 081213; Sample 7, F1- 2020 Exposure to 6 .67 * = 0 .00 5 .18 * 1 0.00
(F1 stock loaded with 20 % 10 % HP
Example 6 . Antimicrobial Activity of Samples of nano-ZO )
081213; Sample 8 , F2- 2020 Exposure to 6 .67* + 0 .00 5. 18 * = 0 .00
Example 5 10 % HP
65 081213 ; Sample 9, F1-1520 Exposure to 6.67* + 0.00 5. 18 * + 0. 00
The samples of Example 5 were exposed to 10 % aqueous 10 % HP
HP for one hour, then shaken to remove excess droplets of
 US 9, 999,226 B2
24
TABLE 3 -continued -continued
Antimicrobial Efficacy Against E . coli XR -NSF -WB- F1 UV Curable PUD Formulation
5
Avg Log
Avg Log Component Function Weight %
Reduction
Reduction
Sample versus EC HP Exposure Overnight t= 0 Irganox ® 1520 Photoinitiator 0 .32
Dynol 607 Surface Active Agent 0 .21
081213; Sample 10 , F2 - 1520 Exposure to 6 .67* 0 .00 5 .18 * = 0 .00 10
10 % HP Total 100 .0
Sample 1, Control (0 % Zno ) Exposure to 0 .33 - 1. 17
10 % HP
Sample 2, UV-F2 Control Exposure to 0 .26 - 1.24 15- WB -F1 was then doped with Nanobyk 3840 to get 10 %
10 % HP
and 20 % ZO loadings respectively as shown in Table 4 . The
(0 % ZnO ) coatings were coated on polyester substrates as summarized
below .
20
Example 7 . Preparation of Water-Borne Coatings (b ) Water -Borne Self-Crosslinking Polyurethane Dispersion
and Solvent-Borne Coatings Containing Nano - ZnO (EE PUD ): Water-borne EE PUD from Alberdingk called U
915 is a self -crosslinking polycarbonate /polyester polyure
Two different approaches were used forwater-borne coat- oc thane dispersion . U915 was modified with only a surfactant
ings. since it already has a coalescing solvent. This stock solution
( a ) Water- Borne UV Curable Polyurethane Dispersion (UV was XR -NSF -WB -F2 (WB -F2 for short ).
PUD ): Water-borne UV PUD from Allnex called Ucecoat
7689 was suitably modified with water-based photoinitia
tors, anti -oxidants and surface active agents (surfactants ). A 30 XR -NSF -WB -F2 Self -Crosslinking Formulation
co - solvent (IPA ) was also used in small quantities to help
coatability . This stock solution was XR -NSF -WB -F1 (WB Component Function Weight %
F1 for short).
35
35 IPA Co - solvent 3 .00
Alberdingk U915 Water -borne SXL PUD 96 . 80
XR -NSF -WB -F1 UV Curable PUD Formulation 34 % in water

Component Function Weight % Dynol 607 Surface Active Agent 0 . 21

40
IPA Co -solvent 3 .00 Total 100 . 0

UCECOAT 7689 Water-borne UV Curable PUD 89 .70

35 % in water WB -F2 was then doped with the water -borne Nano ZO
M380 Hydrophilic Oligomer 5 .00 45 (Nanobyk 3840 ) to get 10 % and 20 % ZO loadings respec
GENOCURE * LBC Oxidative Stabilizer 1 .73 tively as shown in Table 4. The coatings were coated on
polyester substrates as summarized below .

TABLE 4
Water -Borne Coating Compositions

Stock Amount PHR CW , 8R

Coating Solution Nano Zn Solution binder solids % NV added For 20 g % Solids Wet 18 .3 gsm
WB-F1 WB -F1
WB - F2 WB -F2
WBF1- 20ZO WB- F1 40 % water 10 40
40 9.7
9.7 1.9
1. 9 3838..7777 77..1010
WBF2- 2OZO WB - F2 40 % water 20 4040 1919..33 33.. 99 38 .87
38 .87 77 ..1111
WBF1 -10ZO WB -Fi 40 % water 10 40 8.33
40 11..77 33..6565
33 66 .. 1616
WBF2- 10ZO WB -F2 40 % water 20 4040 1616..66 33 ..33 34 .. 1010
34 66 .. 2424
 US 9,999,226 B2
26
Two different formulatory approaches were used for sol after drying the water off and assumed most of its
vent-borne coatings. physical property after drying due to self -crosslinking.
( c ) Solvent-borne Coatings Based on Thermoplastic Poly However, the final physical property is only assumed
vinylacetate (VINNAPAS® UW 4 FS ): High MW Polyvinyl after some unknown period due to continued self
acetate (VINNAPAS from Wacker ) has been used as coat- 5 crosslinking.
ings and adhesives. Coatings based on Polyvinylacetate The solvent borne systems are physically drying after
resins give clear, flexible films with good gloss and are solvent removal (2 mins at 180 C ) and assumes its final
resistant to oil and grease . VINNAPAS® UW 4 FS is a solid , physical property immediately due to its high MW
thermoplastic , ultrahigh molecular homopolymer. nature .
The resin was dissolved in MEK at 30 % solids to give 10 The coatings made with nano -ZnO were substantially
high viscosity liquid . It was further modified with a surface transparent, or clear to slightly hazy .
active wetting agent (Byk3440). This stock solution was
XR -NSF -SB - F1 (SB -F1 for short ). SB -F1 was then doped Example 8 . Antimicrobial Activity of Samples of
with the solvent-based ZO Nanobyk 3841 to get 10 % and Example 7
20 % ZO loadings respectively as shown in Table 5 . 15
(d ) Solvent- borne Coatings Based on Polyvinylacetate -Cro The water -borne coating systems (samples designated
tonic Acid Copolymer (VINNAPAS® C 305 ): Polyvinylac - with prefix “ W ” ) and solvent -borne coatings systems
etate -Crotonic Acid Copolymer (VINNAPAS C305 from (samples designated with prefix S ) of Example 7 were tested
Wacker) has been used as coatings and adhesives . VINNA - for antimicrobial activity using ASTM E2180 “ agar slurry ”
PAS® C 305 is a physically drying, thermoplastic binder. 20 method . In particular samples WB - F2 , WBF1 - 20ZO ,
The COOH groups in C305 could potentially give hydro WBF1- 1020 , SBF1- 2020 , and SBF1- 102O from Example
philic coatings . 7 as well as samples UV - F2 , F2 - 10ZH , F2 - 15ZO , and a
The resin was dissolved in MEK at 40 % solids to give blank Mylar film 7 were used for the present study. The
high viscosity liquid . It was further modified with a surface selected samples were exposed to 3 % HP for one hour, and
active wetting agent (Byk3440 ). This stock solution was 25 then tested for antimicrobial efficacy against EC after drying
XR -NSF - SB -F2 (SB -F2 for short). SB -F2 was then doped for at least 24 hours . Samples UV- F2 , F2 - 10ZH , F2 - 1520 ,
with the solvent-based ZO Nanobyk 3841 to get 10 % and WBF1 - 20ZO , and a blank Mylar film were also tested
20 % ZO loadings respectively as shown in Table 5 . All the without exposure to HP. The results are shown in Table 6 . All
doped solutions based on C305 gelled . Most likely the Zno samples NOT exposed to HP showed essentially zero anti
formed a complex with the Crotonic acid and created 30 microbial efficacyway..
crosslinked networks. Thus, no coatings were made with The data confirm that ZnO , even nano - ZnO has very little
SB -F2 solutions. inherent value as a solid antimicrobial surface , despite the

TABLE 5
Solvent-Borne Coating Compositions
Amount/ CW , 8R
Stock Nano Zn binder % Nano - % Resin Wet
Coating Solution Solution solids particle Solution PHR added For 20 g % Solids 18.3 gsm
SB -F1

SBF1- 10ZO SB - F1 40 % *
*

10 40 30 7 .5 1. 5 30..70
30 55 ..62
SBF1 - 2020 SB - F1 40 % *
*

20 30 31. 30 5 .73
SBF2- 10ZO SB - F2 40 % *
*

10 40 40 .00 7 .32
20ZO SB - F2
SBF2 -2020 40 % * 20 40 40
40 20 4 40. 00 7.32
* All NanoZinc solutions were 40 % NB3841 in methoxypropylacetate.

For most of the above coatings we used only one rod size efficacy seen when these particles are dispersed or sus
Rod # 8 (8R ), although 20R was also looked at for couple of pended in liquid form . Interestingly , the uncoated Mylar film
coatings. The theoretical wet CW would be around 18 .3 continues to show minor antimicrobial efficacy (~ 2-log
g /m² for 8R . The theoretical dry CWs are then calculated 55 reduction ) after exposure to 3 % HP for one hour ; however,
based on % solids and given in the respective Tables above . subsequent experiments revealed that this is not always
General observations for the water-borne and solvent - reproducible . Note that the samples were not rinsed prior to
borne coatings of Example 7 were as described below . drying . None of the water -borne (WB) samples showed any
All coatings were made on a PET substrate from SKC antimicrobial efficacy after exposure to 3 % HP. For the
Films called SH41. solvent based (SB ) samples, moderate efficacy (~ 4 -log) was
Compared to the UV -cured coatings of Example 5 the found for the higher ( 20 % ZnO ) loading, but no efficacy was
water -borne and solvent- borne systems were signifi
cantly more uniform in appearance and texture . observed at the lower (10 % ZnO ) loading. This sample may
The UV PDU formulations (WB - F1) are “ physically dry ” show efficacy if higher HP concentrations or longer expo
after drying the water off. However, the final physical 65 sure times were used . For the 100 % - solids UV system , no
property was only assumed after UV curing . The EE efficacy was found for 10 % ZH , but great efficacy (full kill
PUD formulations (WB- F2) were also “ physically dry ” of 6 .6 logs) was found with 15 % ZnO .
 US 9 ,999 ,226 B2
27 28
TABLE 6
Antimicrobial Activity of Water- Borne Compositions Agains EC
Log Reduction Log reduction
Sample versus EC HP Exposure Overnight t=0
082613; Sample 2 , UV -F2 Control After exposure to 3 % HP 0 . 37 0 . 15 - 1. 11 + 0 .15
082613 ; Sample 2u, UV -F2 Control No HP exposure 0 .08 + 0 .06 - 1 . 41 + 0 . 06
082613; Sample 6 , F2- 10ZH After exposure to 3 % HP 0.06 + 0 .41 - 1.43 0 .41
082613; Sample bu , F2- 10ZH No HP exposure - 0 . 18 0 . 36 - 1.67 + 0 .36
082613 ; Sample 10 , F2 - 1520 After exposure to 3 % HP 6 .63 * + 0 . 00 5 . 14 * + 0 .00
082613; Sample 10u , F2 -1520 No HP exposure - 0 . 19 0 . 15 - 1.67 + 0 .15
082613; Sample 11 , Blank Mylar Control After exposure to 3 % HP 2.02 + 0 .66 0 .53 = 0 . 66
082613; Sample 11u , Blank Mylar Control No HP exposure - 0 .20 + 0 . 17 - 1.69 + 0 . 17
082613 ; Sample W3, WBF1-20ZO After exposure to 3 % HP 0 .07 + 0 .01 - 1 .42 + 0 .01
082613 ; Sample W3u, WBF1- 2020 No HP exposure 0 . 11 + 0 . 06 - 1. 38 0 .06
082613; Sample W2, WBF2 Control After exposure to 3 % HP - 0 .06 + 0 . 10 + 0 . 10 - 1.54
082613 ; Sample W5 , WBF1 - 10ZO After exposure to 3 % HP - 0 .06 + 0 .16 + 0 . 16 - 1 .54
082613 ; Sample S8, SBF1- 2020 After exposure to 3 % HP 3 .92 + 2 .41 2 .43 = 2.41
082613; Sample S9, SBF1- 10ZO After exposure to 3 % HP 0 . 10 = 0 . 10 - 1.39 = 0. 10
* " full kill”
20
Further testing was done on selected samples. The 100 %
solids samples # 5 , 7 , 8 , 9 , 10 , and 11 (Mylar control); the
water -borne W3, W4, and W4a (W4 abraded with sandpa
per); and solvent-based sample S8 were exposed to 3 % HP
for one hour, like before , and tested against EC . These
results are shown in Table 7 below .
TABLE 7
Antimicrobial Activity of Selected Samples Against EC
Average Log Average Log
Reduction Reduction
Sample versus EC HP Exposure Overnight t=0
083013; Sample 5 , F1- 10ZH 1 hr. exposure to 3 % HP 0 .13 + 0 .05 - 1 .49 0 .05
083013; Sample 7 , F1- 2020 1 hr. exposure to 3 % HP 6 . 78 * = 0 .00 5 .16 * = 0 .00
083013; Sample 8 , F2- 20ZO 1 hr. exposure to 3 % HP 6 .78 * I 0 .00 5 .16 * I 0 .00
083013 ; Sample 9 , F1- 1520 1 hr. exposure to 3 % HP 6 . 78 * = 0 .00 5 .16 * = 0 .00
083013 ; Sample 10 , F2- 1520 1 hr. exposure to 3 % HP 6 .78 * = 0 .00 5 . 16 * = 0 . 00
nk
082613; Sample 11, Blank 1 hr. exposure to 3 % HP - 0 . 11 + 0.03 - 1.73 + 0 .03
Mylar Control
083013; Sample S8, SBF1- 20ZO 1 hr. exposure to 3 % HP 6 .78 * = 0 .00 5 .16 * = 0 .00
083013 ; Sample WBF1- 2020 1 hr. exposure to 3 % HP 0 .42 0 .46 - 1 . 20 + 0 .46
083013 ; Sample WB-F2 - 2020 1 hr. exposure to 3 % HP 0 .01 + 0 . 14 - 1 .61 + 0 . 14
083013; Sample WB -F2- 20ZO ; 1 hr. exposure to 3 % HP - 0 .04 + 0 .06 - 1 .66 0 .06
with abrasion

45
The water-borne (WB) samples of this example showed
essentially zero efficacy . It will be seen in later examples that XR- NSF -WB -F3 Self Crosslinking Formulation /Hydrophilic
increasing the hydrophilic character of WB coatings will Co -Dispersion
increase efficacy. The solvent-borne sample SBF1- 20ZO
again showed high efficacy. All the 100 % - solidsUV samples 50 Component Function Weight %
( 15 and 20 % ZO ) showed great efficacy. Uncoated Mylar
exposed to HP did not show any efficacy . IPA Co- solvent 0 .99
Alberdingk U915 Water-borne SXL PUD 76 . 97
55 34 % in water
AC2570 Hydrophilic Acrylic 21.87
Example 9. Water-Borne Coatings with Increased Co - dispersion
Hydrophilic Character Dynol 607 Surface Active Agent 0 . 17

The water-borne self-crosslinking polyurethane disper- 60 Total 100 . 0

sion based on Alberdingk U915 (as in Example 7b ) was
modified by adding 25 % (by weight solids) of a hydrophilic
acrylic binder dispersion Alberdingk AC2570 (Stock For The WB -F3 was then doped , separately , with 20 % ZO and
mulation XR -NSF -WB -F3). The two dispersions were com - 65 30 % ZO using Nanobyk 3840 ZO dispersion from Byk
pletely compatible and gave a clear " control” coating (0 % Chemie . The formulation scheme was as shown in Table 8
ZnO ) . below .
 US 9, 999,226 B2
29 30
TABLE 8 (b ) Solvent-borne Coatings Based on Low Molecular
WBF3 -ZO Formulations.
Weight Thermoplastic Polyvinylacetate (VINNAPAS®
B60): The resin was dissolved in methylethylketone at 20 %
Amount
Based PHR For Final CW ,
5 solids to give a low viscosity liquid. It was further modified
NanoZinc on Binder to be 30 % 8R Wet: with a surface active wetting agent (Byk3440 ). This stock
Solution Solids % NV added grams Solids 18 .3 gsm solution was XR -NSF -SB - F3D (SB - F3D for short). SB - F3D
NB3840 20 40 17.7 5. 3 36 . 12 6 .61 was then doped with the solvent-based ZO (Nanobyk 3841)
to get 15 % and 20 % ZO loadings respectively as shown
40 % in water
NB3840
40 % in water
30 4040 26 .6 8.0 36 .40 6 .66
below in Table 9. The viscosity of the final solution was
similar to SB - F1D although the % solids was higher due to
the lower molecular weight of the virgin polyvinylacetate .
TABLE 9
Formulations for the Solvent- Borne Systems
% ZO
based
on PHR PHR to CW , 8R
Polyurethane total to be % % Resin be For Final % Wet:
Dispersion NanoZinc Solution solids added Nanoparticle Solution added 15 g Solids 18 .3 g/m
Vinnapas NB3840 40 % in 15 17.65 10 4 .4125 0 .66 11. 27 2.06
UVV4 20 % methoxypropylacetate
XR -NSF - SB
FID
NB3840 40 % in
methoxypropylacetate
20 25 40 10 6.25 0.94 11. 76 2. 15
Vinnapas
UWV4 20 %
NB3840 40 % in
methoxypropylacetate 15 17.65 40 20 8.825 1.32 21.62 3.96
XR
F3D
-NSF -SB - NB3840 40 % in
methoxypropylacetate 20 25 40 20 12.5 1.88 22.224 .07
30

The dispersions were coated on SKC 's SH41 PET (My- Using the above procedure , the following coatings were
lar ) substrate using a # 8 Wire Rod . The dry coating weights made up from the above solvent- borne solutions :
(CW ) were calculated as shown in Table 8 above. Both
2020 and 30ZO gave excellent coatings on the PET sub
strate. The self-crosslinking polyurethane dispersion /acrylic
combination formulation (WB -F3 ) was “ physically dry” 2) SB -F1D -2OZO (SB - F1D stock loaded with 20 % Nano
after drying the water off and continued to develop its Zinc Oxide)
physical property due to self -crosslinking . The following 3 ) SB -F1D - 15ZO ( SB -F1D stock loaded with 15 % Nano
coatings were prepared by this method . 40 Zinc Oxide)
4 ) XR -NSF -SB - F3D (Control — 0 % ZnO )
5 ) SB -F3D - 2OZO (SB - F3D stock loaded with 20 % Nano
1) XR -NSF -WBF3 (Control) Zinc Oxide)
2 ) WBF3- 20ZO (WBF3 stock loaded with 20 % Nano 45 6 ) SB -F3D - 1570 (SB - F3D stock loaded with 15 % Nano
Zinc Oxide ) Zinc Oxide )
3) WBF3 -3OZO (WBF3 stock loaded with 30 % Nano The solutions were coated on SKC 's SH41 PET substrate
Zinc Oxide ) using a # 8 Wire Rod. The dry coating weights were calcu
lated as shown in the Table 9 above . Each solvent-borne
coating solution gave excellent coatings on the PET sub
strate . There were no rod marks visible , and the coatings
Example 10 . Solvent-Borne Coatings Based on were quite uniform . The solvent borne systems were physi
Thermoplastic Polymers cally dry after solvent removal (2 mins at 180 C ) and
55 assumed its final physical property immediately due to its
Two different thermoplastic polymers were studied as high MW nature .
solvent-borne coatings .
(a ) Solvent-borne Coatings Based on High Molecular Example 11. Water -Borne Coatings with Increased
Weight Thermoplastic Polyvinylacetate (VINNAPAS? UW Hydrophilic Character Prepared from a Physically
4 FS ): The resin was dissolved in methylethylketone at 10 % 60 Drying Polyurethane Dispersion
solids to give a low viscosity liquid . It was further modified
with a surface active wetting agent (Byk3440 ) . This stock
solution was XR -NSF -SB -F1D (SB -F1 for short ). SB - F1D This experiment outlines the preparation of water-borne
was then doped with the solvent- based ZO (Nanobyk 3841) coatings that incorporate a physically drying polyurethane
to get 15 % and 20 % ZO loadings respectively as shown 65 dispersion rather than a self-crosslinking dispersion. The
below in Table 9 . The viscosity of the final solution was new formulation was designated XR -NSF -WB -F4 and com
significantly lower than in Example 7 (with 30 % solids). prised 36 % of the hydrophilic acrylic polymer.
 US 9,999 ,226 B2
31 32
solution was XR -NSF -SB -F1D (SB -F1 for short). SB - F1D
XR-NSF -WB-F4 Self Crosslinking Formulation/Higher Hydrophilic was then doped with the solvent-based ZO (Nanobyk 3841)
Co-Dispersion to get 15 % and 20 % ZO loadings respectively as shown
Component Function Weight % below in Table 11 . The viscosity of the final solution was
Alberdingk Water-borne SXL PUD 70.00
· 5 significantly lower than before (with 30 % solids ).
U 915 34 % in water
AC2570 Hydrophilic Acrylic 29 .80
Co - dispersion (b ) Solvent-borne Coatings Based on Low Molecular
Dynol 607 Surface Active Agent 0 . 17
Weight Thermoplastic Polyvinylacetate (VINNAPAS®
Total 100 .0 B60 ): The resin was dissolved in methylethylketone at 20 %
solids to give a low viscosity liquid. It was further modified
Two different loadings of Zo were used — 20 % and 30 % . with a surface active wetting agent (Byk3440 ). This stock
The following samples were coated on SH41 polyester film solution was XR -NSF - SB -F3D (SB - F3D for short). SB -F3D
15
from SKC , Inc using Rod # 16 : was then doped with the solvent-based ZO (Nanobyk 3841)
1) WB-F4 -2020 (XR -NSF -WB -F4 stock loaded with to get 15 % and 20 % ZO loadings respectively as shown
20 % Nano Zinc Oxide ) below in Table 11. The viscosity of the final solution was
2 ) WB-F4 -3OZO (XR -NSF -WB -F4 stock loaded with similar to SB -F1D although the % solids was higher due to
30 % Nano Zinc Oxide ) the lower molecular weight of the virgin polyvinylacetate.
TABLE 11
Formulatory Schemes for the Solvent -Borne Systems

% ZO
based PHR PHR to CW , 16R
Polyurethane on total to be % % Resin be For Final % Wet:
Dispersion NanoZinc Solution solids added Nanoparticle Solution added 15 g Solids 18.3 g/m
Vinnapas
UVV4 20 %
NB3840 40 % in
methoxypropylacetate 20 25 40 10 6.25 0.94 11.76 4. 31
XR -NSF -SB
F1D
Vinnapas NB3840 40 % in 20
20 25 40
40 20
20 12.5
12 11.88 22 .2222
22 8 8 .. 1313
UVV4 20 % methoxypropylacetate
XR -NSF - SB
F3D

The coating weights of each are shown in Table 10 below : Using the above procedure, the following coatings were
made up from the above solvent -borne solutions:
TABLE 10 401 ) SB -F1D - 20ZO (SB -F1D stock loaded with 20 % Nano
Zinc Oxide )
XR - NSF -WB -F3 Zinc Oxide Formulations 2 ) SB -F3D - 20ZO (SB - F3D stock loaded with 20 % Nano
Zinc Oxide )
Amount The solutions were coated on SKC 's SH41 PET substrate
Based PHR For Final CW , 45 using a # 16 Wire Rod . The dry coating weights were
NanoZinc on Binder to be 30 % 8R Wet: calculated as shown in the Table 11 above. Each solvent
Solution Solids % NV added grams Solids 18 .3 gsm
1
borne coating solution gave excellent coatings on the PET
NB3840 20 40 16 .5 5.0 34.07 12.47 substrate . There were no rod marks this time around and the
40 % in water coatings were quite uniform . The solvent borne systems
NB3840 30 40 24.8 74 34.46 12 .61 50 were physically dry after solvent removal (2 mins at 180 C )
40 % in water and assumed its final physical property immediately due to
its high molecular weight nature .
All coatings had excellent physical characteristics. Example 13 . Antimicrobial Activity of UV Curable
55 Coatings of Examples 5 and 7
Example 12 . Preparation of Higher Coating Weight The UV curable coatings of Example 5 ( Table 1) and the
Solvent- Borne Coatings solvent-borne coatings of Example 7 ( Tables 4 and 5 ) were
exposed to hydrogen peroxide and tested against E . coli
Two different thermoplastic polymers were studied as 60ou difficult
(EC ), and S. aureus (SA ). Note that EC is generally a more
to kill organism than SA . Data for these previously
solvent-borne coatings . described coatings is summarized in Tables 12 and 13 below .
(a ) Solvent -borne Coatings Based on High Molecular Although there is some variation in data from the previous
Weight Thermoplastic Polyvinylacetate (VINNAPAS® UW tests, some general trends are apparent. Most samples per
4 FS ): The resin was dissolved in methylethylketone at 10 % 65 formed very well after 10 % HP exposure . At lower concen
solids to give a low viscosity liquid . It was further modified trations (1 % and 3 % ), the solvent-borne coating formula
with a surface active wetting agent (Byk3440 ). This stock tions did particularly well.
 US 9, 999,226 B2
33 34
TABLE 12 TABLE 12 -continued
Antimicrobial Activity of Coatings Against S . aureus Antimicrobial Activity of Coatings Against S . aureus

Average Log Reduction t = 0 5

Average Log Reduction t = 0

HP
Exposure
HP
HP
Exposure
HP HP
Exposure
HP
Exposure
HP
Exposure
HP
Exposure
Sample versus SA 0% 1% 10 % Sample versus SA 0% 1% 10 %
Sample 1 , XR -NSF -UV - F1 5 .24 * + 0 .00 Sample 8, F2- 20ZO 1 .42 + 0 . 16 1.72 ± 0 .30 5 . 24 * = 0. 00
Control 10 Sample 9 , F1-1520 5 .24 * + 0 . 00
Sample 2 , UV-F2 Control 0 .97 0 .08 0 .64 0 . 25 5 .24 * = 0 . 00 Sample 10 , F2- 1520 1 .03 + 0 .05 1.80 + 0 . 00 5 . 24 * + 0 . 00
Sample 3 , F1-15ZP 5 .24 * + 0 .00 Sample 11 , Blank Mylar - 0 . 13 + 0 .01 0 .06 = 0 . 24 5 . 24 * + 0 .00
Sample 4 , F2 - 15ZP 5 . 24 * = 0. 00 Control
Sample 5 , F1- 10ZH 5 . 24 * = 0 .00 Sample S8 , SBF1-2020 0 .64 0 .03 3.91 + 1. 74
Sample 6 , F2- 1OZH 5 .24 * + 0 . 00 Sample S9, SBF1- 10ZO 0 .42 + 0 .01 1 .43 0 . 22
Sample 7, F1- 20ZO 5 .24 * + 0 .00

TABLE 13

Antimicrobial Activity of Coatings Against E . coli

Average Log Reduction t = 0)
HP Exposure HP Exposure HP Exposure HP Exposure
Sample versus EC
ersus EC 0%
0% 11 %% 3%
3% 10 %

Sample 1, XR -NSF -UV -F1 - 1.17

Control

Sample 2 , UV - F2 Control - 1.41 + 0 .06 - 1 . 11 + 0 . 15 - 1 . 24

Sample 3, F1- 15ZP - 1.21 + 0 .06
Sample 4 , F2- 15ZP - 1.11 + 0 .06
Sample 5, F1- 10ZH - 1.49 1 0 .05 5.18 * = 0 .00
Sample 6, F2-10ZH - 1.67 + 0 . 36 - 1 . 43 + 0 .41 5 . 18 * + 0 .00
Sample 7, F1- 2020 - 0.74 + 0.08 5 . 16 * 0.00 5 .18 * = 0.00
Sample 8 , F2- 2020 - 1.11 + 0.02 5. 16 * = 0.00 5.18* = 0.00
Sample 9 , F1- 1520 - 1.23 + 0.13 5 .16 * =
*

0.00 5 .18 * = 0.00

Sample 10 , F2 - 1520 - 1.67 + 0. 15 - 1. 34 + 0 .05 5. 16 * =
*

0.00 , 5 .18* $ 0.00

5 . 14 * = 0 .00

Sample 11 , Blank Mylar - 1.69 + 0 .17 , 0.20 = 2.49 - 1.73 + 0.03 ,

Control - 0 .70 + 1 .26 0 .53 = 0 .66

Sample S8 , SBF1 -20ZO - 1.42 = 0.07 5. 16 * 0 .00 ,

2.43 2.41
Sample S9 , SBF1- 10ZO - 1 .47 + 0 .09 - 1 . 39 + 0 . 10
Sample W2, WBF2 - 1.54 = 0 . 10
Control

Sample W3, WBF1-2ozo - 1.38 0.06 - 120 + 0 .46 ,

- 1.42 0 .01
Sample W4, WB -F2 -20ZO - 1 .61 + 0 . 14
Sample W4a , WB-F2 - 1 .66 + 0 .06
2020 ; abraded

Sample W5, WBF1- 10ZO - 1 .54 + 0 . 16

 US 9 ,999,226 B2
35 36
Example 14 . Further Testing of Solvent-Borne exposure to HP, significant antimicrobial efficacy was appar
Coatings ent. Samples were tested after drying for at least 24 hours
The solvent-borne (SB ) coating formulations were further after HP exposure . See Table 14 for data . Sample S8 was
tested . Sample S8 (SBF1 - 20ZO ) was selected and a time- 5 also exposed to a commercial HP -based cleaning product
study for exposure to 3 % HP was done. Samples were then (Clorox ) containing 1. 4 % HP, but no efficacy was seen after
tested against EC . We found that even after only 3 minutes simple wiping with the product.
TABLE 14
Antimicrobial Activity of Solvent- Borne Coating S8 Against E . coli
Average Log Average Log
Reduction Reduction
Sample versus EC HP Exposure Overnight t= 0
091213 ; Sample 8 , F2- 20ZO ; A 1 min soak in 3 % HP 0 .05 + 0 .03 - 1.35 + 0 .03
091213; Sample 8 , F2- 2020 ; B 5 min soak in 3 % HP 3 .55 + 4 . 48 2 . 15 + 4 . 48
091213 ; Sample 8, F2- 20Z0 ; C 15 min soak in 3 % HP 6 . 72 * = 0 .00 5 .32* $ 0 .00
091213; Sample 8 , F2-2020 ; D 30 min soak in 3 % HP 6 .72 * = 0 .005 .32* $ 0 .00
091113; Ci, Solvent coating, 30 min soak in 3 % HP 0 .06 + 0 .03 - 1 .34 + 0 .03
0 % Zn
091213 ; Sample 8 , F2- 20ZO ; E wiped with 3 % HP - 0 .04 + 0 .05 - 1.34 + 0 .05
paper towel
091213; Sample 8, F2- 2OZO ; F wiped with Lysol - 0 .10 + 0 .13 - 1.44 = 0. 13
cleaner paper towel
091113; C2 , Solvent coating , wiped with Lysol - 0.22 + 0 .12 - 1.61 + 0.12
0 % Zn cleaner paper towel
091113; CO , Solvent coating , No HP exposure 0 .03 + 0 . 04 - 1 . 37 + 0 .04
0 % Zn

Example 15 . Incorporation of ZnO into

30
Commercial Floor Wax Composition
Commercial ZnO powder (micron sized , Aldrich Chemi
cal) was incorporated into an aqueous-based floor wax
composition ( Stampede ) at loadings of 20 % and 50 % (dried
solids basis ). These were tested after exposure to 3 % HP for
35 30 minutes against EC and SA , and allowed to dry at least
24 hours . The 50 % sample, and also previous sample S8
were also exposed to Clorox HP cleaner for 5 minutes, then
wiped and allowed to air dry overnight . All samples showed
excellent efficacy against EC and SA in the standard ASTM
agar slurry test. See Tables 15 and 16 .
TABLE 15
Floor Wax Composition Comprising Coating Compositions
Average Average
Sample versus EC Log Reduction Log Reduction
N = 2 HP Exposure Overnight t=0
091813; Floor wax coating , 0 % ZnO 30 min soak in 3 % HP -0 .03 0.03 - 1.78 0 .03
091813; Floor wax coating , 20 % ZnO 30 min soak in 3 % HP 6.87 * = 0.00 5. 13 * = 0.00
091813 ; Floor wax coating , 50 % ZnO 30 min soak in 3 % HP 6 .87 * = 0.00 5. 13 * = 0 .00
091813 ; Sample 8 , F2- 2020 Clorox HP cleaner 6 . 87 * = 0 .00 5 . 13 * 0 .00
091813; Wax coating , 50 % ZnO Clorox HP cleaner 6 .87 * = 0 .00 5.13 * = 0.00

TABLE 16
Wax Composition Comprising coating Composition Treated with Cleaner
Average Average
Sample versus SA Log Reduction Log Reduction
N = 2 HP Exposure Overnight t=0
091813; Sample 8, F2- 2020 Clorox HP cleaner application 5.71* = 0.00 5 .29 * = 0.00
091813 ; Wax coating, 50 % ZnO Clorox HP cleaner application 5 .71* = 0 .00 5 . 29 * = 0 .00
 US 9 ,999,226 B2
37 38
Example 16 . Addition of Zinc Oxide to Latex vent-borne coating samples were prepared similar to the
Paints previous batch , but were made from more diluted coating
solutions ( Samples SBF1D - 2020 and SBF3D - 3OZO ).
Valspar Bare Wood Primer was selected as a carrier for These were exposed to 3 % HP for 1 hour, and tested against
inclusion of ZnO particles since it was previously tested and 5 EC after drying for one day . Results are presented below in
showed zero inherent antimicrobial activity . Samples were Table 18 , and all the water- borne and solvent- borne coating
prepared with “ high " and " low ” ZnO content (approxi samples showed high efficacy . The exposure of sample 104A
mately 15 and 30 % ZnO solids basis was added — Sample (Example 16 , above ) to 3 % HP was also repeated , and the
# 104A and 104B , respectively ). Commercial ZnO powder
(micron sized , Aldrich Chemical) was used . Samples of 10 same moderate efficacy was observed .
these coatings were exposed to 3 % and 10 % HP for one The HP -exposed samples tested in Table 18 were stored
hour. Results are shown in Table 17 . Both samples exposed for one week , then retested against EC . Results are shown in
to 10 % HP showed high antimicrobial efficacy ; however, a Table 19 . After storage for a week , the WB samples (20 and
control sample (0 % ZnO ) also showed good efficacy after 30 % ) both retained full efficacy . However, the SB samples
exposure to 10 % HP. With 3 % HP, both samples showed 15 lost all efficacy. The 104A sample lost some efficacy ,butwas
slight to moderate efficacy which was higher than that of the not very high to start with . This is the first data to conclu
0 % control. sively show that the efficacy imparted by HP is not perma

TABLE 17
Antimicrobial Activity Against E . coli of Latex Paint coatings exposed to Zinc Oxide
Average Average
Log Reduction Log Reduction
Sample versus EC HP Exposure Overnight t= 0
100313 ; Stay Fresh 104A ZnO ; A3 After exposure to 3% HP 2.17 + 0. 76 0.61 + 0.76

100313; Stay Fresh 104B ZnO ; B3 After exposure to 3 % HP 1.57 + 0. 40 0.01 + 0.40

100313 ; Control; C3 After exposure to 3 % HP 0 . 45 + 0 . 03 - 1 . 11 + 0 .03

100313; Stay Fresh 104A ZnO ; A10 After exposure to 10 % HP 6 .71* 0 . 00 5. 15 * = 0 .00

100313; Stay Fresh 104B ZnO ; B10 After exposure to 10 % HP 6.71 * = 0.00 5.15 * + 0.00

100313; Control; C10 After exposure to 10 % HP 6 .71* = 0 . 005 . 15 * + 0 .00

Example 17 . Coating Compositions Having Higher 60 nent. We had been working under the assumption that the
Hydrophilic Character residual antimicrobial efficacy seen after samples are
exposed to HP was indefinite . We have determined that the
Formulations having even higher hydrophilic character duration of efficacy can range from 24 hours to at least one
than the previously described formulations of Examples 9 week , depending on formulation . In most of the early testing
and 11 were prepared in a similar manner. The water-borne 65 described above we did not carefully monitor the time
coating compositions were made at 20 and 30 % nano -ZnO elapsed between HP - exposure and antimicrobial testing ;
( samples WBF4 -30ZO and WBF4 - 2020 ) . The newer sol- however, in all cases it was at least 24 hours .
 US 9 ,999, 226 B2
39 40
TABLE 18
Antimicrobial Activity of Coating Samples of Example 20

Average Average
Samples dried 24 hours Log Reduction Log Reduction
Sample versus EC HP Exposure Overnight t=0
101513 ; 104A latex paint w / ZnO added Exposure to 3 % HP for 60 min 1.72 0 . 14 - 0 .37 + 0 . 14
101513; W30 = WB F4 - 30ZO Exposure to 3 % HP for 60 min 6 .78* = 0 .00 4 .70* = 0 .00
101513; W20 = WB F4- 2020 Exposure to 3 % HP for 60 min 6 .78* = 0 .00 4 .70 * = 0 .00
101513; S1 = SBF1D - 20ZO Exposure to 3 % HP for 60 min 6 . 78 * = 0 .00 4.70 * = 0.00
101513; S3 = SBF3D - 20ZO Exposure to 3 % HP for 60 min 6 .78 * = 0 .00 4 .70 * + 0 .00

TABLE 19
Antimicrobial Activity of Coating Samples of Example 20 After 1 -Week Storage
Average Average
Stored 1 Week Before Testing Log Reduction Log Reduction
Sample versus EC HP Exposure Overnight t= 0
101513 ; 109 A latex paint w / ZnO added Exposure to 3 % HP for 60 min 1. 24 - 0 .07 - 0 . 46 + 0 .07
101513; W30 = WB F4 - 30ZO Exposure to 3 % HP for 60 min 6 . 93 * = 0 .00 5. 23 * = 0.00
101513; W20 = WB F4 -2020 Exposure to 3 % HP for 60 min 6 .93* = 0 .00 5 .23* = 0 .00
101513 ; S1 = SBF1D - 2OZO Exposure to 3 % HP for 60 min 0 .31 + 0 . 15 - 1. 39 = 0 . 15
101513; S3 = SBF3D - 20ZO Exposure to 3 % HP for 60 min 0 . 18 = 0 .07 - 1.52 + 0 .07

As a result of the time-decay observations observed , we TABLE 20 -continued

repeated antimicrobial testing on several HP - exposed
samples that had previous given good efficacy results . We Antimicrobial Activity of Water-Borne Coatings Against
Various Organisms
found that most of these lost efficacy after being stored for 30 –
periods ranging from 3 weeks to 2 months. It should be Organism Log Reduction (t = 0 )
pointed out that even a 1 -week duration for residual anti MRSA 4 . 93 * + 0 .00
microbial efficacy is significantly better than the ~ 5 -minute KP 5. 19 * 1 0 .00
efficacy after drying offered by non -ZnO surfaces after 35 * indicates full kill
exposure to HP.
In addition , sample WB F4D ( 20 % ZnO ) was tested for
antimicrobial efficacy against other organisms after expo
sure to 10 % HP for one hour, followed by drying for 24 Example 18. Timed Exposure of Water - Borne
hours. The organisms tested included Staph . Aureus (SA ), 40 Coatings to Hydrogen Peroxide
Methacillin -resistant Staph . Aureus (MRSA ), Klebsiella
Pneumonia (KP ), and Enterococcus faecium (EFm ). All Water -borne coating formulations F4 (of Example 17 )
samples exhibited high antimicrobial efficacy ( full kill) were exposed to 3 % HP for either 5 , 15 , or 30 minutes , or
against these organisms, as shown in Table 20 below . treated with Clorox HP spray (1. 4 % HP ) for 5 minutes.
45 Samples were tested against EC after drying for 1 , 3, and 7
TABLE 20 days.Results are shown in Table 21. Efficacy at 1 and 3 days
drying generally increased with increasing HP exposure
Antimicrobial Activity of Water-Borne Coatings Against time. For the 30 % ZnO HP-exposed samples, efficacy
Various Organisms diminished only slightly (if at all) between day 1 and day 3
or Day 7 . The 20 % ZO sample at 15 minute exposure was
Organism also run separately (both exposure and efficacy ) in another
Log Reduction (t = 0 ) series of assays and achieved similar results to the first set
of testing . The 20 % ZnO sample exposed to Clorox HP
EFm 5 .20 * + 0 .00 s cleaner showed very high efficacy after 1 day, butno efficacy
SA 5 . 19 * + 0 .00 after 3 or 7 days dry storage. The 30 % ZnO sample showed
no efficacy after exposure to Clorox cleaner.
TABLE 21
Antimicrobial Activity of Water-Borne Coating after Timed Exposure
Average Average Average
Log Reduction Log Reduction Log Reduction
Sample versus EC HP Exposure 1 day (t = 0 ) 3 days (t = 0 ) 7 days (t = 0 )
WB F4D 20 % ZO 3 % HP for 5 min 1.89 + 0 .27 1. 92 + 0 .22
WB F4D 20 % ZO 3 % HP for 15 min 2. 34 + 0 .082 .06 + 0 .33
 US 9 ,999,226 B2
41
TABLE 21-continued
Antimicrobial Activity of Water-Borne Coating after Timed Exposure
Average Average Average
Log Reduction Log Reduction Log Reduction
Sample versus EC HP Exposure 1 day (t = 0 ) 3 days (t = 0 ) 7 days (t = 0 )
WB F4D 20 % Z0 * * 3 % HP for 15 min 4.07 + 0 .34 2. 12 + 0 .24 1. 27 + 0 .13
WB F4D 20 % ZO 3 % HP for 30 min 4 .65 = 1.042 . 81 0 .49
WB F4D 20 % ZO Clorox HP 5 . 39 * = 0 . 00 - 1.60 = 0 .12
WB F4D 30 % ZO 3 % HP for 5 min 2 .61 0 .071 . 33 + 0 .04 2 .68 0 .07
WB F4D 30 % ZO 3 % HP for 15 min 1.88 + 0 . 25 1. 73 + 0 .05 1 .89 + 0 .54
WB F4D 30 % ZO 3 % HP for 30 min 5 .39 * 0 .00 4 .50 + 1. 13 5. 18 * 0 .00
WB F4D 30 % ZO Clorox HP - 0 .03 + 0 . 16 - 1 .41 + 0 .07
* indicates full kill
* * additional assay performed for this formulation

Example 19 . Effect of pH on Antimicrobial TABLE 23

Activity of Water- Borne Coatings
Antimicrobial Activity of Water-Borne Coatings versus E. coli
2020 -
Samples of WB-F4 were treated with 3 % HP for 15 3 % HP - 15 min Average Average
minutes at various pH conditions, as shown in Table 22 24 hour dry Log Log
below . Within the uncertainty of the measurements , there Incubation Reduction Reduction
were not any obvious large differences between the various Sample versus EC Time Overnight t = 0)
pH conditions after 1 day or 7 days of drying. The high pH 25
HP solution showed some decomposition , as evidenced by WBF3 - 20 ZO 5 min 1.06 = 0. 14 0 .01 0 . 14
gas bubble formation. Note that the pH = 3 .75 is the “ normal” WBF3 - 20 ZO 10 min 0 .95 + 0 .08 - 0 .09 + 0 .08
(uncorrected ) pH of the HP solution . Addition of 5 % ethanol WBF3-20 ZO 30 min 0 .99 0 .04 - 0 .05 = 0 .04
did not improve efficacy. The general loss of efficacy WBF3 - 20 zo 1 hr - 0 . 19 0 .03 - 1 .23 + 0 .03
WBF3 - 20 ZO 2 hr 0 .90 + 0 .06 - 0 . 14 + 0 .06
between 1 and 7 days for all samples is similar in magnitude 30 WBF3 - 20 ZO 4 hr 1 . 10 + 0 .03 0 .05 + 0 .03
to that described above. 111213 ; WBF3 - 20 ZO Overnight 3.42 4 .79 1.76 £ 4 .79
TABLE 22
Antimicrobial Activity of Water-Borne Coating at Various pH 35
35
TABLE 24
Average Average Antimicrobial Activity of Water-Borne Coatings versus methicillin
Log Log resistant Staph . Aureus (MRSA ).
Reduction Reduction
3 % HP - 30 min
1 day 7 days 40 24 hour dry Average Average
Sample versus EC HP Exposure (t = 0 ) (t = 0 ) Incubation Log Log
Sample versus MRSA Time Reduction Reduction
WBF4 - 30 % ZO ; pH 3.75 3 % HP for 15 min 4 .73 + 0 .71 2 .03 - 1.02 WBF3- 20 ZO 5 min 0 . 17 + 0 .03 0 .02 + 0 .03
WBF4 - 30 % ZO ; pH 1 .65 3 % HP for 15 min 5 .23 * = 0 .00 0 .66 = 0 .92 WBF3 - 20 ZO 10 min 0 .16 + 0 .02 0 .00 + 0 .02
WBF4 -30 % ZO ;, pH 8.85 3 % HP for 15 min 3.93 + 0 .00 1.18 0 .51 45 WBF3- 20 ZO 30 min 0 . 30 0 .02 0 . 14 + 0 .02
WBF4 - 30 % ZO ; 3 % HP for 15 min 3 . 50 + 0 . 17 1 .98 + 0 . 12 WBF3 - 20 ZO 1 hr 0 .53 + 0 . 21 0 . 38 0 .21
WBF3 - 20 ZO 2 hr 0 . 87 + 0 . 14 0 .72 = 0 . 14
pH 3 .75 + 5 % EtOH WBF3- 20 ZO 4 hr 2.81 + 0 .05 2.66 + 0.05
WBF3- 20 ZO Overnight 5.46 * $ 0 .00 4 .97 * $ 0 .00
* indicates full kill
* indicates full kill
50
Example 20 . Additional Studies with Water -Borne Overnight efficacy was excellent against MRSA , and
Coatings of Example 9 good against EC . Significant efficacy is exhibited against
MRSA after 4 hours .
WB F3 samples were made at 20 % nano - ZnO content. Example 21. Antimicrobial Activity of Example 9
Samples were exposed to 3 % HP for 30 minutes , and tested
after 24 hours of drying. Time-kill profile : Note that all of Water-Borne Coatings Activated with Peridox
the testing described in prior examples above has utilized an
overnight ( 18 - 24 hour) bacterial contact (incubation ) time. A sample of Peridox RTUTM , a commercial hydrogen
That is , samples are inoculated with bacteria and the residual peroxide -based cleaner , was obtained from the manufacturer
viable bacteria are enumerated after 18 -24 hours of exposure (BioMed Protect ). The Peridox cleaner contains 4 .4 % HP
to the antimicrobial surface. We performed a time-kill study and 0. 23 % peroxyacetic acid as the active ingredients .
by looking at various contact times ranging from 5 minutes Samples of WB F3 of Example 9 coating were exposed to
to overnight. Data was collected for EC and also for MRSA 65 Peridox for various time periods. Significant efficacy was
(methicillin -resistant Staph . aureus ). This data is presented observed for the 15 minute exposure (see Table 25). See also
in the Tables 23 and 24 , below . data in Table 26 of the next example .
 US 9 ,999,226 B2
43 44
TABLE 25 Example 23. Commercial Floor Wax Compositions
Antimicrobial Activity of Water- Borne Coatings versus E . coli
Samples based on a commercial acrylic floor-wax product
Average Average (STAMPEDE ) containing 10 % and 20 % of nano - ZnO were
Dried 24 hours Log Reduction Log Reduction 5 prepared and tested after exposure to 3 % HP for 15 minute .
Sample versus EC HP Exposure Overnight t = 0 Zero efficacy against EC was found . In a previous report we
WB F3 20ZO ; 2 min Peridox - 0 . 25 + 0 . 00 - 1 .77 + 0 .00 showed that 20 % of micron -sized ZnO in a similar coating
WB F3 2020 ; 5 min Peridox - 0 .21 0 .03 - 1 .74 + 0 .03 based on STAMPEDE showed good antimicrobial efficacy ;
WB F3 2020 ; 15 min Peridox 3.25 + 4 .87 1.73 + 4 .87 however, this was after 30 minutes ( rather than 15 minutes )
10
exposure to 3 % HP. This indicates that larger (micron ) sized
ZnO particles may give higher antimicrobial efficacy than
Example 22 . Antimicrobial Activity of Water -Borne nano ZnO particles when incorporated into coatings, fol
Coatings Containing Micron -Sized Zinc Oxide lowed by exposure to HP. However , the coatings made from
micron -sized ZnO do not have the optical transparency
Water -Borne Coating samples, similar to the WB - F3 and exhibited by those made with nano ZnO .
WB - F4 formulations of Examples 11 and 13 , were prepared
using similar polymer formulations. However, micron sized Example 24 . Treatment of Textiles
ZnO (commercially available from Aldrich ) was used
instead of nano- ZnO used previously. Two formulations 20 A coatings formulation chosen from those described in the
were made using the procedures of Examples 11 and 13 . above examples is used to treat a textile article , which may
Sample 1120A was made using 21 g Alberdingk U915 , 15 g comprise cotton , rayon , polyester , nylon , acrylic or other
H2O , and 2 .6 g ZnO (Dry ), which was then homogenized , material. The treatmentmay consist of wetting said textile
followed by addition of 10 g Alberdingk AC2570 and with the coating formulation by spraying, dipping, padding
mixing by hand . Sample 1120B was made using 41 21. g ,25 or other means , followed by removal of excess coating
Alberdingk U915 , 10 g H20 , and 2 .6 g ZnO (Dry ), which liquid by means familiar to one skilled in the art , followed
was then homogenized , followed by addition of 15 g Alberd
ingk AC2570 and mixing by hand . In addition , a control maydrying
by of the treated article. Said coating formulation
sample (0 % ZnO ) was made. All were coated onto Mylar textilebe. The diluted with solvent or water prior to treating the
dried textile will have ZnO particles immobi
sheets . As shown Table 26 below , the samples with micron 20
ZnO showed excellent efficacy after being exposed to 3 % 30 lized on or in the textile . The ZnO particles can be activated
HP for 1 hour, or 10 % HP for various times, or Peridox or to become antimicrobial by exposure to HP solution , such as
Clorox HP cleaner for 5 minutes, followed by 24 hours during laundering .
drying .
35
Example 25. Inclusion of HP into Coating
TABLE 26 Formulation
Antimicrobial Activity of Water-Borne Coatings Comprising Hydrogen Peroxide may be added to any coating formu
Micron - sized Zinc Oxide versus E . coli
lation described in the above examples , particularly the
Average Average 40 aqueous- based systems. In this manner, the dried coatings
Dried 24 hours Log Log will have antimicrobial efficacy even before subsequent
After HP Reduction Reduction
exposure of the dried surface to HP solution . A preferred
Sample versus EC exposure Overnight t = 0
amount of HP is at least 1 % by weight of the dried coating.
1120A , 20 % ZnO 1 hr, 3 % HP
1120B , 20 % ZnO 1 hr, 3 % HP
6 .70 * + 0 . 00
6 .70 * $ 0 .00
5 . 17 * + 0 .00
5 . 17 * + 0 .00
Having generally described this invention , those skilled in
1120C , Control 1 hr, 3 % HP 051010 101 + 010 45 the art will appreciate that the present invention contem
1120B , 20 % ZnO 5 min , 10 % HP 6 .83 * + / - 0 .00 5 .02 * + / - 0 .00 plates the embodiments of this invention as defined in the
1120B , 20 % ZnO 10 min , 5 % HP 6 .83 * +/ - 0 .00 5 .02* + / - 0 .00 following claims, and equivalents thereof. However, those
1120B , 20 % ZnO 1 hr, 10 % HP 6 .83 * + / - 0 .00 5 .02 * + / - 0 .00
1120B , 20 % ZnO 5 min , Clorox 3 . 73 + / - 0 .21 1.92 + / - 0 .00 skilled in the art will appreciate that the scope of this
HP invention should be measured by the claims appended
1120B , 20 % ZnO 5 min , Peridox 6 .83 * +/ - 0.00 5 .02* +/- 0 .00 50 hereto , and not merely by the specific embodiments exem
HP plified herein . Those skilled in the art will also appreciate
* indicates full kill that more sophisticated technological advances will likely
appear subsequent to the filing of this document with the
The above samples were stored for an additional 17 days, Patent Office . To the extent that these later developed
and the antimicrobial efficacy was reevaluated . Results are 55 improvements embody the operative principles at the heart
shown in Table 27 . of the present disclosure, those improvements are likewise
TABLE 27 considered to come within the ambit of the following claims.
Antimicrobial Activity After 18 -Day Drying Time 60 The invention claimed is :
Average Average 1. A water-borne formulation for imparting durable anti
Dried 18 Days Log Reduction Log Reduction microbial activity to a substrate , wherein said water-borne
Sample versus EC HP Exposure Overnight t=0 formulation is an aqueous dispersion comprising :
11201A , 20 % ZnO 18 day shelf-life 1.31 0 . 34 - 022.31* + 0 . 34 a . a metal derivative , wherein said metal derivative is a
1120B , 20 % ZnO 18 day shelf-life 6 .85 * + 0 .00 5. 23 * = 0.00 65
65 hydroxide, an oxide, or a peroxide of a metal selected
from the group consisting of zinc , magnesium , tita
nium , and zirconium ,
 US 9 ,999,226 B2
45 46
b . a polymer, wherein the water absorbency of said selected from the group consisting of zinc , magne
polymer is between 0 .5 % and 20 % (w /w ), and sium , titanium , and zirconium ,
c . hydrogen peroxide, ii . a polymer, wherein the water absorbency of said
wherein the metal derivative comprises up to 10 % ( w / w ) polymer is between 0.5 % and 20 % (w / w ), and
of the formulation , wherein the polymer comprises up 5 iii. hydrogen peroxide, and
to 36 % (w / w ) of the formulation , and wherein the b . drying said substrate,
hydrogen peroxide concentration is between 0. 5 % and wherein the metal derivative comprises up to 10 % of the
10 % (w / w ). aqueous dispersion , and wherein the polymer com
2 . The water- borne formulation of claim 1, wherein said prises up to 36 % of the aqueous dispersion , and
polymer is selected from the group consisting of polyacry - 10 wherein the aqueous hydrogen peroxide has a concen
lonitrile , acrylonitrile butadiene styrene (ABS ) polymer,
acrylic (PMMA), celluloid , cellulose acetate , ethylene - vinyl tration between 0 .5 % and 10 % .
acetate (EVA ), ethylene vinyl alcohol (EVOH ), fluoropoly 8 . The method of claim 7, wherein said polymer is
mers (PTFE , FEP, PFA , CTFE , ECTFE , ETFE ), ionomers, selected from the group consisting of polyacrylonitrile ,
acrylic /PVC alloy , liquid crystal polymer (LCP ), polyacetal 15 acrylonitrile butadiene styrene (ABS ) polymer, acrylic
(POM or Acetal ), polyacrylates (acrylic ), polyacrylonitrile (PMMA), celluloid , cellulose acetate , ethylene -vinyl acetate
(PAN or acrylonitrile ), polyamide (PA or Nylon ), poly - (EVA ), ethylene vinyl alcohol (EVOH ), fluoropolymers
amide- imide (PAI), polyaryletherketone (PAEK or Ketone), (PTFE , FEP, PFA , CTFE , ECTFE , ETFE ), ionomers ,
polybutadiene ( PBD ), polybutylene (PB ), polybutylene acrylic /PVC alloy, liquid crystal polymer (LCP ), polyacetal
terephthalate (PBT), polycaprolactone (PCL ), polychlorotri- 20 (POM or Acetal), polyacrylates (acrylic ), polyacrylonitrile
fluoroethylene (PCTFE ), polyethylene terephthalate (PET ), (PAN or acrylonitrile), polyamide (PA or Nylon ), poly
polycyclohexylene dimethylene terephthalate (PCT ), poly a mide - imide (PAI), polyaryletherketone (PAEK or Ketone ),
carbonate (PC ), polyhydroxyalkanoates (PHAs ), polyketone polybutadiene (PBD ), polybutylene (PB ), polybutylene
(PK ), polyester, polyethylene (PE ), polyetheretherketone terephthalate (PBT), polycaprolactone (PCL ), polychlorotri
(PEEK ), polyetherketoneketone ( PEKK ), polyetherimide 25 fluoroethylene (PCTFE ), polyethylene terephthalate (PET),
(PEI), polyethersulfone (PES ), polyethylenechlorinates polycyclohexylene dimethylene terephthalate (PCT), poly
(PEC ), polyimide (PI), polylactic acid ( PLA ), polymethyl carbonate (PC ), polyhydroxyalkanoates (PHAS), polyketone
pentene (PMP ), polyphenylene oxide (PPO ), polyphenylene ( PK ) . polvester. polvethylene (PE ). polvetheretherketone
sulfide (PPS ), polyphthalamide (PPA ), polypropylene (PP ), (PEEK ) . polvetherketoneketone (PEKK ), polyetherimide
polystyrene (PS ), polysulfone (PSU ), polytrimethylene 30 (PEI), polyethersulfone (PES ), polyethylenechlorinates
terephthalate (PTT), polyurethane (PU ), polyvinyl acetate (PEC ), polyimide (PI), polylactic acid (PLA ), polymethyl
(PVA ), polyvinyl chloride (PVC ), polyvinylidene chloride pentene (PMP ), polyphenylene oxide (PPO ), polyphenylene
(PVDC ); styrene -acrylonitrile (SAN ), silicone polymers, sulfide ( PPS
thermoplastics, thermosets , elastomers ; and copolymers , 35 polystyrene ),(PSpolyphthalamide
), polysulfone
(PPA ), polypropylene (PP ),
(PSU ), polytrimethylene
blends, and a mixture thereof.
3 . The water-borne formulation of claim 1, wherein said terephthalate (PTT), polyurethane (PU ), polyvinyl acetate
polymer is selected from the group consisting of acryloni- (PVA ), polyvinyl chloride (PVC ), polyvinylidene chloride
trile butadiene styrene (ABS) polymer, acrylic (PMMA ), (PVDC ) ; styrene -acrylonitrile (SAN ), silicone polymers ,
celluloid , cellulose acetate, ethylene-vinyl acetate (EVA ), thermoplastics, thermosets, elastomers ; and copolymers,
ethylene vinyl alcohol (EVOH ), fluoropolymers (PTFE . 40 blends , and mixtures thereof.
FEP , PFA , CTFE , ECTFE , ETFE ), ionomers, polyacrylates 9. The method of claim 7 , wherein said polymer is
( acrylic ), polyacrylonitrile (PAN or acrylonitrile ), poly - selected from the group consisting of acrylonitrile butadiene
amide (PA or Nylon), polyester, polyethylene (PE ), poly - styrene (ABS) polymer, acrylic (PMMA ), celluloid , cellu
propylene (PP), polyurethane (PU ), polyvinyl acetate lose acetate , ethylene -vinyl acetate (EVA ), ethylene vinyl
(PVA ), polyvinyl chloride (PVC ), silicone polymers, ther- 45 alcohol (EVOH ), fluoropolymers (PTFE , FEP , PFA , CTFE ,
moplastics, thermosets , elastomers, and copolymers ,blends, ECTFE , ETFE ), ionomers, polyacrylates (acrylic ), poly
and mixtures thereof. acrylonitrile (PAN or acrylonitrile ), polyamide (PA or
4 . The water-borne formulation of claim 1, wherein said Nylon ), polyester, polyethylene (PE ), polypropylene ( PP ),
polymer is selected from the group of polyurethanes, poly polyurethane (PU ), polyvinyl acetate (PVA ), polyvinyl chlo
acrylates, and mixtures thereof. 50 ride (PVC ), silicone polymers , thermoplastics, thermosets ,
5 . The water-borne formulation of claim 1, wherein said
metal derivative is selected from the group consisting of zinc elastomers , and copolymers , blends, and mixtures thereof.
hydroxide , zinc peroxide , zinc oxide , zinc oxide nanopar selected frommethod
10 . The
the
of claim 7 , wherein said polymer is
group of polyurethanes , polyacrylates, and
ticles, and zinc oxide micron particles .
6 . The water-borne formulation of claim 1, wherein the 55ss mixtures
" 11 . Thethereof .
method of claim 7, wherein said metal derivative
hydrogen peroxide concentration is between 1 % and 5 %
( w / w ). is selected from the group consisting of zinc hydroxide , zinc
7 . A method of enhancing and regenerating durable anti - peroxide , zinc oxide, zinc oxide nanoparticles , and zinc
microbial activity of the surface of a substrate , wherein said oxide micron particles.
method comprises the steps of: 60 12 . The method of claim 7 , wherein said substrate is a
a . providing, on the surface of a substrate on which textile article , wherein said textile article comprises cotton ,
durable antimicrobial activity is desired , a water -borne rayon , polyester, nylon , or acrylic .
formulation for imparting durable antimicrobial activ 13 . The method of claim 7 , wherein the polymer is a
ity to a substrate , wherein said formulation comprises mixture that further comprises a hydrophilic acrylic poly
an aqueous dispersion of, 65 mer.
i. a metal derivative , wherein said metal derivative is a 14 . A regenerable antimicrobial water- borne coating on a
hydroxide, an oxide , or a peroxide of a metal substrate comprising,
 US 9 , 999,226 B2
47 48
a . a metal derivative , wherein said metal derivative is a terephthalate (PET), polycyclohexylene dimethylene
hydroxide , an oxide , or a peroxide of a metal selected terephthalate (PCT), polycarbonate (PC ), polyhydroxyal
from the group consisting of zinc , magnesium , tita kanoates (PHAs), polyketone (PK ), polyester, polyethylene
nium , and zirconium , (PE ), polyetheretherketone (PEEK ), polyetherketoneketone
b . a polymer wherein said polymer is doned with 1 % to 5 (PEKK ), polyetherimide (PEI), polyethersulfone (PES ).
50 % (w /w ) of said metal derivative , polyethylenechlorinates (PEC ), polyimide (PI), polylactic
c . sequestered hydrogen peroxide, acid (PLA ), polymethylpentene (PMP ), polyphenylene
wherein the water absorbency of said polymer is between (PPA ),(PPO
oxide ), polyphenylene sulfide (PPS ), polyphthalamide
0 .5 % and 20 % ( w /w ),wherein said polymer doped withle 10 (PSU ), polypropylene
polytrimethylene
(PP ), polystyrene (PS ), polysulfone
terephthalate (PTT), polyurethane
said metal derivative has been determined to be capable 10 (PU ), polyvinyl acetate (PVA ), polyvinyl chloride (PVC ),
of sequestering hydrogen peroxide when exposed to
said source of aqueous hydrogen peroxide; wherein the polyvinylidene chloride (PVDC ); styrene -acrylonitrile
(SAN ), silicone polymers , thermoplastics , thermosets , elas
antimicrobial activity of said doped polymer can be tomers ; and copolymers , blends, and mixtures thereof.
regenerated on subsequent exposure to aqueous hydro
gen peroxide, 15 16 . The regenerable antimicrobial coating of claim 14 ,
whereby said antimicrobial coating , when tested using wherein said polymer is selected from the group of poly
ASTM Standard Method E2180 at least 24 hours after urethanes , polyacrylates , and mixtures thereof.
17 . The regenerable antimicrobial coating of claim 14 ,
preparation, provides at least a 3 -log reduction of
viable Escherichia coli bacteria greater than that of a wherein the polymer is a mixture that further comprises a
corresponding coating which has not been exposedd toto 2020 nya
hydrophilic acrylic polymer.
18 . The regenerable antimicrobial coating of claim 14 ,
hydrogen peroxide .
15 . The regenerable antimicrobial coating of claim 14 . wherein said substrate
article comprises cottonis, arayon
textile, polyester
article , wherein
, nylon ,said textile.
or acrylic
wherein said polymer is selected from the group consisting 19. The regenerable antimicrobial coating of claim 14 ,
of polyacrylonitrile, acrylonitrile butadiene styrene (ABS )
polymer, acrylic (PMMA ), celluloid , cellulose acetate , eth - 2525 Whe
wherein said metal derivative is selected from the group
consisting of zinc hydroxide, zinc peroxide, zinc oxide, zinc
ylene - vinyl acetate (EVA ), ethylene vinyl alcohol (EVOH ), oxide nanoparticles, and zinc oxide micron particles .
fluoropolymers (PTFE, FEP, PFA , CTFE , ECTFE, ETFE ), 20 . The regenerable antimicrobial coating of claim 14 ,
ionomers , acrylic /PVC alloy , liquid crystal polymer ( LCP), wherein said water -borne coating comprises a self -cross
polyacetal (POM or Acetal), polyacrylates (acrylic ),PAR poly linking linking
acrylonitrile (PAN or acrylonitrile ), polyamide (PA or 3030 "polyurethane acrylic dispersion or a self -crosslinking
dispersion , and further comprises an alcohol, a
Nylon ), polyamide-imide (PM ), polyaryletherketone (PAEK glycol, a defoamer, a photoinitiator , a thermal stabilizer, an
or Ketone ), polybutadiene (PBD ), polybutylene (PB ), poly anti-oxidant, a surfactant, or a mixture thereof.
butylene terephthalate (PBT), polycaprolactone (PCL ),
polychlorotrifluoroethylene (PCTFE ), polyethylene * * * * *