Water‐resistant latex coatings: Tuning of properties by polymerizable surfactant, covalent crosslinking and nanostructured ZnO additive

coa ings A icle Wa e -Resis an La ex Coa ings: Tuning o P ope ies by Polyme izable Su ac an , Co alen C osslinking and Nanos uc u ed ZnO Addi i e Jana Macho o á1, And éa Kalendo á1,*, Denisa S eine o á1, Pe a Máco á2, S anisla Šlang 3, Ja omí Šˇnupá ek 1and Jan Vajdák4   Ci a ion: Macho o á, J.; Kalendo á, A.; S eine o á, D.; Máco á, P.; Šlang, S.; Šˇnupá ek, J.; Vajdák, J. Wa e -Resis an La ex Coa ings: Tuning o P ope ies by Polyme izable Su ac an , Co alen C osslinking and Nanos uc u ed ZnO Addi i e. Coa ings 2021,11, 347. h ps://doi.o g/10.3390/ coa ings11030347 Academic Edi o : Joseph L. Keddie Recei ed: 1 Ma ch 2021 Accep ed: 15 Ma ch 2021 Published: 18 Ma ch 2021 Publishe ’s No e: MDPI s ays neu al wi h ega d o ju isdic ional claims in published maps and ins i u ional a il- ia ions. Copy igh : © 2021 by he au ho s. Licensee MDPI, Basel, Swi ze land. This a icle is an open access a icle dis ibu ed unde he e ms and condi ions o he C ea i e Commons A ibu ion (CC BY) license (h ps:// c ea i ecommons.o g/licenses/by/ 4.0/). 1Ins i u e o Chemis y and Technology o Mac omolecula Ma e ials, Facul y o Chemical Technology, Uni e si y o Pa dubice, S uden ská573, 532 10 Pa dubice, Czech Republic; [email p o ec ed] (J.M.); [email p o ec ed] (D.S.); ja omi .snupa [email p o ec ed] (J.Š.) 2Ins i u e o Theo e ical and Applied Mechanics o he Czech Academy o Sciences, P osecká809/76, 190 00 P ague, Czech Republic; [email p o ec ed] 3Cen e o Ma e ials and Nano echnologies, Facul y o Chemical Technology, Uni e si y o Pa dubice, S uden ská573, 532 10 Pa dubice, Czech Republic; s anisla [email p o ec ed] 4Cen e o Polyme Sys ems, Tomas Ba a Uni e si y in Zlín, Tˇ ída Tomáše Ba i 5678, 760 01 Zlín, Czech Republic; [email p o ec ed] *Co espondence: and [email p o ec ed]; Tel.: +420-466-037-272 Abs ac : This pape deals wi h he de elopmen o ac ylic la exes p o iding high-pe o mance wa e - esis an coa ings. Fo his pu pose, mu ual e ec s o anionic su ac an ype (o dina y and polyme izable), co alen in a- and/o in e pa icle c osslinking (in oduced by allyl me hac y- la e copolyme iza ion and ke o-hyd azide eac ion, espec i ely) and ionic c osslinking (p o ided by nanos uc u ed ZnO addi i e) we e in es iga ed. The la exes we e p epa ed by he s anda d emulsion polyme iza ion o me hyl me hac yla e, bu yl ac yla e and me hac ylic acid as he main monome s. The addi ion o su ace-un ea ed powde ed nanos uc u ed ZnO was pe o med du ing la ex syn hesis, esul ing in s able la exes comp ising dispe sed nanosized addi i e in he con en o ca 0.9 − 1.0 w .% (based on solids). The coa ing pe o mance wi h emphasis on wa e esis ance was e alua ed. I was de e mined ha he applica ion o he polyme izable su ac an imp o ed coa ing adhesion and wa e - esis ance, bu i wasn 0 able o ensu e high wa e - esis ance o coa ings. Highly wa e - esis an coa ings we e ob ained p o ided ha co alen in a- and in e pa icle c osslink- ing oge he wi h ionic c osslinking we e employed in he coa ing composi ion, o ming densely c osslinked la ex ilms. Mo eo e , coa ings comp ising nanos uc u ed ZnO addi i e displayed a signi ican an ibac e ial ac i i y and imp o ed sol en esis ance. Keywo ds: ac ylic la ex; c osslinking; ke o-hyd azide eac ion; polyme izable su ac an ; ZnO nanopa icles; wa e esis ance; wa e whi ening; an ibac e ial ac i i y 1. In oduc ion De elopmen o ecological coa ings has a ac ed pa icula in e es in coa ing and pain indus y, whe e ac ylic la ex binde s a e o conside able in e es due o hei a o able p ope ies, such as low cos , esis ance o a mosphe ic condi ions, ease o p epa a ion, modi ica ion and pigmen a ion. Howe e , hey ha e he disad an age o wa e sensi i i y o coa ings, which o en limi s hei p ac ical applica ion in high-pe o mance p oduc s. The imp o emen o wa e esis ance o ac ylic la ex-based coa ing ilms is he e o e highly challenging and should be add essed p e e ably al eady in he syn hesis phase o an ac ylic emulsion polyme . One app oach o enhance he p ope ies o la ex coa ings including he wa e esis- ance is he employmen o in apa icle and in e pa icle co alen (chemical) c osslinking Coa ings 2021,11, 347. h ps://doi.o g/10.3390/coa ings11030347 h ps://www.mdpi.com/jou nal/coa ings Coa ings 2021,11, 347 2 o 23 chemis y in emulsion polyme s [ 1 , 2 ]. The in apa icle co alen c osslinking, usually in- oduced by copolyme izing mul i unc ional monome s such as di inylbenzene, e hylene glycol dime hac yla e o allyl me hac yla e (ALMA), o en p o ides igid la ex pa icles and esul s in de e io a ed ilm o ma ion [ 3 ]. The in e pa icle co alen c osslinking e e s o a chemical eac ion designed o occu be ween adjacen la ex pa icles in he cou se o ilm o ma ion. As e lec ed by numbe o publica ions and pa en s, he e has been pa icula in e es in one-pack ac ylic coa ing composi ions cu able a oom empe a u e [ 4 – 6 ]. Among hese ma e ials, sel -c osslinking sys ems based on ke o-hyd azide c osslinking eac ion ha e been shown o be pa icula ly e ec i e [ 7 – 9 ]. Diace one-ac ylamide (DAAM) wi h adipic acid dihyd azide (ADH) is he mos a o ed combina ion used in he sel -c osslinking la exes [ 10 – 12 ]. The mos ema kable ea u e o he ke o-hyd azide c osslinking eac ion is as cu ing a oom empe a u e, p o iding minimal consump ion o ene gy du ing p ocessing and easy applicabili y in case o ecoa ing subs a es. Apa om he co alen c osslinking, he imp o ed p o ec i e p ope ies o la ex coa ings can be achie ed by ionic (physical) in e pa icle c osslinking which occu s in he in e acial zones be ween adjacen la ex pa icles, h ough ionic dipola in e ac ions [ 2 ]. In he case o ca boxyla ed la exes, he ionic c osslinks a e gene a ed be ween ca boxylic g oups on he su ace o la ex pa icles in he p esence o sal s and oxides o mul i a- len me als [ 13 – 15 ]. The ionic bonds a e belie ed o ha e he na u e o ion mul iple s o e en la ge clus e s o med by associa ed ionized ca boxylic g oups and me al coun e i- ons [ 16 , 17 ]. Among he sui able ionic c osslinking addi i es, ZnO, ypically in he o m o wa e dispe sion o small pa icles, has been epo ed in he ele an li e a u e as an e ec i e c osslinke o la ex-based ubbe s and coa ings [ 18 , 19 ]. As ZnO has a limi ed wa e solubili y, i neu alizes (ionizes) ca boxyla ed la exes in he we s a e and cu es hem upon d ying. Recen ly, nanosized ZnO has been p esen ed in he connec ion wi h ionic c osslinking o la ex coa ings leading o a p onounced imp o emen o coa ing p o ec i e p ope ies, such as wa e and sol en esis ance, an ico osion p o ec ion and mechani- cal esis ance [ 20 – 22 ]. Nanos uc u ed ZnO has also me wi h conside able en husiasm in he ield o la ex coa ings due o he in oduc ion o UV-shielding and an ibac e ial p ope ies [23–25]. Ano he ool, being ecognized o be e ec i e in he imp o emen o wa e esis ance o la ex coa ings, is he u iliza ion o polyme izable su ac an s in he p ocess o emulsion polyme iza ion [ 26 – 29 ]. In he case o he coa ing ilms made o la exes syn hesized using con en ional su ac an s, he su ac an molecules, adso bed on he su ace o la ex pa icles, can deso b easily and mig a e h ough he ilm o ming agg ega es, which leads o inc eased pene a ion o wa e [ 30 ]. The small and mobile su ac an species may also mig a e o he ai - ilm in e ace a ec ing gloss o he coa ing ilm o o he ilm-subs a e in e ace de e io a ing adhesion [ 31 ]. By using he polyme izable su ac an s, which become co alen ly a ached o he la ex pa icles, he su ac an deso p ion and mig a ion p oblems we e a oided o a leas minimized [ 32 , 33 ]. Posi i e e ec s we e ob ained bo h on he la ex s abili y and on he p ope ies o he d ied coa ing ilms [34–37]. The p esen pape deals wi h he p epa a ion and e alua ion o ac ylic la exes sui able o wa e - esis an high-pe o mance coa ing applica ions. While s udying he op imal and highly e ec i e la ex composi ion, we concen a ed on mu ual e ec s o a ious uncon en ional s a egies, namely, (i) he emulsion polyme iza ion pe o med using a polyme izable su ac an , (ii) employing he co alen in e pa icle c osslinking based on he ke o-hyd azide c osslinking eac ion, (iii) in oducing he co alen in apa icle c osslinking in o la ex polyme by copolyme izing ALMA and (i ) in oducing he ionic c osslinking by means o a nanos uc u ed ZnO addi i e, being inco po a ed in he cou se o he polyme iza ion p ocess. The la ex coa ing pe o mance wi h emphasis on wa e esis ance was e alua ed and mu ually compa ed. Coa ings 2021,11, 347 3 o 23 2. Ma e ials and Me hods 2.1. Ma e ials La exes we e p epa ed o me hyl me hac yla e (MMA, CAS: 80-62-6), bu yl ac yla e (BA, CAS: 141-32-2), me hac ylic acid (MAA, CAS: 79-41-4), allyl me hac yla e (ALMA, CAS: 96-05-9) and diace one ac ylamide (DAAM, CAS: 2873-97-4). All he monome s we e pu chased om Sigma-Ald ich (P ague, Czech Republic). Disponil FES 993 (BASF, P ague, Czech Republic) was used as he o dina y anionic su ac an . HITENOL AR-10 was used as he polyme izable anionic su ac an and was kindly supplied by DKS Co. L d. (Tokyo, Japan). Table 1p esen s he main cha ac e is ics o he su ac an s used in his wo k. Ammonium pe sul a e (CAS: 7727-54-0, Pen a, P ague, Czech Republic) was u ilized as he ini ia o o he polyme iza ion eac ion. Adipic acid dihyd azide (ADH, CAS: 1071-93-8) was u ilized as he co alen c osslinking agen and was pu chased om TCI Eu ope (Zwijnd ech , Belgium). Su ace-un ea ed nanos uc u ed ZnO (NanoGa d ® , CAS: 1314-13-2) ha ing he a e age pa icle size in he ange o 40–100 nm was used as he ionic c osslinking addi i e and was pu chased om Al a Aesa (Kandel, Ge many). All he chemicals we e u ilized as ecei ed wi hou any u he pu i ica ion. Table 1. Main cha ac e is ics o he used su ac an s. Su ac an Type Chemical Composi ion Ac i e Ma e (w .%) C i ical Micelle Concen a ion (mg/L) a Disponil FES 993 Nonpolyme izable Sodium sal o e hoxyla ed a y alcohol e he sul a e 29.7 200 HITENOL AR-10 Polyme izable Ammonium sal o e hoxyla ed s y ena ed p openyl phenol e he sul a e 99.1 250 aDa a gi en by he supplie . 2.2. P epa a ion and Cha ac e iza ion o La exes Fou se ies o ac ylic la exes di e ing in he co alen c osslinking s a egy we e syn hesized by wo-s ep nonseeded emulsion polyme iza ion comp ising a a iable con en o ac ylic monome s (see Table 2). The de ailed ecipe o emulsion polyme iza ion is p esen ed in Table 3. The p opo ions o he ac ylic monome s o ming la ex pa icles we e chosen o achie e a calcula ed T g (using he Fox equa ion [ 38 ]) o app oxima ely 5 ◦ C, so ha ilm- o ma ion was also kep in he case o he densely c osslinked la ex ilms. E e y se ies con ained ou la ex samples which we e syn hesized using he same ypes and p opo ions o he ac ylic monome s; wo samples always being p epa ed wi h an o dina y (nonpolyme izable) su ac an (samples labelled D) and wo samples being syn hesized using a polyme izable su ac an (samples labelled H) ha con ains eac i e double bonds, which can copolyme ize wi h he ac ylic monome s. The amoun s o he pa icula su ac an s we e designed o main ain he same su ace-ac i e ma e weigh concen a ion in bo h ypes o la ex samples. Mo eo e , one o he D-labelled samples and one o he H-labelled samples we e syn hesized by a s anda d syn he ic ou e, while he es wo samples (labelled D _ZnO and H _ZnO ) comp ised nanos uc u ed ZnO as he mul i unc ional addi i e, being inco po a ed in he cou se o he polyme iza ion p ocess o he second s ep polyme . The con en o nanos uc u ed ZnO was 1 w .% wi h espec o he o al monome eeds. The way and expe imen al p ocedu e o he nano-ZnO addi ion we e based on ou ecen expe ience [ 20 , 21 , 25 ]. We ha e demons a ed ha powde ed su ace-un ea ed nanos uc u ed ZnO can be success ully added in o a la ex in he cou se o emulsion polyme iza ion, p o iding a long- e m s able coa ing binde . Coa ings 2021,11, 347 4 o 23 Table 2. Monome ic composi ions o la exes di e ing in he co alen c osslinking s a egy, su ac an ype and he applica ion o nanos uc u ed ZnO addi i e. Sample Composi ion o Monome Feeds (g) Su ac an Type Nanos uc u ed ZnO Addi i e MMA/BA/MAA/DAAM/ALMA Fi s S ep Second S ep Se ies 1: No co alen c osslinking D1 18.5/30/1.5/0/0 18.5/30/1.5/0/0 nonpolyme izable no H1 18.5/30/1.5/0/0 18.5/30/1.5/0/0 polyme izable no D1_ZnO 18.5/30/1.5/0/0 18.5/30/1.5/0/0 nonpolyme izable yes H1_ZnO 18.5/30/1.5/0/0 18.5/30/1.5/0/0 polyme izable yes Se ies 2: In e pa icle co alen c osslinking D2 18.5/30/1.5/0/0 16.5/29.5/1.5/2.5/0nonpolyme izable no H2 18.5/30/1.5/0/0 16.5/29.5/1.5/2.5/0 polyme izable no D2_ZnO 18.5/30/1.5/0/0 16.5/29.5/1.5/2.5/0nonpolyme izable yes H2_ZnO 18.5/30/1.5/0/0 16.5/29.5/1.5/2.5/0 polyme izable yes Se ies 3: In apa icle co alen c osslinking D3 18/30/1.5/0/0.5 18.5/30/1.5/0/0 nonpolyme izable no H3 18/30/1.5/0/0.5 18.5/30/1.5/0/0 polyme izable no D3_ZnO 18/30/1.5/0/0.5 18.5/30/1.5/0/0 nonpolyme izable yes H3_ZnO 18/30/1.5/0/0.5 18.5/30/1.5/0/0 polyme izable yes Se ies 4: In a- and in e pa icle co alen c osslinking D4 18/30/1.5/0/0.5 16.5/29.5/1.5/2.5/0nonpolyme izable no H4 18/30/1.5/0/0.5 16.5/29.5/1.5/2.5/0 polyme izable no D4_ZnO 18/30/1.5/0/0.5 16.5/29.5/1.5/2.5/0nonpolyme izable yes H4_ZnO 18/30/1.5/0/0.5 16.5/29.5/1.5/2.5/0 polyme izable yes Table 3. Recipe o emulsion polyme iza ion by using di e en su ac an s and nanos uc u ed ZnO addi i e. Componen Reac ion Flask Cha ge (g) Fi s S ep Monome Emulsion (g) Second S ep Monome Emulsion (g) Wa e 35.0 47.5 72.5 Disponil FES 993 a0.24 3.7 3.7 HITENOL AR-10 b0.07 1.1 1.1 Ammonium Pe sul a e 0.2 0.2 0.2 Monome s – 50.0 50.0 Nanos uc u ed ZnO c– – 1.0 a Nonpolyme izable su ac an used o he p epa a ion o he D-labelled la ex samples. b Polyme izable su ac an used o he p epa a ion o he H-labelled la ex samples. c Ionic c osslinking addi i e inco po a ed in he cou se o he p epa a ion o he D_ZnO−and H_ZnO−labelled la ex samples. In he Se ies 1, no co alen c osslinking was in oduced in o la ex polyme s. In he Se ies 2, he composi ion o he la ex samples was designed o p o ide co alen in e pa icle c osslinking based on he ke o-hyd azide c osslinking eac ion. Fo his pu pose, a cons an amoun o DAAM (5 w .% wi h espec o he second s ep monome eeds) was inco po a ed in o he second s ep polyme o in oduce ke one ca bonyl g oups in o la ex polyme s o he subsequen in e acial co alen c osslinking by he eac ion wi h ADH, added du ing la ex o mula ion. The Se ies 3 was ep esen ed by la exes employing co alen in apa icle c osslinking, which was achie ed by in oducing a cons an amoun o ALMA (1 w .% wi h espec o he i s s ep monome eeds) in he i s s ep polyme . In he Se ies 4, he la exes we e designed o p o ide bo h co alen in e - and in apa icle c osslinking by copolyme izing DAAM and ALMA in he same manne as desc ibed abo e. In he case o all se ies, ca boxylic unc ionali ies (in a ela i ely high con en , conside ing s anda d ac ylic la ex coa ing composi ions) we e inco po a ed in o he s uc u e o he i s and second s ep polyme s by copolyme izing MAA (3 w .% based on o al monome eeds) o h ee easons: (i) s abiliza ion o la ex pa icles, (ii) acid ca alysis o he ke o-hyd azide Coa ings 2021,11, 347 5 o 23 co alen in e pa icle sel -c osslinking eac ion, (iii) enabling he ionic c osslinking ia Zn2+ ca ions. The la exes we e p oduced in a 500 mL glass eac ion lask unde a ni ogen a mo- sphe e a a polyme iza ion empe a u e o 85 ◦ C. The eac ion lask cha ge (consis ing o dis illed wa e , ini ia o and he espec i e su ac an , see Table 3) was placed in o he eac ion lask and hea ed o he polyme iza ion empe a u e. The monome emulsion was consequen ly dosed in o he s i ed eac ion lask a a dosing a e o abou 2.5 mL/min in wo s eps ( i s polyme syn hesis, second polyme syn hesis), while a 15 min-long pe iod be ween he wo dosing s eps was kep . The polyme iza ion was hen comple ed, du ing he 2 h o he hold pe iod. The syn hesis o la exes added wi h nanos uc u ed ZnO was conduc ed modi ying he abo e desc ibed p ocedu e. Fi s , a inely dispe sed ZnO aqueous dispe sion was p epa ed by adding nanos uc u ed ZnO o wa e ha was designed o he p epa a ion o he second s ep monome emulsion. To acili a e he agmen a ion o agg ega es o med by ZnO p ima y nanopa icles, a p ope dispe sion p ocess using a Silen C ushe M dispe se (Heidolph, Schwabach, Ge many) a 14,000 pm was ca ied ou o 20 min ollowed by 1 h-long ul asonica ion. The ine nanos uc u ed ZnO aqueous dispe sion was hen gen ly mixed wi h he monome s, su ac an and ini ia o designed o he p epa a ion o he second s ep monome emulsion (using a s i e a low speed o 3 min). In he end, he esul ing second s ep monome emulsion wi h nanos uc u ed ZnO was dosed o he eac ion lask immedia ely a a dosing a e o abou 2.5 mL/min. A e he syn hesis, he la exes we e il e ed and he coagulum, consis ing o il e able solids and solids deposi ed on he s i e and he eac ion lask walls, was collec ed. The solids con en , coagulum con en and monome con e sion we e measu ed by g a ime ic me hod and we e calcula ed acco ding Equa ions (1)–(3) [39]. solids con en (w . %)=m3−m2 m1×100 (1) coagulum con en (w . %)=mC solids con en ×mL 100 +mC×100 (2) monome con e sion (w . %)= solids con en ×mT 100 −(mI+mS+mZnO) mM×100 (3) whe e m 1 is he ce ain quan i y o a la ex sample cas on o a Pe i dish; m 2 is he weigh o he Pe i dish; m 3 is he weigh o he la ex sample and he Pe i dish d ied o a cons an weigh a 110 ◦ C; m C is he weigh o he d ied coagulum; m L is he weigh o he il e ed la ex; m T is he o al weigh o all he ma e ials pu in he eac ion lask; m I is he weigh o he ini ia o ; m S is he weigh o he su ac an (ac i e ma e ); m ZnO is he weigh o he nanos uc u ed ZnO; and mMis he weigh o he o al monome s. The la ex pH was consequen ly adjus ed o 8.5 wi h ammonia solu ion. Finally, an aqueous solu ion o ADH consis ing o 1.25 g ADH and 11.3 g wa e was added o he la ex samples o Se ies 2 and 4 wi h agi a ion. The p epa ed la exes we e e alua ed om he poin o iew o hei minimum ilm- o ming empe a u e (MFFT) and pa icle size. The minimum ilm- o ming empe a u e (MFFT) was de e mined acco ding o ISO 2115 [ 40 ], using he MFFT-60 ins umen (Rhopoin Ins umen s, S Leona ds, UK). The a e age pa icle sizes o polyme pa icles in he wa e phase we e ob ained om dynamic ligh sca e ing (DLS) expe imen s pe o med using a Li esize 500 ins umen (An on Paa , G az, Aus ia). All he DLS measu emen s we e conduc ed a 25 ◦C. 2.3. Tes ing o La ex S abili y The s abili y o p epa ed la exes was e alua ed using se e al es ing me hods. The hea s o age s abili y es ing was ca ied ou by s o ing la exes o 60 days in an o en wi h a se empe a u e o 50 ◦ C. The mechanical s abili y o la exes was e alua ed by cen i uging 10 mL o la ex in a sealed cen i ugal ube o 15 min a a speed o 4000 pm in a cen i ugal Coa ings 2021,11, 347 6 o 23 machine. The eeze- haw s abili y es ing was ca ied ou by s o ing 10 mL o la ex in a plas ic can a − 5, − 10 and − 18 ◦ C, espec i ely, o abou 17 h and hen allowing o haw o 48 h a RT. The s abili y es s men ioned abo e we e e alua ed by obse ing whe he he e was no coagula ion p oduced a e he pa icula la ex s abili y es and also, whe he he es ed la ex p o ided smoo h coa ing ilms wi hou a signi ican loss o hei gloss (below 10 el.%). In ha case he la ex was conside ed o display he pa icula s abili y. A calcium ion s abili y es was ca ied ou by d opping a small amoun ( wo o h ee d ops) o he la ex o CaCl 2 solu ion o a speci ic concen a ion (1, 1.5, 2 and 5 w .%). I he e was no p ecipi a ion, he la ex was conside ed o ha e calcium ion s abili y a he gi en CaCl2concen a ion. 2.4. P epa a ion and Cha ac e iza ion o F ee-S anding Films The ee-s anding ilms we e p epa ed by pou ing and d ying he la exes in silicone molds. The samples we e i s ai -d ied a oom empe a u e (RT, 23 ± 1 ◦ C) o a mon h and hen acuum-d ied a 30 ◦ C o wo weeks. The we hickness o he ee-s anding ilms was app oxima ely 0.7 mm. The ee-s anding ilms we e used o he in es iga ion o la ex polyme s uc u e, namely he chemical composi ion, he glass ansi ion empe a u e (T g ) and he deg ee o c osslinking. In he case o he ilms based on he la exes com- p ising he nanos uc u ed ZnO addi i e, he dis ibu ion and he ac ual con en o ZnO- based nanopa icles inside he coa ing ilms we e also de e mined. In addi ion, he ee- s anding ilms we e used o he es ing o wa e abso p ion and an ibac e ial ac i i y o he la ex ilms. The chemical s uc u e o he p epa ed la ex polyme s was s udied employing a Fou ie ans o m in a ed (FT-IR) spec oscopy on a seconda y module iZ10 o Nicole iN10 ins umen (The mo Fishe Scien i ic, Wal ham, MA, USA). The in a ed spec a we e ob ained by a enua ed o al e lec ance (ATR) on a buil -in all- e lec i e diamond c ys al in a ange om 4000 cm −1 o 525 cm −1 using he esolu ion o 4 cm −1 (64 scans pe spec um). T g o d ied la ex polyme s was measu ed by means o di e en ial scanning calo ime y (DSC) using a Py is 1 DSC ins umen (Pe kin-Elme , Wal ham, MA, USA). The measu emen s we e pe o med unde N 2 a mosphe e a a hea ing a e o 10 ◦ C/min om −50 o 120 ◦C and he second hea ing cu e was used o Tgde e mina ion. The deg ee o c osslinking in oduced in o la ex polyme s was e alua ed acco ding o gel con en and c osslink densi y. The gel con en was de e mined by he ex ac ion in a Soxhle ex ac o wi h e ahyd o u an (THF) o 24 h acco ding o CSN EN ISO 6427 [ 41 ]. The c osslink densi y was e alua ed om swelling expe imen s pe o med on d y gel polyme samples (a ound 0.2 g) which we e imme sed in oluene a 50 ◦ C o one week. A swelling ime o one week was chosen on he basis o he es esul s on se e al samples, which mani es ed no signi ican changes a e one week o imme sion in oluene. A he end o he imme sion pe iod, he sample was emo ed, apidly blo ed wi h issue and ans e ed o a weighing bo le o ob ain he swollen weigh o he sample. Equa ions (4)–(7) [ 42 ], employing he heo y o Flo y and Rehne [ 43 ], we e used o calcula e he a e age molecula weigh be ween c osslinks (M c ) and he c osslink densi y (exp essed as moles o c osslinks pe cm3o a polyme ne wo k), as gi en in he ollowing: Mc=V1ρp[φ1 3−φ/2] −[ln(1−φ)+φ+χφ2](4) φ=Wpρs Wpρs+Wsρp(5) χ=0.34 +V1 RT(δ1−δ2)2(6) C osslink densi y = ρp/Mc(7) Coa ings 2021,11, 347 7 o 23 whe e V 1 is he mola olume o oluene (106.3 cm 3 /mol); ρp is he densi y o polyme ha was calcula ed o be 1.103 g/cm 3 o he BA/MMA/MAA (60/37/3 by weigh ) copolyme om 1.06, 1.18 and 1.015 g/cm 3 o poly(BA), poly(MMA) and poly(MAA), espec i ely; ϕ is he olume ac ion o he gel polyme in he swollen gel; W p and W s a e he weigh ac ions o he gel polyme and sol en ( oluene) in he swollen gel, espec i ely; ρs is he densi y o sol en (0.8669 g/cm3); χis he polyme and sol en in e ac ion pa ame e ; δ1 is he solubili y pa ame e o polyme ha was calcula ed o be 9.135 (cal/cm 3 ) 1/2 o he BA/MMA/MAA (60/37/3 by weigh ) copolyme om 9.0, 9.3 and 9.8 (cal/cm 3 ) 1/2 o poly(BA), poly(MMA) and poly(MAA), espec i ely [ 44 , 45 ]; and δ2 is he solubili y pa ame e o oluene, 8.9 (cal/cm3)1/2. The ac ual con en o he nanos uc u ed ZnO addi i e, embedded in he d ied la ex coa ing ilms, was de e mined by means o an induc i ely coupled plasma op ical emission spec ome y (ICP-OES) using a spec ome e INTEGRA XL 2 (GBC, Dandenong, Aus alia), equipped wi h a concen ic nebulize and a glass cyclonic sp ay chambe (bo h Glass Expansion, Dangenong, Aus alia). The ZnO addi i e concen a ion was calcula ed using he simpli ied assump ion ha all he de e mined zinc in he coa ing ilm was only in he o m o ZnO. The dis ibu ion o ZnO addi i e in he coa ing ilm was in es iga ed by scanning elec on mic oscopy (SEM) and mic o-Raman spec oscopy 2D mapping. The SEM mea- su emen s we e pe o med using a LYRA 3 scanning elec on mic oscope (Tescan, B no, Czech Republic). Obse a ions we e conduc ed on ac u ed su aces a he accele a ing ol age o 5 kV. Samples we e placed on ca bon ape and ca bon coa ed wi h a 20 nm hick laye . The 2D mapping on coa ing su aces was pe o med using a mic o-Raman spec ome e Nicole DXR3xi (The mo Fishe Scien i ic, Wal ham, MA, USA) equipped wi h EMCCD de ec o . The lase beam (532 nm) was ocused wi h a 100 × objec i e (N.A = 0.90) and lase powe o 5 mW. Maps we e collec ed o e an a ea o 50 × 100 µ m using a 0.5 µ m s ep size in a spec al ange om 3400 o 50 cm −1 . Fi e exposu es o each spec um we e eco ded wi h he exposu e ime o 0.2 s. The analysis o collec ed da a was done by a mul i a ia e cu e esolu ion. The wa e abso p ion exp essed in e ms o wa e up ake by he la ex ilms was es ed by imme sing specimens o he app oxima e dimensions 20 × 20 × 0.7 mm 3 in dis illed wa e a RT o 30 days. The soaked ilm was consequen ly emo ed om he wa e and he su ace o he ilm was ca e ully d ied by ouching he polyme wi h il e pape . The wa e abso p ion (A) was calcula ed acco ding Equa ion (8). A= 100(w −w0)/w0(8) whe e w 0 is he ini ial weigh o a specimen be o e dis illed wa e exposu e and w is he weigh o he specimen a e pe o ming he imme sion es . The an ibac e ial ac i i y o he coa ing ilms o he Se ies 4 ( he samples D 4 , H 4 , D 4_ZnO and H 4_ZnO ) was e alua ed and compa ed using he modi ied ISO 22,196 me hod [ 46 ]. Fou bac e ial s ains we e used o he an imic obial es s, namely, S aphylococcus au eus (S. Au eus, CCM 4516), Esche ichia coli (E. coli, CCM 4517), En e ococcus aecalis (E. aecalis, CCM 3956) and Klebsiella pneumoniae (K. pneumoniae, CCM 4425). All he mic obial s ains we e p o ided by he Czech Collec ion o Mic oo ganisms (CCM, B no, Czech Republic). The coa ing ilms we e cu in o squa es o 25 × 25 mm 2 , s e ilized by UV adia ion and hen placed in s e ile Pe i dishes. This was ollowed by inocula ion o he samples using 0.1 mL o a pa icula s anda dized bac e ia suspension, namely S. au eus (6.3 × 10 6 c u/mL), E. coli (7.5 × 10 6 c u/mL), E. aecalis (5.1 × 10 6 c u/mL) and K. pneumoniae (1.8 × 10 6 c u/mL). The samples we e co e ed by polyp opylene oil (20 × 20 mm 2 ) disin ec ed wi h 70% e hanol. Incuba ion o he inocula ed samples was pe o med a 95% o ela i e humidi y a 35 ◦ C o 24 h. The polyp opylene oil was hen emo ed, and he coa ing samples we e imp in ed on Pla e Coun Aga (HIMEDIA Labo a o ies P ., Mumbai, India). Each coa ing sample was imp in ed h ee imes on di e en a eas o he Pla e Coun Aga , and incuba ed a 35 ◦ C o 24 h. The esul s we e hen ead and he inc ease in he Coa ings 2021,11, 347 8 o 23 numbe o bac e ial colonies was e alua ed based on scaling om 0 o 5, whe e 0 ep esen s he bes an imic obial e ec , wi h no g ow h o bac e ia colonies. All o hese analyses we e pe o med using h ee di e en coa ing samples o ensu e eliable an ibac e ial e iciency esul s. 2.5. P epa a ion and Cha ac e iza ion o Coa ings Cas on Glass Subs a es Liquid la exes we e applied on o glass panels using a blade applica o . The hickness o he we coa ings was 120 µ m. No coalescing agen s we e used. The coa ings we e ai -d ied a RT and ela i e humidi y o 45 ± 5% o se en days. The coa ing ilms we e e alua ed o hei gloss, anspa ency, sol en esis ance, adhesion and wa e whi ening. The d y coa ing hickness was measu ed using a h ee-poin ins umen (BYK-Ga dne , Ge e s ied, Ge many). The gloss o coa ings was e alua ed by a mic o-TRI-gloss µ in- s umen (BYK-Ga dne , Ge e s ied, Ge many) using a gloss-measu ing geome y a 60 ◦ . Coa ings cas on glass panels coa ed wi h black ma e pain (RAL 9005) we e used o he gloss measu emen s. The anspa ency o he coa ings was e alua ed by ligh ansmission (measu ing he ansmi ance a he wa eleng h 500 nm) using a Colo Ques XE Spec ome- e (Hun e lab, Res on, VA, USA). The sol en esis ance was es ed by me hyl e hyl ke one (MEK) ubbing ollowing ASTM D 4752. The adhesion o coa ings was e alua ed by means o he pull-o es acco ding o ISO 4624 using an Elcome e 510 Au oma ic Adhesion Tes e (Elcome e Ins umen s, Aalen, Ge many). All he abo e-men ioned expe imen s we e ca ied ou a RT. The wa e whi ening o coa ings was e alua ed by measu ing he change in ans- mi ance a a ixed wa eleng h (500 nm, nea he g een ligh , which is mos sensi i e o he human eye) using a Colo Ques XE Spec ome e (Hun e lab, Res on, VA, USA). The coa ings we e imme sed in dis illed wa e a RT o 24 h, ollowed by he immedia e measu emen o he ansmi ance o he exposed coa ing ilm a ea. The ex en o wa e whi ening (W) was calcula ed acco ding Equa ion (9). W= 100(T0−T )/T0(9) whe e T 0 is he coa ing sample ansmi ance be o e imme sion in dis illed wa e and T is he sample ansmi ance a e imme sion in dis illed wa e o 24 h. 3. Resul s and Discussion 3.1. Cha ac e iza ion o La exes The cha ac e is ic p ope ies o he p epa ed la exes, di e ing in he co alen c osslink- ing s a egy, su ac an ype and nanos uc u ed ZnO addi ion, a e lis ed in Table 4. In all he polyme iza ions, ega dless o he ype o he used su ac an and polyme composi ion, s able la exes wi h low amoun s o coagulum (<1 w .%) we e ob ained. This ac indica es a su icien la ex colloidal s abili y du ing he syn hesis in he case o using he o dina y o he polyme izable ype o su ac an . The addi ion o nanos uc u ed ZnO, ca ied ou du ing he p ocess o emulsion polyme iza ion, was also shown no o inc ease signi ican ly he coagulum con en in he espec i e la exes, sugges ing no ma kedly nega i e e ec o he in si u ZnO addi ion on la ex s abili y du ing he syn hesis. Coa ings 2021,11, 347 9 o 23 Table 4. Cha ac e is ics o la exes, di e ing in he co alen c osslinking s a egy, su ac an ype and he applica ion o nanos uc u ed ZnO addi i e. Sample Coagulum Con en (w .%) Solids (w .%) Con e sion (w . %) Pa icle Size (nm) MFFT (◦C) Se ies 1: No co alen c osslinking D1~0 a38.1 ±0.1 95.3 ±0.3 123.4 ±0.8 <0 H1~0 a39.7 ±0.1 99.5 ±0.3 114.3 ±0.9 <0 D1_ZnO ~0 a37.8 ±0.1 94.0 ±0.2 118.3 ±1.8 3.6 ±0.2 H1_ZnO 0.2 39.2 ±0.1 97.8 ±0.2 104.9 ±1.5 4.5 ±0.1 Se ies 2: In e pa icle co alen c osslinking D20.4 38.3 ±0.2 95.9 ±0.4 120.4 ±1.0 <0 H2~0 a39.8 ±0.1 99.7 ±0.2 112.3±1.0 <0 D2_ZnO 0.6 37.0 ±0.2 91.9 ±0.4 117.9 ±1.6 4.1 ±0.1 H2_ZnO ~0 a39.3 ±0.1 97.8 ±0.2 100.6 ±1.3 4.8 ±0.2 Se ies 3: In apa icle co alen c osslinking D3~0 38.3 ±0.1 95.9 ±0.3 123.7 ±1.0 0.6 ±0.2 H30.3 39.4 ±0.2 98.7 ±0.4 114.7 ±0.7 <0 D3_ZnO 0.1 37.2 ±0.2 92.4 ±0.5 124.7 ±1.1 3.8 ±0.2 H3_ZnO 0.8 38.8 ±0.1 96.6 ±0.3 112.7 ±1.7 5.3 ±0.3 Se ies 4: In a- and in e pa icle co alen c osslinking D40.2 38.6 ±0.0 96.7 ±0.1 118.3 ±1.2 1.0 ±0.3 H4~0 a39.7 ±0.2 99.5 ±0.5 105.7 ±1.1 <0 D4_ZnO ~0 a37.6 ±0.1 93.4 ±0.2 121.1 ±1.9 4.8 ±0.1 H4_ZnO 0.7 38.9 ±0.1 96.8 ±0.2 110.8 ±1.2 5.9 ±0.2 aNo coagulum was p esen in la ex. When compa ing he con e sion and pa icle size o he la exes o he same compo- si ion bu di e ing in he ype o su ac an , a highe monome con e sion and simul a- neously a lowe inal pa icle size we e achie ed in he case o using he polyme izable su ac an . This phenomenon has al eady been epo ed in he ele an li e a u e [ 47 – 50 ]. I has been asc ibed o he inc eased numbe o micelles, leading o a highe polyme iza ion a e and a highe numbe o smalle polyme pa icles gene a ed du ing he polyme iza ion p ocess using he polyme izable su ac an . In addi ion, he mu ual e ec s o co alen c osslinking s a egy, su ac an ype, and addi ion o nanos uc u ed ZnO on MFFT o la exes we e also in es iga ed (see Table 4). As expec ed, a pe cep ible inc ease in MFFT alues appea ed in he Se ies 3 and 4, bo h employing in apa icle co alen c osslinking ia ALMA copolyme iza ion, which is gene ally ega ded o in oduce igidi y in o la ex polyme pa icles [ 51 ]. I was also ound ha he la exes added wi h nanos uc u ed ZnO exhibi ed inc eased MFFT alues in compa ison wi h he co esponding la exes wi hou he ZnO addi i e. This e ec may be asc ibed o he occu ence o ionic in e pa icle c osslinking, p oceeding in he cou se o he ilm- o ma ion ia ca boxylic acid unc ional g oups o emulsion polyme and dissol ed Zn 2+ ions. When compa ing he MFFT alues o he co esponding la exes di e ing in he su ac an ype, no ema kable di e ence was de e mined. 3.2. S abili y o La exes F om a p ac ical poin o iew, a a o able coa ing binde has o exhibi a sa is ac o y s abili y unde a ious condi ions. Fo ha eason, we also es ed he s abili y o he p epa ed liquid la exes. We used se e al me hods, simula ing isks du ing s o ing and applica ion, o e alua e he impac o la ex composi ion, including su ac an ype and ZnO addi ion on he colloidal s abili y o la exes. In he case o he hea s o age s abili y and he mechanical s abili y (see Table 5), all he la exes apa om he sample D 4_ZnO we e ound o be s able. The esul s o eeze- haw es s (Table 5) based on he eezing cycle a − 5 ◦ C indica ed no coagula ion and no signi ican change in he coa ing gloss o all he p epa ed la exes, whe eas he eezing cycles a lowe empe a u es ( − 10 and − 18 ◦ C) we e ound o des abilize he la ex samples polyme ized wi h he o dina y su ac- Coa ings 2021,11, 347 16 o 23 Figu e 5. Two-dimensional Raman mapping o he coa ing su ace o he sample D 4_ZnO . G een colo co esponds o he spec um o he s udied la ex polyme . A ib a ion band o sul a e anion a 975 cm−1was no de ec ed. 3.4. Coa ing P ope ies The p ope ies o coa ings di e ing in he co alen c osslinking s a egy, su ac an ype and nanos uc u ed ZnO addi ion a e p esen ed in Table 8. The hickness o he d ied coa ings d awn down on glass subs a es was abou 50 µ m. All he p epa ed coa ings exhibi ed a high gloss and anspa ency wi hou any p onounced di e ence. We can he e o e assume ha no signi ican deso p ion, mig a ion and agg ega ion o su ac an molecules and ionic species a he ilm-ai in e ace occu ed ( he isk conside ed especially o he coa ings comp ising he o dina y su ac an ). When compa ing MEK esis ance o coa ings, he esul s indica ed ha he sol en esis ance wasn’ inc eased ma kedly by co alen in a- o /and in e pa icle c osslinking. In con as , ZnO addi i e in oducing ionic c osslinks was shown o be a e y e ec i e ool o ob aining a high sol en esis ance. The coa ing samples D 2_ZnO and D 4_ZnO e en passed he MEK es wi hou ailu e, which was in all p obabili y caused by he combina ion o ionic and co alen in e pa icle c osslinking. The esul s o he MEK es also e ealed ha he D _ZnO− labelled coa ing samples exhibi ed a highe MEK esis ance in compa ison wi h he co esponding H _ZnO− labelled coa ing samples. This inding may be ela ed o he enhanced mola mass and igidi y o he H-labelled la ex polyme s (p epa ed by he polyme izable su ac an ). As he ionic c osslinks be ween he ca boxylic g oups and zinc ions a e supposed o be o med o some ex en al eady du ing he syn hesis o he emulsion polyme , we can assume ha mo e igid la ex pa icles composed o longe polyme chains linked o each o he by ionic bonds (in apa icle c osslinks) we e o med in he case o he H _ZnO− labelled la exes ( esembling he co alen in apa icle c osslinking by ALMA copolyme iza ion). As he esul , a po ous ilm s uc u e was appa en ly o med due o he de e io a ed pa icle de o ma ion and supp essed polyme chain in e di usion, allowing he sol en molecules o pene a e mo e easily inside he coa ing. This e ec can be obse ed mo e dis inc ly in he case o a poo MEK esis ance o coa ings o he Se ies 3, composed o ALMA-c osslinked la ex pa icles. Coa ings 2021,11, 347 17 o 23 Table 8. P ope ies o coa ings cas on glass subs a es. Sample Thickness (µm) Gloss 60◦(GU) T anspa ency (%) 1 MEK Resis ance (Numbe o S ikes) Se ies 1: No co alen c osslinking D158.4 ±8.1 80.5 ±0.2 90.1 ±0.3 10.3 ±0.6 H163.2 ±7.3 85.1 ±0.1 90.2 ±0.3 12.3 ±0.6 D1_ZnO 61.5 ±6.2 85.5 ±0.1 89.6 ±0.4 210.4 ±19.2 H1_ZnO 48.8 ±5.4 85.2 ±0.2 90.0 ±0.3 133.2 ±15.1 Se ies 2: In e pa icle co alen c osslinking D251.8 ±7.8 85.0 ±0.3 91.0 ±0.2 11.8 ±1.5 H258.6 ±6.3 85.2 ±0.1 90.2 ±0.4 18.7 ±0.6 D2_ZnO 55.2 ±6.7 86.0 ±0.1 89.9 ±0.2 abo e 300 2 H2_ZnO 60.5 ±7.0 85.4 ±0.3 90.7 ±0.3 213.7 ±18.2 Se ies 3: In apa icle co alen c osslinking D361.9 ±5.5 84.3 ±0.2 91.1 ±0.3 8.0 ±1.0 H358.5 ±7.3 84.0 ±0.1 90.6 ±0.4 10.7 ±0.6 D3_ZnO 65.0 ±6.7 81.5 ±0.4 90.5 ±0.2 102.3 ±2.4 H3_ZnO 53.5 ±4.9 84.3 ±0.1 90.6 ±0.3 23.1 ±4.7 Se ies 4: In a- and in e pa icle co alen c osslinking D457.5 ±6.8 85.2 ±0.1 91.1 ±0.2 29.4 ±4.6 H448.1 ±8.5 85.5 ±0.2 90.2 ±0.3 24.6 ±6.0 D4_ZnO 45.7 ±9.7 85.6 ±0.1 89.8 ±0.3 abo e 300 H4_ZnO 56.5 ±6.1 84.9 ±0.1 90.6 ±0.3 236 ±14 1T ansmi ance measu ed a 500 nm. 2Maximum e alua i e alue ( ep esen ing he bes p ope y). In addi ion, he adhesion o he coa ings o a glass subs a e was e alua ed (see Figu e 6). Focusing on he su ac an ype, he esul s con i med ha he use o he poly- me izable su ac an p o ided imp o ed adhesion o coa ings, as has been expec ed. This e ec can be a ibu ed o he co alen a achmen o su ac an molecules on he su ace o la ex pa icles, disabling hei deso p ion and mig a ion a he subs a e– ilm in e ace. When compa ing he coa ing adhesion in e ms o he co alen c osslinking s a egy, he bes adhesion o he glass subs a e was de ec ed o he coa ings o he Se ies 2 (in e - pa icula ly c osslinked by he ke o-hyd azide eac ion). The eason is in all p obabili y ela ed o he p esence o he addi ional pola unc ionali ies inco po a ed in o he molec- ula s uc u e o he la ex coa ings by he ke o-hyd azide c osslinks which oge he wi h he pendan ca boxylic g oups on polyme backbone p o ided seconda y in e ac ions be ween he ac ylic polyme chains and he glass subs a e. This e ec was also mani es ed in he case o coa ings o he Se ies 4 and explains hei enhanced adhesion in compa - ison wi h he co esponding coa ings o he Se ies 3. The weake coa ing adhesion o he Se ies 4 in con as o Se ies 2 can be a ibu ed o he ixa ion o polyme chains by ALMA c osslinking, which hinde ed he o ien a ion o pola unc ionali ies owa ds he ilm–subs a e in e ace du ing ilm- o ma ion. Focusing on he e ec o ZnO addi ion causing u he polyme chain ixa ion by ionic c osslinks, he coa ings added wi h nanos- uc u ed ZnO we e su p isingly ound o p o ide signi ican ly imp o ed adhesion in compa ison wi h he co esponding coa ing samples wi hou he ZnO addi i e. The im- p o emen o coa ing adhesion can be explained by ioniza ion o he ca boxylic g oups by dissol ed zinc hyd oxide, which esul ed in s onge seconda y in e ac ions and bonding o glass subs a e. Coa ings 2021,11, 347 18 o 23 Figu e 6. Adhesion (exp essed as pull s eng h) o coa ings based on la exes, di e ing in he co alen c osslinking s a egy, su ac an ype and addi ion o nanos uc u ed ZnO. Wa e esis ance o he la ex coa ing ilms was e alua ed in e ms o wa e abso p ion (i.e., wa e up ake) and wa e whi ening (symbolized by a dec ease in ansmi ance). I was e idenced ha wa e esis ance o la ex coa ings can be enhanced ma kedly by in oducing c osslinking [ 1 – 4 , 21 , 58 ]. The imp o ed wa e esis ance is usually a ibu ed o he enhanced s i ness o c osslinked polyme , which es ic s he in lux o wa e and does no allow wa e domains o g ow. In he case o wa e whi ening, i is belie ed ha only wa e domains exceeding a ce ain size wi hin he ilm a e esponsible o he wa e whi ening e ec (ligh o longe wa eleng hs becomes mo e s ongly sca e ed as he domains g ow la ge ) [ 54 , 59 ]. The la ex ilms composed o densely c osslinked polyme s, a e being exposed in wa e , usually exhibi low wa e up ake and con ain smalle wa e domains, he e o e hey a e obse ed less cloudy o he human eye. In con as , he nonc osslinked o sligh ly c osslinked la ex ilms gene ally su e om high wa e swelling and p onounced wa e whi ening. The esul s o wa e abso p ion and wa e whi ening measu emen s a e demons a ed in Figu es 7and 8, espec i ely. I is ob ious ha simila ends can be obse ed o bo h expe imen s. Focusing on he co alen c osslinking s a egy, he assump ions we e ul illed; he highe he c osslink densi y (see he esul s p esen ed in Figu e 3), he inc eased wa e esis ance o he coa ing ilms. As expec ed, he coa ings o he Se ies 1 wi hou any co alen c osslinking we e he mos wa e -sensi i e, while he mos densely c osslinked coa ings o he Se ies 4, combining he in a- and in e pa icle co alen c osslinking, we e shown o be he mos wa e - esis an in e ms o bo h wa e up ake and wa e whi ening. When compa ing he esul s om he poin o iew o he su ac an ype, he coa ings comp ising he polyme izable su ac an always p o ided highe wa e esis ance, which is in all p obabili y ela ed o he smalle in e s i ial a eas ( illed only wi h ini ia o -based sal s) in con as o he la ge in e s ices ( illed also wi h deso bed su ac an molecules) in he case o he o dina y su ac an -based coa ings, leading o dec eased osmo ic p essu e (as he main wa e pene a ion d i ing o ce) and supp essed in lux o wa e . Wi h ega d o he ZnO addi ion, i can be s a ed ha he coa ing ilms added wi h nanos uc u ed ZnO displayed inc eased wa e esis ance in compa ison wi h he co esponding blank coa ings (wi hou ZnO addi i e), which co esponds o he inc eased c osslink densi y due o he con ibu ion o ionic bonds. Howe e , his claim was con adic ed by he esul s o wa e abso p ion o he H _ ZnO− labelled samples o he Se ies 1 and 2 ha exhibi ed highe wa e abso p ion in compa ison wi h he blank samples o he same composi ion. The con lic be ween he esul s can be explained by he dissolu ion o a ce ain po ion o nanos uc u ed ZnO, p o iding a highe amoun o ionically cha ged ino ganic componen s, apped in in e s ices be ween coalesced la ex pa icles. I should be no ed a his poin ha he la exes o he Se ies 4, namely he samples H 4 , D 4_ZnO and Coa ings 2021,11, 347 19 o 23 H 4_ZnO we e ound o p o ide highly wa e whi ening esis an coa ings, which was caused by he occu ence o in a- and in e co alen and ionic c osslinking, esul ing in a highly dense polyme ne wo k. Figu e 7. Wa e abso p ion in o coa ings based on la exes, di e ing in he co alen c osslinking s a egy, su ac an ype and addi ion o nanos uc u ed ZnO. The wa e abso p ion was measu ed a e 30-day imme sion in dis illed wa e a RT. Figu e 8. Wa e whi ening o coa ings, exp essed in e ms o ansmi ance dec ease. The wa e whi ening was e alua ed a e a one-day exposi ion o coa ings cas on glass panels in dis illed wa e . T ansmi ance alues we e measu ed a 500 nm. Nanos uc u ed ZnO has been success ully employed as he an ibac e ial agen in o ganic coa ings [ 21 , 60 – 63 ]. I s an ibac e ial e ec is s ill no ully unde s ood, al hough se e al mechanisms ha e been p oposed, namely (i) di ec con ac o nanopa icles wi h cell walls, esul ing in des uc ing bac e ial cell in eg i y [ 64 ], (ii) libe a ion o an imic obial Zn 2+ ions [ 65 ], and (iii) o ma ion o eac i e oxygen species including hyd ogen pe oxide [ 66 , 67 ]. The an ibac e ial e iciency o he la ex coa ing ilms o he Se ies 4, p o iding he bes wa e esis ance, was es ed and compa ed agains majo ood and hospi al pa hogens, namely S. au eus,E. aecalis (g am-posi i e bac e ia) and E. coli,K. pneumoniae (G am-nega i e Coa ings 2021,11, 347 20 o 23 bac e ia). Tes ing e ealed (see Table 9) he s ong an ibac e ial ac i i y o all he ZnO-added coa ings agains S. au eus,E. coli and K. pneumoniae and mode a e an ibac e ial e iciency agains E. aecalis, he la e e ec being p obably ela ed o he excep ional an ioxida i e mechanisms in E. aecalis [ 68 ]. Conside ing almos he same con en o he ZnO addi i e in he espec i e coa ings, i can be supposed ha simila esul s would be also ob ained in he case o he Se ies 1–3. I can be concluded ha he addi ion o nanos uc u ed ZnO p o ided a signi ican an ibac e ial ac i i y o coa ings and, he e o e, he nanos uc u ed ZnO can be conside ed no only as an e ec i e ionic c osslinking addi i e bu also as an an ibac e ial agen . Table 9. Resul s o an ibac e ial ac i i y o he coa ing ilms o he Se ies 4. Sample G ow h o Bac e ial Colonies a S. au eus E. coli E. aecalis K. pneumoniae D45,5,5 5,5,5 4,5,4 5,5,5 H45,5,5 5,5,5 5,4,5 5,5,5 D4_ZnO 0,0,0 0,0,0 3,3,3 0,0,0 H4_ZnO 0,0,0 0,0,0 3,3,3 0,0,0 a The scale o assessing he g ow h o bac e ial colonies: 0—wi hou g ow h; 1—de ec able amoun (single colony); 2—de ec able amoun (combined colony); 3—second imp in , dis inguishable colonies, hi d imp in can be de ec ed; 4— hi d imp in , dis inguishable colonies; 5—o e g own, con inuous g ow h. 4. Conclusions The p esen s udy is de o ed o he de elopmen o la ex-based wa e - esis an ac ylic coa ings sui able o high-pe o mance applica ions. To dec ease he wa e sensi i i y o coa ing ilms, we in es iga ed he combined e ec s o co alen c osslinking (ALMA-based in apa icle and/o ke o-hyd azide-based in e pa icle), su ac an ype (nonpolyme - izable and polyme izable), and ionic c osslinking (nanos uc u ed ZnO addi i e). The addi ion o nanos uc u ed ZnO, ca ied ou du ing he p ocess emulsion polyme iza- ion, p o ed o be an e ec i e ool o in oducing ionic c osslinks in o la ex polyme s wi hou de e io a ing he coa ing gloss and anspa ency. In e - and in apa icle ionic c osslinks we e in all p obabili y o med ia su ace and in e io ca boxylic unc ionali ies and Zn 2+ ions. The esul s o wa e esis ance es ing ( ocused on wa e abso p ion and wa e whi ening) con i med ha he coa ings comp ising he polyme izable su ac an exhibi ed imp o ed wa e esis ance in con as o he o dina y su ac an -based coa ings, in all p obabili y due o he p esence o smalle in e s i ial a eas ( illed only wi h ini ia o - based sal s), leading o dec eased osmo ic p essu e and supp essed in lux o wa e . I was u he p o ed ha in oducing o he co alen c osslinking p o ided inc eased wa e - esis ance o coa ings, he highe he c osslink densi y, he mo e wa e - esis an coa ing. In addi ion, he ZnO addi i e was also shown o in oduce imp o ed wa e esis ance o coa ings, which co esponds o he inc eased c osslink densi y due o he con ibu ion o ionic bonds. Highly wa e - esis an coa ings we e o med ega dless o he su ac an ype in case o a concu en employmen o h ee c osslinking s a egies, namely ke o-hyd azide c osslinking, ALMA copolyme iza ion and ZnO-based ionic c osslinking. Ne e heless, he applica ion o he polyme izable su ac an was shown o imp o e signi ican ly coa ing ad- hesion, appa en ly due o he co alen a achmen o su ac an molecules o la ex pa icles, disabling hei deso p ion and mig a ion a he subs a e– ilm in e ace. Mo eo e , ZnO addi ion was shown o p o ide p onouncedly imp o ed MEK esis ance and signi ican an ibac e ial ac i i y o he coa ing ilms. I can be concluded ha en i onmen ally iendly coa ing binde s using nanos uc u ed ZnO in he ole o an ionic and an ibac e ial addi i e we e de eloped, p o iding wa e - and sol en - esis an hygienic coa ings, sui able o he p o ec ion o a ious ma e ials. Au ho Con ibu ions: Concep ualiza ion, J.M.; me hodology, J.M., A.K., and J.V.; alida ion, J.M.; in es iga ion, J.M., P.M., and D.S.; w i ing—o iginal d a p epa a ion, J.M.; w i ing— e iew and Coa ings 2021,11, 347 21 o 23 edi ing, J.Š.; isualiza ion, D.S., P.M., and S.Š.; supe ision, J.M.; p ojec adminis a ion, A.K. All au ho s ha e ead and ag eed o he published e sion o he manusc ip . Funding: This esea ch was unded by he Minis y o Educa ion, You h and Spo s o he Czech Republic (p ojec LM2018103) and he Czech Academy o Sciences, Ins i u e o Theo e ical and Applied Mechanics (p ojec RVO 68378297). One o us, J.V., acknowledges he suppo o an in e nal g an om TBU in Zlín (IGA/CPS/2020/001) inanced om unds o speci ic academic esea ch. Ins i u ional Re iew Boa d S a emen : No applicable. In o med Consen S a emen : No applicable. Da a A ailabili y S a emen : No applicable. Acknowledgmen s: The au ho s would like o hank Roman S oboda (Uni e si y o Pa dubice, Facul y o Chemical Technology, Depa men o Physical Chemis y) o he DSC measu emen s. Con lic s o In e es : The au ho s decla e no con lic o in e es . Re e ences 1. Winnik, M.A. In e di usion and c osslinking in he mose la ex ilms. J. Coa . Technol. 2002,74, 49–63. [C ossRe ] 2. Taylo , J.W.; Winnik, M.A. Func ional la ex and he mose la ex ilms. Jc Res. 2004,1, 163–190. [C ossRe ] 3. Macho o á, J.; ˇ Ce noško á, E.; Honzíˇcek, J.; Šˇnupá ek, J. Wa e sensi i i y o luo ine-con aining polyac yla e la ex coa ings: E ec s o c osslinking and ambien d ying condi ions. P og. O g. Coa . 2018,120, 266–273. [C ossRe ] 4. Rucke o a, A.; Macho o a, J.; S oboda, R.; Puko a, K.; Bohacik, P.; Valka, R. 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