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1 w œwz, 48«1y 2011 Textile Science and Engineering Vl. 48, N. 1, 2011»Ÿy w PVA v Ÿy w³p» Á y 1 w w š œw, 1 w ƒ w ( / k) Phtactive and Antimicrbial Prperties f PVA Films Cntaining Varius Organic Phtactivatrs Ki Sub Lim and Kyung Wha Oh 1 Department f Fiber and Plymer Engineering, Hanyang University,G Seul , Krea 1 Department f Hme Ecnmics Educatin, Chung-Ang University, Seul , Krea (Received January 2, 2011/Accepted February 4, 2011) Abstract: Antimicrbial PVA films cntaining varius phtactivatrs were prepared using a slutin casting methd. Benzphenne, 4,4'-bis(dimethylamin)-benzphenne, 1-hydrxycyclhexyl phenyl ketne, 2-methyl-4'-(methylthi)- 2-mrphlinprpiphenne, thixanthen-9-ne, and 4,4'-dihydrxybenzphenne were selected as the phtactive additives. The UV absrptin, transmittance and radical frmatin, thermal stability, structural and antimicrbial prperties f the prepared films were examined by ESR, UV-vis, DSC, XRD and an antimicrbial test. The results shwed that the UV activated benzphenne, 4,4'-bis(dimethylamin)-benzphenne and thixanthen-9-ne prvided excellent antimicrbial prperties after UVA (365 nm) irradiatin. Keywrds: antimicrbial, ply(vinyl achl), phtactivatr 1., ³ w y l x w z ƒ š [1-3]. p z w ƒ w yw»w ƒwš, š w xw., z jš ƒœ s» y,» ³ w y y jš [4,5]. w w y ƒ š. ƒ, ƒ t» w yw ù ³ ww w w, w w, ƒ w y w š. w³ w w š w ù, ù y» ƒ» ã w Crrespndence t Kyung Wha Oh (kwhah@cau.ac.kr) 2011 The Krean Fiber Sciety /2011-1/ [1-3]. w w³ ƒœ w³» w ƒ ù t ƒ w f ƒ š w yy w ww w w w w [6]. Ÿ w y y ww w ³ Ÿ ƒ» š [7]. Ÿ (phtcatalyst) œ» ƒ w yw ü, ü e ƒ. Ÿ ¾ ww» ypk (TiO 2 ) w ƒ w š [8,9], t TiO 2 gqw w» ³ yw q w Á òw w ³ š ³ k w ƒ [10]. ypk (TiO 2 ) Ÿ nx (400 nm), œ ƒ x w y ƒ w e( OH) r (O 2 ) w» yw y w g k ƒ y j w / y w [8,9]. ù y» w t f w 42

2 »Ÿy w PVA v Ÿy w³p 43 ƒ š š, Ÿ yw œ w w,» Ÿ ypk (TiO 2 ) e ùkü» e ƒ y ù yy ƒ w [9,11].» Ÿ w» Ÿ w, x» Ÿ benzphenne ƒ» Ÿ z e š. benzphenne w³ p š» Ÿ ypk (TiO 2 ) j z ü» Ÿ ü t. q Ÿy 50 ƒ Ÿ q w benzphenne sww» Ÿy 6 w ply(vinyl alchl)»» Ÿy w v w. v UV-vis spectrmeter»» w Ÿ p d w. ƒ q (nm) ƒ j w UVA light(365 nm) z ESR(electr spin resnance) d w UVA z free e y d w. w» Ÿy ƒ w PVA v w DSC(differential scanning calrimetry) X- ray diffractin d w p y p y w š,» Ÿy ƒ w PVA v UVA light(365 nm) z UV-vis spectra d w n y d w. Ÿy w PVA v w w³ l p ww » Ÿy benzphenne (99% pure), 4,4-bis (dimethylamin) benzphenne (98% pure), 4,4 -dihydrxybenzphenne (99% pure), 1-hydrxycyclhexyl phenyl ketne (99% pure), 2-methyl-4'-(methylthi)-2-mrphlinprpiphenne (98% pure) š thixanthen-9-ne(97% pure) Sigma-Aldrich l w w, š ply(vinyl alchl)(atactic, 87-89% hydrlyzed, average M w 85, ,000) w Sigma- Aldrich l w w.» Ÿy acetne w v PVA 80 C 2 k w ww,» Ÿy acetne ww w» w q w e 1 w [11,12].» Ÿy /acetne PVA/distilled water z yw 24 p» w. z plyimide v yw slutin castingw 48 k z»(jeio TECH, OV-11) w 60 C 8 w v w Ÿw p :» Ÿy ƒ w PVA v Ÿw y w» w UV-vis spectrmeter(scinc C., S-4100, Krea) w q 200~800 nm Ÿ (absrbance) d w š, UV-vis spectra d q ƒ j» Ÿy 3 w. z pristine PVA v» Ÿy ƒ w PVA v w UVA(365 nm) n d w w. Ÿy p : UV-vis Ÿ k UV Ÿy ƒ» Ÿy PVA w free e y w» w ESR(electrn spin resnance) Spectrmeter(JEOL C., JES-FA200) w MHz frequency X-band d w. UVA light(spectrline C., CC-81, bandwidth: 365 nm, 8 Watt) 30 z ESR d w free e y w. y p : p DSC(TA Instruments, DSC2010) k 10 C/min 250 C¾ g w (T m ) ( H m ) d w. v X-ray diffractin (Rigaku-denki, Japan) d sƒw Cu K α X-rays (α =1.54), w date 2θ =0.05 Step 5-60 (WAXD)» w. w³ p : w³ Ÿy ƒ w PVA v pristine PVA v y s ³(Staphylcccus aureus ATCC 6538P) ³(Escherichia cli, ATCC 8739) w v (JIS Z 2801) ww.»³ 2.2~ w 5 Petril dish 5 5cm v š v 0.4 ml ³ š r 4watt 8 watt UVA(365 nm) light 2 w 1 2 z 20 ml v û ³ ü v ³ w z 1ml w 9mlƒ x w ³ w. ³ 1ml w Petri dish š š w z C w ³ d w (1) (2) w. Textile Science and Engineering, Vl. 48, N. 1, 2011

3 44» Á y Mb Mc Mb Mc (%) = (2) Mb w³y e(s) = lg (1) Ma: t x³ z ³ s³ Mb: t z ³ s³ Mc: w³ƒœ z ³ s³ Ma x³ w z ³ s³ Mbƒ w s³ ³ ƒ z s³ ³ ù y y y w» w» w. Ma Mb d y w w x š w. w³y e(s) (%) t w³ ƒœ z s³ ³ w Ma sw, x q». 3. š 3.1.» Ÿy Ÿp z ƒ»ÿy» w q Ÿ Figure 1. UV-vis spectra f pristine PVA film and PVA films cntaining 6 types f phtactivatrs; (a) benzphenne, (b) 4,4'- bis(dimethylamin)benzphenne, (c) thixanthen-9-ne, (d) 2-methyl-4'-(methylthi)-2-mrphlinprpiphenne, (e) 1- hydrxycyclhexyl phenyl ketne, and (f) 4,4'-dihydrxybenzphenne. w œwz, 48«1y 2011

4 200~400 nm Ÿƒ w r wš Ÿy kw Ÿp w. Figure 1 pristine PVA v Ÿy (1.0 wt%) w w PVA v 6 w UV-vis spectra Ÿ d ùkü. Ÿy w w PVA film pristine PVA v Ÿ ƒ Ÿy q ƒ [12]. benzphenne 250~300 nm, 4,4'-bis(dimethylamin) benzphenne 300~ 400 nm, thixanthen-9-ne 230~300 nm 350~400 nm, 2-methyl-4'-(methylthi)-2-mrphlinprpiphenne 210~240 nm 300~330 nm, 1-hydrxycyclhexyl phenyl ketne 230~260 nm, š 4,4'-dihydrxybenzphenne 250~400 nm w Ÿp ù kþ. q Ÿp w q w» Ÿy ƒ w d m 200~400 nm q sw k Ÿy 3 w. 4,4'-bis(dimethylamin) benzphenne, thixanthen-9-ne 4,4'-dihydrxybenzphenne sww 3, x w [12] Ÿy z ƒ benzphenne ƒ g 4ƒ Ÿy x ww.»ÿy w PVA v Ÿy w³p » Ÿy Ÿy Figure 2 pristine PVA 4 Ÿy UVA (365 nm) w UV z w ESR (electrn spin resnance) d w free e y w. UV chamber 30 UVA w z ESR d w. PVA UV z vjƒ ùkù 4 Ÿy 4,4'-dihydrxybenzphenne w 4,4'-bis(dimethylamin) benzphenne, thixanthen-9-ne benzphenne UV z magnetic field 340~350 mt vjƒ ùk û. Ÿy sw carbnyl grup(c=o) UV π π * triplet biradical x w» [13]. vj ƒ ƒw free e ƒw w [14]. d Ÿy 4,4'- bis(dimethylamin) benzphenne vj ƒ ƒ f UV z vj ƒ ƒw free e û. thixanthen-9-ne e x y UV z vj ƒ ƒw e x y w. benzphenne UV vj dw ù UV z ƒ w vjƒ ùkû. 4,4'-dihydrxybenzphenne v Figure 2. ESR spectra f pristine PVA and the 4 types f phtactivatrs scanned immediately after UVA (365 nm) irradiatin fr 30 min; (a) UV irradiating and (b) n UV. Textile Science and Engineering, Vl. 48, N. 1, 2011

5 46» Á y j ùkù e x ù y w. 3.3.» Ÿy w PVA v p l q UV Ÿ e 4,4'-bis(dimethylamin) benzphenne thixanthen-9-ne z»ÿy wš sww v w ƒ ƒ r» benzphenne w. Figure 3 pristine PVA v 3 Ÿy 1.0 wt% PVA yww v DSC d w ƒ w v. Table 1 DSC d ey w, T m ( C) H m (J/g) ùküš. ƒ T m ( C) w, 4,4'- bis(dimethylamin)benzphenne wš Ÿy w w PVA v T m pristine PVA v T m w y w. ù 1% ƒ vj ƒw H m ƒw ³ w ƒw v ƒ w š. Ÿy 1wt% w w PVA v DSC curve pristine PVA wš Ÿy T m vjƒ ùkù p (T m ) 47~51 C benzphenne vjƒ ùkù» PVA Ÿ y yww v x ƒ w š w ƒ ³ w x [12]. 3.4.» Ÿy w PVA v y Figure 4 pristine PVA v 3 Ÿy 1.0 wt% w w PVA film X-ray diffractin d w ùkü v. pristine PVA v vj [15] semicrystalline vj ùkü [16]. benzphenne 1.0 wt% w PVA film pristine PVA film v j ƒ 2θ=19.5 w ù 4,4'-bis(dimethylamin) benzphenne w w 2θ =19.8 vj ƒ ƒw y ƒ ƒw 2θ =11.7 vjƒ š, thixanthen-9-ne PVA ƒ 2θ = 20.0 vj ƒ ƒw š 2θ = 11.85, 14.9 vjƒ ƒ û. 4,4'- bis(dimethylamin)benzphenne thixanthen-9-ne xk X-ray diffractin ƒ d, e vjƒ ù ƒ Ÿy PVA ùkù v y ƒ k. Ÿy ƒ v y ƒ DSC ew y w. Figure 3. DSC thermgrams f (a) pristine PVA film and PVA films cntaining 1.0 wt% varius phtactivatrs; (b) 4,4'- bis(dimethylamin)benzphenne, (c) benzphenne, and (d) thixanthen-9-ne. Table 1. Thermal characteristics f the pristine PVA film and PVA films cntaining varius phtactivatrs (1.0 wt%) Phtinitiatr T m ( C) H m (J/g) Pristine PVA ,4'-bis(dimethylamin) benzphenne Benzphenne Thixanthen-9-ne Figure 4. X-ray diffractin patterns f (a) pristine PVA film and PVA films cntaining 1.0 wt% varius phtactivatrs, (b) 4,4'-bis(dimethylamin)benzphenne, (c) thixanthen-9-ne, and (d) benzphenne. w œwz, 48«1y 2011

6 »Ÿy w PVA v Ÿy w³p 47 Figure 5. UV-vis spectra (transmittance) f the pristine PVA film and PVA films cntaining 1.0wt% phtactivatrs after UVA (365 nm) irradiatin fr (a) 1 hur, (b) 2 hurs, and (c) 3 hurs. 3.5.» Ÿy w PVA v Ÿw p Figure 5 3 Ÿy 1.0 wt% w w PVA v pristine PVA v UVA(365 nm, UV light 16 cm) 1, 2 š 3 w z v n d w. q 200~800 nm, 4 film UV ƒw n ƒ w y w. UV ƒ v y ù t UV w w [13] n ƒ ù š ƒw. benzphenne ƒ n w 4,4'-bis(dimethylamin)-benzphenne, thixanthen-9- ne n ƒ. 3.6.» Ÿy w PVA v w³ p w [12] 0.5 wt% 1.0 wt% benzphenne PVA w w v z w³ l p w w w w³ y w. ù» ³ 10 v 3 w, 8 watt UVA(365 nm) light 5 w 1 w Ÿy w w v ³ ³ š. ü w» ³ m 10 wš 5 [v (JIS Z 2801)] x ww, UVA û ww x 0.5% w w w³ w Ÿy 1wt% w. Table 2 Figure 6 benzphenne, 4,4'-bis(dimethylamin)-benzphenne thixanthen-9-ne 1wt% w w PVA v pristine PVA v y s ³ (Staphylcccus aureus ATCC 6538P) ³(Escherichia cli, ATCC N ) w v (JIS Z 2801) w³ sƒw. UVA(365 nm) w³ sƒw» w v ³ w z UVA 1 2 w z w³ s ƒw. Ÿy w³ Ÿy carbnyl UV w triplet e wš PVA H dnr l H ñ š w H 2 O 2 w w³ w [17]. Ÿy sww ³ y s ³ w w³ w ùkû. UVA w 4,4'-bis(dimethylamin)-benzphenne thixanthen-9-ne Ÿy ƒ w PVA v y s ³ ³ ³ 87.5% Textile Science and Engineering, Vl. 48, N. 1, 2011

7 48» Á y Table 2. Antimicrbial test results f pristine PVA and PVA film cntaining varius phtinitiatrs (1 wt%) with UVA irradiatin fr 1 and 2 hurs UV (1H) UV (2H) UV (1H) UV (2H) Staphylcccus aureus Ma Mb Mc Antimicrbial activity (S) Reductin (%) Pristine PVA Benzphenne ,4'-bis(dimethylamin)benzphenne Thixanthen-9-ne Pristine PVA Benzphenne ,4'-bis(dimethylamin)benzphenne Thixanthen-9-ne Escherichia cli Ma Mb Mc Antimicrbial activity (S) Reductin (%) Pristine PVA Benzphenne ,4'-bis(dimethylamin)benzphenne Thixanthen-9-ne Pristine PVA Benzphenne ,4'-bis(dimethylamin)benzphenne Thixanthen-9-ne CFU/ml: clny frming unit. w w w³ ùkþ. ³ 4,4'-bis(dimethylamin) benzphenne w PVA v ƒ ³ 98.5% ³. Ÿy ESR e j ùkû w³ sƒ 1 UV w y s ³ 98.5%, ³ 95.7% ³ w w³ ùk þ 2 z y s ³ 99.5%, ³ 98.2% w w³ ƒw. thixanthen-9-ne w PVA v 1 UV z y s ³ 93.1%, ³ 87.5%. 2 z y s ³ 96.6%, ³ 90.2% ³ ƒw. w [12] w w³ benzphenne w 4,4'-bis(dimethylamin) benzphenne thixanthen-9- ne ³ benzphenne y w. Hng Sun[12] û UVA w 4,4'-bis(dimethylamin) benzphenne thixanthen-9-ne UV ƒ û w w³ ùký y w. 4. ey x» Ÿy w š ƒ w ww, p» p, ü w y w» y wš w. w Ÿy»» s wš Ÿy p š» Ÿy w w p w.» z»ÿy benzphenne sww» Ÿy 6 w ply(vinyl alchl)» w» Ÿy w w v w. v UV-vis spectra»» w Ÿ p d w Ÿ q ƒ š Ÿ w w ESR(electr spin resnance) d w free e sƒw. 4,4'-bis(dimethylamin) benzphenne, thixanthen-9-ne benzphenne UV z magnetic field 340~350 mt vj ùk ü w Ÿy x. v w g ƒ w v, w œwz, 48«1y 2011

8 유기광활성제 함유 PVA 필름의 광활성 및 항균특성 49 Images shwing the effects f pristine PVA and PVA films cntaining 1 wt% varius phtinitiatrs with UVA irradiatin fr 1 and 2 hurs n and in petri dishes. Figure 6. Staphylcccus aureus Escherichia cli 적, 광학적 특성 및 항균특성을 파악하였다. 그 결과 선정 된 광활성제 함유시 필름의 열적 특성 및 결정화도는 1wt% 첨가시 별 변화가 없었으며 4,4'-bis(dimethylamin) benzphenne, thixanthen-9-ne의 경우 약간의 결정화도 가 상승하는 것을 보였다. 필름의 투과도는 benzphenne, Textile Science and Engineering, Vl. 48, N. 1, ,4'-bis(dimethylamin) benzphenne, thixanthen-9-ne 순으로 우수하였다. 항균성은 기존에 자가청정제로 사용된 benzphenne과 비교하였을 때 4,4'-bis(dimethylamin) benzphenne과 thixanthen-9-ne 모두 benzphenne 보 다 낮은 강도의 UVA에서 더 우수한 항균성을 보여 우수

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