r.",,.*
Transkrypt
r.",,.*
PleParation oi new Polyorganosiloxane acrylate and th€ PIoPe ies of Uv-cured acrylate compositions containing it sunnary A nc'! pliyoĘ 1ośilonn. lrv la te ( llosA ) has bee| obtained .y.lohcxvlinD. wtlr m.thyl .nd sroups (McAPs) akl h.xan.dn,l diacrv r.",,.* '. ,l t.tu' .. "r.' - .;, h alyyli.Sroups ofnDD^ pOS^ hasbccn ofN-H Sroups ofMCAMPSw lale l .poxv_dia.q,lat! resn'' k has loty{dyli. sys.ń blel (HDD^ + bu\1a.ry. łihd d'at .vcn small PosA .onlcnt (] ]]$l li).a$!ś li8|ifi.atrl d'anlles ofŚlrlac ProPc ics of.urcd.oat Egs NaltlY .ontict ind rśhy*crcsjs i]trcłsc' 8lsŚ dc.tĘses jl. 'Ęh Iijn]hirtlncs docs notdFngc' UsjnAxDsDtthod ił !vłŚ show.d thł !os^ h td on thc str Kcy wolds| polyorganosilonne lavlak, cPoxy aÓylic s}.lcms, modih.i. tiotr,Uv{llinA,fffa.!ptop.łi!ś,\'!hability' sclcdivc ly .on.cn bi Th. Uv.umble syslcDt IiId jmPoń tapPli!żtio|! i,r mafr i'du*rial liclds roi thcp itcns in rom orfilms, chmi s,.o i',8s, pigDr.r6, adhcsivś .r Pri't d .irĆuih, altl i'r ty. Thef lse lcsulb floń th.n u Iollows h !3 h .u rc sFccd, cncĘ]' .oNcn'a tion solvcn L ' łlcc fornn]lit]oI and c\.!llcnt Ph],si.al PropUti.s l)-71 Thc uv-curabrc s$.nE gcnualr ajo' .onrPoneŃ: rca.ti|c poly'nclizable oligom.A, h l5,el ro obbnr drc sulfa.c (Btirgs drowin8 lirticuLłr Prc},crhs,lhc us. ot monomcs an,r oliaomcE coirhnlirg sili.oncs or si]ox r.s ń vcr], aitacŃt, owing io thc P.n'liit lnam. brktiś3Ńen b]r th! preseM.of silicDtratom lr0,]rl. Itś Per publiśhed n11ł,lńe!v" n2l A sj]i.on. cońPounds PrcPżĘtjon oli od ]s thc iLi|c yl funchonil rcichon of h-V' to producc adyliĆ fundi]nal silno|e <,ńPound, With ń. Hcl.s i by' prcdudlr0, lrl Anothcrpro.csolphotopolyncLizabl. poryorsarosiloxin.s pEpaniion by Lca.rion or hy drosilonres w h icnliics iir rhcprscn.coraphtnN) .iial]'* hłs bcc|r ł]sodcs bld ll]]' h or prcs.r t rm* a ncw pol)'orga nosj roxa m adv lai. Js synlhcsized by Mi.hłol a Dkoduccd into ePoxy dj..lvlii. (B|DA) 5],ś.ń5 it 3.ciusc no . ilvśN.s uscn and noby Pnrducb Wc'c thcsvnth$śind puriricatiotr r!c!csinplc. Unu$ml $rrac.prop$hcsorihc 'omcd, FÓlymdi( nLms obiin]cd l i]? UvcuriĘ hch|iquclfse Thc b.s..ompon!!k oI IÓrńlla ol shc]l cpoiy rg\jń5 E 327 Wih a duct ot]tained ńdń L 327 !!ós dc avcla8cmÓkĆula!wci8htwis.ssuncdlo],c.quil!) Hetanediol dnovl.ic (HDDA) łnd buil] (BA) as adiYc dih'enb wer. pur i yliI! Mcthyl.nded ĆyĆlohrxylańi'l. fl]dj1i!d Polvor gżnosilox.ne (McAPs' M , = 3r 02' Mi = 379r) l'as 5!F Plicd by Hcn8zho! DalU lńd!*ł Ltd 2-hydroxt 2,2 d,rdhyl'r Fhc (Darc.ur 1173, Ciba'Ccisr, switz. and) wis uscd is Fhobinitńlor lor Uvculilu' AIr rhe narmiib nr ihis udv . nsed rs re.crv.ir v houtrunhcr Pu ri. ion Th. polyorEano5iloxań! i.lvlab (PosA) Was PIc' ParĆd bv ńŃln8 JlDD^ v h \4c^],s i'] ProPo ion 2 ] vol/vorGcc Equihof 0)l ,'., *, ,,.1 . ,,! . , 1oln.d in i.tahvdtolurłn solft talt-vńgd 1o]Aólumtru'dsthc.p."i l o-u-l l Th..ontaĆt Źnglc mcłsurcmcnb wcr. pcllo'nd trsi'u Ema nśrumc|t The meas i'' ail ar iljon tcmP.rłturc fol clli samFlc l!a* 5i\ ńeisurcmcnb weio Pctf.!ńcd, Fl dnhucd wai.r il1 dirf.renrprtu ol ihc smptc surfi.c Th€ di'I!fun.cs jn ivcraAc valucs wclc m morc lhan 2'' 1or rh.'dlan.iIgłn31ca|d the Eedi'l3 ń'.c of inaryzed lstus x !,), .n Eosco$] (xDs, orntrd Is]+300) Thc sŻc ot t,rDr was 3l.' U\:.uIcJ i smph Hłntn.$ ofUv curcd film wis clah'iicd NijrN aEY c Tianjb IŃrumdt comPafy Thc films w.r! appl (95x3Bx5 ńm)byacoatfi wirha 100!m s.P r+\ ,;.,,,L\ 25'cU'nga surfa.! fusi*i]rc t$t.rot tyPc Zc3ó lrorn shan8hailNtuńcntco Thc t.st \oltigcMs ]000v ,r' ThcsP.Ćllar glosof tlrlrccdtli ingshe 60iFFio shc ln rumetrLśLTD T tlt glis(rcIla.tjVcindc\ ł!= ] 5ó7)Msdclimdas]00. fus froń 70'c n' 24 h, wfth mcchaIi.i]łiiiij]8 Thc l]quid Pro. IJ N\,lRsp.Ćhn of Pos^ is s]rownin Fig. ] Thcn łIcih.sigmls l.lit.d to aayli. lroups {5'73ł r0 PPm) sholn i,r rhe\Pc.rum orihc prodr pdaks or by BEDA (6a wL,D'HDD^ c0 nł'' " ), lros^ (various ltnmnbłtiońs) an.l Phoioiniińtor l] wt ,]lJ in thc liqlid loinuhtfuńs uscd ln thc rcpo &1 rvs..o cd onro a gla$ plaie wr 5uPFo 'Thc| th. sanPl.s vs. o'cd usi'rg łhc Ulta ljoht High PresŚllc !'c!.uł' LJmP 0 k$' 31] W/cń' Huiyixfu [llcbical Llght souru T.durolÓ8y Devek,r mcni Lrd, Brijins) vsii€ated waś ]25 Frc.lilmswcr.obbimd by Pecling r! NMR amlysis Ni" Fc.romcd at a Bruklr a00 Nhnn.nt !Śitu cDcl] is solvcni FTt( łnalvsiŚ \'as Psfum.d usi|E Rrx 65A FTjR \'tsŻ sp.drophotonclcr (^nłhct, UsA) Molrula! wcrshi dlshr,uiiotr (,L1wD) of PosA vis measllĆd bv gc] Pcmc ion dłomak'graPhr' (cPc) icyli. sroups i', thc pod! 06ł0o ) Thcnunbo ,.rłgcmo a!d w.ight łvcrag. mo]ĆĆ|lil ') nEsur.d bv crc !!ci! 3łl7 rJ PosA FTIRsp{tum wejghł ( LccuLiI wcighł (Mi ) or ,lł26, Hp.chvdl s the MWD Vallc t!Ź5 r 3] wer? performcd on lhc .ur.d ńlńs Peeled off from gla$ rsżsl'bcn.dńc the bsb P GIaŚ) sid?' Tnc oniact anglc of a ńiafute .ÓmP$ed of Pure ePoxy- i(ylic min (BEDA), HDDA and aboui40"onilE gl.ssidcand42oon thcatrsidc when PosA wa added to $is.ulłblc fomulahon' and ihc ńixfur. Ms pla.ed on lhe same sub nte (j. 8las) ihe wdtibil ych rgcd, as evidenced in Fis.2 by the.onrad an31e lesult' oblańcd wth n'atc. Th. dła d.arly Ił 3 xDs rs!łs oi't al PasAtonc"tdion onnrrdr rcirs atbd r.0wr 'r ThnPhcooneńoni5 tyPidl ('a hyd!,Phobic n,id lloś '7A ol UV{!{/ Iil ExccPt for the direĆt mrasuremenb ol conbct hcr iŃomation.Ón..rnińg lhe lained by conh.t ań8l. hyslcl$is, !: Iu lween łdvancin8 a.d Pe'ed sholled th losA w.s .frc.fi\c o Uv culcd {j|!ś, whjlc thc 3la5s 5 PoPcrhcs łs ol lhc purc rcsin lt ncłns ihłt ihc lcs poldiirsideisen chPd wth PosA ]]le.dvan.ing.ontad aĘl€s of Uv rcd lilms in_ .reased lvilh ińdssing of PosA . Ó1 PosA shows a "PlatełL va]L.'' (]0]'') th l'aŚ a'' {or ńajo t-v aĘl.' rc€dln8ing of thc miiciik, PinicuLłrly thos .onhinin8 both hydroPhobiĆ and hydroPhili. 8iouPs ai the surfa.. For tho Pur. r$lń śvallc as 25'aid 3d' , rcsP..tivlly on thc glaŚsidi in rh.Prcs.n(oiPolyolgan6ikxahełdt]ai!, thc.onhd anglc hyslmsś dd |ot the ail śidoas Fig' 4 shoq lh4c }' kr6is. k was ako depend?rt on P 111e rcsuks can be explain.d by the racr ilmt hydropho. bic mononEr lÓrms ł hłdÓ8rml Thc sclcdivc modiri.ation of filn surfa.c was on' limcd by xDs r6ulb. Thcy allowcd rhc cstimarion ol ihe rn.enbation or si elem.nt in th UV{[cd As slmwn m FĘ 3 'iln surfacc rmPosiiion between the air sid€ łnd lhe 8laŚ sidc wm notcd. Nam.ly, thc absorpiion pe* or si elemeni on the glaŚ side r'as lety ]ow on tlP Óntary an evident absorPtiÓn Feak ol si s gl.n IrosA <,n.cnrahon in uv olabl ofS, clcncnt on thc an sdc ircrcrfd. So wctabilily ls dearry coirelatud b si (i.. PosA) FiŚ' 4 rffnt hwkl{iŚ tl o| thć PosA aldnnń;on d| nI żi, sią. rł Uv..llll ti't\ ańrl h.r.rÓgoneiry inĆrcased ai fiEt, tl'€n, as previously, kePt a coĄśhnt valle o wt' 'r' o1 ?06A) indj.łii$ lhe foma_ hon ofin cqu $riuń surIaĆe layĆr Hadncs was onc of lhc imPo an'Pop..ńelofUv .!ied films lor nany apPlicalions' łnd ii was r.lihd io thcqoŚslinkiń8fu8vdkdemii-va icy]i. gfuuPs iI th. ńole.!lal ch Table 1 shÓUŚ th. sJrlace rĆŚńta the air side of rhc LrVrled filń is en ri.l,ed with PosA and ros^ n b.tu tl'an thc ot)rs r.rylic omPoncnś, thc vłlLlśoI surli.c rc'śin.c of rmPositions .ÓnhniĘ FosA wcn highcl thinth one of Plle adyliĆ filń lilłrs' Be.aLse filldry'jlms.rc ako sńParcd ń Tablc 1' fiis Pbpcny ol Purc aol]lr Iilń was ibout ]17'6, whil€ PosAintodudion siBnil a new PosA, which .an b. i smd idd ivc ,!.., MCAI'S with nr krdars dffd n'fun uvrrtu littF .I Poś,{ aJ a prolo|s.ho| of thc Frdńbo| iiń. in hirdncss to som. linit bc.rus .auses higher conyeNion of acrylic Sroups. Unfo unatell,, nrrdn$s d Lw dr.d riln w ińal śa3ąśo1ifadia hon' with Prolongłtion of trk dń ńon iim.' hird ńcs of rrL\eprueneor effsti!.phobiniiiaroriheaolir. ic5i(s {dc rapidly dGdink d am Pol)frÓdatiÓn ń€hłńiln oui rs oI uv Michaela spc.hosopi. mlsis .ofrirn.d ł0] =t Fł 5 qr|dl HDDA for hatdn6s .an bc dPlaincd fusP b}, solubiliĘ of Po6A in pure ofrjv nbl.liqJ lohn en.y ]ition dNcmcd, whrh lc'ds b thc lows cIńc]cn.y oa Uv itridńtion. At tjr $mc hmc' only a ltlc anount of PosA miy Lt nrfudu..d iŃo orcd fiLn' so th. chłnfc o( thc ooślinkin8 deNilt of łh. ńLns was liltlq whió lcd lo thc rcŚjn Thai n' rhc d grcups of McAPs lith rhe aÓyliĆ siouPś .l IIDDA Uv .urahlc Ęsin ńlńs wc'c Prcparcd by urtoducho| of l,06A inro thc fomut.hon. xDs D that Pos^ cnńchcd ihe łir side of rhcn surfaes show sha9ly r lincd hydiophobi. dm radcr (i'r spit€ .I the Pl*en@ of ńań]r Polal ol I grÓLFs in d'e Polymcic nctuork) ind i h ra.t angrc Thc hlglrGr conhd in8lc of uv-amd films włh Nato rach€d 1010. Uv{nrcd fitms with Pos^ showhishcr$trraccr6ishrcc d rorrcrspcd,r 31cs, l Blrak L. / ce,' 2' cÓjdĆnR:/ {. Lrvorchak N! J, nrb.ri Trł Novcnb. orJ t.,! 1997,69,No 37],33 3. YtQ',NauFąns.,sanhrEl'll,Żha s. l ĄPl lr B Dekel ch., MÓUsa K': H /. I / crrr rdr o{, Irnouc,sordatA,crvczz,n J: I c,D, rdob roneui ^., c, roslli M: /. L{fr,, BołliĘ K'' Adańs J'sbucksi / cI l' ^PPl Błtc! R ,ąn J., rer2, 61, cr, rd ree5, fo,r s.i T.tl ]996, 9ci 1997,66,1997' Dłvidson R s ' El1js R J, w krjEon s