New generation of cationically Uv

TOUMERY 20M,49, nr7
7bl' \lFń cŻa cc
€
MALDALINA
( RBA| Ą:,
DA' VAnA
VARF\l'
New generation of cationically Uv-cured epoxT adhesives
containing dyes
RAIID COMMUNICATION
sJnnaiy
A ne\' da$ ol.ahonl.au], Uv-orcd ePoxy rsin base adhesivś
dy6
and allyl or l'ProPcnyl cthq modilieE ha. bccn clżbola'cd
ońbining
Thc dyes (.ońmm.ial prcdud of ciba) wer dire.tly aPPlicd into the systens
and showcd vcry Sootr solubiliry in .onposiiions sbdicd Model e$eE rnhi'ring oH 8rouPs, i. nonoallylornono 1 pbPenylcthdofbntłne ],4 diol
(MoAlE and MoFnE, respe.tiv.ly) h
ol the iyP. of dy! on Lrv Ęnedioń, adhesion to glis and th. shea! 5teńgth
Thc obblncd
wct. ińtensively .olorcd,
'dhcsives
bansParcnt'łnd.hind.riz€d byveiy8oodadhesion
lo glasandhĘh.ollc
Xe y w ord
s epoxv
a
uvradi^rion .u!ns his bccomc
dhes ivĆs,
i wcl
dy.s, Plaśilying nod ificre, ratiońic L^,:cu
iccepied
b.hńÓlo8y vh(h, b.cusc of its distindatlmntłgs, ]li5
found ninifold induśd.l a pplicai
dl],in8 protetive mati\gs, PriŃhB
A
sollcnlfre liquid
rin
.an be
ł
sbnily iŃo a soLl polynd ńaEial sińPly by cxPosur
brjv llglt ł ańbi. bmPsrforc,without lmksionoI
volatil. oBanic conPounds n__nl Uudtrin8 i€.hno
l%y of ePÓxy !.5ń5 h:s showe,l rapi'l .onńe.ial
Brovth wnhm thc hst I0-20 y.ars. Ii seens ro be vrry
abachvc 6on both chemi.al d tÓńońi.al Poin6 of
vic\! Uv_ red epoxy po]ymex Śho\' ńany uscful Prc.
ies ('. exĆelleńr adhesion, lood chcmicalEistan.e
and
'e good
meĆhanidlploPshc' b
bushncs
Then.xibili'}andothcrPlope ies of ihe re$'lting FÓly
n.rs Ćań bc adjushd by
of nexibiliiy 3mntin3
'hc.hoi.c
.losslinkinE a8enis' Re.eŃly,
drcre have bccn ńżny ap.
Pl@chs b modiĄ'iĘ of dre lotń
r.ms with theaim b inprov. rhe bushnss t4l.
oul previols lśealches hav. dcm
mośeff€Ćtiv. m.dific( of cPoxy bisPhcnol A-bas€d
r*in ate nlltifundlonil illyl oI ProFleńyl etheĄ of
schclcd dlols' 1l was ako Ón.lJded that allyl oI PIoP'] _
'cny l ethas .ollain ing !ńFlorśbd Pliń'ry oH grouPs
wcrc Gpe.ially r.aĆtive and could bc includcd i'no
satjsfado4r in rcsPcd ol
a
new Ćlass ol thc monomeB
2łjon (.all.d no|ofers)
!ńs,
a.tiv.
l5
ilr
7i k
.aiioli. pÓlyndi
1łat d.ńoNt cd
ouscd aPPre.iable d!,P ń 7'' and sjnrukancolsly im.
Plovcd I].xibjliry ofUv.urcd ctoxy polymcE (Plaśify.
The .Poxy rśinsare .haraĆtetized by a 3.Ód \'rting
powel of solid $'bstab alrhough a PrÓPcr disPclsioń ot
o*ani. pigmerr or dy! in a re!
achjcvc. ThUs' ihc olorańon o' cpo1y rcsin Ę rclihvcly
comPli.aled' Th. usc of dycs is.olonnh ń Photorea.
hve syśems śhows no ncgłiivc influcn.c on th. croŚlirkinB pb.ss inftiared bv Uv light 11r dy$ cihibii
rcry high cłilttion !.efiĆienls (ab$rPiiÓn), thus relŹ
tively low dyc .on.entations ar. s
intuNiv.ly colored lirns 13t.
ln ihis Papet we pioŚ.nr a ncN d
ca]ly ooslinked cPoxy lcsnr bas*rdhśnc ijrcludiĘ
commscially avair,brc dycs ind nodct iltvl or prcp-].
-.nyl dher (AlE or PnE, r?spcdivclv) as Uv{eidiv!
modifiĆt(Mo)'Thcallylolplop] elyletherol]+dj
hydldybulanc oniailring Pdmł}' oH 8loup,;. ,] al
lyloxybutłne 1ol (MoAlE) lFo.ńula (l)l oI łlPrcPł.
'cnvl)ołbLlan.l ol (MoPnD lFormula (U)lw.rcUmd'
To our beŚt kno(lcd8c, in lilcIiiu
rcporb on thr uv{urcd colorcd cp
PoL]MEFYŻ00]
siv6 B6ides
49,
'tr7
3
ihe le.hnolog(al novelty wni.h ań intÓ
dudion of the dy.s to thc syśms
have inv*ligahd ako the dyes cIfu.ś on the adhsile
ch aderistiG of the joinb obbin€d.
In the Prelińińar-v sfudi6, lve ha
intoduĆlon ofMoAlE oI MoPńE a5 Flaśjfyf8 ńodj
figB (in a la$e ofamounb 3_r5 w.'%) into EPidńn6
Ein
did
no t
d€kriora le olher physi.i
adheŚiv. produ
PtoPłli6 ol fiml
Thc cpoxy bisph.nol A hased resi" Epidian 6 was
purchascd frcm z ch Nowa saŹyna (Poland) Thc
nodificB _ nonoauyl and ńonoPńE] enyl ethere oI
buiane-r,4'diol wcrc prcpard as d*dibed Previorsly
The. ionicPhotoinihalor(c]ql) tiaryl6lllońiln
salls wirh sbr; aniol (as 50 'r]' soluiion in PoPylcńc
rlbrnate), srpFlied by Aldri.h chcmi.al co., G m.ny,
Thc adhcsjvcs wł. Ólored by seled€d dys, i.. Mi
cmlith Rcd 2C-A, Midolith Creen G A, Mi.mli$ Blue
.1c.A' Mjctolilh Bl..k 3G A, suPPliod by ciba (C€!
1
and
ne.hanirl
sered ihat the Preśene of dyes (in mount ol1 wt' ob)
in sfudied Uv{urcd sy*eńs had ń
on thctr usclul prope iG In th.lu hc' rcsc .hcs rhc
prcviously n€nlioned opiimal wei8hi nlio of rcsin/
monoethel/ilitjłror/dyc o00/r0l1/]) was Ghblishcd
siBnifi.ant advanragś ol the desribed flGslinking
pm.es aią d'anĆbiized already in experjm.nt.l p t,
ib .ondiiioN i.' vły sl'Ót illad
teńperafure and ln thean aińosPh
hBŃes o( good quiliiy Wth vsy g
were achiev.d (Fig.l), ihough,n ihc cisc oI lvri.rclith
BlżcL 3GA dyc, r |cJrly 2 słold rc
adhsion w.s norcd in.onrpi sn with un.olorcd il.
r6ivc But also adhAion value or this dyc n ichc thc
tange ac..ptabl. fÓr rhĆ ind!*iv e]30 N/2'5 .m)'
Ptparłlion ol.olored epoxy.dhesivćs
cońPositiois of .poxy resij'/monoethe'cłtioni. ]n'
itiato!/dyc, uscd at optimal (100/10/1/l) weishi ratio,
wcrc prcparcd. Thc dycs were initially dissolvcd i']
MoAIE o. MoPnE and thc obiained
ponled into thc adhśilcfomulah
iing aPpeared io b. sulńocnt lo achĘvc good homÓ
garizaiio| of all .omponcnb PnoI dnsolvjng oI lhĆ
dy* in ńonodhcrŚ apPearcd io be
stifiing Ófall the cÓńFoMnG simulianlously lcd b hc
tcÓ€cncous
syścns' forńatbn Th! us.d weighl laiio
of lhc conponcnB was s.lcded .ń ń! bash of plevions
(rłliłtjon .unng)
duded bcM.cn o
llis plates Ghlckncss of thĆ lay.r.oilosponded wiih
Iiyin8 on 30 g onto ń]) !nde! ł50 W arlańp' Irndiition (t = 315_.100 nm) wm Pcrio!ńcd at q)ń fumPeta
dr!,n] airaimNphflc'dunng5 mń As ihc lesullś, rhĆ
baBparent, iŃeNivcly rlor.d ind aoŚlinkcd solid
Polyńd jÓinh \'d. obiai'red'
ł"'
Ii! 1 EtrLl ł kild af Ą[ al adlrsbn nj lr$
6lMoAlE)cPl|t|!l loł]Pasilh s oaa|1anr)| 1
Thc PhotÓińitiatĆd Pol],metizliion
Uvłenedion nean'remmb vcle Pcnorned usińg
Grła3 MaĆbr.h spPckomctcI (Gcrnany) 5hcar
mincd u9n3 zwiĆk
Pc sofh'ł z7005 h*iĘ nł.hinc (Gcmany) a(ording
FERA 4012 Ghcar
l'_
Fq'r.Eftd|,fM
fitn6 rl Eridk'
r1E
n)
r1'M'A]EQ) 1uvrłlnh\)
'hntĘI)tlcPl
POLIMERY
2004,
'19,
nr
7
3
dys inlo ul.
.onposiiions improves
shca' stcnElh' so, ihe intÓductjol ol
cPory/nonoeih€r/iniijator
onthebasisofslearsbcńgthandUvj.fledionin
v6tigatioń5 tvc ondudcd th.i lhc mtoduchon of dycs
lo the ońposihons imprcv.d ability of UV absoPhon
dunn8 the Polyrłizaiion, and whał lollowed in_
oeascd readivilies Ó1rheę ŚyJem in th. procs' l']re
adhesiv€s obłainrd shoLv v.ly EÓÓ
sion płrańetds' cspNń]]ywhcn MKolilh Black3c A
dye is uscd (6 L oI Uv.rncdion = 370-750 nm, shcar
sbeńgth = 37r N), and aP chiracteriz.d by tinsparcnry
F'e 3 E|bl a|kilil o| dlt d! uvł4lnli lr]łŚ a| ąaal
6]MoA|ElcPldlr fuIPnsit)nns 0aala|111): 1 Mnft]łlh
Thc n.xinum yalrcs oI uvrcllccrion of th. obhined iDints modiried by MoAIE or MoPnE wirh MiclolirhcĘeńG Aa5 a dye ale eqlal ab.ur 50'x' ot 40'Ł,
rGpcchvcly lFis.2) Howcvcr, thc rjv{ellEhon values
włs lowcl in iheciscol MoPnE nodificl than MoAlE
me itruldbeonnetdwithl glu reacrivity of prop.
-]_e'ryl .thet nononł in lhe .ationnżlN i''iliał€d pho.
bpolyn.rization ProĆ*s l4, 5]' Fig
ihe kind ol dy. on relledion valu
Bluqcieenor Red dye5 nrarly dÓ
value of this FoPdty' th.y iud di1lcr in narińa posi
in ń5 on th. wiYclcngth żxis. Black
Prachcc' ilr sPitc ol diłcrni conEcs oI thc cuncs plc'
sŃed m Fi!' 3, all tlt d}{s i'N6łigalcd onb.sut6y
lully used ror prepararion or .olo
cPoxy Ę$ins based adhesivc5'
słeĘth of exaninelt epoxy adhP
sivs syś€ms allł Uv<JriĘ'
As €Ypeded, an in-easc in shc sbcńgth (Tabh r)
and a dedsse ln adhśion b glas {Fi8 l) of ePoty
adhsivo.onrammg divcFc dys.oncspond io thc !c
ll(hon level in tte ndiaiionarea and io the maxina oi
r.nR on for dy$ evalLahd (FiE. 3).
so lhe Eul!śof cvaluirion of thc dys Ćffe.h on lh.
Ćoating Plop. ies, biscd on idh
(shcrr sbcngth) aM rncdion mpasurcncnts,lit iir cach
with oth.r Dab presenred in this paper lei sab ihai
neq .oloied, EańsParent ePoxy lel
we d€veloPld alc sułibl. fo! ad!
uscd, thc hi8hel sh&r
r
Ż
Maśon F, D(kc. c JaworcL T, s.hwarlr
orj.c r 2000,3t t15'
Allen N' s: ] jj]idlf]id,
crivdloJ.v'Jox':/ Polł' s.
Day R' ] Lovcll ll
'
5
Ma yy
A,
Man
'
R
l.1]
A A' rjd]rł l'
xrcmPi..
MłtyszD,Urbal'M,^ asu.z,Tzynv'f
shearsEen8lh, beinE a ĆfitdĘn o
hcsion b glas, is. lcly lnPo int Propcliy, dcsńbmg
th.qualityof adhc$vcsyscru Data P.ścntcd jnT'blc
I show thc cffc.b of thc prcscnr and t-vpc oI a dyc on
IruJl
rł' a]Łł
D , Anroy.zyszvn M., Uńala M,
Po]yadylaibasi\",
I
awka
wyd rolfud iki szŹdńskiej'
hnus E, Anb*.zyszyn rvr, urr,ib NJ: