Professional Documents
Culture Documents
Tauber 2002
Tauber 2002
Tauber 2002
INTRODUCTION
he market for pressure sensitive adhesives is domi-
Real-timeFTIR spectroscopy was used to study
T nated by w a t e r - a n d solvent-based systems. ~They
contain, for example, high molecular weight acrylic
or rubber loased polymers. Coating is done at room tern
the LIVqight induced crosstinking of a pressure
sensitive adhesive bossed on a saturated ac~llic
perature or slightly elevated temperatures. After the evapo-
ration of water or solvent, an adhesive film is formed on polymer bearing a pluAoreactivefhnctionat group
the substrate. The application of photopolymerizable pres
sure sensitive adhesives offers advantages with respect to
in the side chain. To simulate production
processing time, space, and energy requirements, as well parameters, e.g., cure speed m ~dnumber of required
as reduction of solvent emission. 2,3 Hence, UV curable UV h~mps, single or multiple UVqight flash
adhesive prepolymers were developed which could be
polymerized either by free radical or cationic reactions. 4~ experimeJr were performed which l~ve shozc,~
Another important class of conventional pressure sen that the amount qf crosstinked potyn~er chains in
sitive adhesives is based on styrene/butadiene (SBS) or the adhesive depends o~ the applied UV dose. The
styrene/isoprene (SIS) copolymersJ These solvent free
systems are applied as hot melts to a substrate with coat sa,~e result was observed by vaqfing the intensity
ing temperatures of 160~ and higher. High coating qf the UV-tight. The properties qf the pressure
weights at high production rates are possible in compari-
son to waterborne or solventborne systems. However, these sensitive adhesive, e.g., peel and shear strength,
hot melt adhesives still have some disadvantages, a low were determined by UV curing using a laboratory
aging resistance and limited adhesive properties at el-
evated temperatures, e.g., poor shear resistance above irradiate1 unit. These results were compared zAth
100~ The latter might be overcome using UV curable SIS those qflthe RTIR spectroscopy experin~n is.
or SBS adhesives. 6 UV-curable acrylic hot-melt adhesives
are promising alternatives since acrylic polymers possess
excellent resistance towards aging. ~;~s These adhesives
consist of high molecular weight polymer chains. After
coating onto a substrate, the acrylic polymer chains have
to be crosslinked to achieve the final adhesive properties. ~6 ,6 1,6
.1 t~ II I~ !m
This is done by copolymerization of photoreactive func
tional groups ~,7~(Scheme 1). 1
The pressure sensitive adhesive investigated in this
s t u d y is an already commercialized UV-curable acrylic
hot-melt adhesive.~s UV-light induced crosslinking of the
acrylic polymer chains occurs via a copolymerized ben
zophenone derivative. The mechanism of the crosslinking
reaction is shown in Scheme 1. -~OH-CH~H-CH~H--CH~-
6-O ' ~&O
Excitation of the carbonyl group of the benzophenone i6 1
derivative with UV light eventually leads to the lowest
Scheme l--Photochemlcal crossfinking of sa#Jrated
acrylic polymer chains (P~ and P:) bearing a copoty-
~Perm,:,ser~r. 1 r, B~1147,1:-:Leir,zl,J ,Yermanv Tel: +49 ~,41 2~, ~D749. fax: +49 .~,41 2.~, merized benzophenone derivative in the side chain.
2584. en ~ail: tauL,er@rz.uni-leipzi~.l.de.
I o~ 0.8
_.c E
(3 [
::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
(/)
::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
o
C3
42
o f GsI-LObefore ~ ) and after 60 sec con tin uous
irradiation (..). Inset. relative benzophenone
concentration as a function of time.
g 0.8
t..)
oE 750 9,e 9 c
E
9 9 3
o
r
0.6
m 500 .0 O
r
9 ;e
. 911
.ee 0.4
8 250 0e 0%
E3 e"
continuous irradiation
m 0.2
9~ , I D , I , t q n im,,lll, i
._
-10 -5 0 5 10
O 9 I . I . i 9 L
Irradiation Zone / cm 0 10 20 30 40
|
t Figure 4--1rradiance profile of the UV lamp l Time / s
used in this study (100% intensity. 6 m min-7).
I Figure 5--RTIRspec troscop y: UV curing by con-
EXPERIMENTAL
t .................................. F
tinuous and pulsed irradiation (6 sec duration).
I
Laboratory Scale UV Curing
and peel strength as a function of the UV dose
Laboratory scale UV-curing experiments were carried at 100%( e ) and 50% (J) intensity of the lamp
out using a m e d i u m - p r e s s u r e m e r c u r y arc lamp (120 W (coating weight: 65 g m-:].
1~ pulse
i 0.8 1.5
\~'-X<,~ Ise
0 0.6 r
,J0
g 1.0 x.X 250 27~na?O 325
o
N
c-
o.4
t
/
3 ra pulse
<
o
O,5
L
- I~ ' ~ - I ' ~ ~i ,]1" ] , 17 4. ZZ LT .,, i I ,, i ,i
or- 0 5 10 15 250 300 350 400
Time / s Wavelength / nm
I
Figure 7IRTIR spectroscopy, UV curing by I
t
Figure 9--UV spectrum of the UV-curable
multiple light pulses (duration :2 sec and in terval,
2 sec).
I pressure sensitive adhesive (coating weigh t,
45 g m-Z). Inset. spectral output (245-330 nm)
of a medium-pressure mercury UV lamp as
used in this study.
The adhesive w a s coated at t e m p e r a t u r e s up to 160~
on a substrate. After single or multiple passes t h r o u g h the
U V l a m p the adhesive properties were d e t e r m i n e d ac
cording to the following procedures. Peel strength: 90 ~ RESULTSAND DISCUSSION
peel test on stainless steel at a test s p e e d of 100 m m rain-l;
tests w e r e carried out at r o o m t e m p e r a t u r e within one In Figure 5, the b e n z o p h e n o n e conversion u p o n continu
hour after contact of the adhesive to the steel. Shear strength ous irradiation followed b y RTIR spectroscopy is shown.
(stainless steel, 1.25 cm x 1.25 cm contact area, and 206.9 g A t the beginning, a fast reaction can be observed, then it
load): starting at 50~ the t e m p e r a t u r e w a s raised b y 5~ starts to slow d o w n , and after 30 sec irradiation no fur
e v e r y 10 minutes until the adhesive failed. ther conversion of the photoreactive g r o u p can be ob
served.
In a commercial U V curing process, the adhesive is
exposed to UV light for v e r y short periods only. D e p e n d
ing on the s p e e d of the web, the d u r a t i o n can be in the
~ 1.0 range of milliseconds to seconds; e.g., r e g a r d i n g Figure 4,
I~ I ~ 5o b at 6 m rain 1 a m a x i m u m exposure time of two seconds
can be calculated f r o m the irradiance profile of the U V
I~" 57~176
~2SL~
0
l a m p used in this study. Such commercial curing condi-
O tions can be simulated with the help of RTIR spectroscopy
g \ XN/~ 2s so rs since flash like irradiation p r o c e d u r e s can be easily car
ried out with the electronic shutter (see Figure i and refer-
ences 12 a n d 13). The d u r a t i o n of the short UV pulse can
Q. be related to a certain s p e e d of the web. The result of a
No 0.4 single pulse investigation simulating one U V l a m p is
e-
00 % s h o w n in Figure 5. It can be seen that the conversion of the
rn 0.2 b e n z o p h e n o n e in the adhesive stops i m m e d i a t e l y w h e n
._>
(I)
the light is switched off. This is in contrast to the b e h a v i o r
in other p h o t o p o l y m e r i z a t i o n reactions, such as the free
rr
radical induced p o l y m e r i z a t i o n of acrylates. In this case,
0 10 20 30 40 up to 80% of the functional g r o u p s are converted after the
Time t s end of the U V light flash. 1~,1s Hence, the a m o u n t of
crosslinked p o l y m e r chains in the adhesive (Scheme 1)
FigureS--RTIRspectroscopy.'pulsedirradiation and consequently its properties should d e p e n d on the U V
at different UV in tensities but constant UV dose ; dose which is applied d u r i n g the U V flash. Postcuring
100%(6 sec pulse), 57% (10.5 sec p ulse) and24% does not take place.
(25 sec pulse). Inset, benzophenone conver- In Figure 6 the results of l a b o r a t o r y UV-curing experi-
sion at the end of the pulse, m e n t s are shown. Shear a n d peel strength of the adhe
l
Figure lO--Photon absorption according to
simulation is s h o w n in Figure 7. A stepwise conversion of Beer-Lambert law. inset, absorption of the ad-
the b e n z o p h e n o n e after each UV pulse can be seen. This hesive at 254 n m ( e ) and 300 nm (J) as a
clearly demonstrates that the reaction is reinitiated w h e n function of the coating weight.
the next UV flash strikes the sample.
Comparing Figures 5 and 7, the same a m o u n t of ben
w h i c h match the a b s o r p t i o n spectrum of the b e n z o p h e
zophenone (~ 60%) is converted if one pulse of six seconds
none derivative.
duration or three pulses of two seconds with an interval of
two seconds are applied to the adhesive. Therefore, the D e p e n d i n g on the application of a pressure sensitive
properties of the adhesive, e.g., shear and peel strength, adhesive, d i f f e r e n t coating w e i g h t s are r e q u i r e d , e.g.,
should d e p e n d only on the applied UV dose and not on 20 g m ~ for labels and 80 g m ~ or more for tapes. The
the irradiation regime. Hence, in practice, the speed of the a b s o r p t i o n of the a d h e s i v e s t u d i e d as f u n c t i o n of the
web can be increased by increasing the n u m b e r of irradia coating weight (see inset in Figure 10) has some conse-
tion units. Results of such laboratory scale experiments quence with respect to the practical application. Reac
are s h o w n in Table 1. It can be seen that at a speed of 24 m tions induced by UV light, e.g., the formation of the excited
min -1 the UV dose of 225 mJ cm -2 applied to the adhesive triplet state of the b e n z o p h e n o n e derivative [reaction (1)
after one pass through the lamp is not sufficient to obtain in Scheme 1], are triggered in general by the absorption of a
a high shear strength (see Figure 5). After four passes the
dose is almost the same as one pass at 6 m min -1, conse-
quently comparable adhesive properties were obtained E
(Table 1). g 1.0
The influence of the intensity on the b e n z o p h e n o n e
conversion is shown inFigure 8. The conversion rate slows
d o w n w h e n the intensity of the UV lamp is decreased. On g o.8 6 X CW ~
the other hand, the conversion is still the same with re- 8
spect to the applied UV dose (- pulse length x intensity,
see inset in Figure 8). Hence, at a given dose, the adhesive 0.6
properties are i n d e p e n d e n t of the dose rate (see Figure 6). 8
A high p r o d u c t i o n rate with a m i n i m u m of irradiation
g
units could be achieved by using UV lamps with a high
intensity. However, one has to bear in mind that the adhe
~ 0.4
Table l--Laboratory Scale UV Curing: Peel and Shear Strength After Single or Multiple reduction of the rate of ben-
Passes Through lhe UV Lamp (100% Intensity) at Different Speeds of the Web (Coating z o p h e n o n e conversion with
Weight: 65 g m -2)
increasing d e p t h of the coat
W e b Speed Dose Per Pass Tolal Dose Peel Slrength Shear Slrenglh
ing, as can be seen in Figure
m min -~ Passes through Lamp mJ c m -2 rn.J c m -2 N c m -I ~ 11.
The influence of the coat
6 .................................... 1 910 '~ 910 '~ 5.2': 184 'J
1 9 ..................................
2 470 '~ 940 L' 5.3': 186 d
ing weight on the adhesive
] 8 ..................................
3 299'~ 897b 5.1': 189a properties can be seen in Fig-
24 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 225 '~ 900 b 4.9': 175 d ure 12. Cohesive failure of the
adhesive, shown by the maxi
(G) rl 1~.181jr~d
I~-,) ,-al,-ulated m u m of the peel strength,
C,-) failure ,:,f t h e a d hesiv@ shifts t o w a r d s h i g h e r UV
cd) failur~ ,:,f t h ~ c a r r i e r
doses on increasing the coat
ing weight. This is a conse
quence of the reduction of the
single photon. In Figure 10, the absorption of photons rate of b e n z o p h e n o n e conversion (Fig~re 11), since a cer-
according to the Beer-Lambert law is shown. 2 It can be tain a m o u n t of crosslinked polymer chains is required to
observed that, u p o n increasing the absorption, the light achieve sufficient cohesion in the adhesive layer. The
intensity and therefore the p h o t o n distribution inside the same holds for the shear strength (inset in Fig~re 12).
photoreactive layer becomes inhomogeneous. While at the lower coating weight a rise of the shear
The inset of Figure 10 shows the absorption of the strength can be observed at low UV dose, in the case of the
adhesive at 254 and 300 nm as a function of the coating increased coating w e i g h t a higher dose is required. The
weight. C o m p a r i n g this data with the Beer-Lambert law difference in the shear strength (180~ vs. 100~ at high
(Fig~re 10) shows that at the m a x i m u m absorption of the UV doses (see inset in Figure 12) m a y result from the
b e n z o p h e n o n e derivative (around 254 nm) the light dis adhesive itselL e.g., distribution of the molecular weight of
tribution in the adhesive layer rapidly becomes inhomo- the acrylic polymer chains.
geneous upon increasing the coating weight. In this wave-
length region the photoinitiator acts as an inner filter that
gives a high degree of crosslinking at the surface and
reduced conversion in the b o d y of the adhesive.17 A r o u n d
CONCLUSION
300 nm, where the b e n z o p h e n o n e also matches lines of The c o n v e r s i o n of the p h o t o r e a c t i v e f u n c t i o n a l g r o u p s
the spectrum of the UV lamp used (see Figure 9 and inset of a U V - c u r a b l e acrylic p r e s s u r e sensitive adhesive was
therein), the p h o t o n absorption is less i n h o m o g e n e o u s studied with RTIR spectroscopy. Experiments were per
(Fig~tre 10 and inset therein). Hence, in this w a v e l e n g t h f o r m e d u n d e r close to technical curing conditions. Single
region the inner filter effect is less p r o n o u n c e d and a a n d multiple UV-light flash e x p e r i m e n t s , as well as
d e e p e r cure is obtained. In general, one w o u l d expect a v a r i a t i o n s of the intensity, have s h o w n that the c o n v e r
sion of the c o p o l y m e r i z e d b e n z o p h e n o n e and, there
fore, the a m o u n t of crosslinked p o l y m e r chains in the
a d h e s i v e , o n l y d e p e n d s o n the a p p l i e d UV dose.
P o s t c u r i n g d o e s not take place. H e n c e , the p r o d u c t i o n
::01.11
.
rate can be i n c r e a s e d b y using successive i r r a d i a t i o n
units. RTIR s p e c t r o s c o p y results w e r e c o n f i r m e d b y
16 ~,, ~, m e a s u r i n g the peel and shear s t r e n g t h of the a d h e s i v e
after UV curing in l a b o r a t o r y scale. The c h r o m o p h o r e of
the a d h e s i v e acts as an inner filter t o w a r d s UV light.
z 12 T h e r e f o r e , the c o n v e r s i o n rate of the b e n z o p h e n o n e
slows d o w n u p o n increasing the thickness of the a d h e
!~11 \ ^ Dose I r~J Cr~ r2 1 sive layer. L a b o r a t o r y e x p e r i m e n t s h a v e s h o w n that at
an i n c r e a s e d coating w e i g h t a higher UV dose is re-
8 ~..~ q u i r e d to obtain a d h e s i v e failure in c o m b i n a t i o n w i t h
ACKNOWLEDGMENT
1000 2000 3000
The a u t h o r s w o u l d like to t h a n k Mr. Karl H e i n z
Dose / mJ cm 2 S c h u m a c h e r a n d Mr. Ralf Fink f r o m BASF A G
(Ludwigshafen) for supplying us with the adhesives used
t Figure 12--Laboratory-scale UV curing; shear in this study.
and peel strength as a function of the coating
weight: 65 g m-~'( e ) and 130g m-~'(A).
46 Journal of C o a t i n g s T e c h n o l o g y
UV Curing of a Pressure Sensitive Adhesive Coating
Re~rences (9) Crivello, J.V. and Dietliker, K,, Phetei~itiaters for Free RadL'al
Cationic & Anienic PhotopoIymerization, John Wiley & Sons/
(1) Schumacher, K. H., Dftsterwald, U., and Fink, R., "'UV Acrylic SITA Technology Ltd,, London, 1998,
Hotmelts--C ombining Hotmelt Coating Teclmology with Acrylic (10) Decker, C. and Moussa, K., "Photopolymerization of Multi-
High Performance Chemistry," Prec. RadTech Eurepe 99, Befli~, functional Monomers in Condensed Phase," J. AppL Pelym.
55o (lOOO). Sci., 3'4, 1603 (lO87).
(2) Mehnert, R,, "Radiation Curing: Definition and Basic Charac (11) Decker, C., "Kinetic Analysis and Performance of UV Curable
teristics/" in UV & EB Curing Technolovy & Equipment, Melmert, Coatings," in Radiation Curing: Science atd Tech~wlogy, Pappas,
R,, Pincus, A,, and Janovsk.9, I. (Eds.), John Wiley & Sons/ S,P. (Ed.), Plenum Press, New York, 1992,
SITA Tedmology Ltd., London, 1000. (12) Scherzer, T. and Decker, U., "Real-Time FTIR-ATR Spectros-
(3) Kauffman, T, and Mitry, M,, "'A New Cure for Sticky Situa copy to Study the Kinetics of Ultrafast Photopolymerization
tions. Examining Tedmology Advances and Market Opportu- Reactions Induced by Monochromatic UV Light/" Vibr. Spectr.,
nities for UV/EB Curable Pressure Sensitive Adhesives," Adhe 19, 385 (1999).
sires Age, 2, s8 (2000). (13) Tauber, A., Scherzer, T., and Mehnert, R., "'UV Curing of
(4) Glofelter, C, "'Valuable Properties. Tg Region Breadth is Criti Aqueous Polyurethane Acrylate Dispersions. A Comparative
cal to UV-Curable PSA Performance," Adhesives Age, 2, s24 Study by Real-Time FTIR Spectroscopy and Pilot Scale Cur-
(2000). ing," J,:,UP-NAL:F C :ATI~3 TE,_~HN,:,L,:,,Yi', 72, No. 911, 51 (2000),
(5) Erickson, J.R. and Mancinelli, P.A., "'UV-Curable PSAs Offer (14) Colflmp, N.B., Daly, L.H., and Wiberley, S.E., Intreduction to
Excellent Performance and Fast Production Rates. High Speed, h~frared asr Ramasr Spectroscopy, Academic Press, Inc., San
Hi-Tech/' Adhesives Age, 2, s l l (2000). Diego, 1002.
(6) Dupont, M., Masse, M., and Schneider, J,, "'Rubber Based (15) Mehnert, R., "UV Curing Equipment Polychromatic UV
Radiation Curable Pressure Sensitive Adhesives/" Prec. RadTech Lamps," in UV & EB Curing Techtsof%nd & Equipment, Melmert,
Europe 99, Befli~, 551 (1999). R,, Pincus, A., and Janovsk~, I. (Eds,), John Wiley & Sons/
(7) Z61li~er, S., "UV-Curable Acrylic Pressure Sensitive Adhesives. SITA Technology Ltd., London, lOOO.
Features, Mechanisms, Milestones," Prec. RadTech Eurepe 99, (16) Mttller, R., "UV Systems for Curing of Radiatio~Curable U V
Berlitz, 543 (lOOO). Acrylates," Prec. RadTech Europe 99, Berlitz, 501 (.1990).
(8) Schumacher, K. H. and Sandbom, T., "'UV Acrylic Hot Melts~ (17) Herlihy, S.L, and Battersby, G,C., "UV Inner Filter Effects and
Performance and Processing of an Attractive I~aw Material for Photoinitiation Efficiency," Prec. RadTech Nerth America 94,
Self Adhesive Articles," Tech. Prec. RadTech North America 2000, Orlas~do, 156 (1994).
Baltimore, 185 (2000).