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2005 Adhesion Conference on Adhesion Adhesion Performance of UV- crosslinked SBS-based PSA : Effects of
2005 Adhesion Conference on Adhesion
Adhesion Performance of UV-
crosslinked SBS-based PSA
: Effects of SIS contents
Dong-Hyuk Lim 1 , Hyun-Sung Do 1 , Hyun-Joong Kim 1 , Goan-Hee Yoon 2
1 Lab. of Adhesion & Bio-Composites, Major in Environmental Materials Science,
Seoul National University, Seoul 151-921, Korea
2 Vixxol, 220-10, Anyang-7 dong, Manan-gu, Anyang-shi, Kyonggi-do, Korea
hjokim@snu.ac.kr / www.adhesion.org
www.adhesion.org Introduction Classification of PSA manufacture Solution-borne Emulsion (Water-borne) PSA Hot melt
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Introduction
Classification of PSA manufacture
Solution-borne
Emulsion (Water-borne)
PSA
Hot melt (SIS/SBS)
Irradiation (UV)
UV-polymerizable
UV-crosslinkable
Lab. of Adhesion & Bio-Composites
www.adhesion.org Introduction UV-curable Pressure Sensitive Adhesive Overall process UV-curing PSA Coating Wind-up
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Introduction
UV-curable Pressure Sensitive Adhesive
Overall process
UV-curing
PSA
Coating
Wind-up
Compositions
1. Oligomer + Monomer + Tackifier + Photoinitiator System
2. Block copolymer + Monomer + Photoinitiator System
3. Rubber System, Acrylic Hot Melt System
Lab. of Adhesion & Bio-Composites
www.adhesion.org Introduction SBS based PSA High solubility parameter Harder polymers More difficult to tackify
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Introduction
SBS based PSA
High solubility parameter
Harder polymers
More difficult to tackify
SBS/SIS based PSA
High entanglement
Good heat resistance
Lab. of Adhesion & Bio-Composites
www.adhesion.org Introduction Block copolymer based UV curing system polybutadiene polystyrene polystyrene SBS
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Introduction
Block copolymer based UV curing system
polybutadiene
polystyrene
polystyrene
SBS
Semi-Interpenetrated Network
UV
RSH (thiol)
Lab. of Adhesion & Bio-Composites
www.adhesion.org Purpose of this study SBS block copolymer SIS block copolymer AdhesionAdhesion
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Purpose of this study
SBS block copolymer
SIS block copolymer
AdhesionAdhesion
PerformancePerformance ofof
UVUV--crosslinkablecrosslinkable
hotmelthotmelt PSAPSA
Thiol-ene polymerization
Lab. of Adhesion & Bio-Composites
www.adhesion.org Experimental Materials SIS : Vector 4111 (Exxonmobil) SBS : D KX-405-CP (Kraton) CH 2
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Experimental
Materials
SIS : Vector 4111 (Exxonmobil)
SBS : D KX-405-CP (Kraton)
CH
2 CH
CH 2 CH
CH 2 CH
CH
CH 2
CH 2 CH
n
n
CH
CH 2
x
m
Chemical structure of UV curable SBS with vinyl pendant group
Photoinitiator : Micure BK-6 (2,2-dimethoxy-2-phenyl acetonphenone)
from Miwon Commercial Co.
Photocrosslinker : TRIS (trimetylolpropane mercaptopropionate) Aldrich
O
CH 2 O
C
CH 2 CH 2 SH
CH 3 CH 2
C
CH 2 O
C
CH 2 CH 2 SH
O
CH 2 O
C
CH 2 CH 2 SH
O
Lab. of Adhesion & Bio-Composites
www.adhesion.org Experimental UV-crosslinkable hotmelt PSA composition SIS SBS Tackifier Oil 1 TRIS 2 PI IB1
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Experimental
UV-crosslinkable hotmelt PSA composition
SIS
SBS
Tackifier
Oil
1
TRIS
2 PI
IB1
0
30
50
20
4.5
9
IB2
7.5
22.5
50
20
4.5
9
IB3
15
15
50
20
4.5
9
IB4
22.5
7.5
50
20
4.5
9
1. TRIS : Photocrosslinker TRIS (trimetylolpropane mercaptopropionate)
2. PI : Photoinitiator Micure BK-6 (2,2-dimethoxy-2-phenyl acetonphenone)
Lab. of Adhesion & Bio-Composites
www.adhesion.org Experimental Film Casting Automatic applicator No. 22 bar applicator UV irradiation UV lamp :
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Experimental
Film Casting
Automatic applicator
No. 22 bar
applicator
UV irradiation
UV lamp : high-pressure mercury
lamp (100W/cm 2 , main
wavelength : 365nm)
UV dose : 0, 200, 600, 1000, 1400
1800 mJ/cm 2
Lab. of Adhesion & Bio-Composites
www.adhesion.org Experimental FTIR-ATR Pressure plate PressurePressure plateplate Substrate Equipment : Nicolet
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Experimental
FTIR-ATR
Pressure plate
PressurePressure plateplate
Substrate
Equipment : Nicolet Magna
550 Series II
Resolution : 8 cm -1
UVUV UVUV -- ---curedcuredfilmfilm curedcured filmfilm
Coating
45 o
Horizontal ATR crystal
Infrared beam
Gel contents
W 24
Gel contents (%) =
× 100
W 0
Toluene
W 24 : weight after dipping for 24 hrs
W 0 : weight before dipping
Film
Lab. of Adhesion & Bio-Composites
www.adhesion.org Experimental Probe Tack Peel Strength 5mm stainless steel cylinder Contact force : 100g Dwell
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Experimental
Probe Tack
Peel Strength
5mm stainless steel cylinder
Contact force : 100g
Dwell time : 1 sec.
Separation rate : 60mm/min
Peeling angle : 180º
Separation rate : 300mm/min
Force
Debonding
force
Start up
Operation
Time
region
region
Bonding
Distance Peeled
force
Bonding
Debonding
process
process
Lab. of Adhesion & Bio-Composites
Peel Strength
www.adhesion.org Experimental Shear Adhesion Failure Temperature (SAFT) Constant load : 1kg Heating rate : 0.4
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Experimental
Shear Adhesion Failure Temperature (SAFT)
Constant load : 1kg
Heating rate : 0.4 ℃/min
SUS
SUS
Shear
Failure
PSA
Temp.
Specimen
Checked
Constant
Load
Constant
Load
Oven
Lab. of Adhesion & Bio-Composites
www.adhesion.org Results and Discussion Characteristic peak of 910.8 cm -1 , 964.7 cm -1 Sites
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Results and Discussion
Characteristic peak of 910.8 cm -1 , 964.7 cm -1
Sites of Chemical Reaction
Lab. of Adhesion & Bio-Composites
www.adhesion.org Results and Discussion Efficiency of UV curing by thiol-ene polymerization UV dose : 0,
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Results and Discussion
Efficiency of UV curing by thiol-ene polymerization
UV dose : 0, 200, 1000, 2200 mJ/cm 2
1.00
1.1
0.95
0.90
1.0
0.85
910.8 cm -1
0.9
0.80
910.8 cm -1
0.75
0.8
0.70
0.65
0.7
0.60
0.55
0.6
0.50
964.7 cm -1
0.5
0.45
0.40
0.4
964.7 cm -1
0.35
0.30
0.3
0.25
0.20
0.2
0.15
0.1
1000
950
900
1000
950
900
Wavenumbers (cm-1)
Wavenumbers (cm-1)
Only SBS
SBS+Photoinitiator
+TRIS
Lab. of Adhesion & Bio-Composites
Absorbance
Absorbance
www.adhesion.org Results and Discussion Gel content 100 SBS 80 SBS+PI SBS+PI+TRIS 60 40 20 0
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Results and Discussion
Gel content
100
SBS
80
SBS+PI
SBS+PI+TRIS
60
40
20
0
0
400
800
1200
1600
2000
2400
UV dose (mJ/cm 2 )
Gel contents of UV crosslinked SBS
Lab. of Adhesion & Bio-Composites
Gel content (%)
www.adhesion.org Results and Discussion Mechanism of Thiol-ene polymerization Photoinitiator hv CH 2 CH CH 2
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Results and Discussion
Mechanism of Thiol-ene polymerization
Photoinitiator
hv
CH 2 CH
CH 2 CH
.
R
CH
2 CH CH
2 CH
CH 2 CH
CH 2 CH
R CH
2 CH CH
.
2 CH
SBS & Photoinitiator
SBS & Photoinitiator
& Photocrosslinker
Inter reaction
Intra reaction
CH 2
CH
2 CH
CH 2 CH
CH
CH 2 CH
CH 2 CH
.
R CH
2 CH
. CH
R CH 2
CH
CH 2 CH
CH 2
CH
2 CH
Lab. of Adhesion & Bio-Composites
www.adhesion.org Probe tack Probe tack of SBS/SIS based UV curable PSA SBS+SIS+PI SBS+SIS+PI+TRIS 1000 1000
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Probe tack
Probe tack of SBS/SIS based UV curable PSA
SBS+SIS+PI
SBS+SIS+PI+TRIS
1000
1000
No TRIS
TRIS
SIS:SBS=0:30
SIS:SBS=0:30
800
SIS:SBS=7.5:22.5
800
SIS:SBS=7.5:22.5
SIS:SBS=15:15
SIS:SBS=15:15
SIS:SBS=22.5:7.5
SIS:SBS=22.5:7.5
600
600
400
400
200
200
0
0
0
400
800
1200
1600
2000
0
400
800
1200
1600
2000
UV dose (mJ/cm 2 )
UV dose (mJ/cm 2 )
Lab. of Adhesion & Bio-Composites
Probe tack (gf)
Probe tack (gf)
www.adhesion.org Peel strength Peel strength of SBS/SIS based UV curable PSA SBS+SIS+PI SBS+SIS+PI+TRIS 3500 2000
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Peel strength
Peel strength of SBS/SIS based UV curable PSA
SBS+SIS+PI
SBS+SIS+PI+TRIS
3500
2000
No TRIS
TRIS
SIS:SBS=0:30
SIS:SBS=0:30
3000
SIS:SBS=7.5:22.5
SIS:SBS=7.5:22.5
SIS:SBS=15:15
1500
SIS:SBS=15:15
2500
SIS:SBS=22.5:7.5
SIS:SBS=22.5:7.5
2000
1000
1500
1000
500
500
0
0
0
400
800
1200
1600
2000
0
400
800
1200
1600
2000
UV dose (mJ/cm 2 )
UV dose (mJ/cm 2 )
Lab. of Adhesion & Bio-Composites
Peel strength (gf)
Peel strength (gf)
www.adhesion.org SAFT (Shear adhesion failure temperature) SAFT of SBS/SIS based UV curable PSA SBS+SIS+PI
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SAFT (Shear adhesion failure temperature)
SAFT of SBS/SIS based UV curable PSA
SBS+SIS+PI
SBS+SIS+PI+TRIS
100
100
No TRIS
SIS:SBS=0:30
SIS:SBS=0:30
SIS:SBS=7.5:22.5
SIS:SBS=7.5:22.5
SIS:SBS=15:15
80
80
SIS:SBS=15:15
SIS:SBS=22.5:7.5
SIS:SBS=22.5:7.5
60
60
40
40
20
20
0
200
400
600
800
1000
0
200
400
600
800
1000
UV dose (mJ/cm 2 )
UV dose (mJ/cm 2 )
Lab. of Adhesion & Bio-Composites
SAFT ( o C)
SAFT ( o C)
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Failure mode of holding power (40 o C)
Adhesive failure
0
200
600
1000
1400
SBS+SIS+PI
UV dose
(mJ/cm 2 )
+TRIS
SBS+SIS+PI
UV dose
(mJ/cm 2 )
0
200
600
1000
1400
Cohesive failure
Lab. of Adhesion & Bio-Composites
www.adhesion.org Conclusion Not detected Adhesion performance of SBS/SIS based UV curable PSA SIS content Only
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Conclusion
Not detected
Adhesion performance of
SBS/SIS based UV curable
PSA
SIS content
Only SBS
UV dose
SIS content
SIS content
Only SBS
Only SBS
UV dose
UV dose
Lab. of Adhesion & Bio-Composites
Peel strength
SAFT
Probe tack