1
“ KarenzMTTM”
SHOWA DENKO K.K.
-Multifunctional Thiol-
http://www.karenz.jp/ http://www.karenz.jp/en/mt/index.html
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1. KarenzMT® is…
KarenzMTⓇ BD1
OO
SH O
O SH
N
N
N
O
O O
OO
O
O SH
OSH
OSH
KarenzMTⓇ NR1
O
O
O
O
O
O
O
O
SH
HS
SH
SH
KarenzMTⓇ PE1
・Secondary Thiol Structure
・Weak Odor
・Improve UV curing process
・Rapid Curing with Epoxy
・Strong Adhesion
・Improved Shelf-life
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ORGATECHNO 2006
Monomer : BPDA
Thiol : KarenzMT® PE1 2wt%
Initiator : Irgacure184 2wt%
KarenzMT™ was added
7cm
Without KarenzMT
Non-cured
Used KarenzMT® Without KarenzMT®
Monomer : BPDA
Thiol : KarenzMT® PE1 50wt%
Initiator : Irgacure184 2wt%
UV Exposure
S ・
Radical Reaction
H S
Additional Reaction
Activation
SH OO ・
Peroxide radical
Used KarenzMT
2.As the radical chain transfer agent
Provide the good balance of Reactivity and Flexible
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Method: IR imaging
Measurement area: 70 μm x 70 μm
SEM picture of UV curing film
Upper side of
Curing film 70 μm
3-2. Evaluation of UV curing films -Micro IR Imaging -
Low conversion
of double bond
PE1 conc.(%) 0wt%(N2) 0wt%(Air) 5wt%(Air) 10wt%(Air)
Tack Good Not-Good Good Good
IR-imaging picture
High conversion
of double bond
Detected by IR absorption of double bond
peak at 1408 cm-1.
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3.As radical chain transfer agent
TMP3A
PE1
Fig.1 Conversion of C=C Double Bond vs. PE1 Amount
Con
ve
rsio
n o
f C
=C
do
ub
le b
on
d (
%)
Reactivity of double bond measured IR(=CH2 ;
810cm-1 )
Monomer : TMP3A
Thiol : KarenzMT® PE1 0, 5, 10wt%
Initiator : Irgacure184 2 wt%
Test : Used KarenzMT(PE1) to Triacrylate
→ Enhance the reactivity of double bond
→ Enhance the efficiency of PI, Oxygen inhibition become small
=can reduce PI to avoid yellowing
0
20
40
60
0 200 400 600 800 1000 1200 1400
Exposure dose(mJ/cm2)
Conve
rsio
n o
f C
=C
bond(
%)
Without PE1(Air)
PE1 5%(Air)
PE1 10% (Air) withoutPE1 (N2)
O
O
O
O SHHS
HS SH
O
O
O
O
O
O
O
O
OO
6
0
0.5
1
1.5
2
2.5
0 10 20 30 40
Contents of KarenzMT® PE1(wt%)
Adhesio
nStrength
(N
/m
m2)
0
0.5
1
1.5
2
2.5
0 10 20 30 40
Contents of KarenzMT® PE1(wt%)
Adhesio
nStrength
(N
/m
m2)
0
0.5
1
1.5
2
2.5
3
3.5
4
0 1 2 3 4 5 6
KarenzMT™ PE1 Contents(wt%)
Adh
esi
on S
trengt
h(N
/m
m2)
0
0.5
1
1.5
2
2.5
3
3.5
4
0 1 2 3 4 5 6
KarenzMT™ PE1 Contents(wt%)
Adh
esio
n Str
engt
h(N
/mm
2 )Glass Stainless steel
カレンズMT® PE1 添加量 (wt%) カレンズMT® PE1 添加量 (wt%) カレンズMT® PE1 添加量 (wt%)
PET
4-1 Adhesion Strength
Monomer : BPDA
Thiol : KarenzMT™ PE1
Initiator : Irgacure184 2wt%
Exposure : 0.5J/cm2
Fig.4 Adhesion vs. KarenzMTTM PE1 Contents
KarenzMT™ PE1 also makes it possible to improve adhesion strength to
glass, stainless steel and plastic substrates.
KarenzMT™ PE1 Contents(%) KarenzMT™ PE1 Contents(%) KarenzMT™ PE1 Contents(%)
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4-2. Outgas Analysis /Effect on Addition of PE1
PE1
(0 part)
PE1
(10 part)
PE1 0 part 10 part
TMPTA 100 part 90 part
Irg184 2 part 2 part
UV(J/cm2) 1.0 1.0
The weight loss became smaller by the addition
of Karenz MT™PE1.
Generated gas were assigned as followings;
0~350℃ :Component from Irg184, TMPTA
350℃~ :Decomposed component from PE1
Weig
ht L
oss(%
)
Temp. (℃)
Close up PE1 (10 part)
PE1 (0 part)
Weig
ht L
oss(%
)
Temp.(℃)
PE1 (10 part)
PE1 (0 part)
The contamination of equipment by low boiling components can be avoided by reducing the amount of outgas.
( This contamination is highly problematic in electronics applications)
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4-3. Applications -UV curing system-
Table 1 Application in Various Items
Expecting advantages Applications, for instance
Coatings Reduce yellowing Film coatings for mobile phone
Ink Reduce yellowing Inkjet ink
Color Filter resist Sensitivity FPD
OCA Transparency, Flexibility, Reduce out gasses
Touch panel
Adhesives Reactivity, Flexibility Adhesives for Electironic deviced
Gasket Elongation, Flexibility Liquid gasket
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5. Characteristics of Epoxy Curing Agent
1.Rapid curing with epoxy under base conditions 2.Thiols can react with epoxy at low temperature such as
-5℃ 3.Depends on the catalyst and its dosage, can design the
curing speed/pot life. 4. Hardly coloration Thiols are useful for rapid curing agent for epoxy.
R'R SH
O OH
R'RS+
塩基base
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6. Stability
1
10
100
0 5 10 15 20 25 30
Time (days)
Vis
cosi
ty (
Pa・
s)
KarenzMT® PE1 + Bisphenol-A type epoxy
Primary Thiol (PEMP) + Bisphenol-A type epoxy
Gelation
Stability at 60℃
1) The mixture of Karenz MT™PE1 and epoxy resin was stable for more than
one month at 60°C.
2) The mixture of Karenz MT™PE1 and amine was also more stable
compared with the mixture of primary thiol and amine.
Fig. 4 Viscosity Measurement
Thiol & Epoxy
Fig. 5 Viscosity Measurement
Thiol & Amine
0.1
1.0
10.0
100.0
1000.0
0 5 10 15 20 25 30Time (days)
Vis
cosity (
Pa・s) a
t 25℃
□ KarenzMT® PE1 + Accelerator. (TDMAP)
○ Primary Thiol (PEMP) + Accelerator. (TDMAP)
Stability at 60℃
◇ KarenzMT® PE1 + Amine C.A. (DETA)
△ Primary Thiol (PEMP) + Amine C.A. (DETA)
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7. Rapid cure/Low temperture cure
Cured faster than Polyamidoamine
240
720
90
240
30 60
0
100
200
300
400
500
600
700
800
900
1000
23℃ 5℃
ポリアミドアミン(100)
ポリアミドアミン(100)+PE1(35)
PE1(70)
Curing Temp.
Curing T
ime (
min
) Measured the curing time as the formulation of BisA Epoxy,
Polyamidoamine/KarenzMT PE1.
Polyamidoamine(100)
Polyamidoamine(100)+PE1(35)
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8. Design the curing time
Depends on the dosage of the base catalyst, the curing time/pot life
can be designed.
0E+00
2E+03
4E+03
6E+03
8E+03
1E+04
0 15 30 45時間(min)
粘度
(Pa・
s)
PE1/jER828/TAP =70/100/10 増粘開始:約10min
PE1/jER828/TAP =70/100/1 増粘開始:約40min
Viscosity (Pa・s)
Time (min.)
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8-2. Characteristic of Catalysts
Low temp cure
Rapid cure Heat curing
Low yellowing Latent base
Long potlife Rapid cure
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9. Comparison with Amine Hardener
Karenz MT™PE1 showed:
1) Curing at low temperature
2) Higher transparency
3) Less toxic: Ames-test Negative, LD50 >2,000mg/kg
Fig.6 Curing Speed at 5℃
カレンズMT® PE1 アミン 0
5
10
15
20
25
30
35
40
45
0 50 100 150 200 250 300
Time ( min )
Tem
pera
ture
of c
uring
(℃
)
PE1Primary Thiol
Amine C.A.(denatered PXDA)
Fig.7 Hydrolytic Stability Test (Dip into hot water)
Before test
After 24hrs at
98℃
Karenz MT™PE1 Amine
17KarenzMT PE1 for Epoxy Hardner (2010)
SHOWA DENKOCONFIDENTIAL
4‐5. Hydrolytic Stability
Before Test After Test
PE1
Stable
D‐amine
Whiten
PEMP
Soften & whiten
It was observed that hydrolytic stability of KarenzMT™ PE1 resin was good.
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10. Summary
Characteristics of KarenzMT™ PE1 as epoxy curing
agent are the followings:
・PE1 has more useful properties than amine ①Useful for rapid or low temperature curing ②Good stability for acid ③Fine mechanical and adhesion strength raise strength for bending, stretch and shear.
lower Tg and compressive strength because crosslinking density decreases.
④Hardly coloration
・PE1 has more useful properties than primary thiol ①Very weak odor ②Long pot life ③Higher Tg than 3-800 or PEMP ④Good hydrolytic stability and alkali resistance ⑤Excels in the preserving stability (For one-component adhesive)
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11. Applications - Epoxy system -
Expecting advantage Application, for instance
Adhesives for constructions
Rapid cure, Flexibility Adhesive agent for temporary adhesion, Repair agent
Floor Rapid cure, Low temp cure Floor coatings for winter
Floor maintenance Adhesion, Flexibility Floor maintenance agent
Encapsulant Low temp cure, Rapid cure LED, IC
Adhesives for lenses
Transparency, Flexibility Films, adhesives for lenses
FRP Rapid cure For cars