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℃

ﾎﾟﾘｱﾐﾄﾞｱﾐﾝ(100)

ﾎﾟﾘｱﾐﾄﾞｱﾐﾝ(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