複合材用途向けエポキシ樹脂のご紹介 · hardener : dds...

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED. 1

Polymer Technical Div.1 Polymer Technical Group 5

June 2018

複合材用途向けエポキシ樹脂のご紹介

～Comparison data of Epoxy / DDS cure～

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED.

背景：CFRPマトリックス樹脂に対するニーズ（特に航空機用途）

高弾性率高耐熱性低粘度 ××

複合材料と基材繊維の力学的関係Ec＝EfVf + Em（1 - Vf）

Ec :弾性率（複合材料）

Ef :弾性率（繊維）

Em :弾性率（マトリックス）

Vf :繊維のマトリックス内体積含有率

Vf + Vm = 1

■CFRPの技術的課題圧縮強度の向上（3点曲げの上面破壊が相当）

■Vf（繊維含有率）を高くすることで、複合材料が高弾性率化・・・マトリックス樹脂の低粘度化が必須

■マトリックス樹脂の高弾性率化が複合材料の強度向上に効果的

■様々な環境に耐えうる耐熱性は必要不可欠

2

COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED.3

EPICLON® EXA-850CRP

EPICLON® 840-S

EPICLON® 850-S

EPICLON® 860

EPICLON® 1055

･･･

Control resin -1

Control resin -2

今回ご紹介する製品ラインナップ-1 (低粘度品：液状～半固形）

BPF & EPN resin

NOT DIC product

高弾性率低粘度 ×

Naphthalene type

Multi-Functional type

Modified-Novolac type

高耐熱性低粘度 ×


COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED.4

EPICLON® EXA-850CRP

EPICLON® 840-S

EPICLON® 850-S

EPICLON® 860

EPICLON® 1055

･･･

Control resin -1

Control resin -2

今回ご紹介する製品ラインナップ-2 （高粘度品：固形）

Naphthalene type (solid-type)

高弾性率高耐熱性×

高耐熱性

高弾性率高耐熱性×

NOT DIC product


樹脂の評価方法(樹脂板）

樹脂板の作成手順

Mix

Degas

エポキシ樹脂と硬化剤（4,4’-DDS）を当量配合*

*エポキシ当量：活性水素=1.0：1.0

均一化した樹脂配合物を減圧脱気*必要に応じて加熱（ca.80~100℃）

Casting mold

Cure

Cutting

脱気した樹脂配合物を注型

注型した樹脂配合物を加熱硬化（乾燥機）*硬化条件：150℃/1hr + 180℃/3hrs

樹脂硬化物を各種試験毎のサイズに切出し*評価項目：動的粘弾性（DMA）、機械物性（曲げ、引張 etc）


Di- or Multi-functional / liquid ~ solid

• TSCA : Listed

• REACH : Listed

• ENCS(Japan) : Listed

• ECL(Korea) : Listed

• IECSC : Listed

Typical property

EPICLON® E.E.W. Viscosity

g/eq. 25C, mPa･s

830-S 169 3,450

N-730A (n=2.6) 174 31,700

N-740 (n=3.7) 181 Semi-solid

N-770 (n=6.0) 187 Solid


N-740TGDDM

N-730A

830-S (BPF)

N-770

850-S (BPA)



BPA

TGDDM

EPN

BPATGDDM

TGDDMBPA

Flexural test

BPFEPN

BPF

EPN

BPF <機械物性（曲げ）>

BPF & EPN型エポキシ樹脂は、

BPA型対比で“低粘度”でありながら、

“高弾性率”と“高強度 ”を硬化物に付与

■ Hardener : DDS (4,4’-Diamino-diphenylsulfone), Stoichiometric ratio

■ Cured condition : 150C1hr + 180C3hr

(小)分子量 (大)

Tg vs Modulus

Tg vs Strength

Tg vs Strain


Modified-novolac type / multi-functional / semi-solid

• TSCA : Listed ( non-5(e) SNUR )

• REACH : Listed (10~100ton/year)



• IECSC : Listed

EXA-7250

Typical Property

AppearanceBrown

Semi-solid

E.E.W. g/eq 162

Viscosity 150C mPa･s 20

N-740 (EPN)

TGDDM


0.0

0.5

1.0

1.5

1.00E+06

1.00E+07

1.00E+08

1.00E+09

1.00E+10

0 100 200 300 400

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600

EXA-7250

ref. BPADGE

ref.TGDDM


BPADGETGDDM

(Td5=324℃)

耐熱分解性(TG-DTA)

EXA-7250 (Td5=386℃)



■ Test condition : N2, ■ Heat rate : 10℃/min

重量保持率

/wt%

サンプル温度/℃


Temperature (℃)

E’(P

a),

E’’(

Pa)

tanδ

Hot-Wet試験(DMA比較)

0.0

0.5

1.0

1.5

1.00E+06

1.00E+07

1.00E+08

1.00E+09

1.00E+10

0 100 200 300 400Temperature (℃)

E’(P

a),

E’’(

Pa)

tanδ

EXA-7250

TGDDM

Wet Tg(E’) = 333℃

Wet Tg(E’) = 200℃

■ Hot-Wet condition : 70C water 2Weeks


BPA

TGDDM

BPA

TGDDM

TGDDM

BPA

EXA-7250

EXA-7250

EXA-7250




<機械物性（曲げ）>

EXA-7250は、“多官能”且つ“狭分子量分布”

を有する分子デザイン

最大特徴は、TGDDM（Control-2)を凌駕する

耐熱性（Tg、Td5）を発現。耐湿熱性も優れる。

Tg vs Modulus

Tg vs Strength

Tg vs Strain Before Hot-Wet test

After Hot-Wet test

Flexural test & Hot-wet test


Naphthalene / Di-functional / Liquid

Typical Property

AppearanceBrownish Liquid

(Crystalline)

E.E.W. g/eq 143


• TSCA : Listed ( 5(e) SNUR )

• REACH : not Listed

(Under registration 1-10 ton/Y at 2017)



• IECSC : Listed


N-740 (EPN)

TGDDMHP-4032SS

850-S



BPADGE

TGDDM

HP-4032SS

BPFDGE

Flexural Strength (MPa)

TGAP

機械物性（曲げ）

“高強度”＝”高弾性”×“高伸び”

吸水率(70℃浸水試験)

Water Absorption (%)

60 80 100 120 140 1601.0%1.5%2.0%2.5%3.0%3.5%4.0%



■ Hot-Wet condition : 70℃ water x 2weeks

“耐熱性”×“機械物性”×“耐水性”の優れた特性バランス



HP-4032SS TGDDM BPADGE

Tg , DMA(E’)

[℃]

Dry 209 261 200

Wet 156 200 146

Flexural Modulus

[MPa]

Dry 3,630 3,590 2,990

Wet 3,530 3,230 2,780

Flexural Strength

[MPa]

Dry 163 129 126

Wet 131 89 110

Flexural Strain

[%]

Dry 7.0 4.6 9.7

Wet 5.0 3.1 6.4



■ Hot-Wet condition : 70℃ water x 2weeks

硬化物物性 (70℃浸水試験前後)


TGDDM

HP-4032SS




HP-4032SS

<機械物性（曲げ）>

HP-4032シリーズは、

“弾性率”と“強度”を高いレベルで兼備

ナフタレン構造により、高い耐熱性を有し

TGDDM比較でHot-Wet耐性にも優れる

特徴有する。

Tg vs Strength

BPA

TGDDM

Tg vs Modulus

Flexural test & Hot-wet test

TGDDM

Before Hot-Wet test

After Hot-Wet test

BPA

Tg vs Strain

BPA


Naphthalene / Di-functional / Solid

• TSCA : not Listed ( Under Preparation )




• IECSC : Listed

* 150C ICI

Typical Property

Appearance Brown Solid

E.E.W. g/eq 204

Softening Point C 72


15

N-740

(EPN)

TGDDM

HP-4770



Naphthalene / Tri-functional / Solid

• TSCA : not Listed




• IECSC : Listed

* 150C ICI

Typical Property


E.E.W. g/eq 185



N-740

(EPN)

TGDDM

EXA-4750



Naphthalene / Tetra-functional / Solid

• TSCA : Listed ( non-5(e) SNUR )

• REACH : not Listed (necessary to register monomer A)



• IECSC : Listed

* 150C ICI

Typical Property


E.E.W. g/eq 165



TGDDM

HP-4700

N-740

(EPN)



Naphthalene / Tetra-functional / Solid

• TSCA : Listed ( non-5(e) SNUR)

• REACH : not Listed (necessary to register monomer A)



• IECSC : Listed

* 150C ICI

Typical Property


E.E.W. g/eq 170



N-740

(EPN)

TGDDM

HP-4710



Flexural test

BPA

TGDDM

BPA

TGDDM

TGDDMBPA

HP-4770

HP-47xx series

EXA-4750

HP-47xx series




HP-4700/-4710

<機械物性>

・ HP-4770,EXA-4750は、2-ナフトール構造

による“高弾性率”が特徴。ナフタレンの剛直

性により、広い温度帯で高い剛性を発現

・ HP-4700/-4710は、ナフタレンの剛直性

且つ多官能化により、エポキシ樹脂系で

最高レベルの“耐熱性”を発現。

Tg vs Modulus

Tg vs Strength

Tg vs Strain



0.0

0.5

1.0

1.5

1.00E+06

1.00E+07

1.00E+08

1.00E+09

1.00E+10

0 100 200 300 400

薄線：Hot-Wet試験前／濃線：Hot-Wet試験後

E’(P

a),

E’’(

Pa

)

Temperature (℃) Temperature (℃)

tan

δE

’(P

a),

E’’(

Pa

)

tan

δ

Hot-Wet試験 (DMA比較)

0.0

0.5

1.0

1.5

1.00E+06

1.00E+07

1.00E+08

1.00E+09

1.00E+10

0 100 200 300 400


■ Cured condition : 150C1hr + 180C3hr ■ Test condition : 70℃ x 2weeks“高耐熱”×“高耐湿熱性”を兼備

HP-4700 TGDDM

Dry Tg (E’) = 261℃

Wet Tg(E’) = 200℃

⊿Tg = -61℃

Dry Tg (E’) = 346℃

Wet Tg(E’) = 334℃

⊿Tg = -12℃


熱耐性 (Mechanical properies)


1,500

2,000

2,500

3,000

3,500

4,000

4,500

0 50 100 150

1,500

2,000

2,500

3,000

3,500

4,000

4,500

0 50 100 150

HP-4770

TGDDM

BPADGE

Tensile testFlexural test

Fle

xu

ral M

od

ulu

s (

MP

a)

Temperature (℃)

Te

nsile

Mo

du

lus (

MP

a) HP-4770

Temperature (℃)

TGDDM

BPADGE



広い温度域で高弾性率を発現

HP-4770TGDDM

2000

2500

3000

3500

4000


BPADGE

(2.6%)

HP-4770

(1.8%)

TGDDM

(3.6%)

Fle

xura

l M

odulu

s (

MP

a)

Hot-Wet試験(曲げ試験比較)

be

fore

aft

er


■ Cured condition : 150C1hr + 180C3hr ■ Test condition : 70℃ x 2weeks

■ ()内：Water Absorption

p-TGAP

(4.1%)

BPFDGE

(2.3%)

低吸水率効果もあり、湿熱処理後も高い弾性率を保持

3,1803,230

3,010

2,780

3,660


COPYRIGHT © DIC CORPORATION ALL RIGHTS RESERVED.

Product nameProduction

ScaleTSCA REACH Features

EXA-850CRP / -830LVP Liquid Commercial Listed - Low viscosity /High purity (Low chlorine content)

HP-4032D Liquid Commercial SNUR Listed ~10t/year High curability / High Tg / Low CTE

HP-4700 / HP-4710 Solid Commercial Non-5(e) SNUR - Ultra High Tg / Low CTE

HP-4770 Solid Commercial Consent order - High modulus / High Tg / High flame retardancy

HP-9500 Solid Commercial Listed - High flame retardancy / High Tg

HP-6000 / EXA-7311-G4 Solid Commercial / Pilot - - High flame retardancy Low CTE

N-700 series Liquid-Solid Commercial ListedListed(except N-

730A)High modulus / High flexural strength / High Tg

N-570 / N-570H Solid Commercial Listed Listed High modulus / High flexural strength / High Tg / High elongation

HP-7200 series Solid Commercial ListedListed(depend

on grade)Low moisture absorption / Low-Dk, Low-Df

HP-5000 / HP-9900-75M Solid Commercial - - Low moisture absorption / Low-Dk, Low-Df / High flame retardancy

EXA-1514 Solid Pilot LVE - High curability / High Tg / Low CTE

HP-820 Liquid Commercial LVE - Low viscosity / Unique solubility

EXA-7250 Semi-Solid Pilot Non-5(e) SNUR Listed ~100t/y Low viscosity / High Tg

TSR-400 Solid Commercial Listed Listed High Tg / High mechanical properties

EXA-4850 series Liquid Pilot LVE Listed Flexibility & Toughness / High adhesive / Low shrinkage

EXA-4816 Liquid Pilot LVE - Flexibility & Toughness / High adhesive / High durability

EXB-X Solid Pilot - - High flame retardancy / High mechanical properties

ATN series Solution type Commercial Listed Listed High flame retardancy / High adhesive / Low CTE

HPC-8000-65T Solution type Commercial - - Low-Dk, Low-Df / Low moisture absorption

Product line-up ~High performance epoxy and hardener~

23

複合材用途向けエポキシ樹脂のご紹介 · hardener : dds...

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