Douglas J. Sober713-503-1558

dsober@kanekatexas.com

Kaneka Texas Corp2 Northpoint Drive

Suite 200Houston, TX 77060

www.kanekatexas.com

Kaneka CoreKaneka Core--Shell Toughening Shell Toughening Systems for Thermosetting ResinsSystems for Thermosetting Resins

What is CoreWhat is Core--Shell Rubber (CSR) ?Shell Rubber (CSR) ?

2-Layer CSRCo-Polymer II designedto be compatible withthermosetting resin.This is the shell.

Co-Polymer I designedfor impact resistance.This is the core.- butadiene/styrene- polybutadiene- siloxane- acrylic

What is CoreWhat is Core--Shell Rubber (CSR) ?Shell Rubber (CSR) ?

2-Layer CSR100nm

Applications of CSR?Applications of CSR?

• Thermoplastic resins systems.- PVC- ABS

• Thermosetting resins systems for:- Adhesives.- Composites.- Electrical Castings- Coatings- Copper-Clad Laminates

Core Shell Rubber Advantages:Core Shell Rubber Advantages:• Outstanding Toughness Improvement:

- Fracture Toughness- T-Peel Strength- Lap-Shear Strength

• No Depression of Tg.• Wide Cure Window.• Consistent Morphology.• Low Ionic and Surfactant Content.• Extremely Stable.• Compatible / synergistic with Secondary Tougheners.• Nano-size particles do not filter.• Composite parts tend to be very translucent.

How does CSR toughen resins?How does CSR toughen resins?

• Core polymer cavitates on impact dissipating energy. Reduced damage area

• Small, evenly dispersed particlesact as a crack terminator.

• Core polymer relieves inherent stress generated during curing.

Inter-laminarbond & peelstrengthimprovement

Dimensional stability& microcrack resistanceNote: Optimization of particle size and inter-particle

distance (volumetric particle concentration) is critical to achieving the best performance

CSR Manufacturing Process

Epoxy

Solid CSRCan only be broken up to 1500 nm minimum with wide particle size

distribution

KANEKA CSR

Process

Epoxy/CSRKane Ace MX

Agglomeration /Drying

Latex

MX Process

Narrow range of 100 nm particles

Basic Properties of MX system

Core Shell Rubber particles are homogeneously dispersed in epoxy resin with long term stability

Core Shell Rubber particles are homogeneously dispersed in epoxy resin with long term stability

Conventional Solid CSR(10 wt%) in epoxy

New MX CSR(25 wt%) in epoxy

Appearance - Cured system“Transparent”

TEM observation - Cured system

Comparison of Kane Ace MX CSR versus Powder CSR

1µm

MX CSR

Powder CSR

Appearance of MX and CTBN (in DGEBA Epoxy)

No toughener

CSR 7.5 phr

CTBN 7.5 phr

What is Kane Ace MX:What is Kane Ace MX:

Kane Ace MX are concentrates comprised typically of 25% by weight of CSR dispersed in various thermosetting resins. The liquids are easily poured after heating and the individual CSR domains remain uniformly dispersed during storage and formulating.

Kane Ace MX Products:Kane Ace MX Products:

Grade CSR Type / Loading Carrier ResinMX 124 St-Bd 25% Liquid Bis A epoxy (lowest viscosity)MX 125 St-Bd 25% Liquid Bis A epoxy MX 133 St-Bd 25% Liquid Bis F epoxy (lower viscosity)MX 135 St-Bd 25% Low crystallizing liquid Bis F epoxyMX 136 p-Butadiene 25% Liquid Bis F epoxy (lower viscosity)MX 153 p-Butadiene 33% Liquid Bis A epoxyMX 156 p-Butadiene 25% Liquid Bis A epoxyMX 210 St-Bd 25% Epoxidized Phenol NovolakMX 227* St-Bd 25% Epoxidized BPA NovolakMX 338 St-Bd 25% Brominated Di-functional epoxyMX 392 St-Bd 25% Brominated Multifunctional epoxyMX 416 p-Butadiene 25% Multifunctional Epoxy Resin (TGMDA)MX 451 St-Bd 25% Multifunctional Epoxy Resin (TGPAP)MX 554 St-Bd 25% Cyclo-Aliphatic epoxy (MX 601* St-Bd 25% Resole NovolakMX 615 St-Bd 25% Di-allyl BPA (for BMI)MX 660 Siloxane 25% Di-allyl BPA (for BMI)MX 715 St-Bd 25% Polypropylene Glycol carrier (mw 400)MX 717 St-Bd 25% Polypropylene Glycol carrier (mw 1000)MX 719 St-Bd 25% Polypropylene Glycol carrier (mw 2000)MX 960 Siloxane 25% Liquid Bis A epoxy

*Developmental grades not yet available in commercial quantities

Example for Comparative TrialExample for Comparative Trial

Part A:

70 parts liquid Bis A resin 52 parts liquid Bis A resin20 parts epoxy resin B 20 parts epoxy resin B10 parts reactive diluent 10 parts reactive diluent

24 parts MX 125

Part B:

30 parts Part B 30 parts Part B

Mix Ratio Part A to B:

100/30 106:30

Core Shell Concentration:

0% 4.4%

Existing System MX Toughened

Basic Properties of MX system

MX 125 Viscosity as a Function of Concentration

0

20,000

40,000

60,000

80,000

100,000

120,000

140,000

0 5 10 15 20 25 30

CSR concentration (wt%)

Visc

osity

(cps

) 25C

50C

WorkingRange

Kaneka Kane Ace MX®Adhesive Applications

T-Peel Strength Kane Ace MX

ASTM D1876

T-Peel Strength of DGEBA Epoxy/MX 120 System

0

5

10

15

20

25

30

35

T-peel S trength / pli

C S R 0% C S R 5% C S R 10%

Lap-Shear Strength OF Kane Ace MX

Adhesive layer

ASTM D1002

0

1000

2000

3000

4000

5000

6000

Lap Shear PSI

0 % Control 5 % CSR 10 % CSR

Lap-shear Strength of DGEBA Epoxy/MX 120

T-peel Strength of MX 120 vs. CTBN in DGEBA Epoxy

C ontrol5%

10%

C TB N

C SR M aster-batch05

1015202530

35

T-peelStrength/pli

Comparison of CSR and CTBNComparison of CSR and CTBNLap-shear Strength of MX 120 vs.

CTBN in DGEBA Epoxy

Control

5%

10%

C T B N

C SR M aster-batch0

1000

2000

3000

4000

5000

6000

Lap-shearStrength/psi

Kaneka Kane Ace MX®Composite Applications

Types of Fractures

Depending on the stress field in the vicinity of the crack tip, three principle fracture modes are possible: Mode I, Mode II, and Mode III.

Mode I bending is tensile, Mode II is shear, Mode III is tearing

Toughening Effect of Epoxy/ Kane Ace MX SystemToughening Effect of Epoxy/ Kane Ace MX System

Three-Point Bending

force

specimen: 6cm x 1.2cm x 0.5cm

pre-crack: 0.6cm depth by blade-tapping

head speed: 1mm/min.

stress

strain

strength

energy

ASTM 5045 CastingASTM 5528 Reinforced

Fracture Toughness of DGEBA Epoxy/MX 120

00.5

11.5

22.5

3

K1c/ MPam1/ 2

CSR 0% CSR 10%

DDSpiperidine

Fracture Toughness of DGEBA Epoxy/MX 120

0

500

1000

1500

2000

2500

G 1c/Jm 2

C SR 0% C SR 10%

DDS

piperidine

Comparison of CSR and CTBNComparison of CSR and CTBNFracture Toughness and Glass Transition Temperature

of MX 120 vs. CTBN in DGEBA Epoxy

0

100

200

300

400

500

600

control CSR Master- batch CTBN

Ｇ１ｃ

／J/

m2

0

50

100

150

200

250

Tg／

C

Tg

Kaneka Kane Ace MX®Coatings Applications

Kaneka Kane Ace MX®Vinyl Ester Applications

9291.700Vinylester/MX153(85/15)

1640.823Vinylester

G1C(J/m2)K1C (MPa⋅m1/2)

Fracture Toughness of Vinylester / MX153 system

Vinylester: Reichhold 9800-05A, Casting: 50C/17hr-120/2hr

Kaneka Kane Ace MX®Copper-Clad Laminates

Applications

Lead-Free Data Sheets IPC-4101B:

Slash Sheet # 99 101 121 124 126 129

Tg min 150 110 110 150 170 170Tg max

Td min 325 310 310 325 340 340

Fillers yes yes no no yes noFlame retardant RoHS BR RoHS BR RoHS BR RoHS BR RoHS BR RoHS BRCuring Agent N/A N/A N/A N/A N/A N/A

Flammability V-0 V-0 V-0 V-0 V-0 V-0

Z-Axis alpha 1 max 60 60 60 60 60 60Z-Axis alpha 2 max 300 300 300 300 300 300% max 3.5 4.0 4.0 3.5 3.0 3.0

T-260 30 30 30 30 30 30T-288 5 5 5 5 15 15T-300 AABUS AABUS AABUS AABUS 2 2

UL MOT AABUS AABUS AABUS AABUS 130 130

Amendment 2

THE REACTION OF DICY WITH EPOXY RESIN:

BASE MATERIAL WORKSHOP

(DICY)

Phenol Novolak Resinspopular curing agentsfor lead-free FR-4

EFFECT OF CROSS LINK DENSITY ON LAMINATE PROPERTIES:

BASE MATERIAL WORKSHOP

TG/Td PEELSTRENGTH

INTERLAMADHESION

CHEMICALRESISTANCE

FRACTURETOUGHNESS

THERMALRESISTANCE

Z-AXISCTE

CROSS LINKDENSITY OF

SYSTEM

Good Good Good GoodBad Bad Bad

Pad Cratering

Pad Cratering

Life ScienceProducts

Synthetic fiber

Electronic Products

Foodstuffs Products

Expandable Products

Co Q10

Functional Plastics

Global Revenue: $5.3 billion 2006“#1 Producer of CSR

Toughening Agents Worldwide”

Kaneka Corporation• Today Kaneka is a world leader in the creation of

innovative technologies in areas such as polymers, construction materials, and pharmaceuticals.

• Kaneka is a global organization with production facilities on four continents and approximately 7000 employees.

• Revenue for our latest fiscal year (ended March ‘06) is estimated worldwide at approximately $5.3 billion.

Kaneka Global Manufacturing• Kaneka currently manufactures “Modifiers” at four sites

around the world. These include:

Kaneka Japan Asia Takasago, JapanKaneka Texas USA Pasadena, TexasKaneka Belgium Europe Oevel, BelgiumKaneka Malaysia Asia Kuantan, Malaysia

• These four sites provide Kaneka with an annual capacity of modifiers of approximately 400 million pounds.

Kaneka Texas Corporation• A wholly owned subsidiary opened in 1983, Kaneka

Texas (KTC) is responsible for marketing several Kaneka product lines throughout the Americas.

• Business operating at KTC include:• 1.) Polymer Modifiers (Kane Ace)• 2.) CPVC Resins (Kanevinyl)• 3.) Foamed Olefins Resins (Eperan, Eperan PP)• 4.) Modified Silicone for Sealants (MS Polymer)• 5.) Polyimide Film (Apical)• 6.) Nutrients (CoQ10)