A “New” Family of VECTOR Styrenic Block Copolymers for the Personal Care & Hygiene Market

“Low Styrene, Styrene-Butadiene-Styrene (LS-SBS) Triblock Copolymers*”

2013 Thermoplastic Elastomer Conference Oct. 16, 2013 Dusseldorf, GmbH

André J. Uzee / B. Grigar/ B. Marino/ F. Brown

TSRC Dexco

VECTOR™ & Taipol™ Styrenic Block Copolymers

* As described in the following: EU Patent EP2121835 B1; US 8653189 B2

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Agenda

• Who is TSRC Dexco Polymers?

• Styrenic Block Copolymers Growth

• Diaper Market Overview & Outlook

• Application of SBCs Elastic Film In Diaper

• Comparison of Elastic Film by SBC Type

• New “Low Styrene SBS Copolymers” In Model Film Compounds

• Summary/ Conclusions

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TSRC Dexco Overview

• Company Established in 1973.

• First TSRC SBS/ SIS Plant in 1988, Taiwan

• Start-up of Dexco Plant in 1989, USA

• Second TSRC SBS/ SIS Production Line, Taiwan

• Developed & Introduced 1st Generation SEBS

Hydrogenation Tech. 1st Generation, Taiwan

• SEBS Commercialized, Taiwan

• Develop & Introduced 2nd Generation SEBS

• Hydrogenation Tech. 2nd Generation, Taiwan

• SEBS & SIS Production, China

• Acquired Dexco Production (SIS & SBS)

• JV w/ CPC for SIS Production, Taiwan

• Largest Global Producer Of “Sequentially”

Polymerized Styrenic Block Copolymers (SBCs)

• Global Presence

- North America, Europe & Asia

Rapid

Development

1990s

Globalization

&

Specialization

2010

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SBCs 2008 & Growth Rates

Percent Annual Growth Rates

• 2003 to 2008 7.0%

• 2008 to 2013 4.9% (Forecast)

2008 Consumption

~1,600,000 Metric Tons

Largest-volume in the thermoplastic elastomer (TPE) family

53%

28%

19%

Source: Fredonia Group 2009

(000 metric tons)

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Baby Diaper Market Overview

Source: AccuSentry

$ B

illi

on

US

D

6.1 7.6

9.4 5.1

5.9 6.4 3.4

5.3

9.3

5.7

5.9

6.3

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

2004 2008 2012

Europe N. American Asia Pacific Others

20

23

31

North America 2-5%

Europe 5-8%

Asia (China) 12-15%

World Diaper Market Size (2004~2012)

- Baby Diaper Market Estimate $31 Billion USD w/ CAGR 4-5%

- Europe & N. America: Largest w/ 50 % Share of Global Diaper Market

- In Asia (especially for China): Highest Growth Rate Region; Higher

Birth Rates; Growing Disposable Income; Rise In Working Women

2004-2012 CAGR : 4-5%

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6

SB

Cs

Gro

wth

in

Dia

pe

rs E

las

tic

s*

Timeline 1995 2000 2012 2005 2018

Growth Of SBCs In Elastomeric Films*

*Dexco Polymers Estimate

Carlos Richer - “Approximately 348 million diapers sold every day

with maximum market potential of 1.41 billion units per day.

Growth Driver:

Comfort, Fit, & Containment

Bubble Size

“Incorporation Of Elastics”

Only 24% world market share.”

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Diapers Across the Globe

Obtained from

Manufacturers

Websites Hygiene market has been the developmental &

commercial driver of stretchable laminates *

* Stretchable Nonwovens - 2010

I like the

Comfort

Fit

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Closure-Type Diaper

Tabs

Waistband

Leg Elastics

Mechanical

Closure

Films/ Strands

Films

Elastomeric Materials Improve The Comfort And Fit Of Diapers

Film/ Netting/

Strands

Landing Zone

Ears /Side Panels

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Pe

rfo

rma

nc

e -

Ela

sti

cit

y

Tabs

Performance Requirements

Varies Based on Diaper Part Side

Panels

Performance of Diaper Components “Stretch Engines” - Elasticity

Ears

Waist

Band

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Types Of Stretchable Materials Focus – Styrenic Block Polymers

•Non-Hydrogenated Family (Highest Volume SBCs)

• Styrene-butadiene-styrene (SBS & SBS/SB) triblock copolymers

• Styrene-isoprene-styrene (SIS & SIS/SI) triblock copolymers

•Hydrogenated Family

• Styrene-ethylene-butylene-styrene (SEBS)

• Styrene-ethylene-ethylene/propylene-styrene(SEEPS)

•Others • Natural Rubber

• Polyolefin Elastomers

• Thermoplastic Polyurethane

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Why Market Interest In NEW SBS Block Copolymers?

Challenges associated with the processing of SEBS copolymers on the market; producing very thin films.

Converters using SEBS, SEEPS, SIS, SIS/SBS blends have strong

interest & need for cost relief; lower cost alternatives

Converters using POE’s desire improved elasticity.

Need for high performing films at a thicknesses of less than 50

microns & preferrably < 35 microns via Direct-Feed Extrusion.

Hypothesized: A New Low Styrene SBS Block Copolymer Might Be Of Value In Meeting Some Of These Unmet Needs.

Can New Low Styrene SBS copolymers be converted into film at a thickness of less than 35 micron?

Are the properties attractive for diaper elastic applications?

Unmet Need - Driving Force For New SBS?

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S,B, Block Structure Definitions

SSSS-BBBBBB-SSSSSS S-B-S Pure Sequential Block Structure Sequential “Pure” Block Chemistry

SSSS-BBBBBB-SSSS/ SSSS-BBB S-B-S/ S-B

Triblock/ Diblock Blend Coupled Chemistry or Sequentially Produced

Blended Products

Factoid*:

– Anionic Sequential Polymerization of SIS and SBS Triblock Copolymers yield products that offer Advantaged Physical Properties vs. similar products produced via Coupling Technology.

* ANTEC SPE 2005, “Highly Transparent Elastomeric Films”

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Determining Right Product - The Application Where do you Start?

• Selection Of The Proper SBC Requires and In-Depth Understanding Of

• the specific application on the diaper

• the requirements for elasticity

• the cost model

• SBC Selection Cannot Be Made Based On The Physical Properties Of The SBC Alone. It Requires A Further Understanding Of the Manufacturers

• history of Processing SBCs

• level of Sophistication

• extrusion Capabilities

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Elastomeric Film Formulations

• SBC Elastic Film Are Typically Blended Products

• Typical Formulations:

• 5-30% Thermoplastic (e.g., PS, PE, PP, etc.)

• 60-95% SBC (e.g., SIS, SBS, SEBS, SEEPS, or blends)

• optionally with Process Oils (e.g., White mineral oils) / Antiblock Additives (e.g., Erucamide/ Silica) , Antioxidants (e.g., Irganox 1010), Pigments (PE masterbatch typically)

• Typically Extruded • A Pre-Compounded Product

• Direct Feed Of A Physical Blend

• Individual Components

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SEBS

SEEPS

20-31% Styrene

SIBS

29-31% Styrene

SBS

Cost

18-31% Styrene

SIS

22-24% Styrene

LS-SBS

w/ Mineral Oil

Polymer Type Cost Sensitivity

31% S, 50-60 µm

31% S, SBS/ Oil

35-45 µm

23% S, SBS/ Oil

~25 µm

75% Butadiene

75% Isoprene

Low Specific Gravity

(~0.91) Compounded Direct Feed

Not to Scale

Low

High

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Elastomeric Applications (Definition; Test Conditions; Requirements)

Definition: Mono or multilayer film that can be elongated to several times its

original dimension & then quickly return, almost to the original dimensions.

Typical Test Conditions (CD) Elongation = 200% to 500%

No. of Cycles = 1 to 5

Temp. = RT & 37°C Sustained Load = 5- 10 hr. @ 37°C

Relax Time = 30 - 60 sec.

Set Time = 60 - 120 sec.

Typical Test Conditions (CD) Elongation = 200% to 500%

No. of Cycles = 1 to 5

Temp. = RT & 98.6°F Sustained Load = 5-10 hr. @ 37°C

Relax Time = 30-60 sec.

Set Time = 60-120 sec.

Recovered Energy = >75%

Sustained Load = < X% loss / hr.

Relaxation % = < 15%

Set % = <10%

2- Cycle Elasticity Testing (Example)

500% Activation/ 200% Extension

US Patent 7,445,831

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Per

form

an

ce -

Ela

stic

ity

SIS/SBS

Blends

SEBS/

SEEPS

Polymers

Polymer (Resin) Performance Sensitivity “Elasticity”

SIS

Polymers

SBS

Polymers

Polyolefin

Elastomers

Performance Varies

Based on Blend Composition

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• Cast & Blown Film

• Monolayer

• Multi-layer (ABA type)

• Flat Film or Breathable Film

• Other*

– Strands - Foams

– Netting - Spandex Yarns

– Printable Strips - Elastic Nonwovens

– Bi-Components *Stretchable Nonwovens - 2010

• Nonwoven Laminate Structures

Types of Stretch Engines For Personal Hygiene Applications

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Experimental Study & Testing

• New Low Styrene SBS (LS-SBS) Copolymers

• Melt Strength of Low Styrene SBS Copolymers

• Physical Properties of Polystyrene (PS) / LS-SBS Copolymer Blends

• Melt Strength

• Ultimate Tensile Strength & Elongation

• Melt Flow Rate

• Elasticity

• Peak Force

• Unload Properties

• Ratio of Peak Force to Unload

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NEW “ Low Styrene” SBS Copolymer Low Styrene SBS Property

Styene Content, Wt.% 22.4

Melt Flow Rate, g/ 10 min. 1.2

Shore A 62.2

Tensile Testing (TD) PropertyUltimate Tensile Strength, Mpa 28.6

300% Modulus, Mpa 2.4

200% Modulus, Mpa 1.9

150% Modulus, Mpa 1.8

Elongation, % 956

Hysteresis Testing (TD) PropertyPeak Force @ 500%, MPa 3.7

Set after 500% strain, % 18.8

Peak Force @ 200%, MPa 1.6

Relaxation@ 200%, % 5.6

Unload @ 50%, MPa 0.7

*US20040049836 A1;Tested on 0.030" thick plaques

Ratio of Load @ 200% to Unload @ 50% 2.44TSRC Dexco

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Melt Strength Data Low Styrene SBS w/ Mineral Oil

Melt Strength Curve

DB 2005-01205-69-16

95% 2005-01205-18-1, 22% Styrene SBS/ 5% Mineral Oil

MFR = 3.2

0

2

4

6

8

10

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce

[c

N]

Melt Strength Curve

DB 2005-01205-69-17

90% 2005-01205-18-1, 22% Styrene SBS/ 10% Mineral Oil

MFR = 5.3

0

2

4

6

8

10

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce [

cN

]

Melt Strength Curve

DB 2005-01205-69-18

85% 2005-01205-18-1, 22% Styrene SBS/ 15% Mineral Oil

MFR = 9.5

0

2

4

6

8

10

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce [

cN

]

5% 10%

15%

RHEOTESTER 2000 Wheels Standard

Gap 0.4

Acceleration a * t, a = 2.4[mm/s²]

Temperature 190.0 [°C]

Piston diameter 12 [mm]

Piston speed 0.265 [mm/s]

Die geometry 30 / 2 [mm]

Shear rate 38.2 [1/s]

Strand length 100.0 [mm]

Vo 9.5 [mm/s]

Vs 9.5 [mm/s]

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Melt Strength Data

PS (15%) / Low Styrene SBS w/ Mineral Oil Melt Strength Curve

DB 205-01205-69-11

15% Nova 3900/ 82%, 22% Styrene SBS/ 3% Mineral Oil

MFR = 2.8

0

3

6

9

12

15

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce [

cN

]

Melt Strength Curve

DB 2005-01205-69-12

15% Nova 3900/ 80%, 22% Styrene SBS/ 5% Mineral Oil

MFR = 3.9

0

2

4

6

8

10

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce [

cN

]

Melt Strength Curve

DB 2005-01205-69-13

15% Nova 3900/ 75% , 22% Styrene SBS/ 10% Mineral Oil

MFR = 6.6

0

2

4

6

8

10

0 50 100 150 200 250 300

Velocity [mm/s]

Fo

rce [

cN

]

Melt Strength Curve

DB 2005-01205-69-14

15% Nova 3900/ 70%, 22% Styrene SBS)/ 15% Mineral Oil

MFR = 12.6

0

2

4

6

8

10

0 50 100 150 200 250 300 350 400

Velocity [mm/s]

Fo

rce [

cN

]

3% MO 5% MO

10% MO 15% MO

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PS/ DPX 623 (LS-SBS) Blends

~23% Styrene, SBS Study

*(200°C/5.0 kg)

Oil Content 10.8 – 22.3 MFR* 4.4 – 16.5 g/10 min.

Sample No. 1 3 4 6 7 9

Crystal Polystyrene, Wt.% 19.1 19.1 24.3 24.3 29.6 29.6

LS-SBS, Wt.% 72.2 65.2 67.0 60.0 61.7 54.7

White Mineral Oil, Wt.% 8.7 15.7 8.7 15.7 8.7 15.7

Total 100.0 100.0 100.0 100.0 100.0 100.0

Wt.% Mineral Oil 10.8 19.4 11.5 20.7 12.4 22.3

MFR, g/ 10 min. (200°C/5kg) 4.4 10.6 5.2 12.6 6.1 16.5

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Monolayer Cast Film Extrusion Conditions Target 25 microns Film Thickness

LabTech 25 mm Lab Cast Film Extruder w/ 250 mm Die

Sample No. 1 3 4 6 7 9Nominal Die Gap, microns 650 650 650 650 650 650

Extruder Profile

Temperature, Zone 1, °C 155 155 155 155 155 155

Temperature, Zone 2, °C 165 165 165 165 165 165

Temperature, Zone 3, °C 180 180 180 180 180 180

Temperature, Zone 4, °C 190 190 190 190 190 190

Temperature, Zone 5, °C 205 205 205 205 205 205

Melt Temperature, °C 207 205 206 205 206 204

Head Pressure, Bar 152 107 144 96 132 86

Screw Speed, RPM 80 80 80 80 80 80

Screw Power (%) 72 61 70 60 68 59

Cast Film/Sheet Panel

Die Temp Zone 6, °C 205 205 205 205 205 205

Die Temp Zone 7, °C 205 205 205 205 205 205

Die Temp Zone 8, °C 205 205 205 205 205 205

Thickness (microns) (Target) 25.0 25.0 25.0 25.0 25.0 25.0

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Physical Property – Results of Testing Wt.% Mineral Oil 10.8 19.4 11.5 20.7 12.4 22.3

MFR, g/ 10 min. (200°C/5kg) 4.4 10.6 5.2 12.6 6.1 16.5

Tensile/ Elongation Test Results

Sample No. 1 3 4 6 7 9

Sample Thickness, microns 51 51 51 51 51 51

Ultimate Tensile Strength, Mpa 23.7 21.7 22.0 18.5 23.8 17.5

150% Modulus, Mpa 1.83 1.4 2.1 1.47 2.61 1.65

Elongation, % 860 927 853 857 843 796

Elasticity Testing

Sample No. 1 3 4 6 7 9

Sample Thickness, microns 51 51 51 51 51 51

Peak Force @ 500%, Mpa 2.95 2.29 3.82 2.85 4.56 3.30

Set after 500% strain, % 21.6 17.3 24.2 17.5 27.9 18.3

Regrip 2nd Cycle, Peak Force @ 200%, Mpa 1.55 1.24 1.68 1.29 1.77 1.27

Relaxation after 200% Elongation, % 8.4 7.5 10.1 8.1 12.1 9.5

Unload Force @ 50%, Mpa 0.70 0.58 0.68 0.59 0.64 0.55

*Descibed in patent application US20040049836 A1;

Ratio of Load @ 200% to Unload @ 50% 2.20 2.13 2.46 2.20 2.78 2.31

Notes: Thickness/ Draw Resonance

25 µ

No Draw

Resonance

25 µ

No Draw

Resonance

25 µ

No Draw

Resonance

25 µ

No Draw

Resonance

25 µ

No Draw

Resonance

25 µ

No Draw

Resonance

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Melt Strength Data 23% Styrene SBS Blend vs. 30% Styrene SBS Copolymers

Melt Strength Curve

DB 2005-01205-69-14

15% Nova 3900 70%, 22% Styrene SBS/15% Mineral Oil

MFR = 12.6

0

2

4

6

8

10

0 50 100 150 200 250 300 350 400

Velocity [mm/s]

Fo

rce [

cN

]

Melt Strength Curve

DPR 2004-01305-31-11

NORDENIA 218

0

2

4

6

8

10

0 50 100 150 200 250 300 350 400

Velocity [mm/s]

Forc

e [c

N]

PS/ 30% Styrene SBS Copolymer Blend w/ Mineral Oil

Melt Flow Rate at 12.0 g/ 10 min. (200C/5kg)

PS/ 23% Styrene SBS Copolymer Blend w/ Mineral Oil

Melt Flow Rate @ 12.6 g/ 10 min. (200C/5kg)

RHEOTESTER 2000 Wheels Standard

Gap 0.4

Acceleration

a * t, a =

2.4[mm/s²]

Temperature 190.0 [°C]

Piston diameter 12 [mm]

Piston speed 0.265 [mm/s]

Die geometry 30 / 2 [mm]

Shear rate 38.2 [1/s]

Strand length 100.0 [mm]

Vo 9.5 [mm/s]

Vs 9.5 [mm/s]

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Introducing TSRC Developmental SIS For Films

Sequentially Produced Pure-Triblock SIS Copolymers

TSRC Production – Nantong, China Sample No. 1 2 3

Low Density Polyethylene, Wt.% 20 20

General Purpose Polystyrene, Wt.% 15

DP-4111N, 18% Styrene, SIS, Wt.% 85 40

DP-4211N, 30% Styrene, SIS, Wt.% 80 40

TOTAL 100 100 100

Dow LDPE 640i; Styrolution 3190 PS; Kemamide E Ultra at ~0.2% added to each blend.

Tensile Properties* 1 2 3

Thickness, mm 0.079 0.076 0.079

Tensile Strength, MPa 19.4 25.0 19.5

300% Modulus, MPa 3.0 1.6 2.4

150% Modulus, MPa 1.9 1.1 1.5

Elongation, % 950 1080 1010

*Tested in accordance with ASTM D412 in Transverse Direction

Elastic Properties* 1 2 3

Thickness, mm 0.079 0.076 0.074

Force @ 500% Strain, Cycle 1, MPa 3.33 1.73 3.10

Set after 500% Strain, Cycle 1, % 25.3 21.3 26.5

Force @ 200% Strain, Cycle 2, MPa 1.55 1.01 1.48

Relax @ 200% Strain, Cycle 2, MPa 10.5 5.8 9.7

Force (Unload) @ 50% Strain, Cycle 2, MPa 0.50 0.47 0.48

Ratio, Force @ 200% to Force, Unload @ 50% 3.13 2.16 3.06

*Described in US patent Application US20040049836 A1. Tested in Transverse Direction

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Summary/ Conclusions New “Low Styrene” SBS Copolymers

Compositions using Polystyrene resin at 19.1 to 29.6 Wt.% polystyrene resin combined with triblock copolymers with a low styrene SBS copolymer (~23 Wt.% Styrene), 10.8 to 22.3 Wt.% mineral oil yield very thin elastic films (25 µm).

New low styrene SBS copolymers show outstanding elastic properties.

Melt Strength data confirms the ability of these new low styrene SBS copolymers to produce thin films.

New Low Styrene SBS copolymers have the potential to offer converters and end-users thinner films at a lower basis weight along with a lower specific gravity.

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Summary Of “Take Aways”

Diapers Incorporating Elastic Films Based On SBCs Are Growing In Use Across The Globe At Both The Major & Private Label Diaper Manufacturers

Non-Hydrogenated SBC Are Well Suited For Elastic Films For Use In Diaper Ears, Tabs & Waistband Applications

Sequential SBCs Give The Best Elastic Properties

Selection Of The Proper SBC Requires In-depth Analysis Of The Diaper Producers’ Performance Needs

Manufacturer’s Extrusion Capabilities

New Low Styrene SBS Copolymers Offer A New Approach To Produce Thin (~25 micron) Films w/ Outstanding Performance

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Co-Authors

W. Grigar - Global Product Marketing Manager, Houston, TX., USA

B. Marino – Lab Tech., Specialist, Plaquemine, LA., USA

F. Brown – Lab Tech., Specialist, Plaquemine, LA., USA

Contributors

M. Myers - Chief Chemist & Sr. Scientist, Plaquemine, LA., USA

T. Bonin - Lab Tech., Specialist, Plaquemine, LA., USA

Special Thanks C. Mudd - President/ General Manager, Houston, TX. USA

B. Witt - Global R&D Technical Manager, Plaquemine, LA., USA

Dexco Team

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