2013 Thermoplastic Elastomer Conference Oct. 16, 2013 Dusseldorf, GmbH. VECTOR & Taipol Styrenic Block Copolymers

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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

1 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 VECTOR & Taipol Styrenic Block Copolymers * As described in the following: EU Patent EP B1; US B2

2 Agenda Who is 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

TSRC SBS/ SIS Production Line, Taiwan Developed & Introduced 1 st Generation SEBS Hydrogenation Tech.

Tech. 2 nd Generation, Taiwan Globalization & Specialization 2010 SEBS & SIS Production, China Acquired Dexco

3 Overview Company Established in First TSRC SBS/ SIS Plant in 1988, Taiwan Start-up of Dexco Plant in 1989, USA Rapid Development 1990s Second TSRC SBS/ SIS Production Line, Taiwan Developed & Introduced 1 st Generation SEBS Hydrogenation Tech. 1 st Generation, Taiwan SEBS Commercialized, Taiwan Develop & Introduced 2 nd Generation SEBS Hydrogenation Tech. 2 nd Generation, Taiwan Globalization & Specialization 2010 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

4 SBCs 2008 & Growth Rates Largest-volume in the thermoplastic elastomer (TPE) family Percent Annual Growth Rates 2003 to % 2008 to % (Forecast) 53% 28% 19% 2008 Consumption ~1,600,000 Metric Tons (000 metric tons) Source: Fredonia Group 2009

5 $ Billion USD Baby Diaper Market Overview - 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 World Diaper Market Size (2004~2012) CAGR : 4-5% North America 2-5% Europe 5-8% Asia (China) 12-15% Source: AccuSentry Europe N. American Asia Pacific Others

6 SBCs Growth in Diapers Elastics* Growth Of SBCs In Elastomeric Films* Carlos Richer - Approximately 348 million diapers sold every day with maximum market potential of 1.41 billion units per day. Only 24% world market share. Growth Driver: Comfort, Fit, & Containment Timeline *Dexco Polymers Estimate Bubble Size Incorporation Of Elastics

7 Diapers Across the Globe I like the Comfort Fit Hygiene market has been the developmental & commercial driver of stretchable laminates * * Stretchable Nonwovens Obtained from Manufacturers Websites

8 Closure-Type Diaper Elastomeric Materials Improve The Comfort And Fit Of Diapers Ears /Side Panels Waistband Films/ Strands Film/ Netting/ Strands Tabs Films Leg Elastics Mechanical Closure Landing Zone

9 Performance - Elasticity Performance of Diaper Components Stretch Engines - Elasticity Side Panels Ears Performance Requirements Varies Based on Diaper Part Tabs Waist Band

10 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

11 Unmet Need - Driving Force For New SBS? 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?

12 S,B, Block Structure Definitions SSSS-BBBBBB-SSSSSS Pure Sequential Block Structure S-B-S Sequential Pure Block Chemistry SSSS-BBBBBB-SSSS/ SSSS-BBB Triblock/ Diblock Blend S-B-S/ S-B 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

13 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

14 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

15 Cost High SEBS SEEPS 18-31% Styrene SIS Polymer Type Cost Sensitivity 31% S, µm 75% Isoprene 31% S, SBS/ Oil µm 23% S, SBS/ Oil ~25 µm 20-31% Styrene SIBS 75% Butadiene 29-31% Styrene SBS 22-24% Styrene LS-SBS w/ Mineral Oil Low Compounded Direct Feed Low Specific Gravity (~0.91) Not to Scale

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

16 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 = C Relax Time = sec. Set Time = sec. Typical Test Conditions (CD) Elongation = 200% to 500% No. of Cycles = 1 to 5 Temp. = RT & 98.6 F Sustained Load = C Relax Time = sec. Set Time = sec. Recovered Energy = >75% Sustained Load = < X% loss / hr. Relaxation % = < 15% Set % = <10% 2- Cycle Elasticity Testing (Example) US Patent 7,445, % Activation/ 200% Extension

17 Performance - Elasticity Polymer (Resin) Performance Sensitivity Elasticity Performance Varies Based on Blend Composition SEBS/ SEEPS Polymers SIS Polymers SIS/SBS Blends SBS Polymers Polyolefin Elastomers

18 Types of Stretch Engines For Personal Hygiene Applications 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 Nonwoven Laminate Structures

19 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

20 NEW Low Styrene SBS Copolymer Low Styrene SBS Tensile Testing (TD) Property Styene Content, Wt.% 22.4 Melt Flow Rate, g/ 10 min. 1.2 Shore A 62.2 Property Ultimate Tensile Strength, Mpa % Modulus, Mpa % Modulus, Mpa % Modulus, Mpa 1.8 Elongation, % 956 Hysteresis Testing (TD) Peak 500%, MPa 3.7 Set after 500% strain, % 18.8 Peak 200%, MPa 1.6 Relaxation@ 200%, % %, MPa 0.7 *US A1;Tested on 0.030" thick plaques Ratio of 200% to 50% 2.44 Property

Force [cn] Force [cn] Melt Strength Data Low Styrene SBS w/ Mineral Oil Force [cn] 10 8 6 4 2 0 Melt Strength Curve DB 2005-01205-69-16 95% 2005-01205-18-1, 22% Styrene SBS/ 5% Mineral Oil MFR = 3.

3 10 5% 8 6 10% 4 0 50 100 150 200 250 300 Velocity [mm/s] 10 8 6 4 2 0 Melt Strength Curve DB 2005-01205-69-18 85% 2005-01205-18-1, 22% Styrene SBS/ 15% Mineral Oil MFR = 9.

21 Force [cn] Force [cn] Melt Strength Data Low Styrene SBS w/ Mineral Oil Force [cn] Melt Strength Curve DB % , 22% Styrene SBS/ 5% Mineral Oil MFR = Velocity [mm/s] 2 0 Melt Strength Curve DB % , 22% Styrene SBS/ 10% Mineral Oil MFR = % % Velocity [mm/s] Melt Strength Curve DB % , 22% Styrene SBS/ 15% Mineral Oil MFR = % Velocity [mm/s] RHEOTESTER 2000 Wheels Standard Gap 0.4 Acceleration a * t, a = 2.4[mm/s²] Temperature [ C] Piston diameter 12 [mm] Piston speed [mm/s] Die geometry 30 / 2 [mm] Shear rate 38.2 [1/s] Strand length [mm] Vo 9.5 [mm/s] Vs 9.5 [mm/s]

Force [cn] Force [cn] Melt Strength Data Force [cn] Force [cn] 3% MO 15 12 9 6 3 0 PS (15%) / Low Styrene SBS w/ Mineral Oil Melt Strength Curve DB 205-01205-69-11 15% Nova 3900/ 82%, 22% Styrene

22 Force [cn] Force [cn] Melt Strength Data Force [cn] Force [cn] 3% MO PS (15%) / Low Styrene SBS w/ Mineral Oil Melt Strength Curve DB % Nova 3900/ 82%, 22% Styrene SBS/ 3% Mineral Oil MFR = Velocity [mm/s] 5% MO Melt Strength Curve DB % Nova 3900/ 80%, 22% Styrene SBS/ 5% Mineral Oil MFR = Velocity [mm/s] 10% MO Melt Strength Curve DB % Nova 3900/ 75%, 22% Styrene SBS/ 10% Mineral Oil MFR = Velocity [mm/s] 15% MO Melt Strength Curve DB % Nova 3900/ 70%, 22% Styrene SBS)/ 15% Mineral Oil MFR = Velocity [mm/s]

PS/ DPX 623 (LS-SBS) Blends ~23% Styrene, SBS Study 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.

23 PS/ DPX 623 (LS-SBS) Blends ~23% Styrene, SBS Study Sample No Crystal Polystyrene, Wt.% LS-SBS, Wt.% White Mineral Oil, Wt.% Total Wt.% Mineral Oil MFR, g/ 10 min. (200 C/5kg) Oil Content MFR* g/10 min. *(200 C/5.0 kg)

24 Monolayer Cast Film Extrusion Conditions Target 25 microns Film Thickness LabTech 25 mm Lab Cast Film Extruder w/ 250 mm Die Sample No Nominal Die Gap, microns Extruder Profile Temperature, Zone 1, C Temperature, Zone 2, C Temperature, Zone 3, C Temperature, Zone 4, C Temperature, Zone 5, C Melt Temperature, C Head Pressure, Bar Screw Speed, RPM Screw Power (%) Cast Film/Sheet Panel Die Temp Zone 6, C Die Temp Zone 7, C Die Temp Zone 8, C Thickness (microns) (Target)

25 Physical Property Results of Testing Wt.% Mineral Oil MFR, g/ 10 min. (200 C/5kg) Tensile/ Elongation Test Results Sample No Sample Thickness, microns Ultimate Tensile Strength, Mpa % Modulus, Mpa Elongation, % Elasticity Testing Sample No Sample Thickness, microns Peak 500%, Mpa Set after 500% strain, % Regrip 2nd Cycle, Peak 200%, Mpa Relaxation after 200% Elongation, % Unload 50%, Mpa *Descibed in patent application US A1; Ratio of 200% to 50% 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

26 Melt Strength Data 23% Styrene SBS Blend vs. 30% Styrene SBS Copolymers Force [cn] Force [cn] Melt Strength Curve DB % Nova %, 22% Styrene SBS/15% Mineral Oil MFR = 12.6 PS/ 23% Styrene SBS Copolymer Blend w/ Mineral Oil Melt Flow 12.6 g/ 10 min. (200C/5kg) Velocity [mm/s] Melt Strength Curve PS/ 30% Styrene SBS DPR Copolymer Blend w/ Mineral Oil NORDENIA 218 Melt Flow Rate at 12.0 g/ 10 min. (200C/5kg) RHEOTESTER 2000 Wheels Standard Gap 0.4 a * t, a = Acceleration 2.4[mm/s²] Temperature [ C] Piston diameter 12 [mm] Piston speed [mm/s] Die geometry 30 / 2 [mm] Shear rate 38.2 [1/s] Strand length [mm] Vo 9.5 [mm/s] Vs 9.5 [mm/s] Velocity [mm/s]

27 Introducing TSRC Developmental SIS For Films Sequentially Produced Pure-Triblock SIS Copolymers TSRC Production Nantong, China Sample No Low Density Polyethylene, Wt.% General Purpose Polystyrene, Wt.% 15 DP-4111N, 18% Styrene, SIS, Wt.% DP-4211N, 30% Styrene, SIS, Wt.% TOTAL Dow LDPE 640i; Styrolution 3190 PS; Kemamide E Ultra at ~0.2% added to each blend. Tensile Properties* Thickness, mm Tensile Strength, MPa % Modulus, MPa % Modulus, MPa Elongation, % *Tested in accordance with ASTM D412 in Transverse Direction Elastic Properties* Thickness, mm % Strain, Cycle 1, MPa Set after 500% Strain, Cycle 1, % % Strain, Cycle 2, MPa % Strain, Cycle 2, MPa Force 50% Strain, Cycle 2, MPa Ratio, 200% to Force, 50% *Described in US patent Application US A1. Tested in Transverse Direction

28 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.

29 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

30 Dexco Team 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

A New Styrenic Block Copolymer Designed for Polyolefin-like Processing for Compounding, Films and Fibers

A New Styrenic Block Copolymer Designed for Polyolefin-like Processing for Compounding, Films and Fibers Dale Handlin, TSRC, Shelby North Carolina, Ziv Cheng, The TSRC, Kaohsiung, Taiwan, and Mark Berard,