Recent Development in Polylactic Acid, TERRAMAC. HIROMASA SHIRAI TERRAMAC Business Development Department Unitika Ltd., JAPAN

Recent Development in Polylactic Acid, TERRAMAC HIROMASA SHIRAI TERRAMAC Business Development Department Unitika Ltd., JAPAN

CONTENTS Unitika Ltd. Japanese Bio-plastic Market What s PLA? Why PLA? TERRAMAC 1 : Unitika PLA Products TERRAMAC 2 : Unitika Improved PLA Products Heat Resistance and Durability TERRAMAC 3 : Unitika Improved PLA Products Heat Resistant Foam Potential Japanese PLA Market Next Steps for Japanese PLA Market Growth

History of Unitika 1889 Cotton Wool Vinylon Nichibo Natural Fiber 1969 Synthetic Fiber 1930 Rayon Nylon PET PVOH Nippon Rayon Unitika Resin Film 1999 Unitika Textiles LTD. Advanced Material Medical Non-woven Environmental Engineering Unitika Fibers LTD. 1999

Unitika Position Film Business the largest manufacturer of biaxially oriented PA 6 films in the world Resin Business producing PA 6/clay nanocomposite resins Non-woven Business top share of each PET spunbond and cotton spunlace market in Japan Fiber Business the largest manufacturer of polyester conjugated staple fibers for non-wovens in the world

Bio-plastics Market Analysis in Japan (2007) PBAT PEST PBS 12,330 t PLA PLA 46.6% Aliphatic Polyester 17.0% Aromatic Polyester 16.6% PVA 1.9% Esterified Starch 4.1% Other 13.8%

Commercial Applications of Bio-plastics in Japan (2007) 12,330 t Packaging Cushioning 2.4% Mulch Film 13.0% Compost-bag 4.9% Packaging 51.9% Fiber 11.4% E&E, Auto 4.6% Other 11.8%

Classification of Plastics Biomass-based Oil-based Biode egradable Non- Chemical Synthesis PLA : NatureWorks LLC (Ingeo) Zhejiang Hisun Group (Revode) Bio-PBS:Mitsubishi Chemical Microbial Production PHA : Kaneka Corp. Natural Polymer Esterified Starch:Novamont(Mater-Bi) Bio-PA11 : Arkema Bio-PTT : DuPont Bio-PE: Braskem Dow Chemical Bio-PP: Braskem Bio-PET, PC Aliphatic Polyester PBS : Showa Highpolymer(Bionolle) Mitsubishi Chemical(GSPla) Aromatic Polyester PBAT : BASF (Ecoflex) PEST : DuPont (Apexa) Commodity LDPE, HDPE, PP, PS Engineering PA6, PET, PC Super-Engineering PPS, PI, LCP, PEEK, PEI, PES

Chemical Structure of PLA CH 3 -O-C*-C- H O n C* : Asymmetric Carbon L-lactic acid, D-lactic acid PLA : PLLA, PDLA, PLDLA Aliphatic Polyester Tm : 170 ºC Tg : 58 ºC HO CH 3 OH C=O HO H OH C=O H L-lactic acid and D-lactic acid CH 3

Optical Composition and Melting Point Melting Poi int (ºC) Amorphous D-lactic Acid Content (mol%)

Melting Points and Glass Transition Temperatures of Biodegradable Polymers Tg ( ) 80 PLA 60 40 20 0 PHA -20 PBS -40 PCL -60-80 -100 40 60 80 100 120 140 160 180 200 Tm ( )

Why PLA? 1. Biomass-based Plastic Renewable and Sustainable Raw Material Reduction of Petroleum Dependence Reduction of Negative Effects on Human Health and Environment 2. Biodegradable Plastic Two-step Degradation Process: Hydrolysis and Biodegradation Stability in Normal Environment; Easy Degradation in Composting System 3. Commodity or Engineering Plastic Two Contradictory Properties : Durability and Degradability Possibility of Structural and Consumer Durable Material

Material Circulation System of TERRAMAC Lactic Acid Polylactic acid UNITIKA TECHNOLOGY TERRAMAC Products Films, Sheets, Non-wovens, Compounded Resins, and Fibers Starch Biomass Resources CO2 H2O PLA applied to TERRAMAC is made by NatureWorks LLC.

TERRAMAC Business Segments Film Business Division Biaxially Oriented Films, Blown Films, and Sheets Resin Business Division Resins for Extrusion, Foamed-extrusion, Injection, and Blow Molding Non-woven Business Division Spunbond Fabrics, Spunlace Non-wovens, and Needlepunched Non-wovens Fiber Business Division (Unitika Fibers LTD., Unitika Textiles LTD.) Multifilaments, BCF, Staple Fibers, Short-cut Fibers, Monofilaments, and End Products

Characteristics of PLA ADVANTAGES Physical Properties Transparency, Rigidity, Dead-fold Property Chemical Properties Water- & Oil-proof, Weather Stability Thermal Properties Heat-sealability, Flame-retardance

Applications of TERRAMAC Films Envelope Window, Vegetable Packaging, Compost Bag - - -

Applications of TERRAMAC Resins Case for Cosmetic, Name Card Case, Ballpoint Pen - - -

Applications of TERRAMAC Non-wovens 1 Civil Engineering Sheet, Soil Stabilizer, Agricultural Sheet - - -

Applications of TERRAMAC Non-wovens 2 Plant Pot, Headrest Cover - - -

Applications of TERRAMAC Fibers Garbage Bag, Tea Bag - - -

Characteristics of PLA DISADVANTAGES Heat Resistance : Hot Water Filling, Microwave Reheating, Ironing Crystallinity Durability : Long shelf life (Electronics Device Housing, Automobile Cabin Parts, Returnable Tableware) Impact Strength Gas Barrier Property Hydrolysis Resistance

Factors Controlling Crystallinity Crystallinity depends on Crystal-nucleation rate Crystal growth rate Heat Resistant PLA Chemical Structure Processing Condition Nuclear Agent Regularity Molecular Weight Flexibility Branching Cooling Rate Draw Ratio Type Amount Size

Rate of Crystallization of Improved PLA 1.0 Crystallinity Relative 0.8 0.6 0.4 0.2 Improved PLA PLA with 5% Talc Neat PLA 0.0 0 1 10 100 1000 Time (min) DSC : 200 ºC 130 ºC (isothermal condition) -500 ºC /min

Factors Affecting Hydrolysis Resistance Improving hydrolysis resistance under high temperature/high humidity condition Durable PLA Structural Residual Processing Factor Substance Condition End Group Lactide Moisture content Temperature Crystallinity Catalyst Circumstance Heating Temp. Humidity Alkaline Heating Time ph

Hydrolysis Resistance of Improved PLA Flexural Strengt th Retention (%) 100 80 60 40 20 0 under 50 ºC, RH95% Heat & Hydrolysis Resistant Grade Heat Resistant Grade Neat PLA 0 200 400 600 800 1000 Time (hrs)

Application Multifunction Device ApeosPort-III C3300 FUJI XEROX Ltd.

Application Cellular Phone FOMA N701iECO (NTT DOCOMO) TERRAMAC containing Kenaf fiber studied with NEC and UNITIKA

PLA Bottles Improved vapor properties by lamination of polyolefin Applications Nanocomposite PLA Men s cosmetic cases Reusable Tableware Bowls with polyurethane paint

Development of PLA Resin for Extruded Foam with High Heat Resistance It is relatively difficult to apply PLA (neat) to foaming or blow molding because the melt tension, elongational viscosity, and crystallization rate are too low for such applications. We have studied techniques to increase melt tension of PLA and achieved a unique process to obtain an extruded PLA foam with high heat resistance.

Elongational Viscosity of PLA for Foam 1.E+07 Neat PLA Temp : 170 ºC Viscosity y(pa s) 1.E+06 1.E+05 1.E+04 HV-6250H Strain hardening 1.E+03 1.E-01 1.E+00 Time(s) 1.E+01

MI and Melt Tension of PLA for Foam Melt Index and Melt Tension of PLA Resin for Foam MI (g/10 min) (190 ºC X 2.16 kgf) Melt Tension (mn) (190 ºC) Neat PLA 8.0 10 HV-6200 1.2 460 HV-6250H 2.0 580

Maximum Expanded Ratio by Using Foaming Agent Maximum Expanded Ratio of HV-6250H Foaming Agent Maximum Expanded Ratio Chemical Foaming Agent 3 CO 2 9 Butane 25 CFC Substitute 12

Effect of Molding Condition on Heat Resistance Heat Resistance of PLA Foamed Sheet after Thermoforming Temperature of Molding-die (ºC) 30 60 90 110 130 Heat Resistance Temperature (ºC) 50 60 80 100 120 molding time : 10 S

Applications PLA Resin for Heat Resistant Foam Foamed sheet Foamed plastics by beads method TOSHIBA Lighting & Technology Corporation SEKISUI PLASTICS CO., LTD.

Plastic Packaging and Container Material Market Analysis in Japan (2007) Foam 0.3 mt Film-Sheet 2 mt Molding 1.4 mt 4 million tons Film-Sheet 48.1% Molding pack, container 33.9% Laminating Flexible 8.3% Stretched flat yarn 2.2% Foam 7.4% Source : Japan Packaging Institute

Break-down of Raw Materials for Film-Sheet (2007) PET : 290 kt 2 million tons LDPE PS : 330 kt HDPE PP LDPE 27.7% HDPE 14.2% EVA 3.3% EVOH 0.5% PP 18.4% PS 17.2% PET-Sheet 11.6% PET-Film 3.5% PA 3.8%

Break-down of Raw Materials for Molding (2007) PS : 50 kt PET : 560 kt 1.4 million tons LDPE 12.4% HDPE 14.6% PP 24.1% PET 43.9% PS 3.9% EVA 1.1%

Break-down of Raw Materials for Foam (2007) 0.3 million tons PS (Bead molding) 47.4% PSP 28.6% PSP (Laminating) 15.7% High Foam PE 8.3%

PLA Market Forecast in Japan 60 50 40 Fiber, Resin, Others kt 30 20 10 0 Film-Sheet 2007 2008 2009 2010 2011 2012 2013 2014

Next Steps for Japanese PLA Market Growth 1. Neat PLA Steady Supply (Multiple Suppliers) Quality Cost Raw Material : Agricultural Wastes or Non-Food Plants 2. Technology Improvement Flexibility (Impact Strength, Abrasion Resistance) Control of Crystalline Rate Flame Retardance 3. Others Legal Support Consumer Awareness

Thank you for your attention. Unitika Ltd. Terramac Business Development Department TEL: +81-6-6281-5245 (Osaka) TEL: +81-3-3246-7556 (Tokyo) E-mail : info-terramac@unitika.co.jp

Recent Development in Polylactic Acid, TERRAMAC HIROMASA SHIRAI TERRAMAC Business Development Department Unitika Ltd., JAPAN