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Recent Development in Polylactic Acid,

“TERRAMAC”

HIROMASA SHIRAITERRAMAC Business Development Department

Unitika Ltd., JAPAN

CONTENTS

Unitika Ltd. Japanese Bio-plastic MarketWhat’s PLA?Why PLA?Why PLA?TERRAMAC 1 : Unitika PLA ProductsTERRAMAC 2 : Unitika Improved PLA Products

Heat Resistance and DurabilityTERRAMAC 3 : Unitika Improved PLA Products

Heat Resistant FoamPotential Japanese PLA MarketNext Steps for Japanese PLA Market Growth

Nichibo

1889

1969

1999Unitika Textiles LTD.Cotton Wool Vinylon

History of Unitika

Medical

Non-woven

Unitika Advanced Material Natural Fiber

Nippon Rayon

1930

1969

Unitika Fibers LTD.

Rayon Nylon PET PVOH

Non-woven

Resin

Environmental Engineering

FilmSynthetic Fiber

1999

Unitika Position

Film Businessthe largest manufacturer of biaxially oriented PA 6 films in the world

Resin Businessproducing PA 6/clay nanocomposite resinsproducing PA 6/clay nanocomposite resins

Non-woven Businesstop share of each PET spunbond and cotton spunlace market in Japan

Fiber Businessthe largest manufacturer of polyester conjugated staple fibers for non-wovens in the world

CONTENTS

Unitika Ltd.Japanese Bio-plastic MarketWhat’s PLA?Why PLA?Why PLA?TERRAMAC 1 : Unitika PLA ProductsTERRAMAC 2 : Unitika Improved PLA Products



Bio-plastics Market Analysis in Japan (2007)

12,330 t PLAPBATPEST

PLA 46.6% Aliphatic Polyester 17.0%

Aromatic Polyester 16.6% PVA 1.9%

Esterified Starch 4.1% Other 13.8%

PBS

PEST

Commercial Applications of Bio-plastics in Japan (2007)

12,330 t

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%

12,330 t

Packaging

Classification of Plastics

Chemical Synthesis PLA : NatureWorks LLC (Ingeo) Aliphatic Polyester PBS : Bio-PBS：：：：Mitsubishi Chemical Microbial Production Aromatic Polyester

Biomass-based Oil-based

Showa Highpolymer(Bionolle)Mitsubishi Chemical(GSPla)

Bio

degr

adab

le

Zhejiang Hisun Group (Revode)

Microbial Production Aromatic Polyester PHA : Kaneka Corp.Natural Polymer

Bio-PA11 : Arkema Commodity Bio-PTT : DuPont LDPE, HDPE, PP, PS Bio-PE：：：： Engineering

PA6, PET, PC Bio-PP：：：： Braskem Super-Engineering Bio-PET, PC PPS, PI, LCP, PEEK, PEI, PES

PBAT : BASF (Ecoflex) PEST : DuPont (Apexa)B

iode

grad

able

Non

-

Esterified Starch:Novamont(Mater-Bi)

BraskemDow Chemical

CONTENTS




Chemical Structure of PLA

ＣＨ３３３３

－Ｏ－C*－Ｃ－

ＨＯn

C* : Asymmetric Carbon

L-lactic acid, D-lactic acid

PLA : PLLA, PDLA, PLDLA

L-lactic acid and D-lactic acid

Aliphatic PolyesterTm : 170 ºCTg : 58 ºC

CH3

H

HO

CH3

H

HO

OH

C=OOH

C=O

Mel

ting

Poi

nt (

ºC)

Optical Composition and Melting Point

Mel

ting

Poi

nt (

ºC)

D-lactic Acid Content (mol%)

Amorphous

80808080

20202020

40404040

60606060PLAPLAPLAPLA

Melting Points and Glass Transition Temperatures

of Biodegradable Polymers

0000

-20-20-20-20

-60-60-60-60

-100-100-100-100

-80-80-80-80

-40-40-40-40

40404040 60606060 80808080 100100100100 120120120120 140140140140 160160160160 180180180180 200200200200

Tm Tm Tm Tm （（（（℃℃℃℃））））

Tg

Tg

Tg

Tg (( ((

℃℃ ℃℃））））

PCLPCLPCLPCL

PBSPBSPBSPBS

PHAPHAPHAPHA

1. Biomass-based PlasticRenewable and Sustainable Raw MaterialReduction of Petroleum DependenceReduction of Negative Effects

on Human Health and Environment

Why PLA?

2. Biodegradable PlasticTwo-step Degradation Process: Hydrolysis and BiodegradationStability in Normal Environment;

Easy Degradation in Composting System

3. Commodity or Engineering PlasticTwo Contradictory Properties : Durability and DegradabilityPossibility of Structural and Consumer Durable Material

CONTENTS




Polylactic acid TERRAMAC

LacticAcid

Products

Material Circulation System of TERRAMAC

UNITIKA TECHNOLOGY

Films, Sheets, Non-wovens, Compounded

Resins, and Fibers

Starch

Products

CO2

H2OBiomass

Resources

PLA applied to TERRAMAC is made by NatureWorks LLC.

TECHNOLOGY

TERRAMAC Business Segments

Film Business DivisionBiaxially Oriented Films, Blown Films, and Sheets

Resin Business DivisionResins for Extrusion, Foamed-extrusion, Injection,

and Blow Molding

Non-woven Business DivisionNon-woven Business DivisionSpunbond Fabrics, Spunlace Non-wovens, and Needle-

punched 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 PropertiesTransparency, Rigidity, Dead-fold PropertyTransparency, Rigidity, Dead-fold Property

Chemical PropertiesWater- & Oil-proof, Weather Stability

Thermal PropertiesHeat-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 - - -

Plant Pot, Headrest Cover - - -

Applications of TERRAMAC Non-wovens 2

Applications of TERRAMAC Fibers

Garbage Bag, Tea Bag - - -

CONTENTS




Characteristics of PLA

Heat Resistance : Hot Water Filling, Microwave Reheating, Ironing Crystallinity

DISADVANTAGES

Durability : Long shelf life (Electronics Device Housing, Automobile Cabin Parts, Returnable Tableware)

Hydrolysis Resistance

Impact Strength

Gas Barrier Property

Crystallinity depends on・・・・Crystal-nucleation rate・・・・Crystal growth rate

Factors Controlling Crystallinity

Heat Resistant PLA

TypeAmount

Size

Chemical Structure Processing Condition Nuclear Agent

RegularityMolecular Weight

FlexibilityBranching

Cooling Rate

Draw Ratio

Improved PLA

PLA with5% Talc

0.4

0.6

0.8

1.0

Rate of Crystallization of Improved PLA

Cry

stal

linity

0 1 10 100 1000

Time (min)

5% Talc

0.0

0.2

0.4 NeatPLA

Rel

ativ

e

DSC : 200 ºC 130 ºC (isothermal condition) -500 ºC /min

Improving hydrolysis resistance under high temperature/high humidity condition

Factors Affecting Hydrolysis Resistance

Structural Residual ProcessingCircumstance

Durable PLA

Structural Residual ProcessingFactor Substance Condition

End Group Lactide Moisture content Temperature

Crystallinity Catalyst Heating Temp. Humidity

Alkaline Heating Time pH

Circumstance

under 50 ºC, RH95%

Hydrolysis Resistance of Improved PLA

60

80

100F

lexu

ral S

tren

gth

Ret

entio

n (%

)

Heat & Hydrolysis Resistant Grade

0

20

40

0 200 400 600 800 1000

Time (hrs)

Fle

xura

l Str

engt

h R

eten

tion

(%)

Heat Resistant Grade

Neat PLA

Multifunction Device ApeosPort-III C3300

Application

FUJI XEROX Ltd.

Cellular Phone FOMA N701iECO (NTT DOCOMO)

TERRAMAC containing Kenaf fiber studied with NEC and UNITIKA

Application

PLA BottlesImproved vapor propertiesby lamination of polyolefin

Nanocomposite PLA

Men’s cosmetic cases

Applications

Reusable Tableware

Bowls with polyurethane paint

CONTENTS




Development of PLA Resin Development of PLA Resin

for Extruded Foam with High Heat Resistancefor 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 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.

1.E+051.E+051.E+051.E+05

1.E+061.E+061.E+061.E+06

1.E+071.E+071.E+071.E+07

Viscosity(Pa････ s)

□□□□　　　　Neat 　　　　PLA

▲▲▲▲　　　　HV-6250H

Temp : 170 ºC

Elongational Viscosity of PLA for Foam

1.E+031.E+031.E+031.E+03

1.E+041.E+041.E+041.E+04

1.E+051.E+051.E+051.E+05

1.E-011.E-011.E-011.E-01 1.E+001.E+001.E+001.E+00 1.E+011.E+011.E+011.E+01

Time(s)

Viscosity(Pa

Strain hardening

MI and Melt Tension of PLA for Foam

Melt Index and Melt Tension of PLA Resin for Foam

MI (g/10 min)(190 ºCX 2.16 kgf)

Melt Tension (mN)(190 ºC)(190 ºC)

Neat PLA 8.0 10HV-6200 1.2 460HV-6250H 2.0 580

Maximum Expanded Ratio of HV-6250H

Foaming Agent Maximum Expanded Ratio

Chemical Foaming Agent 3

Maximum Expanded Ratio by Using Foaming Agent

Chemical Foaming Agent 3

CO2 9

Butane 25

CFC Substitute 12

Heat Resistance of PLA Foamed Sheet after Thermoforming

Temperature ofMolding-die (ºC)

Heat ResistanceTemperature (ºC)

30 50

Effect of Molding Condition on Heat Resistance

306090

110130

506080

100120

molding time : 10 S

Foamed plastics

by beads methodFoamed sheet

ApplicationsPLA Resin for Heat Resistant Foam

SEKISUI PLASTICS CO., LTD.TOSHIBA Lighting & Technology Corporation

CONTENTS




Plastic Packaging and Container Material Market Analysis in Japan (2007)

Film-Sheet 2 mt

Foam 0.3 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%

Molding 1.4 mt

4 million tons

Source : Japan Packaging Institute

Break-down of Raw Materials for Film-Sheet (2007)

PET : 290 kt

2 million tons

LDPE

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%

PS : 330 kt

2 million tons

PP

HDPE

PS : 50 kt

Break-down of Raw Materials for Molding (2007)

LDPE 12.4% HDPE 14.6% PP 24.1%

PET 43.9% PS 3.9% EVA 1.1%

PET : 560 kt1.4 million tons

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%

0.3 million tons

40

50

60

Fiber, Resin, Others

PLA Market Forecast in Japan

0

10

20

30

2007 2008 2009 2010 2011 2012 2013 2014

Film-Sheet

kt

Next Steps for Japanese PLA Market Growth

1. Neat PLASteady Supply (Multiple Suppliers)QualityCostRaw Material : Agricultural Wastes or Non-Food Plants

2. Technology ImprovementFlexibility (Impact Strength, Abrasion Resistance)Control of Crystalline RateFlame Retardance

3. OthersLegal SupportConsumer Awareness

Thank you for your attention.

Unitika Ltd.Unitika Ltd.

Terramac Business Development Department

TEL: +81-6-6281-5245 (Osaka)

TEL: +81-3-3246-7556 (Tokyo)

E-mail : [email protected]

Recent Development in Polylactic Acid,

“TERRAMAC”

HIROMASA SHIRAITERRAMAC Business Development Department

Unitika Ltd., JAPAN

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