recent development in polylactic acid - nia forum/recent development... · recent development in...
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Recent Development in Polylactic Acid,
“TERRAMAC”
HIROMASA SHIRAITERRAMAC Business Development Department
Unitika Ltd., JAPAN
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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
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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
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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
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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
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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
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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
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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
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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
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Chemical Structure of PLA
CH3333
-O-C*-C-
H On
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
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Mel
ting
Poi
nt (
ºC)
Optical Composition and Melting Point
Mel
ting
Poi
nt (
ºC)
D-lactic Acid Content (mol%)
Amorphous
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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
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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
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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
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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
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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
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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
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Applications of TERRAMAC Films
Envelope Window, Vegetable Packaging, Compost Bag - - -
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Applications of TERRAMAC Resins
Case for Cosmetic, Name Card Case, Ballpoint Pen - - -
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Applications of TERRAMAC Non-wovens 1
Civil Engineering Sheet, Soil Stabilizer, Agricultural Sheet - - -
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Plant Pot, Headrest Cover - - -
Applications of TERRAMAC Non-wovens 2
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Applications of TERRAMAC Fibers
Garbage Bag, Tea Bag - - -
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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
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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
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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
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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
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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
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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
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Multifunction Device ApeosPort-III C3300
Application
FUJI XEROX Ltd.
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Cellular Phone FOMA N701iECO (NTT DOCOMO)
TERRAMAC containing Kenaf fiber studied with NEC and UNITIKA
Application
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PLA BottlesImproved vapor propertiesby lamination of polyolefin
Nanocomposite PLA
Men’s cosmetic cases
Applications
Reusable Tableware
Bowls with polyurethane paint
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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
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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.
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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
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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
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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
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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
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Foamed plastics
by beads methodFoamed sheet
ApplicationsPLA Resin for Heat Resistant Foam
SEKISUI PLASTICS CO., LTD.TOSHIBA Lighting & Technology Corporation
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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
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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
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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
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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
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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
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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
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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
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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]
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Recent Development in Polylactic Acid,
“TERRAMAC”
HIROMASA SHIRAITERRAMAC Business Development Department
Unitika Ltd., JAPAN