Open new market opportunities with BioPBS TM /PLA InnoBioPlast 2016 September 15, 2016
Agenda • Introduction to BioPBS TM • BioPBS TM /PLA compound • Takeaway Points • Acknowledgement
More People, More Plastics
We produce more waste, and most of it isn’t disposed in the most environmentally-friendly method.
Bioplastics Biodegradable PHA BioPBS PBAT, PCL PLA Petro-based Bio-based Non-biodegradable Conventional Plastics: Starch blends with PE Bio-PE PE, PP, PS, PET, ABS, Bio-PP PC, PMMA, Nylon, etc. Bio-PA PTT
Who are we?
• Renewable content • Continuous process • More efficient purification • Higher drying capability • More uniform products • Very low moisture • Very low impurity • Longer shelf-life
Introduction to BioPBS produced by batch process in Japan O X O O m n p O Petro-Succinic Acid 1,4-butanediol Polybutylene Succinate, PBS produced by continuous process in Thailand O X O O m n p O Bio-Succinic Acid 1,4-butanediol Polybutylene Succinate, PBS
Injection Molding Properties Properties Unit FZ71 FZ91 FD92 Melt Flow Rate (190ºC/2.16kg f ) g/10min 22 5 4 g/cm 3 Density 1.26 1.26 1.24 Glass Transition Temperature ºC -33 -33 -47 Melting Point ºC 115 115 84 Yield Stress MPa 40 40 17 Tensile Strength at Break MPa 30 36 24 Tensile Strain at Break % 170 210 380 Flexural Modulus MPa 630 650 250 Flexural Strength MPa 40 40 18 kJ/m 2 Izod Impact Strength (23ºC) 7 10 47 Heat Deflection Temperature (0.45 MPa) ºC 95 95 63 Vicat Softening Point ºC 109 109 75 Rockwell Hardness (R-scale) kJ/mm 107 107 56 Note: These values are typical and not to be construed as specifications.
Film Properties Properties Unit FZ91 (20 µm) FD92 (20 µm) Melt Flow Rate (190ºC/2.16kg f ) g/10min 5 4 g/cm 3 Density 1.26 1.24 MD MPa 575 280 Tensile Modulus TD MPa 590 320 MD MPa 39 18 Yield Stress TD MPa 38 17 MD MPa 42 32 Stress at break TD MPa 30 27 MD % 350 600 Strain at break TD % 180 580 MD N/mm 2 2 Elmendorf Tear Strength TD N/mm 4 5 g/m 2 •d WVTR 20 / 50 µm 510 / 210 1,050 / 510 cm 3 /m 2 •d•bar OTR 20 / 50 µm 490 / 140 2,040 / 760 Puncture Impact Strength kJ/mm 4 6 Haze (25 µm) 45 22 Note: These values are typical and not to be construed as specifications.
CEDAR GROVE Certified Compostable
Biodegradation in SOIL 100 90 80 70 % biodegradation 60 50 40 30 20 10 0 0 100 200 300 400 500 600 700 Days Cellulose BioPBS FZ71PB BioPBS FZ91PB BioPBS FD92PB
Excellent heat seal strength even at low temp. Heat Seal Condition: Strength Measurement Condition: • Pressure 0.2 MPa • Specimen: Film 15 mm width with 20µm thickness • Time 1 sec • Chuck Interval: 60 mm • Test Speed: 300 mm/min • Seal width 5 mm
BioPBS Heat Seal Property 10 Heat seal strength （ N/15mm ） • Coating conditions : 9 Structure: Kraft/resin (20 μ m) 8 Processing temperature: PBS 270ºC 7 LDPE* 320ºC 6 Corona treatment • Heat seal conditions : 5 Seal surface: Resin/paper 4 Seal bar width : 5 mm 3 Pressure / time : 0.2 MPa/1.0sec 2 * MFR 8.2 g/10min 1 Paper Film Density 0.919 g/cm 3 0 100 120 140 160 180 Heat seal temperature (deg.C) GS Pla PBS LDPE LDPE+corona
Food Contact Safety Complies with EU FCN No. 1574 and 1643 Listed in JHOSPA directives 10/2011 All raw materials FZ-grade: Condition of Use B-H Positive List on positive list FD-grade: Condition of Use C-G Migration test All food types except alcoholic passed OM-6 foods (100 C, 4 hours)
BioPBS for Paper Coating Excellent process as fast as LDPE Stable and narrow neck-in Excellent adhesion and seal strength Compostable at room temperature Recyclable in paper mill BioPBS BioPBS BioPBS Source: MCC’s internal laboratory
BioPBS as Sealing Layer in Flexible Packaging Excellent process in existing LDPE extrusion coating machine Excellent seal strength seal strength Compostable without composting facility Excellent printability without pre-treatment Good to retai retain aroma aroma such as limonene Suitable for food packaging Example of a Example of a film film structure structure Utilizing BioPBS as a sealing layer Utilizing BioPB as a sealing layer Metallized Metallized Cellulose Cellulose BioPBS TM BioPB TM Cellulose Cellulose
Agenda • PTTMCC and BioPBS TM • BioPBS TM /PLA Compound • Take Away Points • Acknowledgement
Properties comparison of BioPBS vs PLA Flexible Flexible Flexibility Flexibility Rigid Rigid Higher Higher Lower Lower Impact strength Impact strength Faster Faster Slower Slower Biodegradability* Biodegradability* BioPBS PLA Higher Higher Lower Lower Heat resistance Heat resistance Lower Lower Higher Higher Process temp. Process temp. Lower Lower Higher Higher Heat-seal temp. Heat-seal temp. Translucent Translucent Transparency Transparency Transparent Transparent * in soil at 30 C (86 F), 50%RH
Potential of PBS/PLA Compound Potential PBS-PLA Compound PBS Compound BioPBS
Compatible to PLA Compound resin of PBS with PLA showed good dispersion 75 / 25 50 / 50 25 / 75 PBS / PLA 1 μ m
Improve thermal stability 450 400 Degradation Temperature 350 300 250 200 150 100 HDT 50 %crystallinity 0 0 10 20 40 60 80 100 %BioPBS FZ71
BioPBS can improve service temperature PLA PLA PLA PLA ７５ % 0% 30% 60% PLA PLA 90% 100% 60ºC for 1 hour 70ºC for 1 hour 80ºC for 1 hour
Tensile Properties 300 3500 3000 250 Tensile Modulus, MPa 2500 Tensile Strength, MPa 200 Elongation, % 2000 150 1500 100 1000 50 500 0 0 0 10 20 40 60 80 100 %BioPBS FZ71 Tensile Strength Elongation Tensile Modulus
Flexural Properties 4000 120 Flexural Modulus 3500 Yield Stress 100 3000 Yield Stress, MPa Flexural Modulus, MPa 80 2500 2000 60 1500 40 1000 20 500 0 0 0 10 20 40 60 80 100 %BioPBS FZ71
Izod Impact Strength 25 20 Izod Impact Strength, ft·lb/ft Notched 15 10 5 0 0 10 20 40 60 80 100 %BioPBS FZ71
Opportunities are endless
How can you use BioPBS?
Takeaway Points • Properties alike LDPE plus biodegradable at ambient • Food contact safety in USA and EU • Improve flexibility, impact, and thermal properties of PLA
Acknowledgement PTT Research Institute of Technology • Dr. Narin Kaabbuathong and his team • Dr. Jirawut Junkasem Mitsubishi Chemical Corporation • Dr. Uyeda Tadashi
Mr. Chinnawat Srirojpinyo Marketing Technical Service Manager +66-9-2260-7226 Email: chinnawat.s@pttmcc.com
Test Condition Material: PLA Ingeo 4032D PBS BioPBS FZ71PM Sample Preparation: 1. Compounded by twin-screw extruder at 320°F 2. Injected specimen at 375°F 3. Conditioned at 73.4±3.6°F, 50±5%RH for 40 hours before evaluation
Bio-based Certificates Certificates FZ71 FZ91 FD92 50-85% 50-85% 20-50% Din Certco (51%) (51%) (35%) BiomassPla 33.5% 48.5% 48.5%
Compostable Certificates Certificates Standard FZ71 FZ91 FD92 74µm 68µm On process BPI (USA) ASTM D6400 (Q2/2016) 74µm 69µm 87µm OK Compost (EU) EN13432 85µm OK Compost EN13432 --- --- HOME (EU) at 28±2°C OK Biodegradable EN13432 2-year test 2-year test 2-year test Soil (EU) at 25°C Up to Feb 2018 Up to Feb 2018 Up to Feb 2018 On process On process On process GreenPla (JBPA) JBPA (Q3/2016) (Q3/2016) (Q3/2016) On process On process On process ABA (Australia) AS 4736 (Q3/2016) (Q3/2016) (Q3/2016)
EU 10/2011 BioPBS FZ-grade (PBS) 50µm: OM-6 condition, simulant A, B, D1, D2 BioPBS FD-grade (PBSA) 50µm: OM-3 condition, simulant A, B, D1, D2 Raw materials including chain extenders are in positive list 2 Overall migration limit < 10 mg/dm Specific migration limit are met 1,4-BDO < 5 mg/kg SML(T) Grade Condition 1,4-BDO FZ71PM 50 µm OM-6 <0.1 - 0.2 mg/kg FZ91PM 50 µm OM-6 <0.1 mg/kg FD92PM 50 µm OM-3 <0.1 - 0.2 mg/kg
MFR 190°C, 2.16 kg f 25 20 MFR, g/10min 15 10 5 0 0 20 40 60 80 100 %BioPBS FZ71 in PLA
Viscosity 190°C 10,000 0:100 10:90 20:80 40:60 1,000 60:40 Viscosity, Pa-s 80:20 100:0 100 10 10 100 1,000 10,000 Shear Rate, s-1
Summary MFR Crystallinity HDT Thermal Degradation Temperature FZ71PM Ingeo 4032D % g/10min Tc, °C °C °C 0 100 3.2 - - 52.2 360 10 90 3.8 - - 52.2 360 20 80 4.2 - - 50.8 360 40 60 7.1 81.2 50.3 52.0 360 60 40 10.9 80.7 53.4 55.6 395 80 20 14.4 82.1 59.7 81.0 400 100 0 21.4 64.7 55.5 93.3 401 Tensile Flexural Izod Impact FZ71PM Ingeo 4032D Modulus, MPa Strength, MPa Elongation, % Modulus, MPa Stress, MPa Notched, ft•lb/ft 0 100 2,860 75 4 3,610 110 8.7 10 90 2,390 62 8 2,970 85 9.2 20 80 2,240 58 13 2,880 80 10.3 40 60 1,890 50 2,710 80 42 17.1 60 40 1,280 38 66 1,510 60 23.1 80 20 900 39 41 1,010 50 20.0 100 0 660 40 16 690 40 23.8
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