Post on 17-Mar-2018
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 11
Nucleating Agents for Inducing the Crystallization of PLA
- ECOPROMOTE -Yoshinori Kasai
NISSAN CHEMICAL INDUSTRIES, LTD.
Innovation Takes Root ConferenceFebruary 21, 2012 Orlando, FL
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 22
AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findingsNEW !
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 33
AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 44
Nissan Chemical CorporationNissan Chemical Corporation Founded in 1887 as Japans First Chemical Fertilizer
Manufacturer Head Office: Tokyo, Japan Employees: 1,750 Financial Information, Fiscal Year 2010
Net Sales (consolidated): US$ 1,855 Million Net Income (consolidated): US$ 156 Million
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Nissan Chemicals World Wide OfficeNissan Chemicals World Wide Office
US(Houston)
TAIWAN
CHINA Head Office(TOKYO)
FRANCEKOREA
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Nissan Chemicals BusinessNissan Chemicals BusinessOperations
Chemicals Electronic materials Agricultural Chemicals Pharmaceuticals Trading
Chemicals26%
ElectronicMaterials14%
AgriculturalChemicals18%
Pharmaceuticals5%
Trading23%
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Advanced Materials & Planning DivisionAdvanced Materials & Planning Division
Our Divisions Target Organic Nano Sized Materials Environmental Harmony Materials Life Science Materials
Ecopromote[Nucleating Agent for PLA]
Nissan Chemicals Core Areas of Expertise Fine Organic Synthesis Ultrafine Particle Control Technology Functional Polymer Design Evaluation to Elucidate Biological Activity
Hypertech[Hyper-branched Polymer]
Nanofibergel[Supramolecular Gelator]
100 nm
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AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 99
Green PlasticsGreen Plastics
StarchCelluloseChitin
Natural Resources
PBS PolyButyleneSuccinatePVA PolyVinylAlcoholPA PolyAmidePE PolyEthylenePLA PolyLacticAcid
Chemical Synthesis
PHA Poly (3-HydroxyAlkanate)Microbe Production
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Why attracted PLA attention ?Why attracted PLA attention ? Low Cost Expectation because of Industrial
Production by NW
Good Performance for Future MaterialsHigh TransparencyHigh IntensityAppropriate Melting Point
Biodegradable, moreover Biomass
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Disposal Products
Long-lived Products
Commercial Trends
Transparent Package Dish Tray
Computer PrintersVehicle Parts Mobile Phone
Garbage bagClear Sheet
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Technical Problems and SolutionsHeat Durability Polymer Composite
Nucleating AgentStereo Complex
Strength FillerPolymer CompositeImpact Modifier
Cycle Time Nucleating AgentFlammability Flame RetardantHydrolysis Cross Linker
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Nissans BackgroundNissans Background Expansion in Long-Lived Products Market in
the Near Future
The Issue of Low Heat Resistance and Long Molding-cycle Time of PLA
Growing Needs for Good Nucleating Agents for PLA
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Image of CrystallizationImage of Crystallization
Melt State Crystallization
Neat Resin
Good Nucleating Agent Additive
Large Crystal
Small Crystal
[Nuclei]
A Large Number
FewLow speed crystallization
High speed crystallization
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AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 1616
SEM IMAGE 50,000
> 500 DecompositionWhite PowderAppearance
7.3pH of 5% slurry
0.16[g/ml]Bulk Specific Gravity
PROPERTIES
Ecopromote Ecopromote
Aromatic Phosphonate
1 m
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38135Ecopromote [1phr]
24112None32119Talc [1phr]
Hc[J/g]Tc[]Nucleating Agent
Effect of Nucleating Agents
20010min
5/min10/min
Estimation of Exothermic Peak by DSC
PLA: TOYOTA Uz S-09
[Test Conditions]
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Neat PLA
Talc
[1phr]
Compound
Ecopromote
[1phr]
Compound
T i m e m i n1 2 0 . 01 0 0 . 08 0 . 06 0 . 04 0 . 02 0 . 0
DSC
mW
6 . 0 0 0
4 . 0 0 0
2 . 0 0 0
0 . 0 0 0
- 2 . 0 0 0
- 4 . 0 0 0
- 6 . 0 0 0
TEM
P
2 2 0
2 0 0
1 8 0
1 6 0
1 4 0
1 2 0
1 0 0
8 0
6 0
4 0
2 0
0
1 5 . 4 m i n1 6 4 - 5 . 5 6 5 m W
1 2 2 . 1 m i n1 6 1 - 6 . 3 0 4 m W
1 1 3 . 2 m i n7 3 - 0 . 4 1 5 m W
6 5 . 2 m i n1 1 2 0 . 9 8 9 m W
5 8 . 2 m i n1 2 5 0 . 1 9 7 m W
7 1 . 7 m i n1 0 0 0 . 1 2 7 m W
2 7 . 5 m J / m g
3 8 . 9 m J / m- 3 3 . 9 m J / m g
1 8 . 7 m i n1 9 4
2 3 . 4 m i n1 9 4
1 1 1 . 7 m i n6 2
1 2 6 . 2 m i n1 9 4
: Exothermic peak by crystallization PLA: MITSUI LACEA H-100
DSC Study
T i m e m i n1 2 0 . 01 0 0 . 08 0 . 06 0 . 04 0 . 02 0 . 0
DSC
mW
6 . 0 0
4 . 0 0
2 . 0 0
0 . 0 0
- 2 . 0 0
- 4 . 0 0
- 6 . 0 0
- 8 . 0 0
- 1 0 . 0 0
TEM
P
2 2 0
2 0 0
1 8 0
1 6 0
1 4 0
1 2 0
1 0 0
8 0
6 0
4 0
2 0
0
1 5 . 4 m i n1 6 4 - 6 . 1 7 m W
1 2 2 . 5 m i n1 6 4 - 9 . 1 4 m W
5 5 . 9 m i n1 3 0 3 . 8 7 m W
5 1 . 7 m i n1 3 8 0 . 2 4 m W
6 9 . 5 m i n1 0 4 0 . 1 8 m W
- 4 4 . 8 m J / m g
3 1 . 3 m J / m g
4 7 . 0 m J / m
1 8 . 8 m i n1 9 4 2 3 . 3 m i n
1 9 4
1 1 1 . 5 m i n6 1
1 2 5 . 6 m i n1 9 4
T i m e m i n1 2 0 . 01 0 0 . 08 0 . 06 0 . 04 0 . 02 0 . 0
DSC
mW
6 . 0 0 0
5 . 0 0 0
4 . 0 0 0
3 . 0 0 0
2 . 0 0 0
1 . 0 0 0
0 . 0 0 0
- 1 . 0 0 0
- 2 . 0 0 0
- 3 . 0 0 0
- 4 . 0 0 0
- 5 . 0 0 0
- 6 . 0 0 0
TEM
P
2 2 0
2 0 0
1 8 0
1 6 0
1 4 0
1 2 0
1 0 0
8 0
6 0
4 0
2 0
0
1 5 . 4 m i n1 6 4 - 3 . 6 1 2 m W
5 . 6 m i n6 7 - 0 . 2 8 5 m W
5 9 . 5 m i n1 2 3 0 . 0 8 4 m W
6 8 . 1 m i n1 0 6 0 . 2 5 6 m W
8 2 . 2 m i n8 6 0 . 0 5 0 m W
1 1 3 . 1 m i n7 2 - 0 . 2 3 4 m W
1 2 2 . 2 m i n1 6 2 - 3 . 7 7 9 m W
2 5 . 4 m J / m g 3 6 . 2 m J / m- 2 2 . 5 m J / m g
1 8 . 7 m i n1 9 4
2 3 . 0 m i n1 9 4
1 1 1 . 7 m i n6 2
1 2 6 . 0 m i n1 9 4
1. High Temperature2. Large3. Sharp
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 1919
30secMelt 0sec
Ecopromote[phr]Compound
Neat PLA
60sec
Observation of the Crystallization Speed
185100/min
110
0 sec
FinishStart
PLA: MITSUI LACEA H-100
Start
Polarization Microphotograph
[Test Conditions]
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2020
AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2121
100m 100m 100m
Neat PLA(after 90min)
PLA/Talc=100/1(after 7min)
PLA/Ecopromote=100/1(after 1min)
185
100/min
130
0 sec
PLA: MITSUI LACEA H-100
The End of Crystallization
[Test Conditions]
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Relationship between spherocrystal size of PLA crystals and isothermal crystallization time
EcopromoteCompound
TalcCompound
Growth of the Crystal
Inductive Time
Growth Time
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Analysis of Crystal Growth
28.8810.59c axis []6.165.17b axis []
10.6614.47a axis []
OrthorhombicMonoclinicCrystalsystem
PLAECOPROMOTE
Lattice parameter
SPring-8 : The worlds largest synchrotron radiation facilities
x 2
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2424
Image of Crystal GrowthImage of Crystal GrowthPLA Crystal
The distance of PLA molecular chain and the interlayer distance of Ecopromote are almost equal.
Ecopromote
PLA CrystalPLA Crystal
Ecopromote
PLA crystals grow from the flat surface side of Ecopromote.
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AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2626
Functional GradesFunctional Grades
Ecopromote Ecopromote- NP Ecopromote- HD
Mixture of Ecopromote and Zinc Salt
Particle Size 0.1 - 0.2 m
Particle Size 2 - 3 m
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2727
Ecopromote Compound
Dispersed StateDispersed StateCross-sectional SEM Images of PLA Compound
1 m
Ecopromote-NP Compound
1 m
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2828
AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findings
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 2929
Injection Molding TestInjection Molding Test
ExcellentGoodBad
Test Conditions : PLA : Nature WorksIngeo3001D, Sample thickness : 1 mm, Kneading temperature : 190 , Cool temperature : 110
The test piece change
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3030
Test ResultsTest Results20 25 30 35
Ecopromote[1 phr] Compound
40
ExcellentGood
45Cooling time (sec)
Ecopromote - NP[1 phr] Compound
360
Ecopromote - HD[1 phr] Compound
Other Nucleating Agent[1 phr] Compound
Talc [10 phr] Compound
Neat PLA
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3131
Regulatory InformationRegulatory Information
-ListedCHINA-Not Listed
(REACH)EU
Registered (JHOSPA)
Listed (ENCS)
JAPAN
Not Submitted (FDA)
Listed (TSCA)
USAFood ContactInventory
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3232
AgendaAgenda
Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test
The latest findingsNEW !
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3333
The Latest FindingsThe Latest Findings NEW !1. Ecopromote - BD
Biodegradable nucleating agent The performance is better than Ecopromote - NP
2. Transparency Improving Agent (on the way)
Ecopromote - BD
Ecopromote - NP
HAZE : 83%Crystallinity : 42%
HAZE : 39%Crystallinity : 41%
Ref.)
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3434
SummarySummary Nucleating agent technology becomes more
important with improvement in heat resistance as well as molding processability, both of which are the problem of PLA.
We will continue innovating the new high performance additive.
Nissan Chemical strongly believe that our Ecopromote contributes to expand future PLA market.
2/21/2012 Innovation Takes Root2/21/2012 Innovation Takes Root NISSAN CHEMICAL INDUSTRIES, LTD.NISSAN CHEMICAL INDUSTRIES, LTD. 3535
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