Yoshinori Kasai NISSAN CHEMICAL INDUSTRIES, LTD .../media/ITR2012/2012/presentations/... ·...

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


AgendaAgenda

Whos Nissan Chemical ?Nissan Chemicals ApproachEcopromoteEffect of AdditionAnalysis of CrystallizationFunctional GradesMolding Test

The latest findingsNEW !


AgendaAgenda


The latest findings


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


Nissan Chemicals World Wide OfficeNissan Chemicals World Wide Office

US(Houston)

TAIWAN

CHINA Head Office(TOKYO)

FRANCEKOREA


Nissan Chemicals BusinessNissan Chemicals BusinessOperations

Chemicals Electronic materials Agricultural Chemicals Pharmaceuticals Trading

Chemicals26%

ElectronicMaterials14%

AgriculturalChemicals18%

Pharmaceuticals5%

Trading23%


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


AgendaAgenda


The latest findings


Green PlasticsGreen Plastics

StarchCelluloseChitin

Natural Resources

PBS PolyButyleneSuccinatePVA PolyVinylAlcoholPA PolyAmidePE PolyEthylenePLA PolyLacticAcid

Chemical Synthesis

PHA Poly (3-HydroxyAlkanate)Microbe Production


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


Disposal Products

Long-lived Products

Commercial Trends

Transparent Package Dish Tray

Computer PrintersVehicle Parts Mobile Phone

Garbage bagClear Sheet


Technical Problems and SolutionsHeat Durability Polymer Composite

Nucleating AgentStereo Complex

Strength FillerPolymer CompositeImpact Modifier

Cycle Time Nucleating AgentFlammability Flame RetardantHydrolysis Cross Linker


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


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


AgendaAgenda


The latest findings


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


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]


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


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]


AgendaAgenda


The latest findings


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]


Relationship between spherocrystal size of PLA crystals and isothermal crystallization time

EcopromoteCompound

TalcCompound

Growth of the Crystal

Inductive Time

Growth Time


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


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.


AgendaAgenda


The latest findings


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


Ecopromote Compound

Dispersed StateDispersed StateCross-sectional SEM Images of PLA Compound

1 m

Ecopromote-NP Compound

1 m


AgendaAgenda


The latest findings


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


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


Regulatory InformationRegulatory Information

-ListedCHINA-Not Listed

(REACH)EU

Registered (JHOSPA)

Listed (ENCS)

JAPAN

Not Submitted (FDA)

Listed (TSCA)

USAFood ContactInventory


AgendaAgenda


The latest findingsNEW !


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.)


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.


Thank you for your kind attention.

Please come to our Booth.

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