DIC Engineering Plastics

CFP Journée Plastiques très Techniques

19/06/2012-

PPS – Situation du Marchépropriétés & perspectives

Ph. MatrayDIC Europe GmbH

Table of Content

• Introduction to DIC: DIC Group, DIC EP & DIC.PPS portfolio

• Introduction to PPS : History, Demand, Market share & Capacities

• PPS Positionning : Types de résines, compounds Strength & Weaknesses

• Overview of the application fieldso Automotiveo E&E o Home appliances & Others

• New product developments / applicationso Impact Modified – Super tougth PPSo High Molecular Weight (& Impact Modified) for extrusion & Blow moldingo Long Glass fibers o Blends / Copolymerso ... Ultra fine powders / Adhesion modified / High purity (halogen free / food & water contact) / Thermoconductive

• Questions & Answers

Slide

3101416

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• DIC Corporation– Head Office: Tokyo, Japan– Foundation: 1908– Subsidiaries and affiliates (including sun Chemicals) : 209

• 47 Japan, 67 Asia, 58 Europe, 16 North America, 13 South America, 2 Oceania, 6 Africa

– Number of employees: > 23.000• DIC is one of Japan’s most diversified chemical companies present

in more than 60 countries worldwide.• Business operation & Divisions :

– Printing Inks & Supplies– Neo-Graphic Arts Materials– Synthetic Resins– Chemical Solution Materials

o …o Engineering Plastics (EP)

Introduction to DIC: DIC Group

4

Introduction to DIC: DIC EP & Europe

• DIC EP (Engineering Plastics) is one division of DIC Corporation, whereas PPS is the principal products : – Polymers & Compounds : PPS– Compounds : LCP & PBT (available only in Asia)– Number of employees: > 220

• DIC Europe GmbH: – European headquarter in D’Dorf since 30 years – Dedicated DIC.PPS activity since 5 years– Vienna Compounding plant as from 2013 (6000 tons capacity / 2 Lines)

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Penang (Ma)Singapore

Victoria

Düsseldorf

New Jersey

TaipeiShanghai

SeoulQingdao

Hong Kong

Introduction to DIC: DIC EP - Global Presence

● Sales● Polymerization● Compounding● R & D

DIC is establishing a compounding facility in Vienna (Au) in 2012

Japan●Tokyo HQ●Osaka●Nagoya●Kashima●Sodegaura●Komaki●Chiba

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Introduction to DIC: DIC EP - Production plants

Kashima 2008 PlantIbaragi, Japan

7000 tons

Kashima PlantIbaragi, Japan

5000 tons

Sodegaura PlantChiba, Japan

5000 tons

Komaki PlantAichi, Japan

23000 tons

DIC compoundsPenang, Malaysia

4500 tons

PolymerizationPlants

CompoundingPlants

… Vienna 2013 PlantAustria

6000 tons

… Kashima 2013 PlantIbaragi, Japan

10000 tons

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Introduction to DIC: 2011 Market share (tons) & Market Segment

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PPS CF/FillerPPS/PTFE GF30PPS/PTFE CF30PPS CF30

GF / MineralGF 30 GF 40

Super Tough

Introduction to DIC:DIC.PPS Product Portfolio Summary

Z-650

CZ-1030

PAN CF30 Mechanical PTFE & PAN CF30

Z-200-E5

High Flow

Z-240

Linear

Cross-linked

SpecialitiesCZL-2000

Pitch CF30 Friction PTFE & Pitch CF

PTFE & GF30 Conductive

Z-230-T3

Drinking water appr.

FZ-6600FZ-2140FZ-2130 FZ-6800FZ-2140-B2

FZ-2140-D9

FZ-2140-T3

High Flow

High flow& low flash

Lowflash

Z-230 BK-2(B)

Z-230High Flow

FZ-2130-T3 Lowflash

Unreinforced

FZ-1130-D5 FZ-1140 FZ-3600

High Flow

High flow& low flash

High Strength& Low flash

For H2O/glycol applications

Z-240-DS Z-650-B2

Z-650-T6High Flow

High Strength

~ 50% filled

High Strength

LowOutgassing

For H2O/glycol applications

Dimensionalstability

FZ-6600-B2

FZ-6600-D5

FZ-6600-R1

High Flow

High Strength

High Strength

~ 55% filled

~ 60-65% filled

~ 60-68% filled

Impact modified

CZ-1130 CZL-4033 FZL-4033 CZE-1200

FZ-1140-B2

FZ-1140-D9

FZ-1140-D5

FZ-1140-R5

FZ-3600-D5

FZ-3600-H5

FZ-3600-R5

FZ-3600-L4

Z-200-J1

Z-200-T3

FZ-2140-F1Long glass fibers

B-100-C / PQ-208

FZ-2100

Fine powders for coatings

Primef® PPS product lines:• Primef® 4000 series:

– Compounds with 40% glass fiber reinforcements– Food Contact (FDA & EU10/2011)

• Primef® 7000 series:– High-filled materials, glass fibers and mineral fillers

Introduction to DIC: Primef® PPS Grades

Primef® Key Properties Color4010/0000 GF40%, Improved mechanical properties Natural

4010/9000 GF40%, Improved mechanical properties Black

7002/0000 High-filled GF/MF, High flow Natural

7002/9000 High-filled GF/MF, High flow Black

7002/0005 High-filled GF/MF, High flow, Lubricated Natural

7002/9005 High-filled GF/MF, High flow, Lubricated Black

7010/0003 High-filled GF/MF, Improved mechan. properties Natural

7010/9003 High-filled GF/MF, Improved mechan. Properties Black

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Introduction to PPS:History of PPS Industry

PHILLIPS ＤＩＣ TOHPREN BAYER FORTRON TORAY KUREHA TOSOH

1972 Start PPS PlantTX, USA

1976 Start PPS Compoundswith Phillips PPS Polymer

(at the same time, Hodogaya/Shinetsu/Asahi Glass started, now only Asahi Glass is keeping small compound business)

1980Introduce Phillips Compound Technology

1984 Expire Patent of PPS Polymer Technology

Nishiki Plant, Fukushima Pref.Kashima Plant, Ibaragi Pref. Sodegaura Plant, Chiba Pref. Germany Tokai Plant, Aichi Pref. Yokkaichi Plant, Mie Pref.

1987 Start PPS Polymer Plant Start PPS Polymer Plant

Start PPS Polymer Plant

Start PPS Polymer Plant

Start PPS Polymer Plant

Start PPS Polymer Plant

Capacity=750t/Y (Considering to expand to 1,500t/Y)Capacity=1,800t/Y (Considering to

Expand to 3,600t/Y)

Capacity=3,000t/Y Capacity=5,700t/Y Capacity=3,000t/Y Capacity=2,000t/Y

Substitute of Phillips Polymer Contracted with Phillips

Investment Ratio : Tohto Chemical/Tonen Chemical 55/451990

Expire Compound Technical License with Phillips

Wilmington, USA

1991 Investment Ratio : TohtoChemical/Tonen Chemical 10/90

Stat PPS Polymer Plant

Capacity=3,000t/Y

Withdrawal from PPS Business

Investment Ratio : KUREHA/TICONA 50/501993

(Supplied PPS Polymer to GE Plastics, GE withdrew in 2004)

1994Introduce BAYER Polymer Technology Transfer Polymer

Technology to DIC For USA/EU Market

2000Expire Contract with TORAY

(Remaining Market Segregation)Transfer to DIC

2001Acquire TORPREN, Establish DIC-EP

with Kashima Plant and Sodegaura Plant

2004～2006 Investment for De-Bottle Necking Investment for De-Bottle Necking

Expand 3 lines to 5 LinesInvestment for De-Bottle

Necking Capacity=2,000t/Y

After De-Bottle Necking(Capacity=9,800t/Y) Capacity=10,000t/Y Capacity=8,500t/Y Capacity=9,000t/Y Capacity=10,000t/Y

2007～2009 NewPlant Plan New Plant Expansion Investment New Plant Plan

(Linear Type) (New Process, Mainly Linear Type) Capacity=15,000t/Y (Cross-Link/Linear)

2011 Acquire Primef PPS Coumpounds

2012 Launch Coumpounding in Austria

2013 Next Plant Plant(New Process, Mainly Linear Type)

TYPE Cross-Link/Linear Cross-Link/Linear Linear Cross-Link/Linear Linear Cross-Link

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Introduction to PPS: Global PPS Compounds demand

Europe20,000 tons

North America10,000 tons

Total Asia50,000 tons

Total demand ≈ 80,000 tons

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Introduction to PPS :Global Compounds Market Share

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Introduction to PPS :Nominal Polymer capacity (not production)

Top 3 PPS ProducerCapacity (Tons)

ytd Future

DIC Japan 13500 > 20000

CPChem USA 15000 to 20000 > 20000

Fortron * USA 15000 15000

Kureha Japan 10000 10000

Toray Japan 11500 14000

Tosoh Japan 2500 2500China ? ?

TOTAL > 67500 > 81500(*) JV Ticona & Kureha

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PPS Positionning:Linear or Cross-linked resin ?

– Why linear PPS?Example charge air cooler=> Linear PPS performs often better when

impact & fatigue resistance are required

– Why cross-linked PPS?Example brush holder=> Cross-linked PPS is often used when creep

resistance and stiffness is required

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PPS Positionning: S&W, Targets & Use

StrengthsHeat resistance Long term service temperature up to 240ºCUL94 V-0 - flammability without flame retardantExcellent Dimensional stabilityTight molding tolerances, low warpage, low water absorption, low thermal expansionSuperior mechanical propertiesHigh strength & modulus, Low CreepChemical resistance closed to PTFE…

StrengthsHeat resistance Long term service temperature up to 240ºCUL94 V-0 - flammability without flame retardantExcellent Dimensional stabilityTight molding tolerances, low warpage, low water absorption, low thermal expansionSuperior mechanical propertiesHigh strength & modulus, Low CreepChemical resistance closed to PTFE…

Targets Alternative to MetalsAlternative to Thermo-set resins

Targets Alternative to MetalsAlternative to Thermo-set resins

Used forAutomotive partsE & E partsHome appliances

Used forAutomotive partsE & E partsHome appliances S

n

DIC-PPS are compounds based onPPS resin (Polyphenylene sulfide)

WeaknessesImpact resistance & Elongation Quit low Glass TransitionModerate Molecular Weight…

WeaknessesImpact resistance & Elongation Quit low Glass TransitionModerate Molecular Weight…

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Alternator Parts IC regulator & rectifier

Electronic devices Pressure, position, velocity and temperature sensors

Distributor-less ignition coil

Overview of the applications:Automotive

fuel, transmission, lighting, …

Coolant circuitThermostat housingWP Impellers

BrakesHydraulic / Pneumatic

ActuatorsThrottle BodyEGR ValveCombination valve

Fuel pump partsbrush holderimpellersin/outlet covers

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Overview of the applications:Hybride & Electric Vehicles

IPM / Power Module

Condenser case

ECU / Control UnitMotor insulators

LIB Gaskets

PPS Application in New Toyota Prius:1.8 kg for Hybrid systems + 0.8 for other applications

à 2.5 kg

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Overview of the applications:Electricity & Electronic

Connectors

Lamp HousingLCD projector

Pick-up Sliding BaseCD & DVD pick-up slide bases

Micro-switch & potentiometer

Circuit BreakerInternal mechanism parts

HDD Actuator

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Watch Base Watch base plate

Hot Water Supply SystemValve, connector and pump

General Purpose Pump Impeller & housing

Overview of the applications: Home Appliance & Others

Water meter partsInternal parts, caps & housing

Induction plateInsulating supportFittings

Plumbing industry

Hot potable water approvals à Z-230BL

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New Product Development:Impact modified PPS

What is “Super-Tough” PPS ?

It’s an elastomer-modified Linear PPS providing:

• Superior Elongation at Break• High Strength and Elongation at Weld• Excellent Thermal Shock Property• Low flash level• Very good Fatigue Resistance• Great Performance under High Humidity and High Temperature

Dedicated to Injection molding but also extrusion applications

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New Product Development: Super-Tough PPS vs. PPS and PA66

a) MD = Mold Direction, TD = Transverse Direction

Super tough PPS shows high elongation at break and high strength at weld

Method Unit Z-230 Linear PPS GF30

Linear PPS GF40

PA66 GF30

Physical ASTM Specific Gravity D-792 - 1,53 1,56 1,66 1,39 Water absorption, 23°C, 24 Hrs, in water D-570 wt. % 0,02 0,02 0,02 1,00 Mold Shrinkage, MD/TDa D-955 % 0,30/1,20 0,27/1,2 0,25/1,10 0,50/1,20 Mechanical Tensile Strength D-638 MPa 150 165 180 180 Tensile Strength at Weld D-638 MPa 90 85 75 80 Tensile Elongation at Break D-638 % 2,4 2,0 1,8 3,0 Flexural Strength D-790 MPa 230 250 270 260 Flexural Modulus D-790 MPa 8500 10000 13000 8000 Izod Impac Strengtht, notched / unnotched

D-256 J/m 140/750 90/550 100/550 95/600

Thermal HDT, 1,82 MPa D-648 °C 255 265 265 250 Coeff. of Therm. Exp., -30°C…100°C D-696 m/mK 2,2x10-5 2,3x10-5 2,0x10-5 3,0x10-5 Electrical Volume Resistivity D-257 Ohm*cm 1016 1016 1016 1014

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Morphology DIC-PPS Z-230 Morphology Compet ProductDispersion size: 0.2~0.3µm Dispersion size: 1~2µm

Type & Perfect dispersions guarantees outstanding performance of Super Tough PPS

New Product Development: Super Tough PPS – DIC Technology

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0 200 400 600 800 1000 1200

FZ-2140

Z-240

FZ-2130

Z-230

Number of Heat Cycles

Heat cycle tests from -40 to +140°Cexceeds that of standard PPS by far

Z-230: Super Tough PPS, 30% GF(Impact modified PPS)

FZ-2130: Linear PPS, 30% GF(Standard PPS)

Z-240: Super Tough PPS, 40% GF(Impact modified PPS)

FZ-2140: Linear, 40% GF(Standard PPS)

The number of heat cycles after which first cracks can be detected are registered

Specimen:

Metal Block (S55C) fully overmolded with PPS(1 mm thickness)

New Product Development: Super Tough PPS - Thermal shock improvment

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New Product Development: HMW (Impact modified) for Tubes

§ Targets:– Fuel and Water Tubes– Corrugated Tubes

§ Requirements:– Melt strength compatible with Extrusion process– Heat resistance– Chemical resistance

§ Recommendable Materials - Unreinforced Series modified or not

– FZ-2100 / FZ-2100-A1– FZ-2200-A5– Z-200-E5

• Status : Development

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New Product Development:HMW (Impact modified) for Films

• Targets:– Insulating foils– HT capacitors– …

• Requirements:– Good process-ability– Perfect surface– Thickness starting from 50µm– bi-stretched-able

• Recommendable Materials :– Z-200-E5– Other unfilled and impact

modified grades

• Status: Development

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New Product Development:HMW for Fibers

• Targets:– Monofilament Applications for

• Filter bags• Non-wowens• Technical textiles

• Requirements:– High viscosity– High linearity– High purity

• Recommendable Materials :– PS-111-1326– MA-520– …

Status: Development

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New Product Development: HMW & Impact Modified for Blow Molding

• Targets:– Automotive Applications

• Metal Replacement è Weight Saving & Easier Processing

• Alternative to PA è Improved Thermal and Chemical Resistance

– Chemical Container• Alternative to Fluorine Resins è Cost

Saving• Alternative to Polyethylene è Improved

Thermal and Chemical Resistance

• Recommended Materials:– Z-215-G1 / Z-220-G1: 15 to 20% GF IM– Unfilled IM

New Product Development:HMW & Impact Modified for Blow Molding

• Application : Turbo outlet pipe

• Material: Z-215-G1 black

• Requirements:

– Blow-moldable grade

– Heat resistance:• Maximum use temperature 240°C

– Good dynamic properties:• Cyclic loads of up to 2,5 bars

• Status: Commercial

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New Product Development:Long Glass fiber à FZ-2140-F1

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Conceptual diagram - Impact fracture of GF reinforced plastics

Impact

General GF40%FZ-2140-F1

Impact

0

10

20

30

40

50

60

70

with notch without notch

kJ/m

2

Charpy impact at 23℃FZ-2140-F1

GeneralGF40%

Strength v/s regular glass filled : • Higher rigidity @ high temperature. • Excellent durability @ elevated temperature.• Marvelous impact resistance.• Specific gravity is same as general GF 40%. • There is no change about other properties of PPS.

FZ-2140-F1 FZ-2140-B2Shape of pellet

Glass length 10 mm 0.2～0.3 mm

Glass direction One direction RandomGlass contend 40 wt% 40 wt%Type of glass Continuous strand Chopped strand

Production method Pulltrusion Melting compound

3～5 mm10 mm

New Product Development:FZ-2140-F1 – Tensile properties (0 to 240°C)

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0

2000

4000

6000

8000

10000

12000

14000

16000

18000

0 50 100 150 200 250

Temperature, ℃

Tensile Modulus (MPa) vs. Temperature

In case of 150℃, FZ-2140-F1 Strength and Modulus are 1.6 times superior to general glass fiber grade and elongation is 1.8 times lower

New Product Development:FZ-2140-F1 – Long term properties in Temp

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In case of stress amplitude 50MPa, FZ-2140-F1 is 1000 times superior to general glass fiber grade

Tensile Strength at RT, ISO 527After Thermal Aging at 240oC

0

50

100

150

200

250

1 10 100 1000Time, hour

Tens

ile S

treng

th, M

Pa

From 100 to 1000h, FZ-2140-F1 is 1.3 times superior to general glass fiber grade

S-N Curves Under Flexual Stress at 150oC

0

10

20

30

40

50

60

70

80

1.E+03 1.E+04 1.E+05 1.E+06 1.E+07Number of Cycle to Failre, N

Stre

ss A

mpl

itude

, MP

a

New Product Development:PPS Blends / Copolymers : AMORVON

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• Tg of PPS is around 90°C & Hardly impossible to increase by modifications of the chemical structure:

à Proposal:– PTES Copo (Poly Thio Ether Sulfone)

• Melting Point = 285°C & Tg ~ 120°C• Better mechanical properties at higher temperatures• Chemical resistance is somewhat lower compared to PPS.

– Blends with higher Tg materialMaterial Tg HDT/A value for neat resin

PPS ~90°C 110°C

PEEK ~145°C ~160°C

PPSU ~220°C ~207°C

New Product Development:PPS Blends / Copolymers: AMORVON

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New Product Development:Ultra fine powders for Coating

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Particle diameter distribution

0

5

10

15

Diameter, μm

Fre

quency,

%

0

20

40

60

80

100

Tota

l, %

1 10 100

B-100-C#0047

Good for dispersion in slurry

and for smooth coating surface

PQ-208#0039

B-100-C#0047

Properties Units

ColorFormMelt Viscosity, 300℃Particle diameterDp10%Dp50%, medianDp90%Distribution index1)

--

Pa･s

μmμmμm-

WhitePowder

8

6.61735

0.72

WhitePowder

8

6.637

1371.3

1) Distribution index = log ( Dp90% / Dp10% )

Particle diameter distribution

0

5

10

15

Diameter, μm

Fre

quency,

%

0

20

40

60

80

100

Tota

l, %

1 10 100

PQ-208#0039

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GF 20%High Flow, High Adhesive, ElongationStandard for Stick CoilLots of experiences in Japan

FZ-820

FZ-825

FZ-830

GF/Filler 25%Excellent Electrical Resistance,High Adhesive, High Flow

GF 30%High Strength,High Adhesive, High Flow

Mold release improved FZ-820-DE

“PPS GF30”Impact but not bonding modifiedExcellent Toughness,Lots of experiences in Water supplies, Automobile sensors…

New Product Development:Adhesion modified (EP Bonding)

DIC-PPS FZ-1140-A1… is a • GF40% cross linked based PPS compound material which has

been developed to comply with the recent world’s “low-halogen requirement”.

• has been achieved to stay less than 900ppm of chlorine content in total amount of the compound, by DIC’s distinctive own synthesizing method of the PPS polymer.

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FZ-1140-A1 BLACK FZ-1140 BLACKChlorine Content (ppm)

SGS Method 650 ~ 800*1 2000*2

*1; The range of the value is based on results from several numbers of production lots.*2; Result of a certain lot

New Product Development:High Purity - Low halogen content

New Product Development:High Purity – Food & water contact

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Primef 4010/0000 is a GF40% PPS compound material complying with

• Existing and future “food contact approvals”:– FDA– 2002/72 EC valid until 31/12/2015– EU 10/2011 valid as from 1/1/2016

• Hot potable water approvals– ACS– KTW– BS– NSF

New Product Development:Thermo-conductive grades

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Electric insulated (up to 2.5 W/m.°K)Electric conductive (up to 30 W/m.°K)

Application for :– touch panel display

(5 W/m.°K)– DVD pickup base

(5 W/m.°K)– Heat radiator part for LED lamp

(30 W/m.°K)

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Processing of DIC-PPS

DIC-PPS FZ-1140FZ-2140

FZ-3600FZ-6600

Z-230, Z-240FZ-820 FZL-4033 FZ-8600 Z-200-E5

Processing Parameter Unit GF GF / Mineral Super Tough PTFE modified

Reflector-Type Unreinforced

Melt Temperature °C 300-330 310-340 300-330 300-330 320-340 300-320Cylinder Temperature

Zone 1 (Feeding) °C 290-300 290-300 290-300 290-300 290-300 290-300Zone 2 °C 290-320 300-330 290-310 290-320 310-330 290-310Zone 3 (Nozzle) °C 290-320 300-330 290-310 290-320 310-330 290-310

Nozzle °C 290-320 300-330 290-310 290-320 310-330 290-310Mold Temperature °C 130-150 130-150 130-150 130-150 140-150 130-150Injection Speed mm/s 50-100 50-100 80-150 50-100 60-120 30-30Injection Pressure MPa 80-120 80-120 80-120 80-120 80-120 80-120Holding Pressure MPa 30-60 30-60 30-60 30-60 30-60 30-60Holding Time s/mm 3-4 2-3 4-5 3-4 2-3 7-15Back Pressure MPa 0,5-2 0,5-2 0,5-2 0,5-2 0,5-2 0,5-2Screw Speed m/s (U/min) <0,3 (150) <0,3 (150) <0,3 (150) <0,3 (150) <0,3 (150) <0,3 (150)Drying Temperature °C 130 130 130 130 130 130Drying Time Hours 3-5 3-5 3-5 3-5 3-5 3-5

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All data, statements and recommendations made herein are based upon information we believe, but are made without any representation or guaranty or warranty ofaccuracy and are made with reservation of all patent rights. Our products are sold on the condition that the user himself will evaluate them, as well as our formulae andrecommendations, to determine their suitability for his own purpose before adoption. Also statements regarding the use of our products or processes are not to beconstrued as recommendations for their use in violation of any patent rights or in violation of any applicable laws regulations.

Contact Europe

DIC Europe GmbHImmermannstr. 65DD-40210 DüsseldorfGermany

Phone: +49(211)1643-0Fax: +49(211)1643-819

Website : http://www.dic-europe.de

Thank you very much for your attention!

Contact Ph. Matray

France

Phone: +33 966 91 33 41

Fax: +33 474 65 33 41

Mobile: +33 674 99 62 98