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
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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