Dow Corning Korea Ltd Multibase July 12 th

Dow Corning Korea Ltd. Multibase July 12 th July 2002

OUTLINE Part I. TPE Introduction Part II. Multiflex Introduction Part III. Applications of Multiflex Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Contents 1. Standard definition of TPE 2. Family Draft of TPEs 3. History of TPE 4. Conception of base of TPE 5. Property Comparison between TPEs Multibase Korea July 2002

Part I. TPE Introduction 1. Standard definition of TPE According to ISO 1382, Thermoplastic Elastomer is a polymer or a mixture of polymers which doesn’t need vulcanisation or reticulation when processed, but demonstrates similar properties as vulcanised rubber at service temperature. These properties disappear at processing temperature to allow the ulterior process possible, but reappear as the material returns to working temperature. Multibase Korea July 2002

Part I. TPE Introduction 2. Family Draft of TPEs TPE FAMILY Olefinic TPO Reactor Styrenic TPV Partly vulcanized Base Recycled TPV Totally vulcanized R-TPV P-TPV Metallocene Base F-TPV Base EPDM Compounds Hydrogenated (SEBS, SEPS) Matellocene base (SBS) Pure Compounds ** Compounds Base EPDM Other base materials* PVC Technopolymers Plastified PVC TPU PVC alloys COPE COPA Others * Nitrile, acrylic, naturel rubber. . . **With TPU, acrylic, polyolefin, polyamid. . . Metallocene Base(modified EPDM or Modified PP Copolymer) Multibase Korea July 2002

Part I. TPE Introduction 3. History of TPE 1950 TPU PVC-NBR Thermoplastic Polyurethane (DESMOPAN, ESTANE) (Physical mixture) 1961 TPU Thermoplastic Polyurethane (ELASTOLLAN) 1965 SBS Styrene butadiene styrene Copolymer (CARIFLEX TR) 1970 SEBS Styrene ethylene butylene styrene Copolymer (KRATON G) COPE Ether-ester Copolymer (HYTREL) 1975 TPO-VD Polyolefin/dynamically vulcanised elastomer mixture(not commercialized) 1976 COPE Ether-ester Copolymer (ARNITEL) 1980 COPA-PEBA Ether-amide Copolymer (PEBAX) 1981 TPO-VD Dynamically vulcanised PP-EPDM (Santoprene) 1984 TPE EVA-VC EVA/vinyl chloride (ALCRYN) 1985 TPE PP-NBR Dynamically vulcanised PP/NBR (Geolast) 1987 TPE PP-NR Dynamically vulcanised PP-NR (nitrile) (Vyram) 1988 TPE PP-BIIR PP/bromic butyl (TREFSIN) 1990~~ POP, POE, ESI, TPSi. V, EHPP. . . Multibase Korea July 2002

Part I. TPE Introduction 4. Conception of base of TPE Principle: In all the TPEs, it exists one soft phase and one rigid phase, which endow the material with elasticity. Example 1: SEBS and SBS Rigid phase: Polystyrene Soft phase: Poly-ethylenebutylene Multibase Korea July 2002

Part I. TPE Introduction Example 2: high hardness and low hardness TPU High hardness Soft phase: Ester or Ether Rigid phase: Isocyanate Low hardness Soft phase Rigid phase Others: COPE, COPA. . . Multibase Korea July 2002

Part I. TPE Introduction Example 3: TPV PP/EPDM , Something different, has two phases through a physical mixing process. Soft phase: Vulcanized EPDM, Rigid phase: PP Add. Volcanized rubber Chemical band or bridge Others: TPO, PP/NBR-VD. . . Multibase Korea July 2002

Part I. TPE Introduction 5. Property Comparison between TPEs Hardness Range: 55 COPA 70 80 75 60 35 0 TPV – NBR COPE 75 TPU 75 50 TPO(PP/EPDE) – TPV(PP/EPDM-VD) SBC (SEBS, SEPS, SBS) Thermoelastomers 50 55 Thermoplastics Hardness scale: Shore A, from 0 to 100 Sh. Hardness scale: Shore D from 30 to 100 Sh. Multibase Korea July 2002

Part I. TPE Introduction + Heterogeneity of properties of a material is due to: 1 Anisotropy after transformation 1 Wide hardness range in the same family Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction 3. Compression set vs Hardness Multibase Korea July 2002

Part I. TPE Introduction To continue this comparison, we choose a specimen from each family at same hardness range. But as some materials do not exist in this range, we choose the closest one. (SEBS here means a TPE based on SEBS) Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction Multibase Korea July 2002

Part I. TPE Introduction 12. Ease of processing + Because of the existence of vulcanised rubber, TPV is generally difficult to process, and TPO, which has a property very close to thermoplastic, can be processed very easily. The processing facility of other TPE is between the two. + TPO Other TPEs Multibase Korea TPV July 2002

Part I. TPE Introduction 13. Summary of some points: (5~best; 1~worst) Multibase Korea July 2002

Part I. TPE Introduction Continued: Multibase Korea July 2002

Part I. TPE Introduction +Summary : COPE 1 Advantages • • • Very wide range of service temperature 60°C to 150°C, even to 205°C Excellent resistance to abrasion Good resistance to UV and ozone Excellent resistance to tearing strength Good resistance to impact Good flexibility memory Impermeability to gas Resistance to oils and fuels Colourable Multibase Korea 1 Weaknesses • • Middle compression set No low hardness products Hydrolysis problem Price +Examples of commercialised COPE: • Arnitel of DSM • Hytrel of DUPONT • Lomod of GE Plastics July 2002

Part I. TPE Introduction +Summary : TPO 1 Advantages • • wide range of hardness 50 A-75 D low density 0. 89 -1. 3 Good compromise quality/price Good compatibility with PP Colourable and surface can be made paintable Good weatherability Good performance at low temperature 1 Weaknesses • • • Poor elasticity Poor compression set Poor resistance to oils and fuels Limited mechanical properties Feel not as rubbery as other TPEs + Examples of commercialised TPO: • Hifax of MONTELL • Vistaflex of AES Multibase Korea July 2002

Part I. TPE Introduction +Summary: TPV (PP/EPDM-VD) 1 Advantages • • Wide range of hardness 45 A-50 D Low density (<1) Service temperature from -60°C~135°C Good weatherability, good heat aging Excellent compression set at 100°C~120°C Good mechanical properties Colourable 1 Weaknesses • • Poor C. S for hard product No transparent grade Limited resistance to fuels Hardness below 40 A not available +Examples of commercialised TPV: • Santoprene of AES • Sarlink of DSM Multibase Korea July 2002

Part I. TPE Introduction +Summary: TPV (PP/NBR-VD) 1 Advantages • • Resistance to petroleum products Good weatherability without pressure Good resistance to ozone Co-extrudability with PE, PP, EVA 1 Weaknesses • Poor C. S for hard product • Deformation at high temperature +Examples of commercialized TPV (PP/NBR-VD): • Geolast of AES Multibase Korea July 2002

Part I. TPE Introduction +Summary: TPU 1 Advantages • • Wide range of hardness 55 A-75 D Excellent resistance to abrasion Excellent resistance to tearing strength Excellent resistance to impact Good resistance to ozone Good resistance to oils and fuels Compatible with PC, ABS, PVC… Good resistance to non-polar fluids. 1 Weaknesses • • • Bad compression set High density 1. 25 Deformation at high temperature Risk of hydrolysis of certain grades Bad resistance to UV Not good for soft-touch application because of low co-efficient of friction +Examples of commercialised TPU: • Desmopan of Bayer • Elastollan of BASF • Pellethane of DOW • Estane of BF Goodrich Multibase Korea July 2002

Part I. TPE Introduction +Summary: TPE-s 1 Advantages • • • Very wide range of hardness 0 A-50 D Good performance at low temperature especially SBS Low density 0. 9 -1. 2 Service temperature -50°C-120°C Wide choices for compounding Colourable Good weatherability Compatibility with polyolefin Transparent products available 1 Weaknesses • • Deformation at high temperature Swelling in oil and fuels • Limited UV resistance for SBS +Examples of commercialized SEBS: • Kraton of SHELL • Tuftec of ASAHI • Septon of KURARAY • Calprene of REPSOL +Compounders • Multiflex of Multibase • Tefabloc of TCT • Thermolast of Kraiburg. . . Multibase Korea July 2002

Part I. TPE Introduction APPLICATIONS OF DIFFERENT TPEs SBC TPV TPO TPU Shoe sole Bitumen modification Polymer modification Adhesives Wire and Cable Compounds Automotive Construction Polymer modification Extruded profiles Automotive Sport Medical Wire and Cable Adhesives Automotive Wire and Cable Shoe sole Films Extruded profiles Multiflex Multibase Korea July 2002

Part I. TPE Introduction This part is concluded with the following graph: Extract: TPV v/s TPE-s Multibase Korea July 2002

Part II. Multiflex Introduction Multibase Korea July 2002

Part II. Multiflex Introduction Contents 1. What is Multiflex ? 2. What is compounding ? 3. What can we obtain with these compounds, Multiflex? 4. Multiflex Family -Nomenclature of TPE Specialities Dept. 5. Multiflex Family -Nomenclature of Automotive Dept. Multibase Korea July 2002

Part II. Multiflex Introduction 1. What is Multiflex ? Multiflex are compounded thermoplastic elastomers based on different polymers, like SBS, SEBS, Polyolefins and other engineering plastics. They are totally different from pure SEBS or SBS. That means all of Multiflex products are Compounds and our producing art is Compounding. Multibase Korea July 2002

Part II. Multiflex Introduction 2. What is compounding ? To mix one base polymer with certain other materials like oils, fillers, additives and other polymers, in order to give some properties to the mixture, so that it can be used for the final application. The final mixture is called compound. Multibase Korea July 2002

Part II. Multiflex Introduction 3. What can we obtain with these compounds, Multiflex? + Enhanced mechanical properties 1 Compression set 1 Resistance to abrasion 1 Resistance to scratch and mar … + Special characteristics 1 Damping characteristics 1 Foamability 1 Flame retardant 1 Resistance to bacteria 1 Compatibility with other engineering plastics + Low cost, sometimes at an acceptable level, sometimes as low as possible. Multibase Korea July 2002

Part II. Multiflex Introduction 4. Multiflex Family -Nomenclature of TPE Specialities Dept. Example : G 60 A 11 B 12345 N 0200 G 60 A 1 1 B 12345 � ��� � � ����� Options Processing code Colour code Hardness scale (A or D) Hardness N 0200 Colour number Development code Base of the product Multibase Korea July 2002

Part II. Multiflex Introduction +Base of product : • • C = based on SBS G = based on SEBS B = based on PA & Polyolefin SG = based on Acrylate Styrene Acrylonitrile (Sunigum) ER = based on Polyolefin GX = foamed G A = Alloys - Multibase Korea A 1000 = compatible with PC, ABS, PMMA, ASA, SAN A 2000 = compatible with PET-PBT A 3000 = compatible with PA A 4000 = compatible with CP, CA, ABS, ASA, SAN, PETG July 2002

Part II. Multiflex Introduction +Colour code • • • 0 = White 1 = Natural 2 = Black 3 = Coloured 4 = Transparent Multibase Korea +Processing Code • 1 = General processing injection and extrusion • 6 = Extrusion July 2002

Part II. Multiflex Introduction +Options : • B = UV stabilised • M = Medical • T = Thermal resistance and good compression set • FR = Flame retardant with halogen in formulation • FRX = Flame retardant without halogen in formulation Multibase Korea July 2002

Part II. Multiflex Introduction ¬ Multiflex C 4 4 4 Transparent grade available Food approval possible Soft touch possible Low service temperature Lower density compared to G range 4 Aggressive price 7 Bad C. S 7 Bad Weatherability 7 No very soft product(< 20 A) Multibase Korea Multiflex G 3 Transparent grade available 3 Food approval possible 3 Soft touch possible 3 Shore A 0 possible 3 UV stabilised 3 More C. S choice compared to C range (Intermediate and T series) 7 Higher price compared to C range July 2002

Part II. Multiflex Introduction An example of comparison between C and G at same hardness (physical properties) Multibase Korea July 2002

Part II. Multiflex Introduction ® Multiflex SR Including B range and certain G products, half rigid product, hardness from 30 D to 55 D; B range has reinforced mechanical properties and low temperature performance, because of PA. ¯ Multiflex TPO ER range, based on polyolefin, very high hardness without reinforced mechanical properties. Multibase Korea July 2002

Part II. Multiflex Introduction ° Multiflex TEA Thermoplastic Elastomer Alloys, including SG range and A range, are compatible with different engineering plastics, which is the most important characteristic of this family. ± Multiflex FG Some G range products, flame retardant, with relative high density. UL 94 V 0 possible. Multibase Korea July 2002

Part II. Multiflex Introduction Conclusiont able : Multibase Korea July 2002

Part II. Multiflex Introduction 5. Multiflex Family -Nomenclature of Automotive Dept. Example : G 60 A 510 804 FXT G 60 A 5 1 0 804 FXT color Family: C G GT GX ER L OR A 1000 A 3000 Hardness + Shore 0: Standard 2: High fluidity 4: Intermediate C, S; weak smell 4: Extrusion 5: Standard 1: Interior 6: Aesthetic 2: Exterior 7: Translucent Last 3 numbers of item number 5: Under bonnet L: High frequency weldable; OR: Resistance to oil Multibase Korea July 2002

Part III. Applications of Multiflex Multibase Korea July 2002

Part III. Applications of Multiflex Contents 1. Applications of pure SEBS. 2. Various Applications of Multiflex 3. Application in development -- To enlarge our sight Multibase Korea July 2002

Part III. Applications of Multiflex 1. Applications of pure SEBS +Base polymers : compounds, adhesives, sealants, coating materials. . . +Modifiers, additives : plastics modifiers, compatibilizers thermosetting resin modifiers, asphalt modifiers. . . +Other : Masterbatch for additives Multibase Korea July 2002

Part III. Applications of Multiflex 2. Various applications of Multiflex ¬ Soft touch applications Building applications ® Sports and leisure applications ¯ Electrical applications ° Other applications Multibase Korea July 2002

Part III. Applications of Multiflex ¬ Soft touch applications + Characteristics of these applications • • • Hardness from 20 A to 70 A, normally Overmoulding processing (95%) Compatible with other engineering plastics Transparent or colourful materials Aesthetic requirement, gloss or mat Multibase Korea July 2002

Part III. Applications of Multiflex Example 1: Toothbrush grip + Important points • Hardness • Processibility • Overmould on what kind of product • Transparency • Colour • Food approval • Gloss or mat surface finish Multibase Korea July 2002

Part III. Applications of Multiflex + Proposed materials • • G 35 A 41 12697 G 60 A 41 13023 G 35 A 11 14009 G 70 A 11 13077 A 4004 35 A NAT 15903 A 4001 65 A NAT (Shiffer) A 1004 70 A NAT 14762 . . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Tool grips + Important points: compared to toothbrush grips, this application has always more mechanical requirements, which leads to the use of more engineering plastics, like PA and ABS. . . + Proposed materials • • A 3001 for PA A 1004 for ABS A 4004 or C for PS G or A for others . . . Multibase Korea * Pruning shears, kitchen utensils, trowel handle. . . July 2002

Part III. Applications of Multiflex Example 3: “Soft touch” out of handle + Important points : inspiration is needed to find such kind of application. * Cosmetic pot and razor grip G 70 A 11 G 70 A 31. . . Soft part Multibase Korea July 2002

Part III. Applications of Multiflex What else : + + + Pen grip (overmoulded and assembled), pen barrel, stapler grip… Flask handle grip, tin opener handle grip, casserole handle grip… Umbrella handle grip. . . Crutch grip… Mobilephone and calculator buttons… Appliance turners… . . . Multibase Korea July 2002

Part III. Applications of Multiflex Building applications +Characteristics of these applications • Hardness from 50 A to 80 A, except products for heel • Extrusion processing (>95%) • Good compression set for dynamic seals • Good UV stability • Weldability (with metal, magnet or other materials) • Colourful products, sometimes. . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 1: Construction seals + Important points • • Extrudability Requirement for C. S UV stability (regional factor) Colour Aspect Service temperature Certification, sometimes. . . Multibase Korea Static seals Dynamic seals July 2002

Part III. Applications of Multiflex + Proposed materials • • • G Standard G Intermediate Compression Set GT Series Hard product for heel Soft product for lip . . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Building profile angle + Important points • Injectability • Economical solution. . . + Proposed materials • • G 50 A 11 B G 60 A 11 B. . . Multibase Korea July 2002

Part III. Applications of Multiflex What else : + Door frame seals, shower cabinet seals. . . + Rain collector. . . Multibase Korea July 2002

Part III. Applications of Multiflex ® Sports and leisure applications + Characteristics of these applications • Very wide hardness requirement. • Injection or overmoulding processing • Compatible with other engineering plastics • Scratch and abrasion resistance • Impact resistance • Colourful products • Comfortability • Different service temperature. . . Multibase Korea July 2002

Part III. Applications of Multiflex A. Summer sports + Important points • • UV stability Thermal resistance Comfortability Transparency, sometimes Colourability Watertightness Salty water resistance Soft touch. . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 1: Diving fins + Special points • Rubber replacement • UV stability • Adherence on EVA . . . + Proposed materials • G 60 A 21 B • G 62 A 21 B • G 90 A 21 B Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Diving mask and snorkel nozzle + Special points • Transparency • Recovery after strain • Economical solution . . . + Proposed materials • G 45 A 41 B . . . Multibase Korea July 2002

Part III. Applications of Multiflex What else : + Diving searchlight, handle for diving dagger, other waterproof parts. . . + Bicycle handle grip. . . Multibase Korea July 2002

Part III. Applications of Multiflex B. Winter sports + Important points • Low service temperature • UV resistance • Strain resistance • Colourability • Scratch resistance • Impact resistance • Soft touch, sometimes . . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 1: Ski boots - cuff + Important points • Scratch resistance • Technical & economical solution between PP and Hytrel • Resistance to dynamic strain • Impact resistance at low temperature. . . + Proposed materials • B 25 MHE 11564 • B 30 MH 10893 • G 44 D 11 B Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Ski mask + Important points • Adherence on PC for A 1004 • Flexibility • Fluorescent coloration for G 52 A 41 • Recovery after strain • Economical solution . . . + Proposed materials • A 1004 • G 52 A 41 Multibase Korea July 2002

Part III. Applications of Multiflex What else : + Ski binding-lever unit(compared to Grilon PA), handle for ski sticks, cross country ski binding flexor thrust, ski carrier frame. . . Multibase Korea July 2002

Part III. Applications of Multiflex C. What else as sports and leisure applications + Roller skate-toe protection cap + Artificial fishing bait (Shore A 0) + Shock absorbing elements for tennis racquets + Toys : wheels for toy cars, baby teethers, dolls and doll limbs. . . + Wheels for prams + Computer or walkman cable reel … Multibase Korea July 2002

Part III. Applications of Multiflex ¯ Electrical applications + Characteristics of these applications • Flame retardant, sometimes • Injection or Extrusion processing • Flexibility • UV stability, sometimes • Economical solution Multibase Korea July 2002

Part III. Applications of Multiflex Example 1: Protective frame for multi-meter + Important points • Flexibility • Easy to colour • Good impact resistance . . . + Proposed materials • G 62 A 31 B . . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Circuit breaker: interphase separator + Important points • Flame retardant: UL 94: V 0 3. 2 mm • Flexibility • Extrudability . . . + Proposed materials • G 35 D 21 FR . . . Multibase Korea July 2002

Part III. Applications of Multiflex What else : + Electrical application + Waterproof cap + Cable sheath. . . Multibase Korea July 2002

Part III. Applications of Multiflex °Other applications Example 1: Ice tray +Important points • Odourless • Colourability • Food approval • High production speeds . . . +Proposed materials • G 45 A 11 • C 30 A 11 . . . Multibase Korea July 2002

Part III. Applications of Multiflex Example 2: Caps for bed slats + Important points • Flexibility • Processability • Colourability • Economical solution . . . + Proposed materials • C 65 A 11 Multibase Korea July 2002

Part III. Applications of Multiflex Example 3: front-tyre for wheelchair or trolleys suitcase + Important points • Abrasion resistant • Processability • Intermediate C. S • Economical solution • Compatible with PP . . . + Proposed materials • G 65 A 11 • G 40 D 11 B • G 90 A 11 Multibase Korea July 2002

Part III. Applications of Multiflex Example 4: Paint protection mask + Important points • Comfortability • Food approval • Processability • Elongation at break point • Strength at break point . . . + Proposed materials • G 52 A 41 M Multibase Korea July 2002

Part III. Applications of Multiflex What else : + + + + Clothes hanger, furniture pad Gear tyre of auto-cleaner Ladder cap Glass washer pipe Absorption sole for flag and baby mirror Plastic teat (one time) Snorkel nozzle Chair spring sheath Interior shoe heel Medical prothesis Flask and container seals Refrigerator seals Casing for torch and binoculars Protector of remote commander Sun glasses frame Rubber . . . Multibase Korea July 2002

Part III. Applications of Multiflex More examples: Multibase Korea July 2002

Part III. Applications of Multiflex 3. Application in development -- To enlarge our sight ¬ Flooring application: + In Europe and U. S. A, “No PVC” is rather an action than a slogan, certain flooring producers has already engaged in looking for “environment friendly” substitute. + This application includes boat deck, hotel floor, and even supermarket floor! + Flame Retardance without halogen, which is quite difficult for a normal TPE-s to achieve, is the biggest handicap in this development project. + Certain Multiflex samples has already met the requirement, but unfortunately, the raw material supplier stops its supplying. + Some new material will be tested soon. + Economy is a very important condition for this application. Multibase Korea July 2002

Part III. Applications of Multiflex Interior seal whisky bottle cap application: + Huge volume of whisky and cognac is exported to East Asia every year, especially to Taiwan and Hongkong. + “No seeping” is very important during the transportation. + No odor, food approval, good C, S and excellent injectability(multi-caves) are the most important conditions for this application. + Considerable potential is behind this application. Multibase Korea July 2002

Part III. Applications of Multiflex ® SBS product range: + SEBS product has no competive advantage compared to TPV. + SBS is accepted in more and more applications, where no special requirements exist, like UV stability, Exellent C, S, or very special soft touch. . . + Nowdays, our most aggressive competitor in Europe is TCT, who focus his developing ability on SBS product. + Multibase is now working for enlarging its SBS(C) product range, to meet the demand of market, especially for Asia. Please read attahed file: SBS and its applications Multibase Korea July 2002

THANKS Thanks a lot for all our colleagues in TPE specialites department and Automotive department, who have helped us to complete this training package. Multibase Korea July 2002