Innovations in Silicone Enhanced Thermoplastics

Transcription

1 Innovations in Silicone Enhanced Thermoplastics Krishna Joshi 乔旭 Multibase, A Dow Corning Company

2 Multibase, A Dow Corning Company Our Vision: We are trusted global partners driven by our passion to create value with innovative and customized thermoplastic solutions Manufacturing Locations : Saint-Laurent-du-Pont, France Copley, Ohio, USA Daman/Mumbai, India Serving customers in 50 countries

3 Multibase World Locations St Laurent du Pont - France Americas Center of Excellence Multibase Inc Copley Road Copley, OH USA Tel: Fax: European Center of Excellence Multibase SA Z. I. Chartreuse Guiers Saint Laurent du Pont Tel: +33 (0) Fax: +33 (0) Copley, OH - USA Asian Center of Excellence Synergy Multibase Ltd. 74/5-6 Daman Industrial Estate Kadaiya Village Nani Daman Daman (U.T.) India Tel: Fax: Daman, Mumbai - India

4 Products and Markets Thermoplastic Elastomers 55% Toll Compounds 4% Rigid Compounds 15% Masterbatches 26% Toll Compounds 4% Transportation 45% Industrial & Consumer 51%

5 Innovations From Multibase Siloxane Masterbatch Easy to handle additives of ultra high molecular weight siloxane in various thermoplastic resin carriers Multiflex SiE (Siloxane Enhanced Elastomers) Unique combinations of SEBS based TPEs and siloxanes to give excellent appearance, mar and scratch resistance TPSiV Patented TPV technology based on silicone rubber

6 Enhancement of Thermoplastics Using Siloxane Masterbatch

7 PolyDiMethylSiloxane (PDMS) CH 3 CH 3 CH 3 CH 3 -Si -O -(Si -O) n -Si -CH 3 CH 3 CH 3 CH 3 Silicones typically have a back bone, which is inorganic like glass The side groups are organic: in most case methyl The degree of polymerisation varies from n=1 to several thousand Silicones show low viscosity, even at very long chain lengths Chain has a spiral shape Mw = 250 Mw = 1,000 Mw = 5,000 Mw = 25,000 Mw = 55,000 Mw = 100,000 Mw = 300,000 1 cst 10 cst 100 cst 1,000 cst 10,000 cst 100,000cSt 10,000,000cSt

8 Polydimethylsiloxane (PDMS) High free volume fluidity at high molecular weights Incompatible with majority of thermoplastics Low surface tension & energy (lubricant, release agent, aestheticfeel) Heat resistant and weather resistant

9 Siloxane in Thermoplastics Siloxane based mold sprays are commonly used in injection molding to aide in part release Siloxane fluids or oils (30,000 to 60,000 cst) are effective internal and external lubricants Limitations: Handling difficulties Surface adhesion problems (migration) Innovation from Multibase is use ultra high molecular weight PDMS (15,000,000 cst) to eliminate these limitations

10 Siloxane Masterbatch 50% UHMW PDMS in various thermoplastic carriers Polyolefins, ABS, PC, nylon, HIPS, EVA, TPU,... Dispersed with an average particle size of 5 microns Si enriches at surface, but UHMW eliminates concerns of blooming and migration after processing

11 Benefits of Siloxane Masterbatch Processing benefits (0.2 2% usage) Added at press, extruder or during compounding Improved mold release Improved mold filling (thin walls,...) Extruder efficiencies (energy, pressure,...) Compounding improvements (disperson, energy,...) Property enhancement (1-8% usage) Reduce COF Low migration (durability) Improved mar and scratch

12 Processing Advantages for Injection Molding Parts released (%) Natural -Consistent Short Shot PP+400 ppm UHMW Si-100% filled MB (%) Effective mold release less scrap, reduce cycle time Effective internal lubricant easier filling of complex parts

13 Effect of Si MB on COF 0.5 Coefficient of Friction No Siloxane Siloxane Masterbatch (3% Si) Velocity (Ms-1)

14 COF BOPP Film C O F 'Non migratory' Slip From DC MB Erucamide 0 Ambient 50oC 60oC Temperature (C)

15 Mar and Scratch Improvement

16 Hot Taber Test

17 Printability Study-3M tape 100% Amoco 3243 PP 0.2% UHMW Si 0.2% Erucamide 1% UHMW Si 1% Erucamide 3% UHMW Si 3% Erucamide 5% UHMW Si 5% Erucamide

18 Effect on Properties/Performance Negligible effect on mechanical properties in typical usage range (data for PC) % PC Based UHMW PDMS Masterbatch Tensile Strength (psi) Flexural Modulus (psi) Izod, Notched (ft-lbs/in) No negative impact on UV resistance (weatherability) or fogging (data for TPE and TPO) Sample Delta E After 2500 KJ 60A TPE % Masterbatch % Masterbatch 0.54 Sample Fog# 1 hour 16 hour Control TPO TPO with 4% UHMW PDMS

19 Case Histories Application Successes Using Siloxane Masterbatch: HDPE Pipe Kodak Camera

20 Summary Siloxane Masterbatch UHMW Siloxane Masterbatch from Multibase, A Dow Corning Company is an unique additive that can: Solve processing issues (mold release, filling) Reduce cycle time and save $ Enhance surface properties of thermoplastics (reduced COF, improved mar and scratch)

21 Siloxane Enhanced Elastomers (SiE)

22 SiE Elastomers Multibase, A Dow Corning Company has commercialized Multiflex SiE technology by combining our experience in SEBS TPEs and siloxane polymers This study offers a comparison of properties and performance of SiE and a standard SEBS TPE for general automotive interior applications

23 SiE General Properties Value Test Method 8009 MU MU MU5 Unit Melt Flow (230oC, 2.16 kg) ISO g/10min Spiral Flow Internal cm Specific Gravity ISO Tensile Strength ISO MPa Tensile Stress at 100% Elongation ISO MPa Elongation at Break ISO % Tear Strength ISO kn/m Hardness (15 sec) ISO Shore A

24 Adhesion to Polypropylene Grade MF SiE A 6009 MU Peak Load 70 lbs T-bar peel test at 12 in/min, bond area ~1 square in.

25 Coefficient of Friction Performance Sample CoF Static Kinetic Control TPE MF SiE A 6009 MU % Reduction 45% 29% SiE technology is able achieve a lower Static and Kinetic Coefficient of Friction contributing to a non-tacky surface feel

26 Scratch Resistance (no scratch whitening) Control TPE SiE Control TPE SiE 10N 7N 6N 3N 2N 10N 7N 6N 3N 2N 10N 7N 6N 3N 2N 10N 7N 6N 3N 2N SiE has better resistance to scratches and no scratch whitening

27 Abrasion Resistance Significant Improvement! Sample Gloss Before Gloss After % Gloss Loss Control TPE % MF SiE A 6009 MU % Sample Original Weight, g Cycles Weight After, g % wieght loss Control TPE , MF SiE A 6009 MU ,

28 Compression Set Performance Log. (6009) Log. (7009) Log. (8009) C 70C 100C 125C SiE technology is able to maintain a low compression set even at 125C

29 Fogging Performance Sample Fog # Microscopic Examination 40X MF SiE A 6009 MU 16 hour 110 C 91.7 No Droplets or Crystals MF SiE A 7009 MU 16 hour 95 C 90.8 No Droplets or Crystals 110 C 77.9 No Droplets or Crystals MF SiE A 8009 MU 16 hour 110 C 91.2 No Droplets or Crystals Testing Conditions: Fogging (LP463DB-12-01, 6h at 95C and 110C heating, 21C cooling, 16 h post SiE technology is able to maintain fogging requirements even at 110C

30 Gas Fading Performance Control TPE SiE A 6009 Before After Before After Sample Gas Fading / Resistance to Burnt Gas Delta E AATCC rating Control TPE Severe color change MF SiE A 6009 MU Slight color change MF SiE A 8009 MU Slight color change

31 Flammability Performance FM VSS 302 Grade Time (sec)burn Rate (in/min) Pass/Fail MF SiE A 8009 MU Pass MF SiE A 7009 MU Pass MF SiE A 6009 MU Pass SiE Materials meet FM VSS 302

32 Soiling and Linting Performance Linting (LP-463KB-38-01) Grade Lint Rentention Rating Pass/Fail (2 min.) MF SiE A 6009 MU 1 Pass MF SiE A 7009 MU 1 Pass MF SiE A 8009 MU 1 Pass Standard TPE 1 Pass Cleanability (LP-463KC-04-01) Grade Soil MF SiE A 8009 MU MF SiE A 6009 MU Standard TPE -IPA no stain no stain no stain -Armor All no stain no stain no stain -Grease no stain no stain no stain -Ketchup stains stains stains -Orange Juice no stain no stain no stain -Coffee no stain no stain no stain -Chocolate no stain no stain no stain -Windex no stain no stain no stain

33 UV Resistance Testing completed using SAE J kj Delta L Delta a Delta b Delta E MF SiE A 6009 MU MF SiE A 7009 MU

34 Oil Resistance Before: After: Paraffin oil rested on part surface at 80 C for 24hrs No adhesion failure (SiE overmolded on PP substrate) and grain was not washed out

35 Cocoamide Resistance Plaques were exposed to the cocoamide for 48 hrs at 23C, 50% RH and then were abraded with a cloth (TSM5100G color fastness to wet crocking). Rating 1 indicates that there was no noticeable change in the grain of the plaques. Cocoamide resistance Grade Rating Pass/Fail MF SiE A 7009 MU 1 Pass MF SiE A 8009 MU 1 Pass Standard TPE 4 Fail

36 SiE Applications Automotive Interior Important Aspects: Excellent appearance Low CoF Smooth touch Excellent flow No blooming Reduced noise

37 2008 Corolla Matrix Deck Lid Strips Skid strips on deck lid

38 Summary - SiE Siloxane enhanced elastomers (SiE) have superior scratch resistance as compared to standard TPEs and are designed specifically for car interior trim applications (meets stringent UV, fogging, gas fading requirements) SiE is also expected to find use in nonautomotive applications that require good scratch resistance and a non-tacky feel

39 Thermoplastic Silicone Vulcanizates (TPSiV )

40 Outline Basics of Thermoplastic Silicone Vulcanizates Technology Platforms (Properties and Applications) Polyamide based TPU based Polyolefin based Summary

41 Basics of Thermoplastic Silicone Vulcanizates ThermoPlastic Silicone Vulcanizate (TPSiV ) Alloy TPV consisting of fully cured silicone rubber particles dispersed in a continuous phase of selected thermoplastic Cured silicone is a clean reaction: no byproducts, no odor, no emission Unique, patented technology of Multibase, A Dow Corning Company (13 patents) Properties depend on type of plastic, type of silicone, ratios and compatibilization

42 Challenges with Silicones Not compatible with majority of thermoplastics Very dissimilar solubility parameters PDMS = 14.9 MPa ½ Nylon 6 = 27.8 MPa ½ Effective compatibilization is required to create a stable TPV morphology and to achieve acceptable mechanical/physical properties 21 mm

43 Compatibilization Example As disclosed in US patent 6,649,704, compatibilization of nylon resins and silicone rubber can be accomplished in situ during dynamic vulcanization if an appropriate functionalized PDMS fluid is added (such as epoxy functional) Forms graft co-polymer of nylon and PDMS, which acts as compatibilizer between nylon and silicone rubber phases Nylon 12 Based Silicone Vulcanizate Tensile Strength Elongation at Sample (MPa) Break (%) No Compatibilizer With Compatibilizer

44 Product Platforms Thermoplastic Silicone Vulcanizates Technology Polyamide D PCT/ TPU 3010, 3011, 3040, 3340, 3111 PCT/ PCT/ PCT/ Polyolefin 5300, 5400, 5500 PCT/

45 PA 6 based Silicone Vulcanizate Property Initial: Specific Gravity (23/23ºC) Hardness (Shore D) Tensile Strength (MPa) Elongation at Break (%) Tear Strength (N/mm) Flex Modulus at 40 C (MPa) 1008 hrs in Air at 140 C: Change in Tensile Strength (%) Change in Elongation at Break (%) Immersion in DOT4 Brake Fluid at 150 C for 168 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%) Immersion in Automatic Transmission Fluid at 127 C for 1008 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%) Immersion in Reference Fuel C at 23 C for 3024 hrs: Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%) Result

46 Automotive Hose Application Jacket for automotive brakehose Outperforms competitive solutions (CoPE and PP- EPDM TPV) in terms of temperature resistance (continue -150 C) sealing in crimped section

47 TPU Based Silicone Vulcanizate Combines the advantages of: Excellent abrasion resistance of TPU Soft touch of silicone rubber Significantly lower COF than TPU As compared to most soft TPU, TPSiV contains no plasticizers Excellent bonding to PC, ABS, Excellent retention of properties after heat aging in air Better compression set than TPU (further improved after annealing)

48 Comparison To PP-EPDM TPV Property Initial: Hardness (Shore A) Tensile Strength (MPa) Elongation at Break (%) 70 hrs in Air at 175 C: Change in Hardness (Shore A) Change in Tensile Strength (%) Change in Elongation at Break (%) 70 hrs in IRM 903 Oil at 100 C: Change in Hardness (Shore A) Change in Tensile Strength (%) Change in Elongation at Break (%) Volume Swell (%) Silicone Based TPV PP-EPDM TPV

49 Benefit of annealing on TPU based Silicone Vulcanizates Mechanical 23 C Tensile Strength Elongation at break Tear Strength Physical Properties Density Hardness Compression Set 22hrs 23 C 70 C 70 C after annealing* 120 C 120 C after annealing* Abrasion Resistance (Taber) Standard Units TPSiV A ASTM D412 MPa 7.1 ASTM D412 % 473 ASTM D624 N/mm 24 ASTM 792 ASTM D2240 ASTM D395 ASTM D1044 Shore A % Mg loss TPSiV A *Annealed at 120 C for 22hrs in air

50 Test for Bonding Strength 1 st 1stShot 1rst Shot Flow Path of 1 st Shot 1 st 1stShot 1rst Shot Hand Hand Hand Load LoadHand Load 2 nd 2 2nd nf Shot 2 nf 2nd 2 nd Shot Shot Shot Plastic Substrate TPSiV Peel Strength tested by ASTM D1876 Flow Path of 2 nd Shot Overmolded T-Bar

51 Bond Strength TPE Elongates Peak Bond Strength Peel starts Peel ends Investigated substrates -PC (cohesive) -ABS (cohesive) -PVC (cohesive) -Nylons (adhesive)

52 Recommended Products for Overmolding on PC, ABS, TESTS ASTM UNITS A A A A A A A A Product Feature Fast Cycle / Overmolding High UV Resistance Hardness (10 sec) D-2240 Shore A Specific Gravity D Tensile Strength D-412 Mpa Elongation at Break D-412 % Tear Strength D-624 N/mm Abrasion Resistance D-1044 mg loss 90 to to to to tot to to to 130 Flammability UL 94 HB HB HB HB HB HB HB HB

53 UV Color Stability Xenon Testing, 5 days, 190 KJ/m Delta E*ab A UV Gray A UV Gray A UV Orange TPSiV A TPSiV A

54 Application Example Overmolded electronics: Nokia Garmin Motorola Others

55 TPSiV A for automotive interior High flow for injection moulded thin layer Matte appearance, low gloss (advantage over TPU) Properties referential Requirements Aliphatic TPSiV TPU Visual aspect GS > 4-5 grey scale Too glossy 5 ( after heat ageing 80 C/10days) Visual aspect GS > 4-5 grey scale 5 5 (after cleaning: dry, wet, cockpit stray, car emulsion, glass cleaner) Scratch resistance Finger test 5N, 10N, 20N 20N No visible visible UV ageing VDA >7 (1 cycle) >4 (3 cycles) CARB emission GS < 1mg GP-MS Total VOC GS < 6500 µg/m Odor VDA 270 < Color matching Black, grey, beige Black, grey, beige Reference is related to BMW testing methods

56 NEW! - Polyolefin based Silicone Vulcanizates Contains no oils or plasticizers! Low COF and unique feel Compatible with TPE-S or O-TPV Properties Units Standard TPSIV 5300-A5501 NAT TPSIV A6502 NAT Hardness Shore A ISO Density ISO R Spiral flow cm MDA Tensile Strength at 100% Tensile strength at 200% Tensile strength at break Elongation at break MPa ISO MPa ISO MPa ISO % ISO Tear strength kn/m ISO

57 Heat Aging Performance Excellent property retention after heat aging for 1000 hrs at 110 C (typical automotive interior requirement, SAE J 2236) Property Method Unit TPSIV 5300 A6502 EML1 TPSIV 5300 A9003 Hardness ISO 868 Change in Shore A +3-2 Tensile Strength ISO 37 % Retention Elongation at Break ISO 37 % Retention Tear Strength ISO 34 % Retention

58 Fluid Immersion Performance Low swell is various fluids Fluid TPSiV 5300 A6502 NAT TPSiV 5300 A9003 NAT 24 hrs, wt% 192 hrs, wt% 24 hrs, wt% 192 hrs, wt% Salt Water (20%) Brake Fluid Ethanol Ethyl Glycol Acetone Mineral Oil (200 cps)

59 Summary TPSiV Thermoplastic silicone vulcanizates are unique patented materials that offer softness and flexibility without addition of oils or plasticizers Low emission, low odor Various property profiles and advantages are gained by the choice of thermoplastic phase Chemical resistance (nylon) Low abrasion, scratch resistance, chemical resistance, bonding to engineering resins (TPU) Low COF, low fogging, hydrolytic resistance (polyolefins)

60 Innovations From Multibase Siloxane Enhanced Thermoplastics Siloxane Masterbatch Easy to handle additive Processing benefits Reduce COF Improve scratch resistance Multiflex SiE Siloxane enhanced TPE Excellent scratch resistance Designed to meet auto Interior requirements TPSiV Patented Si TPV 3 product families (nylon, TPU, polyolefin) No plasticizers or oils

61 GC Contacts 大中华区业务联系人 Krishna Joshi Asia Director Cocoo Lu Customer Service Remeng Guo Sales Guangzhou Eva Bian Marketer Shanghai Carrie Chen Sales Shanghai Kim Li Marketer Shanghai Voly Wang AETS Shanghai GC Non-Auto Segment GC Auto Segment