Total Solution with Advanced Additive Technologies for Polypropylene Based Automotive Applications Shinichi Ishikawa Head of Technical Services, General Manager Additives Solution Department, Polymer Additives R&D ADEKA Corporation July 29 th, 2017 IOCL Conclave
Contents Introduction PP for automobile Demand estimation of automobile worldwide Demand trend of automobile in the future Requirements of PP for automotive parts Advanced additives technologies in automotive parts Weatherability Mechanical Properties Flame Retardancy Summary & Conclusion Proprietary To be maintained in confidence 1
Introduction Proprietary To be maintained in confidence 2
Typical automotive parts made from PP Cowl top Instrumental panel Parts around Engine Bumper Door panel Trim Superiority of PP Low density Recyclability Superior mechanical properties Ease of processing and molding Excellent chemical resistance Low cost, etc. Proprietary To be maintained in confidence 3
million Car Demand Estimation Worldwide Limited growth in Developed countries but high growth in Emerging countries. Emerging Countries Thailand Indonesia Mexico S.Africa China India Russia Brazil Australia Korea Canada USA EU JAPAN (Total) Developed Countries Source: METI JAPAN Based on SC-Abeam estimation http://www.meti.go.jp/policy/economy/keiei_innovation/sangyokinyu/gb/04.pdf Proprietary To be maintained in confidence 4
Car Demand Trend Worldwide Combustion Electric Combustion Electric Combustion Electric PHV and EV type cars will be expanded worldwide in the future PHV Electric vehicle Pure Combustion 84% Pure Combustion 49% Pure Combustion 20% Year Data Source: METI Energy Technology Perspectives 2012/ IEA http://www.meti.go.jp/policy/economy/keiei_innovation/sangyokinyu/gb/04.pdf Proprietary To be maintained in confidence 5
Requirements and Solutions for Automotive parts Requirements Through life time Thermal stability Weatherability Mechanical properties At production Weight saving Fast molding cycle For Future Flame Retardancy (Especially for EV & PHV) Additive Solutions Thermal stability (Processing & Discoloration) High performance phosphite Weatherability Advanced light stabilizer Mechanical properties Advanced nucleating agent Flame Retardancy Advanced Halogen Free Flame Retardant Effective utilization of polymer additives Superior & Excellent automotive parts Proprietary To be maintained in confidence 6
Advanced additives technologies in automotive parts - Weatherability - Proprietary To be maintained in confidence 7
Requirements of HALS for automotive Interior Interior parts are exposed not only by UV radiation but also heat. HALS having low MW and low compatibility may cause migration and fogging issue. Exterior parts such as bumper do not need high thermal stability compared to interior parts. However, low compatibility of HALS may cause a negative effect to the paintability. Exterior Requirement : High performance and High compatibility Proprietary To be maintained in confidence 8
Advanced N-H HALS system For Interior & Exterior ADK STAB LA-402AF Benefits Excellent stabilizing ability Surface gloss and color sustainability Superior compatibility with polymers Lower volatility & less blooming Easy handling master batch form No concern about feeding property Proprietary To be maintained in confidence 9
Light Stabilizers evaluated HALS ADK STAB LA-402AF 50% Active component PP MB ADK STAB LA-94G H N H N ADK STAB LA-77Y) N N N (CH 2 ) 6 N NH CH 2 N n High M.W. (>2000) O O HN O C (CH 2 ) 8 C O NH Low M.W. (481) Additive Package for Evaluation Phenolic AO ADK STAB AO-60 Phosphite AO ADK STAB 2112 Neutralizer Ca-Stearate Proprietary To be maintained in confidence 10
Gloss retained (%) Weatherability of Exterior Parts : Surface Gloss Comparison of light stabilizers in surface gloss stability 120 100 80 60 LA-402AF (0.2) LA-402AF (0.1) Acceleration test Xenon Weather-O-Meter (63 o C, with Water Spray) (ISO 4892-2) 2mm plaque Formulation ICP [60] / Elastomer [30] / Talc[10] Black [3] AO-60 [0.1] / 2112 [0.1] / Ca-St [0.1] / HALS 40 20 Control LA-77Y/LA-94G (0.1)/(0.1) 0 0 1000 2000 3000 Exposure time (h) 4000 LA-402AF improved the surface gloss stability greatly compared with conventional type even with lower loading level Proprietary To be maintained in confidence 11
delta E Weatherability of Interior Parts : Color stability Comparison of light stabilizers in color stability 10 8 6 4 2 Control LA-77Y/LA-94G (0.1)/(0.1) 0 0 500 1000 1500 2000 Exposure time (h) LA-402AF (0.2) Acceleration test Xenon Weather-O-Meter (89 o C, without spray) (Based on ISO 4892-2) 2mm plaque Formulation ICP [60] / Elastomer [30] / Talc[10] Beige [3] AO-60 [0.1] / 2112 [0.1] / Ca-St [0.1] / HALS LA-402AF (0.3) LA-402AF improved color 2500 stability compared with conventional type Proprietary To be maintained in confidence 12
Blooming of HALS from PP Comparison of light stabilizers in surface gloss at oven Acceleration test Oven aging at 80 C 2mm plaque Formulation ICP [60] / Elastomer [30] / Talc[10] Beige [3] AO-60[0.1] / 2112 [0.1] / Ca-St [0.1] / HALS Microscope observation at 1,000h LA-402AF (0.4) LA-77Y (0.2) Control LA-77Y (0.2) LA-402AF (0.4) LA-402AF demonstrated lower blooming on the surface of PP Proprietary To be maintained in confidence 13
Fogging of HALS from PP Test Condition Oven aging at 100 C for 24h LA-77Y (0.3) Formulation ICP [60] / EPR [30] / Talc[10] / Black [3] AO-60 [0.1] / 2112 [0.1] / Ca-St [0.1] / HALS 12 8 LA-77Y/94G (0.15/0.15) Haze 6 4 Control 2 0 LA-402AF (0.3) ~ ~ ~ Haze value 10 Cover glass Beaker Pellet 100 ºC LA-402AF demonstrated less fogging than the conventional products Proprietary To be maintained in confidence 14
Summary : Advanced HALS system for automotive Advanced HALS system ADK STAB LA-402AF could provide Remarkable weathering resistance compared with conventional type at low loading level Excellent performance with less blooming and fogging Proprietary To be maintained in confidence 15
Advanced additives technologies in automotive parts - Mechanical improvement - Proprietary To be maintained in confidence 16
Flexural modulus (MPa) Benefit of Nucleating Agent for Light Weight Our target Engineering Plastics 1800 1600 1400 PP with H-NA* PP with L-NA* PP with 5%Talc PP with 15%Talc PP with 10%Talc PP Without NA 1200 0.85 0.9 0.95 1 1.05 Density *H-NA: Sodium 2,2 -Methylenebis- (4,6-di-tert-butyl-phenyl) phosphate *L-NA: Sodium Benzoate Improved stiffness of PP with NA can contribute to weight saving. Further improvement can boost the change from other materials to PP. Proprietary To be maintained in confidence 17
Requirements of N.A for automotive Requirements Significant improvement in mechanical properties Stiffness Heat resistance Acceleration of polymer crystallization Faster molding cycle Weight saving Proprietary To be maintained in confidence 18
Advanced Nucleating Agent ADK STAB NA-27 Benefits Provides the best mechanical properties of all commercially available Nucleating Agents Cost saving as additive package Performs at lower loading levels Cost saving for operating cost Performs at lower processing temperature Possible thinner molded articles Proprietary To be maintained in confidence 19
Nucleating Agents ADK STAB NA-27 ADK STAB NA-11 Trade Secret Multicomponent NA system CH 2 O O P O ONa NA-3 Aliphatic carboxylic acid salt derivative Additive Package for Evaluation Phenolic AO ADK STAB AO-60 Phosphites AO ADK STAB 2112 Neutralizer Ca-Stearate Proprietary To be maintained in confidence 20
Flexural modulus (MPa) Effect of NA-27 on F.M & HDT of Impact-PP HDT ( o C) 1500 NA-27 110 NA-27 1400 NA-11 100 NA-11 1300 1200 NA-3 Competitor 90 NA-3 Competitor 1100 80 1000 0.00 0.05 0.10 0.15 0.20 Dosage of NA (phr) 70 0.00 0.05 0.10 0.15 0.20 Dosage of NA (phr) NA-27 provided excellent performance in Flexural Modulus & HDT Resin: ICP (MFR=40) Formulation: AO-60(500ppm), 2112(1000ppm), CaSt(500ppm), NA Extrusion: Twin-screw extruder at 230 o C, Injection: at 200 o C(Mold: 50 o C) Proprietary To be maintained in confidence 21
Benefits in talc-filled Impact-PP Talc: 10% Flexural modulus (MPa) 1900 1850 1800 1750 1700 NA-27 NA-11 NA-3 Competitor HDT (ºC) 112 110 108 106 104 NA-27 NA-11 NA-3 Competitor 1650 0 0.05 0.1 0.15 0.2 0.25 102 0 0.05 0.1 0.15 0.2 0.25 Dosage of NA (phr) Dosage of NA (phr) NA-27 provided superior mechanical properties even in presence of talc. Proprietary To be maintained in confidence Resin: ICP (MFR=25) Formulation: AO-60(1000ppm), 2112(1000ppm), CaSt(500ppm), NA Extrusion: Twin-screw extruder at 240 o C, Injection: at 230 o C 22
Crystallization Temperature of nucleated PP 135 130 Impact PP, unfilled, MFR=40 NA-27 NA-11 HDT (ºC) 125 120 NA-3 Competitor 115 110 0 0.05 0.1 0.15 Dosage of NA (phr) NA-27 showed increased crystallization temperature compared with conventional NA, which can result in a shorter molding cycle Proprietary To be maintained in confidence 23
Summary : Advanced N.A system for automotive Advanced nucleating agent ADK STAB NA-27 could provide High stiffness compared with conventional NA types at low loading level Superior mechanical properties, even in the presence of talc Faster molding cycle by raising the crystallization temperature Proprietary To be maintained in confidence 24
Advanced additives technologies in automotive parts - Flame Retardancy - Proprietary To be maintained in confidence 25
Brominated compounds + antimony trioxide Extinguish fire by incomplete combustion Enough performance, but generate a lot of smoke and CO Market wants non-halogenated products from environmental point of view, but there is no alternative at present. Existing FRs and our viewpoint Aluminum hydroxide, Magnesium hydroxide Extinguish fire by releasing heat with the generation of water Generate no toxic gas, but have very poor efficiency Poor mechanical property and high density, because of high loading level 1fire extinguishable 2lower generation of smoke and CO 3enough mechanical property How can we provide such FRs? Proprietary To be maintained in confidence 26
Mechanism of Intumescent type flame retardant What is Intumescent system? Intumescent System Intumescent layer RADIATION Shield it from Heat radiation Pyrolysis gas diffusion O2 Pyrolysis gas Polymer Surface Fire Source Phosphorus nitrogen containing intumescent flame retardants ADK STAB FP-2000 Series Proprietary To be maintained in confidence 27
Applications of flame retarded polyolefins POLYOLEFINS are very COMBUSTIBLE!! Flame retardants should be required for these applications W & C Transportation E & E UL-VW1 FM-3972 Building FMVSS-302 FAR Part25 UL94-V IEC/TC 89 ASTM E84 ASTM E102 Proprietary To be maintained in confidence 28
Combustion behavior of flame retarded PP-h According to UL-94V, both show similar flame retardancy, V-0, but Conventional ADEKA (FP-2500S) BPBPE / Sb 2 O 3 Force of the fire is STRONG. DARK SMOKE is generated FP-2000 Series Force of the fire is WEAK. INTUMESCENT LAYER is generated Proprietary To be maintained in confidence 29
Smoke Density PP-h(V-0) formulation 15 ~Cone calorie meter test~ Smoke density / m -1 12 9 6 3 BPBPE /Sb 2 O 3 Control Mg(OH) 2 FP2200S FP2100JC 0 0 200 400 600 800 Time / s Bad Good Br type>control>mg(oh)2 FP-2xxx Proprietary To be maintained in confidence 30
V-0 ratio (%) V-2 Flame Retardancy after Weathering (PP-b) V-0 V-2 V-2 V-0 Br-FR(18%)/Sb 2 O 3 (6%) APP (32%) ADK STAB FP-2200S (32%) Crack Xenon Exposure time* (h) *ISO 4892-2, C1 Contrary to competition, ADK STAB FP-2000 series could retain V-0 classification after weathering Proprietary To be maintained in confidence 31
Summary : Advanced FR system for automotive Advanced halogen free flame retardant ADK STAB FP-2000 series can realize high safety material in fire accident with maintaining good properties of PP could maintain high flame retardancy, V-0 rating, after long term weatherability test FP-2000 Series can contribute to the development of next generation PP for automotive application Proprietary To be maintained in confidence 32
Summary and Conclusion We can propose the appropriate additives system which will realize Superior surface gloss and color stability against light Excellent mechanical properties and faster molding cycle Excellent Flame Retardancy with environmental friendly These additives packages can enhance the value of the Polypropylene and expand the potential in this application. Proprietary To be maintained in confidence 33
Thank you for your attention Local Contact: ADEKA India Pvt. Ltd. B-206 & 207, Dynasty Business Park, Andheri Kurla Road, J.B. Nagar, Andheri East, Mumbai-400 059 Tel:+91-22-4026-3301/2 Proprietary To be maintained in confidence 34