Document Qk0LxjogkLB1OBn1j4oG15p8k

Request for derogation on the use of PTFE as anti-drip agent in thin wall flame retardant polycarbonate compounds Table of Contents Executive Summary .............................................................................................................. 2 1. Introduction to thin wall flame retardant polycarbonate ............................................. 4 2. Analysis of alternatives for polycarbonate in electronic products ................................. 4 3. Analysis of alternatives for PTFE as an anti-dripping agent in polycarbonate .............. 5 4. Proposed text for derogation for Thin Wall Flame Retardant Polycarbonate ............... 7 5. Critical Safety Need for Flame Retardants in Electronics............................................... 8 6. EU regulatory requirements for flame retardants ......................................................... 9 7. Socio-economic impacts ................................................................................................ 9 8. PFAS tonnages and releases from flame retardant polycarbonate ............................. 10 Appendix 1: Literature review references and patent review references .......................... 11 Executive Summary Flame retardant polycarbonate compounds used in thin-wall consumer electronics applications plays a critical role in consumer safety and requires the use of PTFE as an antidrip additive. Thin walled parts reduce the amount of plastic used and therefore the amount of plastic waste produced during the manufacturing process as well as at the electronic devices' end of life. Before these tough thin-wall flame retardant polycarbonates were available, typical wall thicknesses in consumer electronics were 2-3 mm, which in comparison can lead to a 100% to 200% increase in resources consumption and solid waste generation, depending upon the electronic application design requirements. Thin-walled polycarbonate can also lead to lighter products which require less energy for transportation, resulting in less CO2 emissions. Our justification for requesting derogation of PTFE as anti-drip agent in flame retardant polycarbonate compounds comprises two elements: there are no alternatives to polycarbonate that provide adequate impact resistance and ductility for thin wall (<=1.5mm) applications in electronic products in order to ensure that the polycarbonate thin wall has adequate flame retardancy, it is essential to use PTFE as the anti-drip agent There is no other engineering plastic available today which provides adequate levels of impact resistance and ductility compared to polycarbonate. These properties are crucial to: provide a durable product that does not break during normal use, including drops and other foreseeable events ensure safety by avoiding exposure of life circuitry, and meet EU regulatory requirements on the safety of electrical device The next best material is polyphenylsulfone (PPSU) which has almost half the ductility. By extension, we can expect that electronic products with thin walls (<=1.5mm) made from PPSU would be twice as fragile compared to the same products made with polycarbonate. Increased fragility means increased risk that the device may break after an impact event, which may result in electrical hazard (short circuit, shock hazard) or fire hazard. We have carried out a thorough analysis of the latest available flame-retardant and antidripping technology for polycarbonate, via a patent and literature review, as well as our own in-house technical expertise based on decades of experience with plastics. Our review of patents found that most flame-retardant polycarbonate materials are formulated with PTFE as an anti-dripping agent. We did find some patents which do not use PTFE; however, we did not find any non-PFAS alternatives which are acceptable from the standpoint of environment and human health, and which do not compromise the impact resistance and ductility of the polycarbonate. Our literature review found that all recently developed flame retardants mandate the use PTFE as an anti-drip agent in polycarbonate. Our company has also carried out our own in-house experiments to investigate whether we could develop alternative additives that could be used instead of PTFE. None of the alternatives that we tested was able to provide adequate flame-retardant properties without significantly degrading impact resistance or other mechanical properties. 2 1. Introduction to thin wall flame retardant polycarbonate Injection mouldable polycarbonate resins, polycarbonate blends and polycarbonate copolymer resins are used for thin wall flame resistant enclosures, structural components and/or insulators for the consumer electronics industry. Thin-walled parts produced from these types of polycarbonate resins reduce the amount of plastic used and therefore the amount of plastic waste produced during the manufacturing process as well as at the electronic devices' end of life. Before these tough thin wall flame retardant polycarbonates were available, typical wall thicknesses in consumer electronics were 2-3 mm, which in comparison can lead to a 100% to 200% increase in resource consumption and solid waste generation, depending upon the electronic application design requirements. Thin-walled polycarbonate can also lead to lighter products which require less energy for transportation, which results in less CO2 emissions. Flame retardant polycarbonate is provides an extraordinary combination of mechanical, electrical, and flammability properties and has become increasingly used in almost every electronic device. Electronic devices often rely on unique combinations of properties that polycarbonates can have, including mechanical/impact strength, electrical insulation, flame resistance, corrosion resistance, integral (no-paint) color, and weather resistance. Depending upon the end use application, any combination of these properties could be the deciding factor for using polycarbonates versus other thermoplastic materials. For instance, consumer electronics often need lightweight, molded-in functionality with impact, electrical, and flame resistance that alternate thermoplastic materials cannot meet. 2. Analysis of alternatives for polycarbonate in electronic products For thin (<=1.5mm) injection moulded walls in electronic products, along with fire resistance, impact resistance and ductility are essential requirements. Impact resistance is measured using the Notched Izod impact strength test (ASTM D256-10(2018) standard method1). Ductility is measured using elongation at break testing which measures how much a material can be stretched, as a percentage of its original dimensions, before it breaks2. As highlighted in the table below, polycarbonate offers unmatched impact resistance and ductility compared to other engineering plastics, which is crucial to: provide a durable product that does not break during normal use ensure safety by avoiding exposure of life circuitry, and meet EU regulatory requirements of the electrical device. Polycarbonate ABS Nylon Polyphenylsulfone (PPSU) Polystyrene (PS) Polyethylene (PET) terephthalate Impact resistance Notched Izod strength relative to polycarbonate 100% 48% 7% 83% 17% 4% Ductility Elongation at break relative to polycarbonate 100% 23% 66% 55% 38% 51% 1 https://www.astm.org/d0256-10r18.html 2 https://www.curbellplastics.com/Research-Solutions/Plastic-Properties 3 Poly (methyl methacrylate) 3% 3% (PMMA) Polyether ether ketone (PEEK) 10% 44% Additional considerations: Nylon: in addition to inferior impact resistance and ductility, nylon contains hydrophilic amide groups which makes nylon water-absorbent and causes it to expand. Water absorption results in dimensional changes to the plastic part which can cause the product to fail safety testing. PMMA: PMMA is infrared transparent and is often used in applications requiring infrared remote-control features. However, PMMA is more brittle than polycarbonate, which limits its application for electronic industry. PEI and PEEK: the impact performance is about 20 times lower than polycarbonate. Thermal stability is important for some applications where heat may be generated during operation of the electronic product. Polycarbonate has excellent thermal stability, while plastic like PBT have poor thermal stability, making them unsuitable for those applications. In conclusion, there are no alternatives to polycarbonate that provide adequate impact resistance and ductility for thin wall (<=1.5mm) applications in electronic products. 3. Analysis of alternatives for PTFE as an anti-dripping agent in polycarbonate It would be unacceptable and unsafe to use polycarbonate without an anti-dripping agent to prevent the spread of fire. Doing so could create fire hazards and would not allow products to comply to mandatory fire safety standards. PTFE is currently the anti-dripping agent in polycarbonate in electronic products. The high shear forces in the injection moulding process cause the PTFE to stretch and form fibrillated structures in the polycarbonate. Due to the high thermal stability of PTFE, the fibrillated structure remains intact during combustion process and forms a char which prevents dripping of burning plastic. PTFE also contributes to improved impact resistance and ductility. We have carried out a thorough analysis of the latest available flame-retardant and antidripping technology, via a patent and literature review. Our review of patents found that most flame-retardant polycarbonate materials are formulated with PTFE as an anti-dripping agent. We did find some patents which do not use PTFE; however, we did not find any non-PFAS alternatives which are acceptable from the standpoint of environment and human health, and which do not degrade the impact resistance and ductility of the polycarbonate. Additive/Technology 0.1%-0.5% potassium perfluorobutane sulfonate (KFPBS)1 Observation KFPBS is a PFAS. Conclusion KFPBS is a PFAS and would therefore also be banned from use without a derogation 20% phosphorus-based flame retardant2 Significant reduction of impact resistance, ductility and thermal properties. As the polycarbonate will not meet the mechanical properties required by the EU safety standards, this material cannot be considered as an acceptable alternative Aromatic brominated flame retardants3 The Regulatory Strategy for Flame Retardants published March 20233 proposes to ban the use of aromatic brominated flame retardants. Due to enacted and proposed regulatory restrictions this material cannot be considered as an acceptable alternative 3 https://echa.europa.eu/documents/10162/2082415/flame_retardants_strategy_en.pdf/9dd56b7e-4b62e31b-712f-16cc51d0e724?t=1678871526283 4 The WEEE directive requires selective treatment for plastic containing brominated flame retardants. Ecodesign requirements for electronic displays forbid the use of halogenated (including brominated) flame retardants in the enclosure and stand of electronic displays. Patent References: 1 EP4021978A1, 2 US20210171766A1, 3 CN112745641B We have carried out an extensive literature review to investigate whether there are any new flame retardants recently developed that may not require the use of PTFE. Our review has found that all recently developed flame retardants mandate the use PTFE as an anti-drip agent. FR Additive Polyphenylsilsesquioxanes (cyc-PPSQ)4 Silicon-phosphorus linear polymer5 Observation 0.3% PTFE is added as an anti-dripping agent to meet flame retardant standards 0.45% PTFE is added as an anti-dripping agent to meet flame retardant standards Conclusion This new flame retardant still requires the use of PTFE This new flame retardant still requires the use of PTFE Expandable graphite6 PTFE is added as an anti-dripping agent to meet flame retardant standards This new flame retardant still requires the use of PTFE Literature References: 1 Journal of Materials Science 55 (2020): 10953-109672, Fire and Materials 43 (2019): 685693, 3 Materials & Design 214 (2022): 110419 Our company has also carried out our own in-house experiments to investigate whether we could develop alternative additives that could be used instead of PTFE. Our research is summarised below. None of the alternatives that we tested was able to provide adequate flame-retardant properties without significantly degrading impact resistance or other mechanical properties. The results of our in-house experiments on anti-drip agents are presented in the below tabular format. These chemicals were selected for experimentation as the most promising potential alternatives based on our own in-house expertise and literature and patent searching. As explained below, based on our experimental results, none represents an acceptable alternative to PTFE. Tested technology CAS# Experimental result Conclusion Talc-based Trade secret Burning drips developed during flammability testing Significant reduction of mechanical properties Does not provide adequate flame retardant properties Sufur-based Trade secret Burning drips developed during flammability testing Does not provide adequate flame retardant properties Silicone-based Trade secret Burning drips developed during flammability testing Does not provide adequate flame retardant properties Boron-based Trade secret Burning drips developed during flammability testing Significant polymer degradation. Does not provide adequate flame retardant properties. Additionally, it is an SVHC which would be a regrettable substitution Phosphorus-based Trade secret Significant reduction of impact resistance, ductility, and thermal properties. As the polycarbonate will not meet the mechanical properties required by the EU safety 4 Journal of Materials Science 55 (2020): 10953-10967 5 Fire and Materials 43 (2019): 685-693 6 Materials & Design 214 (2022): 110419 5 standards, this material cannot be considered as an acceptable alternative In the Regulatory Strategy for Flame Retardants7, ECHA also acknowledges that fluoropolymers, especially high molecular weight (HMW) PTFE, provide flame retardancy to polymers used in various industrial applications. PTFE, when incorporated into the polymer compound, reduces the dripping of the polymer upon burning and thereby retards the spread of flames. PTFE is added with loadings up to 0.5 wt%. 4. Proposed text for derogation for Thin Wall Flame Retardant Polycarbonate There are no alternatives to PTFE available today for thin wall flame retardant polycarbonate. A wide range of potential alternatives have already been tested and found to fail to provide the necessary properties. A new round of extensive, fundamental laboratory research will be needed to attempt to identify a completely new material, unknown today, that may potentially be developed into an alternative to PTFE. We expect it may take up to 8 years to carry out this basic research. If a new alternative material is identified it would take several more years to test, qualify, certify, and start manufacturing parts from this replacement material. Companies may need to make changes to their manufacturing equipment and processes to use the new material in their injection moulding lines. These changes to manufacturing equipment and processes may be significant and require extensive time and capital investment. Product requalification is a very time-consuming exercise which will require extensive resources over many years. The completion of this task will require sufficient test house capacity and transition time to requalify all existing thin wall flame retardant polycarbonate parts in products which are used in Europe for safety and performance. For a company with a wide range of existing product designs, we estimate it could take up to 5 years to carry out the necessary manufacturing equipment changes and product re-qualifications. In view of this, we recommend a minimum 13.5 year derogation for flame retardant polycarbonate compounds for the production of thin walled parts, as follows: By way of derogation, paragraphs 1 and 2 shall not apply to: [xx] flame retardant polycarbonate for the production of thin walled parts until 13.5 years after EiF 5. Critical Safety Need for Flame Retardants in Electronics Statistics from several European countries reveal that electrical equipment account for 25 30% of all domestic fires, estimated in 273,000 fires per year. Fires can be generated by 7 Materials & Design 214 (2022): 110419 6 devices connected to the mains power, or battery powered devices. Lithium-ion batteries, in a fault condition, are also capable of overheating leading to ignition and subsequent explosion.8 Flame retardancy has been proven to work and continues to be a powerful tool in the overall efforts to prevent fire related injuries and save lives. One of the most important benefits of flame retardancy in product design is they can stop small ignition events from turning into larger fires. Even if ignited material with flame retardancy also delay the spread of fire to give people sufficient time to escape. For example in the EU, due to the introduction of increased fire safety standards -- the number of fire victims fell by more than 48% in France from 1982 to 2012, and by 56% in the UK from 1982 to 2013. Overall Europe has achieved substantial improvements in fire safety, with fire fatalities dropping by 65% over the last 30 years9. Since 2017, nearly different 500 types of electronic products have been recalled, withdrawn, or banned from sale in the EU due to fire hazards10. Other materials and components used in electronics are insufficient to prevent or delay the spread of fire from electronics. For example, protective components within electronics can reduce but not eliminate the risk of fire from electrical malfunction/failures. For example, a thermal fuse in a motor operated appliance will offer protection against an abnormal overload condition but it will not protect against other component failures like overheated power switches, connectors, wiring etc. Another example is current-limiting components such as circuit breakers that are triggered by current rather than voltage. Once they are triggered, current limiting devices restrict power from reaching the equipment being protected without having to dissipate that power as heat. Therefore, there is virtually no limit to the amount of energy that they can handle. However, current-limiting devices do not generally respond fast enough to protect equipment from fast transient overvoltage's generated by lightning or electrostatic discharge which can lead to a flashover/arcing. It is therefore essential to continue to guarantee the availability of PTFE and flame-retardant polycarbonate for the safety of electrical equipment on the European market until an effective and safe alternative can be found. 6. EU regulatory requirements for flame retardants Polycarbonate with flame retardancy is used especially in electrical and electronic equipment including IT applications, household appliances such as a hair dryer, adapters, charger, notebook computer, smart meters, lighting applications, and charging stations for electric vehicles. Polycarbonate is selected due to its unique combination of properties including fire retardancy, heat resistance, dimensional stability and impact resistance, which are critical to the ensure the safety of the final application (e.g., prevent electrical shocks). The European low voltage directive (2014/35/EU) sets safety requirements for electrical equipment within certain voltage limits. Those safety requirements are defined by the EN 60335-series standard, which includes stringent flammability requirements. Standards EN 60695-11-10 (test flames methods, ignition source with a nominal thermal power of 50 W) defines the burning classification of plastics materials. The flame behaviour of plastic materials is described as their ability to burn / extinguish and spread fire. V-0 materials are the highest flame-retardant class (most flame-retardant), offering the highest protection against fire hazard. Materials classified as V-0 shall not burn (burning stops within 10 seconds 9 Modern building alliance Europe: Fire Death Rate Trends: An International perspective 10 Safety Gate: the EU rapid alert system for dangerous non-food products 7 on a vertical specimen) and shall not spread fire (drips of particles are allowed as long as they are not inflamed). Materials classified as V-1 (the second highest flame-retardant class) shall stop burning within 30 seconds on a vertical specimen, and drips of particles shall not be inflamed. Similarly, according to standard EN 60695-11-20 (test flames methods, ignition source with a nominal thermal power of 500 W), to be rated 5VA, a material must stop burning within 60 seconds on a vertical specimen, no drips are allowed, and the plaque specimens may not develop a hole. 5VB rated materials must stop burning within 60 seconds on a vertical specimen, no drips are allowed, and the plaque specimens may develop a hole. In order to achieve compliance with those standards, flame retardant additives, to stop the burning, and anti-dripping additives, to prevent fire spreading, are included in the formulation of V-0, V-1, 5VA and 5VB rated materials. The role of PTFE in flame retardant polycarbonate is to prevent the formation of dripping particles, and therefore ultimately to prevent a fire from spreading. 7. Socio-economic impacts The Electrical and Electronics (E&E) sector represents the second largest market for polycarbonate in the EU. In 2015, 23 % (147,200 t) of the total polycarbonate consumption in the EU (ca. 640,000 t*) was used to make products in the E&E-sector. Polycarbonate helps manufacturers meet the need for continuously higher standards of appearance, sustainability and safety, and satisfying emerging regulatory and eco-design standards. In 2010, the total European E&E sector supported 26 million jobs and generated value added of 139 billion, of which polycarbonate applications made as substantial contribution. Together with applications in the domestic appliances/household sector which consumed 8% (51,200t), these two market sectors account for nearly one third of all polycarbonate consumption in the EU. Besides being the material of choice to meet the regulatory requirements in E&E sector, polycarbonate is also used in automotive, aircraft, railway, construction, and many other applications, due to its unique combination of characteristics. Please refer to the confidential Annex for additional information. 8. PFAS tonnages and releases from flame retardant polycarbonate Please refer to the confidential Annex for information on our uses. PTFE is `encapsulated' into the polymer matrix, and it is not expected to migrate or leach out of polycarbonate during service life of the products. Directive 2012/19/EU on Waste from Electrical and Electronic Equipment (WEEE) regulates the end of life of electrical and electronic equipment and sets targets for the separate collection and recovery and recycling of this equipment, and the proper treatment of residual un-recycled fractions. In view of this, it is not expected that PTFE used in polycarbonate will make significant contribution to the releases of PFAS in the environment. 8 Appendix 1: Literature review references and patent review references 1. Yan, C., Xu, B., Shan, D., Zhang, W., Xu, Y., Chen, Y., ... & Liu, L. (2023). Fabrication and mechanism research of high-efficiency water-resistant flame retardant, transparent and mechanically reinforced polycarbonate composites. Polymer Testing, 119, 107937. 2. Amirabadi, S., Kakroodi, A. R., Dias, O. A. T., Sain, M., & Park, C. B. (2022). Tailoring nanofibrillated polystyrene composite with enhanced fire retarding properties for foam applications. Materials & Design, 214, 110419. 3. Wu, X., Qin, Z., Zhang, W., Guo, X., Pan, Y. T., & Yang, R. (2020). Halogen-free and phosphorus-free flame-retarded polycarbonate using cyclic polyphenylsilsesquioxanes. Journal of Materials Science, 55, 10953-10967. 4. Song, W., Zhang, W., Li, Y., Ma, H., Lin, T., Lu, C., ... & Chen, Z. (2019). Construction of novel silicon-phosphorus linear polymers with DDSQ and DOPO derivatives for effective flame retardancy of PC/ABS. Fire and Materials, 43(6), 685-693. 5. Jiang, J., Wang, Y., Luo, Z., Qi, T., Qiao, Y., Zou, M., & Wang, B. (2019). Design and application of highly efficient flame retardants for polycarbonate combining the advantages of cyclotriphosphazene and silicone oil. Polymers, 11(7), 1155. 6. Gelmont, M., Yuzefovitch, M., Yoffe, D., Eden, E., & Levchik, S. (2020). Alkylation of aromatic compounds with pentabromobenzyl bromide and tetrabromoxylene dibromide as a new route to high molecular weight brominated flame retardants. Polymers, 12(2), 352. JP2020189942A JP2020111668A US20220112369A1 EP3858919A1 EP3858919A4 WO2020066535A1 CN112752797B CN112752797A JP06976453B2 TW202026359A JP07072589B2 JP2022147096A EP3247742B1 CN107207863B TWI691552B JP2020066710A CN111073248A JP2020189944A JP2022097753A WO2021233774A1 CN115516035A EP3560997A4 WO2022045616A1 KR2022028623A KR2200871B1 CN112480637A CN113278275A CN106398096A CN104693735A CN104710743A CN104710738A CN101134839B CN104693772A CN111019179A CN110591326A CN102863749A CN104672838A CN104629308A CN110093023A CN107828202A CN103772954A CN104845333A CN111286163A CN100346051C US7728059B2 CN103772949A CN103360735B CN104845315A CN105062031A NL197713813A JP2021024877A JP2022070453A WO2020100727A1 WO2022097449A1 CN112236478A JP2022066647A JP2021024878A WO2021020095A1 WO2021020094A1 JP2021024876A JP2022142246A US20210388140A1 EP4098691A1 WO2020004046A1 JP2021014478A JP2020105433A JP06904173B2 JP2022040551A JP2020203963A JP07174602B2 CN114656760A US20220325037A1 CN112745641B WO2021253771A1 JP07075317B2 JP07218085B2 HK40031529A US20200277491A1 CN114716812A CN115029833A KR2494931B1 CN112442072A CN111534885A IN202017020163A EP3480255A4 CN112300570B WO2020184270A1 WO2020184839A1 IL251442A KR2021089896A CN115182068A WO2021205938A1 IN345073B CN112480398A JP07181789B2 CN114196196A WO2022191078A1 CN112795183B CN114957977A CN113174089A 9 EP3733772A1 EP3733772A4 US20200283624A1 EP3733770A1 EP3733770A4 CN111615538A JP2021509125A US11124647B2 EP3564314A4 US10822493B2 CN109988406B JP2023012167A US11208553B2 CN112538252A CN112375359A CN104479319A CN103772921B CN102690507B CN111269548B CN103772946A CN106147192A CN114230891A CN107057319A CN109941068A CN103881332A CN107141718A CN111019314A CN103602051A CN103709708A CN104725820A CN105153662B CN104277440A CN104497523A CN104672846A CN204005729U KR1221690B1 JP2010059316A US20150322261A1 CN107868429A JP2014205591A WO2014088105A1 CN101875767B CN106084576A IT1166576B JP2017226767A US20120220709A1 CN108504069B US7687567B2 CN101619161B CN103772941B US9718956B2 KR1776990B1 US9056978B2 CN101875768B CN102675849A CN105542422A CN107177180A WO2021200841A1 JP6041415A CN206703482U CN113621150A CN113698750A WO2016175604A1 US9365720B2 CN113558356A WO2015008831A1 KR1990162B1 KR2017092143A CN101851407B CN107082586A JP2013103981A CN101538403A CN105694410B CN112876830A WO2022057204A1 US9969876B2 US5326793A EP2138291B1 CN104194284A CN213184308U CN105694205B CN102558699A CN105926068A CN105111706A JP5117513A US8557158B2 KR1622882B1 CN107793731A CN104650571A US4147707A CN105924736A US9688854B2 JP5279562A KR342105B1 US10100196B2 KR2297673B1 IN201617014927A CN103738046A JP2007077334A CN108148298A CN104861371A CN108148373A CN103205092A JP2008230949A JP2015224321A CN105504738A CN111764006A JP05040644B2 JP2000086854A JP2019199490A CN103302927A CN110128809A IN201202210P3 CN108610595A CN106009552A JP7258531A CN108659495B CN102604353B CN111484719A CN103408909B CN102850745A CN113429773A CN105949612A EP2252653B1 EP3700976B1 CN109020798B CN113549402B IN202227020510A CN104559107A CN109233111A CN105038178B KR2019078391A US7208542B2 RU159582U1 CN105086406B CN106633747A CN107892837B CN106867225A CN101875772B CN114350121A CN114369352A WO2021036614A1 CN113861654A EP4011977A1 CN114525026A CN102585476B CN110041668A CN110204880A CN105802181A CN104788929A US20140275366A1 CN106479148A CN104672849A CN104419180A TW202112962A CN107674399A CN213449132U EP2955201A1 CN107541037A CN104072965A CN104072964A CN105670288A CN104031373A CN104031371A 10 JP06239960B2 EP2597120A1 WO2020197132A1 JP2007114264A WO2015046441A1 EP1802696B1 JP06436768B2 CN106751652B CN105331025A RU152873U1 CN104647678A CN106336642A CN104629289A CN104650563A CN107118533A CN111040411A ZA198707297B CN108059810A CN104710754A FR3041283A3 KR2023015342A WO2021233773A1 CN115551945A KR2023014692A CN115362213A KR2022161299A US11352478B2 US20200010641A1 CN110402270B JP07109420B2 JP2021038298A JP2020037632A CN107075140B CN112189033A JP07069306B2 TW202006063A CN112708253A CN115703926A JP06837336B2 JP06836246B2 KR2204271B1 CN109486147B JP05365265B2 CN105060738B CN106189758B CN103571046A JP4006127A JP2012102287A JP3273052A CN106700470A CN107964237A CN210190791U JP04666459B2 GB2165253A CN101722635A JP9290482A GB2138826A KR1481217B1 EP2895555A1 EP2895556A1 CN108997656A JP04971544B2 WO2018050659A2 KR2014494B1 CN103408835B CN103214801B CN106995569A US4113692A CN101350261B CN111704792A CN103881346A DE2756925A1 CN113150527A JP2016084454A JP55019944B2 CN103589123A CN113372706A CN112812532A CN114479408A US10642071B2 CN106751642A CN109575554A JP54094556A FR2936831A1 CN104371293B WO2021036612A1 CN104672841A CN103265801B CN103342884B CN114316560A CN110684334B CN104341754A CN104356625A CN111607210A CN103408915B CN103709711A CN103740078A CN103408908A CN107868428A CN104119665A CN106633778A CN104672883A CN104650554A CN104497532A CN112980152A JP06663292B2 CN112724619A WO2022110663A1 CN112778731A EP694582A2 CN105820539A JP2019206650A WO2020054223A1 CN105713364A JP2002309076A KR2013089340A US20200086539A1 CN105694414A JP2008239940A US5807914A KR1159635B1 CN103254577A CN207106631U CN103724965A CN106995598A CN103013089B CN109749385A CN102898801A CN104962055A CN111117185A CN104419190A CN111875944A CN106893299A JP2018141047A CN105331075A CN104419172A CN108148386A CN104910601B CN103724963B CN103182818B CN106433065A CN104140662A CN111484722A CN104693763A CN106147121B US5175198A CN107278219B WO2020153330A1 BR112012005734A2 KR2244041B1 CN108559256B CN109306176B WO2022214754A1 TW202237744A CN114729186A WO2022158383A1 KR2023025383A WO2022077865A1 IN401832B WO2020243991A1 CN112457343A CN112375377A EP3530698B1 WO2021257531A1 WO2021134733A1 WO2021044880A1 CN113072807A CN113354867A 11 US20220267596A1 WO2021037705A1 CN111675891A WO2021228636A1 CN115461408A KR2023009892A KR2021106846A CN114736500A JP07011899B2 CN112778741B CN112778741A CN112824450A US20210171766A1 EP3733772B1 CN106393894A JP4089859A CN106810841A EP16058A1 TH165272A US20180291197A1 CN104693767A US8829086B2 KR1348534B1 WO2014115475A1 CN102658656A KR2015067740A CN107722587A US20140050815A1 CN101875770B CN104629288A KR2087405B1 CN107298837A CN102850753A CN102382440B CN102181139B JP06652332B2 CN111154246A US20020135161A1 CN202202478U CN105462223B CN103509219A CN103525060B JP05617245B2 US4048133A CN107400276A KR2164977B1 CN111471183A EP4069757A1 EP3564319A4 KR2499710B1 EP3858888A1 JP07093104B2 WO2022231250A1 CN114621586A CN214406735U CN107189098B KR2021047256A CN113150382A JP2020122098A 12