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JP4EE Annex 9 Unfeasibility of other possible substitutes in actual EEE - Review of "possible substitutes" in ChemSEC Guide As of 22 September 2023 Note: The applications of PFAS in EEE have not been investigated in the dossier in details, and possible alternatives described in the dossier is very few. We provided the results of our review for them as our Annex 2, "The unfeasibility of "possible substitutes" in the dossier in the actual EEE". (Reattached as sheet 2 of this excel.) On the other hand, as long as we know, the most collective available information on this matter would be "A guide to PFAS in electronics" by ChemSEC, and we suppose that ECHA may refer to it. However, from the point-of-view from the actual manufacturers of EEE, the listed "possible substitutes" seem to be (still) unfeasible to attain the EEE performances needed in current IT society. Therefore, we prepare this Annex for the legislators' reference. ChemSEC "A guide to PFAS in electronics" https://chemsec.org/reports/check-your-tech-a-guide-to-pfas-in-electronics/ Category of use Function performed Product(s) PFAS identified Contained in the product? Actively used? Electrical Devices Structure/low dielectric constant/insulation Printed Circuit Boards (PCB)/ Printed Wiring Board (PWB) 6:2 FTSA (27619-97-2) Perfluorooctane sulfonamid (754-91-6) PFOS (1763-23-1) PFBA (375-22-4) PTFE (9002-84-0) ethene,1,1,2,2-tetrafluoro-, polymer with 1,1'oxybis[ethene] (102646-47-9) Yes1,2 Confirmed3 Alternatives available? Yes Alternatives Identified Additional Comments FR-4 epoxy, Polyimide laminates, liquid crystal polymer, polyester, polyethylene naphthalate (PEN), bismaleimide triazine (BT), cyantate ester, ceramics 4 cyanate ester PFOS and PFOA are banned so considered unlikely to be still be used for this function. The alternative FR4 contains brominated flame retardants, which might lead to a case of regrettable substitution 62 Noted by industry 62 that for existing designs, PTFE cannot be easily substituted in PCB/PWB without a complete redesign of the equipment (including the mechanical dimensions of the product) and not feasible for spare parts. References 1,2,3,4, 62 Comments on ChemSec-Electronics-Guide All of the materials listed as alternatives have a high relative permittivity (square root proportional to transmission loss), and especially the dissipation factor (proportional to transmission loss) is very large, so it is not a substitute for high-frequency printed circuit boards. This difference in properties will have a significant impact on the social demand for reduced power consumption in the carbon-neutral era, as well as on the dramatic reduction of power consumption for the transmission of millimeter wave band mobile communications (5G/6G) and digital data communications in high-speed servers (224/448 Gbps) that are expected in the future. 6:2 FTSA (27619-97-2) Perfluorooctane sulfonamid (754-91-6) Electrical Devices Final Printed Circuit Boards (PCB)/ Printed Coating/protection/waterproofing Wiring Board (PWB) PFOS (1763-23-1) PFBA (375-22-4) PTFE (9002-84-0) Yes5 Confirmed6 Yes ethene,1,1,2,2-tetrafluoro-, polymer with 1,1'oxybis[ethene] (102646-47-9) Acrylic Resin, Epoxy, Urethane resin, silicone resin 7 The substances listed in the alternatives identified cannot be substituted for all applications. For example, epoxy resin is hard and cannot be used for flexible substrates. In addition, even if it can be used, urethane resin and acrylic resin are inferior to PFAS in moisture-proof, so it is necessary to increase the film thickness to obtain the necessary moisture-proof properties. Silicone resin cannot be used in the vicinity of relays, mechanical switches or membrane switches, where the silicone resin has a risk that siloxanes that deteriorate and release the silicone accumulate 5,6,7 omnaltfhuencctoionndudcuteiotnopcaornt taancdt fcaailuusree. conduction failure and may cause For details, please refer to the high-speed communication section of Annex 6, Smartphone and Protective Coat. Electrical Devices Electrical Devices Liquid impregnates Dielectric films Capacitors Capacitors Electrical Devices Electrical signal; Piezoelectrical material Acoustical Equipment Aliphatic perfluoroalkane (355-42-0) Perfluoromethylcycloalkane (1805-22-7, 255-02-2) Perfluoro-1,3-dimethylcycloalkane (355-27-3) Perfluorotrialkyl amine (311-89-7) Perfluorinated cyclic ethers (?) PTFE (9002-84-0) PVDF (24937-79-9) PVDF (24937-79-9) Copolymers with trifluoroethylene Electrical Devices Acoustic vent membranes Acoustical Equipment Not specified Electrical Devices Dipole moment LCDs(Liquid Crystal Displays) Fluoropolymers Yes1 Unconfirmed Yes Mineral oils, vegetable oils, silicone oils, and biodegradable synthetic oils.8 Various other polymers such as polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), PEN, polyphenyl sulfide (PPS), Yes8 Unconfirmed Yes polyester imides (PEI), polyethyleneterephthalate (PET), polybutyleneterephthalate (PBT), polyetheretherketone (PEEK), polyvinylchoride (PVC), polyimides (PI), polyamides (PA), and polymethylmethacrylate (PMMA) Piezoelectric films seem to all be made of PVDF, but there are other Yes1 Confirmed9 Yes piezoelectric materials that can be used depending on the application, such as ceramic piezoelectric materials or piezoelectric crystals10 We have no information. 1,8 We have no information. 1 1,9,10 Ceramics have been proposed as alternatives to piezoelectric elements, but they are fragile and limited in shape, making it difficult to form large areas. We cannot comment on PFAS or alternatives because there are no examples. Yes Unconfirmed No No alternatives identified Alternatives for moist protection do not seem to be available. REF for this one? Yes1,11 Unconfirmed Yes Can use other screen technologies instead of LCD OLEDs (organic light-emitting diode) cannot replace all LCDs. Compared to LCDs, OLEDs have some challenges to solve such as higher power consumption (contrary to energy saving), shorter life, and inability to repair (high cost). Therefore, it is impossible to replace the LCDs during the proposed five-year grace period. It took 20 years for OELDs to reach their current status, so we think that it will take at least 12 years to solve 1,11 such challenges and replace LCDs. Electrical Devices Protective coating LCDs(Liquid Crystal Displays) PCTFE (9002-83-9) Yes1 Unconfirmed Yes Can use other screen technologies instead of LCD We have no information. 1 Category of use Function performed Product(s) PFAS identified Contained in the product? Actively used? Alternatives available? Alternatives Identified Electrical Devices Electrical Insulation/dust repellent Flat panel display Tetrabutylphosphonium perfluorobutane sulfonate (220689-12-3) Tetrabutylphosphonium perfluoromethane sulfonate Yes1 Unconfirmed Yes Tetrabutylphosphonium perfluorohexane sulfonate (patent) Tetrabutylphosphonium perfluorooctane sulfonate Various other polymers such as polyester and polycarbonate Additional Comments References 1, 12, 13 Comments on ChemSec-Electronics-Guide In flat panel display materials, the required performance (optical properties) of the product can be satisfied by introducing fluorine atoms to the functional molecules in the material. Alternative substances must have the characteristics of "low surface tension", "high wettability to the base material", and "hydrophobicity" equivalent to fluorine, but no substitute substance has been found that satisfies these sufficiently. In addition, general-purpose polymers are listed as alternatives, but as described above, polymers alone cannot meet the required performance (optical properties) and some alternatives have fluorine introduced, so they are considered inappropriate as non-PFAS alternatives. Electrical Devices Electrical Devices Electrical Devices Electrical Devices Not specified Razors Not specified Coating Various (Switches, Vacuum cleaners, Coffee makers, Keyboards, Screens, TVs Electroluminescent lamps in commercial/safety signs Insulation/Fire prevention Wiring and cable insulation Electrical Devices Insultation / heat resistant Wiring and cable insulation Electrical Devices Insultation / heat resistant in combination with specific sensors Wiring and cable insulation Electrical Devices Insulation / chemical resistant Wiring and cable insulation Electrical Devices Electrical Devices Electrical Devices Electrical Devices High frequency electrical insulation Wiring and cable insulation Insulating spacers locate conductive components (Coaxial) cable High voltage insulator Connectors and other parts in submarine long distance telecommunication cable applications Additive in plastic resins (e.g. PC/ABS) Plastic Enclosures PTFE (9002-84-0) Not specified PCTFE (9002-83-9) PVDF-HFP copolymer (9011-17-0) FEP (25067-11-2) ETFE (68258-85-5) ECTFE (25101-45-5) PCTFE (9002-83-9) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) PTFE (9002-84-0) Yes1 Unconfirmed Uncertain Yes1 Yes1 Unconfirmed Unconfirmed Uncertain Uncertain Yes1 Confirmed15 Yes Yes62 Confirmed 62 Yes62 Yes62 Confirmed 62 Yes62 Yes62 Confirmed 62 No62 Yes62 Yes62 Yes62 Yes62 Confirmed 62 Uncertain62 Confirmed 62 Uncertain62 Confirmed 62 Uncertain62 Confirmed 62 Uncertain62 Electrical Devices V0 flame retardancy plastics Adapters, PSUs, wiring PTFE (9002-84-0) Yes62 Confirmed 62 Yes62 Unconfirmed Unconfirmed Unconfirmed Plastics (PVC, PE, PP, etc.) Rubbers (neoprene, silicone, etc) 16,17,18 Rubbers (neoprene, silicone, etc) Rubbers (neoprene, silicone, etc) No alternatives identified Unconfirmed Unconfirmed Unconfirmed Unconfirmed (Unspecified) BFRs, CFRs 62 PFAS are used for lubricity, durability, and antifouling requirements. 1,14 We have no information. 1,14 1 We have no information. Industry note that, in practice PVC is favoured for this use, so in fact PFAS could be used if PVC is not possible. Other materials mentioned as alternatives have some drawbacks 62. 1,15,16,17,18 Flame retardant cables used in harsh conditions must have very good fire resistance. PVC as a flame-retardant material is not satisfactory, and safety cannot be guaranteed at all with other PFAS alternatives. Industry association 62 note that rubbers have less mechanical strength and less abrasion resistance. Thicker insulation might be needed or additional mechanical support. Might lead to partial redesign to accomodate for the additional space required. Flame retardant cables used in harsh conditions must have very good fire resistance. PVC as a flame-retardant material is not satisfactory, and safety cannot be guaranteed at all with other PFAS alternatives. 62 Industry association 62 note that silicone insulation will lead to chemical deposition on the sensors, making them malfunction. Special sensors used in harsh conditions are required to be heat- resistant, chemical-resistant, and durable. Neoprene rubber has lower characteristics than PFAS. In addition, silicone rubber deteriorates and 62 separates siloxanes, which may cause conduction failure of the contacts. Industry association 62 note that no alternative available when chemical resistance is required. Insulated cables used in acidic or alkaline atmospheres and environments where chemicals come into contact are required to have excellent chemical resistance, and no material other than PFAS has been 62 identified that can ensure safety. Industry association 62 note thatPTFE has a very low dielectric constant. There is no comparable alternative. PTFE as an additive (3000-5000 ppm) in PC 62 ; Industry noted that in order for plastics to meet the V0 flame retardancy grade, it is required that there is suppression of dripping of any melted plastic as the plastic is heated. Only alternatives would be brominated or chlorinated flame retardants which are also restricted. No alternatives for high frequency electronic insulating materials have 62 been identified. In the insulated spacers in coaxial cables, PFAS alternatives cannot be 62 identified. No alternative to PFAS has been identified in high-voltage insulators used in connectors and other components for submarine long-distance 62 communication cable applications. 62 We have no information. Resins used in the housings of devices such as TVs and personal computers, and resins used around power supplies and heating elements in electrical parts may be required to be certified as flame retardant according to UL94 standards by law. In order to satisfy these standards, the addition of flame retardants is unavoidable, but especially for advanced resins of V-0 grade or higher, it is necessary to prevent the generation of burning particles that can ignite, and drip prevention is essential. When halogen flame retardants are regulated by law, and inorganic flame retardants and phosphate ester flame retardants may be used, inorganic flame retardants need to be added in large quantities to obtain a sufficient flame-retardant effect, resulting in impaired physical properties of the resin. On the other hand, phosphate ester flame retardants are limited to resins that are easy to exert effects (resins that are easily carbonized including oxygen) due to the flame-retardant expression mechanism (carbonization layer formation during combustion). Flame retardant resins 62 using phosphate ester flame retardants in polycarbonate and styrene resin alloys (PC/ABS) are widely used in home appliances and OA equipment, but because they are easy to drip due to the plasticizing effect of phosphate ester flame retardants. In order to achieve V-0, it is essential to add PTFE, which is an anti-drip agent (fibrillated fluoropolymer increases the melt tension of low-viscosity resins and has an anti-drip effect) as a flame retardant auxiliary. In addition, the addition of an anti-drip agent makes it possible to reduce flame retardants. Category of use Function performed Product(s) Electrical Devices Protective coatings (dirt, scratch, smudge resistance) Radiation Curable Coatings on Smartphones & other screens Electrical Devices Protective coatings (dirt, water, UV) Solar Panels PFAS identified PTFE (9002-84-0) PVDF (24937-79-9) Perfluoropoly-ether and polyurethane blend Contained in the product? Actively used? Alternatives available? Alternatives Identified Yes19 Unconfirmed Yes Silica-based coatings, Polymethylmethacrylate powder coating19 FEP (25067-11-2) ETFE (68258-85-5) FEVE (146915-43-7) Yes19 Unconfirmed Yes PETPCPolyamidesPS Titanium Dioxide nanoparticles19 Additional Comments References Comments on ChemSec-Electronics-Guide PFAS alternatives for antifouling coatings that satisfy solvent resistance have not been identified. 19 Durability, weather resistance, light resistance (especially UV resistance), and antifouling are important for the protective film of photovoltaic panels, but PET, PC, Polyamide, and PS are easily degraded by the ultraviolet light contained in sunlight, which shortens the life of the panel. TiO2 is 19 added to improve hydrophilicity, not an alternative. Electrical Devices Electrical Devices Electrical Devices Electrical Devices Electrical Devices Coating ICT equipment with imaging senors Not specified Yes62 Lubricant ICT equipment Not specified Yes62 Coating Touchscreen displays, camera glass, mousepads, backglass Not specified Yes62 Proton exchange membrane Fuel Cell Ethanesulfonic acid, 2-[1-[difluoro[(trifluoroethenyl)oxy]methyl]- 1,2,2,2,-tetrafluoroethyoxy-1,1,2,2-tetrafluoro-, polymer with tetrafluoroethene (31175-20-9) Yes20 PTFE (9002-84-0) Other proprietary polymers Binder Lithium Ion Batteries PVDF (24937-79-9) Yes22,23 Confirmed 62 Confirmed 62 Confirmed 62 Confirmed Confirmed24 We have no information. Industry association notes that use in coating to fill main ingress path to oleic acid and thus prevent glue failure at imaging sensor. Coating must be able to fill the gap by No62 No alternatives identified capillary action after jet dispensing. 62 Only potential alternative is Silicone but Silicone absorbs oil, is sticky, causes cross contamination and leads to adhesion loss of other components. 62 In ICT equipments, PFAS alternatives for dry coat cannot be used due to Lubrication/coating e.g. for Silicone O ring installation - e.g. to provide good corrosion resistance, low Coefficient corrosion and appearance problems. Also, PFAS alternatives for lubricants do not meet the required properties. of Friction <0.15, good adhesion to substrate, low surface roughness Ra < 0.6 um, harder than Polycarbonate to withstand 30K cycles of REL testing. Coating to fill main ingress path to oleic acid and thus prevent glue failure at No62 No alternatives identified imaging sensor. Coating must be able to fill the gap by 62 capillary action after jet dispensing. Industry association noted that all alternative dry coatings have been tested and failed for either corrosion or cosmetics. Alternative lubricants have been tested and do not meet performance requirements 62. Yes 62 Silicone-based coatings Low surface energy anti-finger printing and haptics enabling coatings Industry association62 note that silicone alternatives absorb oil, are sticky, and cross contamination leads to adhesion loss of other components. Silicone alternatives would create dysfunction in haptics - blocking transmission to sensors in touchscreens. Uncertain Hydrocarbon multi-block copolymer electrolyte membranes [multiblock copolymer poly(sulphonate phenylene)-b-poly(arylene ether ketone)] - under development. 20 Car industry argues that no replacements are available, since for example only PFSA ionomers have reached technological maturity for use in proton exchange membranes for these functions in the harsh environment of a fuel cell. 21 Maybe PI, PAA, CMC, SBR Many suggest that PVDF will soon be replaced with better performing and more environmentally friendly alternatives, but this appears to be largely at research stage.22,23 When a touch display or camera lens is coated with a silicone base alternatives it is not suitable for high-performance products because silicone base alternatives absorb oil, increase stickiness, which causes dysfunction of haptics (blocking transmission to touchscreen sensors) . 62 20, 21 PTFE is the only material that can withstand redox environments. For details, please refer to the comments of the organizations that handle the equipments. Please refer to the input from the battery industries, such as those from RECHARGE (Ref.No. 3925 in RCOM Part.2) or from Battery Association of Japan (BAJ) (Ref.No.4331 in RCOM part 14), for the concrete details. 22.23.24 Electrical Devices Electrolyte Lithium Ion Batteries Electrical Devices Cathode electrode binder material Lithium Batteries LiTFSI (90076-65-6) LiBETI (132843-44-8) LiFAPLiTFAB LiFSI (171611-11-3) LiTA PVDF and copolymers Yes25 Confirmed26 Yes Yes62 Confirmed 62 No LiPF6 is the standard electrolyte for lithium ion batteries, but more efficient PFAS compounds are being developed/implemented. No alternatives identified Industry association 62 consider that there is no alternative to PVDF for cathode electrode binder material. It is noted 62 that over the years many polymers have been tried and PVDF has consistently been found to be the best option to meet the performance and process requirements for binder material. Originally PVDF was used as the binder material for both anode and cathodes. More recently styrene-butadiene copolymer (SBR) was found to be a good alternative for the anode binder material. CMC is used together with SBR as a thickener to control slurry viscosity. CMC/SBR is now the most popular anode binder material due to its low cost and good cell performance. But SBR is not a good option for the cathode binder material as its double bound structure can be oxidized under cathode potential. Replacing PVDF with other polymers will likely cause cell performance and manufacturability issues. 25, 26 62 Please refer to the input from the battery industries, such as those from RECHARGE (Ref.No. 3925 in RCOM Part.2) or from Battery Association of Japan (BAJ) (Ref.No.4331 in RCOM part 14), for the concrete details. Please refer to the input from the battery industries, such as those from RECHARGE (Ref.No. 3925 in RCOM Part.2) or from Battery Association of Japan (BAJ) (Ref.No.4331 in RCOM part 14), for the concrete details. Category of use Function performed Product(s) Electrical Devices Battery separator material Lithium Batteries PFAS identified PVDF and copolymers Contained in the product? Actively used? Alternatives available? Yes62 Confirmed 62 No62 Alternatives Identified No alternatives identified Additional Comments References Comments on ChemSec-Electronics-Guide Please refer to the input from the battery industries, such as those from RECHARGE (Ref.No. 3925 in RCOM Part.2) or from Battery Association of Japan (BAJ) (Ref.No.4331 in RCOM part 14), for the concrete details. Industry association 62 consider that no alternative would result in similar performance of battery. 62 Electrical Devices Creation of important microporous structures Speaker modules Electrical Devices Gaskets Electronic circuits Expanded PTFE Yes62 Confirmed 62 No62 PTFE Yes62 Unconfirmed No62 Electrical Devices Low friction Moving parts, paper handling in printers PTFE Yes62 Confirmed 62 Yes 62 Electrical Devices Low friction - non-stick (e.g. prevent toner sticking) Moving parts e.g. in printers PTFE Yes62 Confirmed 62 No62 Electrical Devices Chemical resistance Printers: ink tubing, sealing, parts in contact with ink Fluoropolymers and fluoroelastomers Yes62 Confirmed 62 No62 Electrical Devices Lubrication Manufacture Chemical resistance, flexibility, sealing Lubricant Tubing, valves, sealing PTFE, PFHxA related substances PTFE, PVDF, fluoroelastomers Yes62 Confirmed 62 Yes 62 No (only used in factory, not in Confirmed 62 No62 electronic product) Manufacture Separation of high voltage components Dielectric Fluids (3MTM NovecTM 7100 Engineered Fluid 3MTM FluorinertTM Electronic Liquids) 1,1,1,2,2,3,4,5,5,5-decafluoropentane (138495-42-8) PTFE Yes1 Confirmed27 Yes No alternatives identified No alternatives identified We have no information. Expanded PTFE for speaker membrane. Industry association62 notes that PTFE has a unique ability to create important microporous structures that allow for proper air permeability and good water and dust-proofing. 62 Industry association 62 consider that using an alternative would result in loss of sound transmission quality and durability, There is no gasket material that is both solvent resistant and heat resistant other than PFAS. Industry association 62 notes that PTFE has unique quality to allow vapor and gas to pass through while preventing liquds from doing so which is required for applications in which venting is very important. This is important in many elecronic circuits that require venting without water 62 entering an enclosure and building up around circuits. Industry association 62 consider that using an alternative would not allow for water proofing simultaneous with gas permeability. Several other materials, depending on the specific use case. Industry association 62 notes that alternatives have to be investigated on case by case basis and there is no dropin replacement. Often a more comprehensive redesign is required. The low-friction properties of PTFE include not only a low coefficient of dynamic friction but also a low coefficient of static friction, as well as heat resistance, electrical insulation, flame retardancy, and chemical resistance. Replacing it with a substitute product causes an increase in power consumption due to an increase in sliding resistance, a 62 ddeetteerriioorraattiioonn iinn qduuireatbnielitsys., and a shortening of service life due to *Please refer to the input from the related industries, such as Japan Business Machine and Information System Industries Association (JBMIA), for the concrete details. No alternatives identified *Please refer to the input from the related industries, such as Japan Business Machine and Information System Industries Association (JBMIA), for the concrete details. 62 No alternatives identified Silicone lubricants No alternatives identified Natural and synthetic esters28,29,30 Industry association 62 consider that for chemcial resistance, there is no alternative Containers and tubes that can maintain the performance of the things contained inside must have multiple functions such as abrasion resistance, heat resistance, chemical resistance, and cleanliness, and such materials have not been confirmed except for PFAS. 62 *Please refer to the input from the related industries, such as Japan Business Machine and Information System Industries Association (JBMIA), for the concrete details. Industry association 62 consider that product redesign could be required due to chemical interactions between the alternative and the product. PFAS are very inert and alternatives might have unwanted interactions with the product Industry association 62 consider that for chemcial resistance, there is no alternative Silicone may be substituted in some applications, but in applications that are overused in harsh environments, silicone lubricants deteriorate and 62 pcorondtaucctes vaonldatuilensloawfe-musoele. cular siloxanes, resulting in poor electrical 62 27,28,29,30 -Alternatives tend to have a flash point, and the lower the viscosity, the lower the flash point. Therefore, when designated as a hazardous material, more caution is required in storage, transportation, and handling than before. In addition, the use of these products requires explosionproof equipment, which entails a huge investment. - Ester-based products deteriorate due to hydrolysis and require caution. Manufacture Manufacture Manufacture Manufacture Liquid burn-in testing Reliability testing Dielectric test media Galden PFPE Hermetic Seal Testing36, 3MTM FluorinertTM Electronic Liquids40 Perfluoroperhydrofluorene (307-08-4) PFPEs Perfluoroalkyl methyl ether (375-03-1) Methyl perfluoroalkyl ether (163702-07-6) Methyl perfluoroisoalkyl ether (163702-08-7) Thermal shock testing Galden PFPE Hermetic Seal Testing36, 3MTM FluorinertTM Electronic Liquids40 Perfluoroisohexane (355-04-4) Perfluoro-1,3-dimethylcycloalkane (355-27-3) Perfluoromethyldecalin (306-92-3) Perfluoroperhydrofluorene (307-08-4) Perfluorotetradecahydrophenanthrene (306-91-2) PFPEs Yes1 Unconfirmed Uncertain N/A Yes1 Unconfirmed Uncertain N/A Uncertain, see reference [32] for a list of compounds and Yes1 Confirmed31 their respective dielectric Use would need high dielectric breakdown strength, be non-flammable1 strengths that may meet manufacturing requirements Yes1 Confirmed33 Uncertain Use would need to be non-reactive1 1 1 PFAS is used because it is a low-dielectric and nonflammable material at the same time, but no alternative has been found. 1,31,32 1,32,33 PFAS is used because it is a material with low dielectric constant and stability at the same time, but no alternative to it has been found. Category of use Manufacture Function performed Gross and fine leak testing Product(s) Galden PFPE Hermetic Seal Testing36, 3MTM FluorinertTM Electronic Liquids40 Manufacture Electrical environmental testing 3MTM FluorinertTM Electronic Liquids 40 PFAS identified PFPEs Perfluorinated fluids Contained in the product? Actively used? Alternatives available? Yes1 Confirmed33 Uncertain Yes1 Confirmed31 Uncertain Alternatives Identified Use would need to be non-reactive1 Use would need to be non-reactive1 Manufacture Use for testing in general Perfluoromethylcycloalkane (355-02-2) Perfluoro-1,2-dimethylcycloalkane (306-98-9) Yes1 Unconfirmed Uncertain N/A Perfluoroperhydrofluoranthene (662-28-2) Manufacture Manufacture Manufacture Heat transfer fluids Heat transfer fluids Heat transfer fluids General heat transfer Total Immersion cooling Evaporative Cooling 1H-Perfluoroalkane (354-33-6) 1,1,2,2,-Tetrafluoroethane (359-35-3) 1,1,2,2-tetrafluoro-ethene, oxidized, polymd., reduced, decaroxylated (161075-02-1) Methyl perfluoroalkyl ether (375-03-1) Ethyl perfluoroisoalkyl ether (297730-93-9) Aliphatic perfluoroalkane (76-19-7) 1,1,1,2,2,3,4,5,5,5-decafluoropentane (138495-42-8) Various proprietary blends on the market that claim to be Yes1 Confirmed35 Yes environmentally friendly; based on "ester chemistry" and others, and generally said to be biodegradable and often halogen free36,37,38,39 Yes1 Confirmed Yes Yes1 Confirmed Yes See row for "General Heat Transfer" See row for "General Heat Transfer" Manufacture Heat transfer fluids Brine Cooling 1,1,1,2,2,3,4,5,5,5-decafluoropentane (138495-42-8) Methyl perfluoroalkyl ether (163702-07-6) Methylperfluoroisoalkyl ether (163702-08-7) Ethyl perfluoroalkyl ether (163702-05-4) Perfluoroindane (374-80-1) Yes1 Confirmed Yes See row for "General Heat Transfer" Manufacture Heat transfer fluids Direct contact cooling Aliphatic perfluoroalkane (335-57-9) 1H-perfluoroalkane (354-33-6) 1,1,2,2,-tetrafluoroethane (359-35-3) Perfluoroisohexane (355-04-4) Perfluoro-2-methyl-3-ethylpentane (354-97-2) Perfluoro-2,4-dimethyl-3-ethylpentane (50285-18-2) Perfluoromethylcycloalkane (1805-22-7) (355-02-2) Perfluoro-1,2-dimethylcycloalkane (306-98-9) Perfluoro-1,3-dimethylcycloalkane (335-27-3) Perfluorodecalin (306-94-5) Perfluoromethyldecalin (306-92-3) Perfluoroperhydrofluorene (307-08-4) Perfluorotetradecahydrophenanthrene (306-91-2) Perfluoroperhydrofluoranthene (662-28-2) Perfluoroperhydrobenzyltetralin (116265-66-8) Yes1 Confirmed Yes See row for "General Heat Transfer" Additional Comments References 1,31,33,34 Comments on ChemSec-Electronics-Guide There is no alternative that is non-flammable, insulating, low-viscosity, inert, low erosive and moderately volatile. It is required to be non-flammable and must contain a certain amount of fluorine. Since alternative products are not nonflammable, using them 1,31 requires investment in explosion-proof equipment. Solvents for thermostatic chambers that measure the temperature characteristics of electronic components with ultra-high accuracy must be non-flammable, insulating, low-viscosity, inert, low-erosive, and highly 1 thermally conductive, and have moderate volatility, and there is no alternative. It must have high volume resistivity, low viscosity, and prevent moisture content from increasing during use. In addition, it must be nonflammable unless it is used in an explosion-proof facility, which requires a huge 1,35,36,37,38,39 iEnsvteesrt-mbaesnet.d products require attention because of degradation due to hydrolysis. See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" See row for "General Heat Transfer" Manufacture Cleaning 3,3,4,4,5,5,6,6,-octafluoro-1-Hexene (159148-08-0) 3,3,4,5,5,5-hexafluoro-1-Pentene (2375-68-0) 1,1,1,2,3,4,5,5,5-nonafluoro-2-(trifluoromethyl)-Pentane (85720- 78-1) 1,1,1,2,2,3,4,5,5,5,-decafluoro-Pentane (138495-42-8) Solvent Systems and Cleaning Methyl perfluoroalkyl ether (22410-44-2), (375-03-1), (163702-076) Yes1 Products Methyl perfluoroisoalkyl ether (22052-84-2) Methyl perfluoroisobutyl ether (163702-08-7) Ethyl perfluoroalkyl ether (163702-05-4) Ethyl perfluoroisobutyl ether (163702-06-5) 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)-ethane (406-78-0) Aliphatic non-branched perfluoroalkanes (76-19-7) Manufacture Carrier fluid/lubricant deposition Carrier fluid/lubricant deposition Perfluoroisohexane (355-04-4) 1,1,1,2,2,3,4,5,5,5-decafluoro-Pentane (138495-42-8) Yes1 Manufacture Etching Piezoelectric ceramic filters PFOS (1763-23-1) No1 Manufacture Pulsed plasma nano-coating Smartphones and Tablets PFOA (335-67-1) Yes1,46 Manufacture Haptics enabling coating Smartphones and Tablets - Yes Confirmed40 Yes Confirmed42 Yes Unconfirmed44 Yes Confirmed47 Yes Unconfirmed Uncertain IPA, Other alcohol cleaners without PFAS added Products listed on Green-Screen website41 When cleaning, low surface tension is required, as well as nonflammability unless the equipment is explosion-proof, which entails a huge investment. 1,40,41 Honeywell fluorinated (but not perfluorinated) Solstice solvents43 1,42,43 It is required to be nonflammable and must contain a certain amount of fluorine. Since the alternatives are not non-flammable, using them requires explosion-proof equipment, which entails a huge investment. Fluoroboric acid45 Epoxy, urethane, acrylic, silicone, paralyne47 PFAS-free nanocoatings48 For touchscreens, which needs haptics enabling coatings, good alternatives are currently lacking. Industry association 62 note that PFOS and PFOA are banned. Unlikely to be still in use 1,44,45, 62 Industry association 62 note that PFOS and PFOA are banned. Unlikely to be still in use There are other types of coatings used in the industry for the same purpose: evaporative curing, moisture curing and heat curing. Examples of non-fluorinated radiation curable coatings are silica-based coatings and polymethylmethacrylate powder. 1,46,47,48, 62 Category of use Manufacture Function performed Air/moisture resistance Product(s) General electronic equipment packaging Semiconductors Photolithography Semiconductors Photoresist matrix, changes solubility when exposed to light Photoresist PFAS identified PCTFE (9002-83-9) PFOA (335-67-1) PFOS (1763-23-1) Perfluoropolymers PFOA (335-67-1) PFOS (1763-23-1) PFHxS (alternative to PFOS/PFOA) [28,29,30] Contained in the product? Actively used? Yes1 Confirmed49 Alternatives available? Yes Alternatives Identified Other moisture and vapor-barrier packaging, such as mylar and a mixture of aluminium foil and various non-fluorine-containing polymers50 Additional Comments Yes Unconfirmed 51 Potentially hydrocarbon-based grepahsoetos,litMhooglyrbadpehnyu) m52 disulfide, graphite (for PFOA and PFOS have been largely phased out References 1,49,50 51, 52 Comments on ChemSec-Electronics-Guide Since aluminum foil does not allow the user to see the parts in the package, fluorine film can only be used where moisture-proofing and transparency are required at the same time. PFOS and PFOA have already been eliminated in Japan, and PFOS and PFOA are not used as identified PFAS (we agree with Additional Comments), but they are used as PFAS. Also, 'Contained in the product? (Column E)' is Yes. As with antireflection films, the resist used in the front-end process does not remain in the final semiconductor product. In other applications, current semiconductor technology uses photoresist in many applications to provide properties by leaving a variety of products in the final semiconductor product. In this case, the PFAS remains in the final semiconductor product. The authorities should review the materials of "Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/" in detail. Hydrocarbon greases, molybdenum disulfide, and graphite (for photolithography) already use carbon films as mask materials, but lithography is essential for patterning mask materials, and resist materials are still needed. KrF (248nm) (active ingredient not disclosed) 53 DOWTM photo-resists (non-PFOS) Yes Confirmed Yes composed of solvents, acrylic, other polymer resins, cross-linking agents, stabilizers and/or surfactants Alternatives should containt fluorine PFOS has been largely phased out 53,54,55,56 KrF resists and DOWTM photo-resists (non-PFOS), which are listed as alternative resists, are of limited use and do not cover all resists with different exposure wavelengths. If non-PFOS is used, PFOS is excluded under the Stockholm Convention, and the resists currently used in Japan are already PFOS-free but not PFAS-free. Photoresist requires several actions such as photoacid generation as well as surface activity, and the authorities only mention some of them, so the difficulty of replacing nonPFAS is clearly underestimated. The authorities should review the materials of "Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/" in detail. It is stated that the replacement of photo-oxidants will take more than 25 years. Semiconductors Increase the photosensitivity of the photoresist Photoresist (photosensitizer) PFOA (335-67-1) PFOS (1763-23-1) Yes Unconfirmed No N/A Semiconductors Generate strong acids by light irradiation Photoresist (Photo-acid generator, PAG) PFOA (335-67-1) PFOS (1763-23-1) Shorter-chain PFAS (PFBS) functionalized fluoroethanesulfonates Aromatic PAGs identified in patents ( WO2009091704) None currently Heteroaromatic PAGs identifed in patents (WO2009091702, (patents US20110183259).Triphenylsulfoniumbenzo[b]thiophene-2-sulfonic Yes Confirmed filed/fluorine free acid, 4(or 7)-nitro-,ion(1-) (TPS TBNO) is identified alternatives have Glodde et al. have proposed a Fluorine free PAG in their 2010 been proposed) publication. Functionally need to generate strong acids Semiconductors Controlling the diffusion of the acid to unexposed region Photoresist (Quencher) Semiconductors Provide low reflectivity Antireflective coating PFOA (335-67-1) PFOS (1763-23-1) PFOA (335-67-1) PFOS (1763-23-1) PFHxS (alternative to PFOS/PFOA, 355-46-4) Yes Unconfirmed Uncertain N/A It is noted the FP coating is not present in the final chip and is spun out and goes to waste/destroyed in the etching process Confirmed -AZ Aquatar 8 (Fluoroalkyl acid ester, homopolymer, hydrolyzed, 67829000004-6092P)[2] -DOWTM anti-reflect (non-PFOS), composed of solvents, acrylic, other Yes polymer resins, cross-linking agents, stabilizers and/or surfactants -FP with a short fluoroalkyl side chain less than C4 -Alternatives should containt fluorine; functionally require low refractive index Semiconductors Facilitate the control of the development process Developer PFOA (335-67-1) PFOS (1763-23-1) Shorter-chain PFAS used as alternatives to PFOA/PFOS Yes Confirmed Uncertain Patent US20080299487 fdoer sucnrfilbueodri.nated surfactant, vaguely Semiconductors Rinsing the photoresist to remove the developer Rinsing Solution Unknown Uncertain Unconfirmed Uncertain Semiconductors Etching PFOA (335-67-1) No (at least there shouldn't be, its PFOS (1763-23-1) reported that Confirmed Yes 3MTM FluorinertTM Electronic Liquids short-chain perfluoroalkyl sulfonates are alternatives in use today PFAS is captured in the waste/it's a closed system) Semiconductors Etching Wetting agent Semiconductors Etching Reduce the reflection of the etching solution Semiconductors Etching agent in dry etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching See General etching Use would require low surface tension Amyl acetate (628-63-7)Anisole (100-66-3) n-Butyl acetate (123-86-4)Ethyl lactate (97-64-3) Propylene glycol methyl ether acetate (108-65-6) Methyl-3-methoxypropionate (3852-09-3) non PFOS-based surfactants are in use for etching application for etching agents with ceramic filters (WSC 2011), Use would require low surface tension Use would require low refractive index Use would require Strong acids PFOS has been largely phased out PFOS has been largely phased out PFOS has been largely phased out PFOS has been largely phased out 57,58 From "SIA PFAS Consortium"page38 https://www.semiconductors.org/pfas/ The authorities need to consider all the material at this URL. "non-PFAS PAGs (CN5 and thiophene sulphonate), which has highlighted the difficulty of developing formulations that meet all performance criteria simultaneously, as shown in Table 4-4. As such, non-PFAS PAGs are for a narrow range of use applications only, as no known non-PFAS PAG/photoacid exhibits the same level of performance for all criteria. While a candidate chemistry might show good acid strength, it will have lower photospeed because of lower acid diffusivity, and at the same time the acid anion might be transparent for a single wavelength only. PFAS PAGs, on the other hand, present simultaneously good to excellent performance for all listed performance criteria with the notable exception of environmental persistence." 19,59 The materials listed in column D has already been published in the Stockholm Convention. Column G is substituted for "present" and column H is substituted for "FP with a short fluoroalkyl side chain less than C4." This indicates that there is no substitute for all applications of semiconductors. The applications are diverse, and it is very dangerous to understand that there is one substitute for all alternatives. The authorities themselves describe FPs whose substitutions eventually have short fluoroalkyl side chains less than C4. Contained in the product? is Yes,but like an antireflection film, no developer remains in the final semiconductor. But, the opinion that "photoresist used in semiconductor manufacturing does not remain in the product" is decades old, and current semiconductor technology uses photoresist in many applications to provide properties by leaving a variety of products in the final product. In this case, the PFAS remains in the final 57 stheamt itchoenPduFcAtSorrpermodauincst.inInthseomfineaal pspelmiciactoionndsu,cittosrhporuolddubcet. eAmutphhoaristiiezesd should review the materials of the Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/ in detail. 57 It seems that the description of equipment coolant is urged from row C, but since PFOS and PFOA are neither etchant nor coolant, it is strange in a double sense. The authorities do not understand the dry etching process of semiconductors. 60 The authorities should review the materials of "Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/" in detail. See row for "General etching" See row for "General etching" The main dry etch is PFC, and those indicated by "PFAS identified" are See row for not used. "Alternatives Identified" are also completely wrong. "General etching" Category of use Function performed Product(s) PFAS identified Contained in the product? Actively used? Alternatives available? Alternatives Identified Additional Comments Semiconductors Etch Cleaning of Silicon Wafers General etching PFOA (335-67-1) PFOS (1763-23-1) PFBS (375-73-5) PFNA (375-95-1) PFHxA(307-24-4) Patent EP 3 588 535 A1 details several surfactants including PFAS and No Unconfirmed (patented) 1 Uncertain non-fluorosurfactants which may be alternatives1 Use would require Strong acids 35 Semiconductors Semiconductors Remove cured epoxy resins/Cleaning of integrated circuit modules Remove dielectric film build up Cleaning vapour deposition chamber Semiconductors Semiconductors Semiconductors Non-stick coating composition on carrier wafer working fluid polymeric PFAS used in inert moulds, pipes, elastomers Wafer thinning Vacuum pumps Technical equipment in contact with process chemical or reactive plasma Unknown Unknown PFOA (335-67-1), PFOS (1763-23-1) likely if used, but unconfirmed Perfluoroalkoxy alkanes (PFA) fluoropolymers Polymeric PFAS Semiconductors Bonding ply composition Multilayer circuit board PFOA (335-67-1), PFOS (1763-23-1) likely if used, but unconfirmed Uncertain Uncertain Uncertain Uncertain Uncertain Unconfirmed Unconfirmed Unconfirmed (patented) 1 Unconfirmed Unconfirmed Uncertain Uncertain Uncertain Uncertain Uncertain N/A Use would require reactive oxygen species (ROS) generation1 Use would require low surface tension1 Use would require alternative be stable, non-reactive1 Use would require alternative be stable, non-reactive1 Uncertain Unconfirmed (patented) 1 Uncertain Use would require low dielectric constant, low dissipation factor1 Semiconductors Vapor Phase Soldering Galden LS and HS grades (LS/HS) 36 PFPEs Yes Confirmed Uncertain References 1, 61 Comments on ChemSec-Electronics-Guide Perfluoroalkyl acids such as PFOA and PFOS (which are already substances subject to the Stockholm Convention) are not used for "etch cleaning of silicon wafer". This usage information for PFOA and PFOS is incorrect. Therefore, the description of line H is completely wrong. It can be guessed from the document of the authority that the description is about photo-oxidizer, but it seems that the answer is not about wafer etching but about photoresist. In addition, the description of the patent is found on the whole, but for this technology to be established as a substitute, many tests and quality assurance are required for mass production. In the end, there are many patents that are not used because the test and quality assurance cannot be satisfied and cannot be applied to mass production. By listing the patent number, authorities that provide alternative cases underestimate the difficulty of substitution. Authorities should review the Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/ document in detail. 1 PFOA and PFOS subject to the Stockholm Convention are described in 1 Wafer thinning, but the meaning of this description is not understood. 1 1 PFOA and PFOS subject to the Stockholm Convention are described, but the meaning of this description is not understood. 1 "Authorities should review the Semiconductor PFAS Consortium https://www.semiconductors.org/pfas/ document in detail. Alternative materials that do not affect the substrate by soldering with high temperature reflow need to be developed. Authorities should review the Semiconductor PFAS Consortium 33 https://www.semiconductors.org/pfas/ document in detail. Alternatives listed in PFAS Annex E and reasons for non-replace Note: This sheet was originally provided as Annex 2 to our previous input, "The unfeasibility of "possible subs EEE", in 13 June 2023. We attach it here again for your convenience. Application PFAS a) Sealing fluoroelastomers b) Wire insulation PTFE, PFA, ETFE, FEP, FEPM, PFPE c) Immersion cooling Heat transfer fluid d) liquid crystal displays (LCD) Hydrofluoroethers Fluorinated amines -CF3 group reasons for non-replacement nput, "The unfeasibility of "possible substitutes" in the dossier in the actual e. Non-PFAS alternatives Ethylene propylene diene monomer (EPDM) silicone rubbers Silicone materials Polyetheretherketone(PEEK) mica EPDM Polyvinyl chloride ceramic based polymer Mineral oils synthetic oils natural oils Hydrocarbon fluids Cyano (-CN) group Reasons why PFAS cannot be replaced by non-PFAS In sealing material applications (e.g. packing), heat resistance, solvent resistance and low gas permeability are important, and EPDM and silicone rubber provide low or medium durability but not enough property, so they cannot replace all applications and fluorinated materials must be used. In cable insulation materials, mechanical, thermal, volume resistance and electrical properties are important, and the alternatives listed as alternatives have low resistance to any of these properties and cannot replace them in applications where they need to be met simultaneously, and fluorinated materials need to be used. For example, silicone has low resistance to mechanical properties (susceptible to tearing/abrasion), PEEK has low electrical properties, mica is hard and not suitable as a cable, etc. Compared to fluorinated materials (liquids), the viscosities of all alternative oils are considerably higher and it is difficult to circulate them and maintain a constant temperature. In addition, the flash point is considerably lower, and significant equipment modifications are required to ensure safety. For liquid crystal molecules, low viscosity, high resistance, low dielectric anisotropy and low birefringence are important, and replacing a liquid crystal molecule with a CF3 group with a cyano group will result in a deterioration in all of these properties and cause adverse effects such as slow response speed and unsmooth display, and high voltage drive and high energy consumption.