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HALOGEN-FREE LAMINATES – SHOULD THE INDUSTRY CHANGE?

HALOGEN-FREE LAMINATES – SHOULD THE INDUSTRY CHANGE?. David W. Bergman, IPC VP Standards, Technology & International Relations November, 2004. Why Use Flame Retardants?. The major human health hazard is fire itself, not which materials are burning Flame retardants must balance: Health

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HALOGEN-FREE LAMINATES – SHOULD THE INDUSTRY CHANGE?

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  1. HALOGEN-FREE LAMINATES – SHOULD THE INDUSTRY CHANGE? David W. Bergman, IPC VP Standards, Technology & International Relations November, 2004

  2. Why Use Flame Retardants? • The major human health hazard is fire itself, not which materials are burning • Flame retardants must balance: • Health • Environment • Performance • Cost

  3. Why Use Flame Retardants • Proper Flame Retardants: • Retard ignition • Delay or eliminate flashover • Reduce heat concentration • Reduce evolution of toxic gases • Increase time for escape

  4. Fires Still Take A Frightening Toll • 1995 data shows an annual worldwide death rate of 11,500 lives due to fires. • 1994 data shows the United States’ costs for both prevention plus fire loss to be $135 billion • 1994 data shows United States lost $30 million due to electronic fires alone (1000+ fires)

  5. BFR Use in Electrical and Electronic Equipment • Brominated Flame Retardants (BFRs) are a family of 75 chemical substances with different properties, characteristics, and performance. • Only common point: all contain bromine – an element that is available in nature. • BFRs are added to plastics used in electrical and electronic equipment (EEE) to slow down or prevent the ignition of fire

  6. Legislation - EU Restriction of Use of Hazardous Substances (RoHS) • Bans PBBs • Bans octa-PBDE and penta-PBDE • Calls for a Risk Assessment of Deca-PBDE, followed by ban assessment • Does not call for study or restriction of TBBPA • PBBs, certain PBDEs • Effective July 1, 2006

  7. Legislation – United States • USEPA does require TBBPA to be reported per Toxic Release Inventory (TRI) • PCB fabricators do not report since TBBPA is reacted into resins • Laminators do not need to report if: • Resins MSDSs do not list TBBPA, or used or process more than 100 pounds of TBBPA is in a year

  8. Legislation – United States • Maine • California • Hawaii

  9. PBBs (Polybrominated Biphenyls) • Found to be persistent, bioaccumulative toxins • Classified possible carcinogens • Most production of PBBs ceased in the 1970s. • Major manufacturers prohibit their use • Result: rarely found in EEE manufactured today

  10. Penta- and Octa- Brominated Diphenyl Ethers (BDEs) • Considered possible endocrine disruptors • Banned in many jurisdictions beginning in 2006 • The chemical industry has voluntarily agreed to stop production of these BFRs in the US by 2004. • Major manufacturers prohibit their use • Result: rarely found in EEE manufactured today

  11. Deca-Brominated Diphenyl Ethers • Deca-BDE is still used as a flame retardant in some plastic housings, particularly in TVs • The use of Deca-BDE is not currently banned in any country. • A recently EU risk assessment concluded that the chemical presents an acceptably low risk to the environment. • To address continuing concerns regarding Deca-BDE persistence and bioaccumulation, the chemical industry will be developing voluntary risk reduction and monitoring strategies.

  12. Tetrabromobisphenol-A (TBBPA) • TBBPA is the leading flame retardant used in circuit boards (95%) and computer chip casings • TBBPA reacts into resin chemistries, not only epoxies. • TBBPA is very effective in low addition levels • Data shows TBBPA is not harmful to health or environment • TBBPA is used because it is cost effective, compatible with circuit board components, and qualified for use on a worldwide basis.

  13. Scientific Studies of TBBPA • The use of TBBPA is not restricted in any country. • The World Health Organization conducted a scientific assessment of TBBPA and found that the “risk for the general population is considered to be insignificant.” • Six separate studies published between 1990 and 1997 support the conclusion that the manufacture, use and disposal of information technology devices containing TBBPA-flame retarded printed circuit boards do not increase human dioxin exposure. • The EU is currently conducting a risk assessment for TBBPA. In October 2003, UK Rapporteur confirmed no health effects of concern for TBBPA. • US National Toxicology Program is currently studying TBBPA

  14. Non-Halogenated Flame Retardants Are Used • Inorganics such as metal oxides and hydroxides, phosphates, and red phosphorus • Essentially fillers (non-reactive) in polymers • Difficult to incorporate • Require high loading to be effective • Organo-phosphors and phosphate esters • This family makes up 20% of all flame retardants • Organo-nitrogen compounds • Very limited use with polymers

  15. Assessment of BFR Alternatives • Lifecycle impacts are key! • Design, Use, and End-of-Life • Is alternative truly better for the environment? • Can it meet same technical and functionality requirements? • Are the alternatives compatible with higher lead-free processing temperatures? • Will it decrease product safety or reliability? • What are the tradeoffs?

  16. Trade-offs of BFR Alternatives in Circuit Boards Source: HDP User Group, International Inc.

  17. Dioxins and Furans • Halogenated aromatics having “similar chemical structures, similar physical-chemical properties and involve a common battery of toxic responses” (USEPA) to 2,3,7,8 Tetrachlorodibenzo Dioxin (TCCD) • Expanded family of dioxins and furans includes Br and Cl species • Formed at low levels during any hydrocarbon combustion where chlorine is present • Of the expanded family, only TCCD is listed as a human carcinogen

  18. Environmental Issues • Furans and dioxins are Backyard barrel burning releases 52 times amount of dioxin compared to municipal incineration. • Residential wood burning releases 5x more dioxin than municipal incineration • Worldwide levels of furans and dioxins are declining due to reduced combustion emissions and changes in bleaching chemistries.

  19. Environmental Issues • TBBPA shows no detectable formation of furans or dioxins: • As pure TBBPA in raw state • During and after 300c stress • After pyrolysis in raw state or reacted into epoxy resins

  20. Environmental Issues • Data shows no effects to air or water with TBBPA and non-brominated FRs • Proper incineration (>800C) of halogenated FRs does not generate furans or dioxins. • From firefighter data, levels of furans and dioxins generated in accidental fires are not a health concern

  21. World Health Organization, Geneva Reports • TBBPA is not acutely nor sub-chronic toxic to mammals • Dermal, oral, and inhalation exposures were evaluated • TBBPA is non-teratogenic to embryos

  22. Additional Information From World Health Organization • TBBPA is rapidly eliminated from mammals • From tissues, blood, digestive tract • No long-term toxicity • Does not accumulate in fat or other tissues • TBBPA is rapidly eliminated from aquatic vertebrates • Continuous exposure for 4 days brought steady-levels • Essentially zero levels in 6 days after introduction ceased • No apparent accumulation in any tissues

  23. What about UBA Document • German Report : “Substituting Environmentally Relevant Flame Retardants: Assessment Fundamentals” • Indicates further use of TBBA cannot be recommended since TBBA has found a way into the food chain. • This report has driven some Japanese positions

  24. BSEF Comments to UBA Document • BSEF – organization of manufacturers of brominated products. • Claims report provided no evidence of TBBPA being a component of food chain nor of high toxicity. • The document fails to assess the degree of hazard or risk represented by the information cited • Comprehensive rebuttal comments available

  25. Recycling and Reclamation • European Studies • 10,000 tons of bromine available annually within the EU • From waste electrical and electronic equipment (WEEE) • Four recovery studies in Europe • Each shows an efficiency of 90% • Recovery is economically feasible

  26. “Halogen-Free” Is Marketing Driven • OEMs in Japan and Europe began “environmental friendly” campaigns with “lead-free” • OEMs now pushing “halogen-free” with their supply chains • OEMs now threaten cut-off of suppliers who fail to comply

  27. Non-Brominated Epoxy Resins are Not “Halogen-Free” • Most PCB Resins are Epoxies • Epoxy resins contain measurable levels of Chlorine (Sapponofiable, Hydrolyzable and fixed Chlorides) • Additional halogens are added to PCB laminates through glass sizes, wetting agents, curing agents and resin accelerators.

  28. Availability & Performance of Alternative • Loss tangent of some bromine free laminates is lower than standard FR-4, resulting in improved electrical/RF performance • Some bromine free laminates exhibit significantly improved z-direction CTE over FR-4, resulting in improved PTH reliability • Bromine free laminates are compatible with high temperature re-flows required for no-lead solders • Volume use of the new material is required to achieve cost parity with best-in-class FR4

  29. Toshiba Chemical Corporation Environment Friendly Laminate Halogen-Free and Antimony-Free Glass Epoxy Copper Clad Laminate TLC-555/Single side, TLC-W-555/Double Side NEMA : FR-4, JIS : GE4F *Halogen-Free Type *Antimony-Free Type *Flammability Class UL94 V-0 *Low Smoking Nature *Easy Waste Disposal *Higher Glass Transition Temperature(Tg) : 170-180C (DMA) *Excellent Peel Strength for Long Term Aging *UL Approval

  30. MarketingEcolabels • Awarded products that meet specific environmental requirements • France • Canada • US • EU • Germany • Nordic Swan • Japan • Netherlands • Enable consumers to know they are buying products that are environmentally sound • Manufacturers use them as marketing tool

  31. Future BFR Use in the Electronic Industries • The production of PBB, penta BDE and Octa BDE has stopped or will stop by 2004. • Existing risk assessments do not demonstrate a public health or environmental concern from Deca-BDE or TBBPA. • Any mandated restrictions on Deca-BDE or TBBPA could cost lives and increase property damage by restricting the industry’s use of effective flame retardants. • BFR restrictions should not apply to recycled plastic resins. • Industry will voluntarily continue to look for alternatives to BFRs.

  32. Industry status & Issues • Most manufacturers have offerings • UL approvals completed • Little to no US sales. • Very little beta site testing • Both 135 and 170 Tg systems

  33. Test Methods For Halogens • IPC • IEC 61189-2C12 below will be submitted to test methods committee in May 2002. • IEC • IEC 61189-2C12 is test method number. • USA industry experts consider this test valid. • Involves combustion and capture. • Ion chromatography. • Determines both chlorine and bromine. • Test method being submitted for participating country approval.

  34. Requirements For Halogens IPC IPC-4101A (published date 12/21/2001) referenceshalogen requirements in paragraph 3.10.1.9 and on the appropriate slash sheets as TBD. IEC • Finalized requirements of IEC 61249-2-21: • 900 ppm maximum chlorine • 900 ppm maximum bromine • 1500 ppm maximum total halogens.

  35. Documents For Halogen Free IPC: • IPC-4101A/92 Tg 110 – 150 Phosphorus • IPC-4101A/93 Tg 110 – 150 ATH • IPC-4101A/94 Tg 150 – 200 Phosphorus • IPC-4101A/95 Tg 150 – 200 ATH IEC: • 61249-2-21 Tg 120 minimum laminate • 61249-2-22 Tg 150 – 190 laminate • 61249-4-11 Tg 120 minimum prepreg • 61249-4-12 Tg 150 – 190 prepreg

  36. Failure Warning: Components Packaged with Phosphorus-Containing Molding Compound • CALCE Posting Date: May 3, 2002 • Failure in components due to internal shorting. • Root-cause is the presence of phosphorus particles (used a substitute fire retardant) bridging wire bonds. • Suggest issue mesh size to sieve their molding compound material. • Most failures occurred within 6 to 12 months of operation.

  37. IPC position paper on halogen-free materials • Provide the industry an overview of the issues surrounding the move to halogen-free materials, including regulatory and market-driven forces. • Discuss the alternatives to halogenated flame retardants and considerations • Published document April 2003 • www.halogenfree.org

  38. Summary: After All Data Has Been Considered, the IPC Believes: • “Halogen-free” is a marketing term currently • The halogenated flame retardant TBBPA is safe for people and environment • No differences exist between TBBPA and non-halogenated alternatives for environmental issues • Reclaimation and recycling of bromine is economically feasible and is strongly supported • Reductions in use of TBBPA is not appropriate and we cannot recommend specific non-halogenated flame retardants • Reports of improved performance needs verification

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