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

2 Who is IPC?

3 IPC Represents n The Electronic Interconnection Industry F Printed Circuit Board F Electronic Assembly F Photonics F OEMs F Designers F Suppliers

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

5 Why Use Flame Retardants n Proper Flame Retardants: F Retard ignition F Delay or eliminate flashover F Reduce heat concentration F Reduce evolution of toxic gases F Increase time for escape

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

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

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

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

10 Legislation – United States n Maine n California n Hawaii

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

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

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

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

15 Scientific Studies of TBBPA n The use of TBBPA is not restricted in any country. n The World Health Organization conducted a scientific assessment of TBBPA and found that the risk for the general population is considered to be insignificant. n 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. n The EU is currently conducting a risk assessment for TBBPA. In October 2003, UK Rapporteur confirmed no health effects of concern for TBBPA. n US National Toxicology Program is currently studying TBBPA

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

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

18 Trade-offs of BFR Alternatives in Circuit Boards ChemicalStrengthsWeaknesses Antimony Trioxide Low toxicity to aquatic organisms May be toxic to humans if inhaled Aluminum Hydroxide Low toxicityDecomposes during soldering Magnesium Hydroxide Low toxicity Zinc BorateLow toxicity to humans Toxic to aquatic organisms Red PhosphorusNon-toxicHighly flammable May degrade Source: HDP User Group, International Inc.

19 Dioxins and Furans n 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) n Expanded family of dioxins and furans includes Br and Cl species n Formed at low levels during any hydrocarbon combustion where chlorine is present n Of the expanded family, only TCCD is listed as a human carcinogen

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

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

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

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

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

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

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

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

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

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

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

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) : C (DMA) *Excellent Peel Strength for Long Term Aging *UL Approval

n Awarded products that meet specific environmental requirements F France Canada F US EU F Germany Nordic Swan F Japan Netherlands n Enable consumers to know they are buying products that are environmentally sound n Manufacturers use them as marketing tool Ecolabels Marketing Ecolabels

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

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

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

36 Requirements For Halogens IPC IPC-4101A (published date 12/21/2001) references halogen requirements in paragraph and on the appropriate slash sheets as TBD. IEC F Finalized requirements of IEC : u 900 ppm maximum chlorine u 900 ppm maximum bromine u 1500 ppm maximum total halogens.

37 Documents For Halogen Free IPC: F IPC-4101A/92Tg 110 – 150Phosphorus F IPC-4101A/93Tg 110 – 150ATH F IPC-4101A/94Tg 150 – 200Phosphorus F IPC-4101A/95Tg 150 – 200ATH IEC: F Tg 120 minimum laminate F Tg 150 – 190 laminate F Tg 120 minimum prepreg F Tg 150 – 190 prepreg

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

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

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