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HALOGEN-FREE LAMINATES – SHOULD THE INDUSTRY

CHANGE?David W. Bergman, IPC

VP Standards, Technology & International Relations

November, 2004

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Why Use Flame Retardants?

The major human health hazard is fire itself, not which materials are burning

Flame retardants must balance:Health EnvironmentPerformanceCost

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Why Use Flame Retardants

Proper Flame Retardants:Retard ignitionDelay or eliminate flashoverReduce heat concentration Reduce evolution of toxic gases Increase time for escape

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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)

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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

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Legislation - EURestriction 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

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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

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Legislation – United States

Maine California Hawaii

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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

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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

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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.

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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.

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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

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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

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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?

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Trade-offs of BFR Alternatives in Circuit Boards

Chemical Strengths Weaknesses

Antimony Trioxide

Low toxicity to aquatic organisms

May be toxic to humans if inhaled

Aluminum Hydroxide

Low toxicity Decomposes during soldering

Magnesium Hydroxide

Low toxicity

Zinc Borate Low toxicity to humans

Toxic to aquatic organisms

Red Phosphorus Non-toxic Highly flammable

May degrade

Source: HDP User Group, International Inc.

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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

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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.

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Environmental Issues

TBBPA shows no detectable formation of furans or dioxins:As pure TBBPA in raw stateDuring and after 300c stressAfter pyrolysis in raw state or

reacted into epoxy resins

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Environmental Issues

Data shows no effects to air or water with TBBPA and non-brominated FRs

Proper incineration (>800C) 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

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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

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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

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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

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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

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Recycling and Reclamation

European Studies10,000 tons of bromine available

annually within the EUFrom waste electrical and

electronic equipment (WEEE)Four recovery studies in EuropeEach shows an efficiency of 90%Recovery is economically feasible

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“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

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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.

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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

Toshiba Chemical Corporation

Environment Friendly Laminate

Halogen-Free and Antimony-Free Glass Epoxy Copper Clad Laminate

TLC-555/Single side, TLC-W-555/Double SideNEMA : 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

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

MarketingEcolabelsEcolabels

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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.

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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

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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.

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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.

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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

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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.

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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

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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