Transcript Document

HALOGEN-FREE LAMINATES –
SHOULD THE INDUSTRY
CHANGE?
David W. Bergman, IPC
VP Standards, Technology &
International Relations
November, 2004
1
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
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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
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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 - 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

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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)


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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

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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

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Organo-phosphors and phosphate esters

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Essentially fillers (non-reactive) in polymers
Difficult to incorporate
Require high loading to be effective
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,


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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?
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What are the tradeoffs?
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
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Source: HDP User Group, International Inc.
Dioxins and Furans
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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

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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
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in bleaching chemistries.
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
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Environmental Issues

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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
22
World Health Organization,
Geneva Reports
TBBPA is not acutely nor subchronic 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
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From tissues, blood, digestive tract
No long-term toxicity
Does not accumulate in fat or other tissues
TBBPA is rapidly eliminated from aquatic
vertebrates

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Continuous exposure for 4 days brought steadylevels
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

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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 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
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“Halogen-Free” Is
Marketing Driven
OEMs in Japan and Europe
began “environmental friendly”
campaigns with “lead-free”
 OEMs now pushing “halogenfree” 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 “HalogenFree”

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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
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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 nolead solders
Volume use of the new material is required
to achieve cost parity with best-in-class FR4
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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
Marketing
Ecolabels

Awarded products that meet specific
environmental requirements
 France
 US
 Germany
 Japan


• Canada
• EU
• Nordic Swan
• Netherlands
Enable consumers to know they are
buying products that are
environmentally sound
Manufacturers use them as
marketing tool
Future BFR Use in the
Electronic Industries

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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 DecaBDE 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

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IEC 61189-2C12 below will be submitted to test
methods committee in May 2002.
IEC

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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) references
halogen 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:
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IPC-4101A/92
IPC-4101A/93
IPC-4101A/94
IPC-4101A/95
Tg 110 – 150
Tg 110 – 150
Tg 150 – 200
Tg 150 – 200
61249-2-21
61249-2-22
61249-4-11
61249-4-12
Tg 120 minimum laminate
Tg 150 – 190 laminate
Tg 120 minimum prepreg
Tg 150 – 190 prepreg
Phosphorus
ATH
Phosphorus
ATH
IEC:
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Failure Warning: Components
Packaged with PhosphorusContaining Molding Compound
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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
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months of operation.
IPC position paper on
halogen-free materials

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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:

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“Halogen-free” is a marketing term currently
The halogenated flame retardant TBBPA is safe for
people and environment
No differences exist between TBBPA and nonhalogenated 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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