1
Reduced Halogen Material Technology
(Halogen-Free Laminates)
Nov. 15th. 2011
Electronic Materials Business Unit
Proprietary
Agenda
2
1. Environmental Activities on Green Materials Today
1) Panasonic Environmental Strategy
2) Global Environmental Concerns, and Why Green?
3) Green Technologies for PWB Materials
2. Environmental Challenges on Green Technologies for Future
1) Future Direction on Electron Products - PWB Materials
2) New Technology Development on Green Materials
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3
Global Environmental Concerns, Why Green?
No Pollution Society
1960 -
Low Carbon Society
1980 ( Society )
Pollution control
1981-
Global
Warming
2000 ( Production Site )
Manage the toxic substance
at the production site (PRTR)
＊Pollutant Release and Transfer Registers
Register discharge and the movement
of the environmental pollution materials
CO2
Reduction
(Source: IPCC)
Electric
Consumption
（BkWh）
50000
40000
2001- Current ( Products )
The management of the toxic
substance to contain to products
World
Energy
Saving
30000
20000
10000
x9.4
（15％out of global electricity
generated ）
x5.7
x3.2
x1.6
0
2006 2010 2015 2020 2025
RoHS
REACH
Green IT
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(Source: Ministry of Economy, Trade and Industry)
4
RoHS moves Lead-Free & Halogen-Free
RoHS
Pb
PWB Assembly
=
Leaded Solder
PWB Materials
High Heat Resistance
・Higher Tg
Lead Free Solder
・Higher Degradation Temp
･
･
･
Mercury
Rise of Melting Point
Cadmium
Lead-Free
Rise of Reflow Temp
Hexavalent
Chromium
PBB
PBDE
Other Bromine
Flame Retardants
Conventional
Type
Non-Bromine
Flame Retardants
Halogen-Free
Proprietary
Green Technologies for PWB Materials
Flame retardants are chemicals which are added to combustible materials to render
them more resistant to ignition. They are designed to minimize the risk of a fire starting in
case of contact with a small heat source such as a cigarette, candle or an electrical fault.
If the flame retarded material or an adjacent material has ignited, the flame retardant will
slow down combustion and often prevent the fire from spreading to other items.
What is a Flame Retardant ?
Flame retardants
protect modern materials such as technical plastics,
building insulation, circuit boards and cables from
igniting and from spreading a fire.
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5
Halogen Free Technologies for PWB Materials
What is a Halogen ?
Halogen Elements are a series of non-metal elements
comprising Fluorine, (F); Chlorine, (Cl); Bromine, (Br); Iodine, (I);
and Astatine, (At).
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Halogen Free Technologies for PWB Materials
Definition – Halogen Free Laminates
(Reduced Halogen Material)
・
Bromine (Br) content:
0.09wt% (900ppm) or less
・
Chlorine (Cl) content:
0.09wt% (900ppm) or less
・
Br & Cl contents:
0.15wt% (1500ppm) or less
By
combustion flask type Ion Chromatography method
JPCA-ES-01-2003, IPC 4101B, IEE 61249-2-21
＜TEST-METHOD FOR HALOGEN-FREE MATERIALS＞
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8
Elemental Technology for Flame Retardants
Elemental Technology ①
Phosphorus
Flame Retardant
NEW
Advantage
Reaction in the solid phase:
The flame retardant builds up a char
layer; shields the material against
oxygen and provides a barrier against
the flame.
Reaction in the gas phase:
Brominated
Flame Retardant
The radical gas phase combustion process is
interrupted by the flame retardant, resulting in
cooling of the system, reducing and eventually
suppressing the supply of flammable gases.
High Heat Resistance
（IPC－TM 650）
（T288）
R-1577 (Meg2) R-1566(W)
18 min
3 min
Conventional
FR-4
1 min
・Brominated Dioxin might be generated.
Mechanism of Combustion
Elemental Technology②
Oxygen
Combustion
Phosphorus flame retardant is reacted with
epoxy resin.
Diffusion
Diffusion
in the solid
Thermal
Decomposition
（Surface）
●To apply reactive phosphorus
raw material.
Reacted with epoxy resin
●No un-reacted additives
Plastic material
No deterioration in cured epoxy
Epoxy resin
characteristics
Reactive phosphorus compound
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Global Presence in Halogen Free Laminates
9
Volume Growth of Halogen-Free Laminate
Industry
History
800
700
Panasonic History Only
600
500
400
300
200
Calendar Year
Proprietary
2012
2011
2010
2009
2008
2007
2006
2005
2004
2003
2002
0
2001
100
2000
Volume Index (2000 = 1.0)
900
Global Presence in Halogen-Free Laminates
10
Halogen-Free Laminate Manufacturers
In 2010
Others
$193M
$267M
(15.6%)
(21.5%)
$82M
(6.6%)
$95M
(7.6%)
Global 2010
$1,241M
$247M
(19.9%)
$135M
(10.9%)
$222M
(17.9%)
[Source: PRISMARK]
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PWB Materials Option for Halogen-Free
Eco Ideas for Products
Typical Applications
R-1566(W)
Mobile Equipments
Halogen-Free and Lead-Free Assembly
Excellent CAF Performance
Low CTE (Z axis - 40ppm)
Through-hole Reliability
•Test Result
Failure Ratio (%)
Cycle
•Test Sample
- 65C (30min)⇔125C (30min)
0.30㎜
R-1766
140Tg FR-4
1.6mm
R-1755C
High Reliable
FR-4
R-1566W
20 - 25um
Throwing power
(Uniformity of plating thickness)
：80% or more
Cycle Number
Proprietary
Automotives
PWB Materials Option for Halogen-Free
Eco Ideas for Products
12
Typical Applications
R-1577
Base Station
High Tg (170℃) and High Td (380 ℃)
LOW CTE-Z (34ppm/ ℃)
High Reliability – T288 (18min ) , T300 (5min )
T-288 （IPC-TM-650 TMA method） T-300 （IPC-TM-650 TMA
No blister time at 288℃
20
18
method）
20
No blister time at 300℃
min
min
10
10
Server
5
3
1
0
Conventional R-1566W
Conventional
FR-4
HF FR-4
R-1577
0
0
0
Conventional R-1566W
Conventional
FR-4
R-1577
HF FR-4
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13
PWB Materials Proposal for Halogen-Free
Basic Properties
R-1577(MEGTRON2) is Halogen free material.
It also has High Tg, High Td and low z-CTE for lead free soldering.
It also has low Dk&Df for low power consumption.
Sample thickness：
0.75-0.8mm
R-1755V
R-1577
(MEGTRON2)
R-5725
（MEGTRON4
）
R-5775
（MEGTRON6
）
4.6
4.4
4.1
3.8
3.6
2GHz
0.012
0.016
0.010
0.006
0.002
Tg
DSC
148℃
173℃
170℃
176℃
185℃
Td
TGA
350℃
350℃
380℃
360℃
410℃
T288（with Cu foils）
IPC
3 min
20 min
25 min
30 min
>120 min
Heat resistance (1H)
－
245℃
265℃
265℃
280℃
280℃
Z-CTE
TMA
40ppm/℃
44ppm/℃
34ppm/℃
35ppm/℃
45ppm/℃
Cu peel strength
（Conventional
35um）
A
1.8kN/m
1.5kN/m
1.3kN/m
1.2kN/m
1.2kN/m
Flammability
UL
94 V-0
Halogen free
94 V-0
Bromine
94 V-0
Halogen free
94 V-0
Bromine
94 V-0
Bromine
Items
Condi
tion
R-1566
Dk
2GHz
Df
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PWB Materials Proposal for Halogen-Free
IST (Interconnect Stress Test)
■ Results
For sever conditions, Materials with High Tg, High Td and Low CTE
are preferable.
Table. Number of Thermal cycles to occur failure (Times)
R-1755V
R-1577
(MEGTRON2)
R-5725
（MEGTRON4）
R-5775
（MEGTRON6）
>1,000
>1,000
>1,000
>1,000
>1,000
6
878
（Mean）
>1,000
>1,000
>1,000
>1,000
245℃
×6cycle
6
582
（Mean）
>1,000
>1,000
>1,000
>1,000
4
260℃
×3cycle
6
972
（Mean）
>1,000
>1,000
>1,000
>1,000
5
260℃
×6cycle
6
467
（Mean）
>1,000
>1,000
>1,000
>1,000
No.
Reflow
condition
Number of
Coupon
R-1566
1
-
6
2
230℃
×6cycle
3
Treating condition : 25℃ 2min ⇔150℃ 3min,
NG Judgment : Resistance changes >10%
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PWB Materials Proposal for Halogen-Free
Transmission loss
R-1577(MEGTRON2) has low loss performance.
It can transfer 1.5 times more amount of signal than R-1766 (Conventional FR-4).
0
PCB construction
-5
T r a n s m is s io n lo s s （ d B / m ）
Copper type：VLP
-10
-15
ＭＥＧＴＲＯＮ６
(R-5775)
-20
ＭＥＧＴＲＯＮ４
(R-5725)
-25
ＨＦ－ＭＥＧＴＲＯＮ２
(R-1577)
-30
Conventional FR-4
(R-1766T)
-35
-40
0
1
2
3
4
Frequency （GHｚ）
5
6
Proprietary
35um
250um
PWB Materials Option for Halogen-Free
■ IC Substrates
Power7 organic module
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IC Substrates Materials History for Halogen Free
1999
2004 2005
2007
17
2008
2010
1999 ～
Halogen
Thick-Core
200～800um
Standard Ver.
R-5715S
FC-Package
(Build-Up PKG)
2004 ～
High Elastic Modulus
R-5715E
FC-Package
(Build-Up PKG)
R-1515S
FC-Package
(Build-Up PKG)
Thick-Core
200～800um
R-1515B
Halogen
Free
2007 ～
2009 ～
High Elastic Modulus
+ Ultimate
Heat Resistance
R-1515S
R-1515A
Evolve
R-1515W
Evolve
2005 ～
High Elastic Modulus
R-1515Ｈ
Thin-Core
40～200um
R-1515B
R-1515E, L
CSP
2008 ～
+ Super High Tg
R-1515Ｈ
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CSP
Green Technologies for IC Substrate Materials
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Basic Properties
Item
Unit
R-1515S
R-1515A
R-1515W
Base resin
－
Epoxy
Epoxy
Epoxy
Flame retardant
－
Organic Resin&
Metal-hydroxide
Organic Resin&
Metal-hydroxide
Organic Resin&
Metal-hydroxide
℃
℃
GPa
GPa
ppm /℃
ppm /℃
ppm /℃
ppm /℃
％
W/mk
205
180
27
10
12
12
30
140
0.5
0.7
205
180
27
10
12
12
30
140
0.5
0.7
250
220
34-35
21
10-9
10-9
≦20
100
0.2
0.7
Tg
Elastic Modulus
CTE X
CTE Y
CTE Z
CTE Z2
Td weight loss
Thermal condutivity
DMA
TMA
20℃
250℃
TMA
260℃
DSC/Flash
Proprietary
Line up of IC Substrate Materials (All Halogen-Free)
Applications Target IC-Packages
CPU
GPU
Chip Set
Color
19
Our Products
High Elastic Modulus
Low CTE x,y,z
Super Heat Resistance
R-1515S
+Ultimate Heat Resistance
R-1515A
FC-xGA
Thick-Core
800-100μm
+Super High-Tg
+Super
High Elastic Modulus
(@RT～250℃)
R-1515W
+Lower CTE x,y
Memory
DRAM
SD Card
SSD
DSP
CSP
Thin-Core
200-40μm
High Elastic Modulus
Low CTE x,y,z
Super Heat Resistance
R-1515B
+Super High-Tg
+High Elastic Modulus
R-1515H
(@250℃)
+Super Low CTE x,y
(9ppm@R1515E, 7ppm@R1515L)
+Super
High Elastic Modulus
Proprietary
R-1515E
/R-1515L
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Halogen Free Technology Roadmap
Halogen Free, Lead Free Compatible (High Tg, High Td and Low CTE)
and Low Energy Consumption (Low Dk and Low Df)
：Developing
：Under research
2011
Mobile
2012
Heat dissipation materials
(1.3-1.5W)
2013
2014
Heat dissipation materials (3W)
Digital
Appliance
High elastic modulus & Low CTEx-y High elastic modulus & Low CTEx-y
E>40GPa, CTE<5ppm Tg 270℃
E>50GPa, CTE<3ppm Tg 270℃
IC Pkg
Low Dk(3.5), Df(0.005) and Low CTE x-y (=8ppm)
Network
Equipment
Halogen free
Low Dk, Low Df
Dk<3.8, Df<0.005
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Thank you!
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