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Halogen free material-Halogen free material-Technical necessity orTechnical necessity ormarketing campaignmarketing campaign

11

Dr. M. CygonIsola AG

October 2000

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Main components of base materialsMain components of base materials

Copper foil

Glass fabric

Thermosets

22

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Brominated epoxy resinBrominated epoxy resin

33

CH2-CH-CH2-O-

O

-C-

CH3

CH3

-O-CH2-CH-CH2

O

-C-

CH3

CH3

-OHHO-

BrBr

BrBr

+

-C-

CH3

CH3

-O--O-

BrBr

BrBr

CH2-CH-CH2-O-

OH

-C-

CH3

CH3

-O-CH2-CH-CH2

O

CH2-CH-CH2-O-

O

-C-

CH3

CH3

-O-CH2-CH-CH2

OH

TBBADGEBA

2

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Hazardous substances (EACEM list)Hazardous substances (EACEM list)Antimony and its compoundsAntimony and its compoundsArsenic and its compoundsArsenic and its compoundsBeryllium and its compoundsBeryllium and its compoundsCadmium and its compoundsCadmium and its compoundsChromium(VI) and its compoundsChromium(VI) and its compoundsCobalt and its compoundsCobalt and its compoundsLead and its compoundsLead and its compoundsMercury and its compoundsMercury and its compoundsMetal carbonylMetal carbonylOrganic tin compoundsOrganic tin compoundsSelenium and its compoundsSelenium and its compoundsTellurium and its compoundsTellurium and its compoundsThallium and its compoundsThallium and its compounds

AsbestosAsbestosCyanideCyanideBenzeneBenzenePhenol (monomer)Phenol (monomer)TolueneTolueneXyleneXylene

Polycyclical aromatic hydrocarbonsPolycyclical aromatic hydrocarbons

CFCs and halonsCFCs and halons(substances that destroy(substances that destroythe ozone layer)the ozone layer)

Acrylonitrile (monomer)Acrylonitrile (monomer)DMA (N,N)-dimethyl acetamideDMA (N,N)-dimethyl acetamideNMA (N)-methylacetamideNMA (N)-methylacetamideDMF (N,N)-dimethyl formamideDMF (N,N)-dimethyl formamideNMF (N)-methyl formamideNMF (N)-methyl formamideDiethylamineDiethylamineNitrosamideNitrosamideNitrosamineNitrosamineEthylene glycol ether Ethylene glycol ether and acetaleand acetalePhthalates (all)Phthalates (all)Formaldehyde (monomer)Formaldehyde (monomer)HydrazineHydrazinePicric acidPicric acid

Halogenated aromaticHalogenated aromatichydrocarbons (general hydrocarbons (general prohibition)prohibition)

PBD, polybrominatedPBD, polybrominateddiphenylsdiphenylsPBDE, polybrominatedPBDE, polybrominateddiphenyl etherdiphenyl etherPCD, polychlorinatedPCD, polychlorinateddiphenylsdiphenylsPCT, polychlorinatedPCT, polychlorinatedtriphenylstriphenylsPentachlorophenolPentachlorophenolDioxinsDioxinsDibenzofuransDibenzofurans

Halogenated aliphaticHalogenated aliphatichydrocarbonshydrocarbonsEpichlorhydrin (monomer)Epichlorhydrin (monomer)Vinyl chloride (monomer)Vinyl chloride (monomer)PVC and PVC mixturesPVC and PVC mixtures

44

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Number of PCDD-chlorine homologues and 2,3,7,8-place isomericsDegree of

chlorinationNumber of isomers Number of 2,3,7,8-chlorine substituted

isomers1 2 -2 10 -3 14 -4 22 15 14 16 10 37 2 18 1 1

Sum 75 7

Number of PCDF-chlorine homologues and 2,3,7,8-place isomericsDegree of

chlorinationNumber of isomers Number of 2,3,7,8-chlorine substituted

isomers1 4 -2 16 -3 28 -4 38 15 28 26 16 47 4 28 1 1

Sum 135 10

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PCDD- and PCDF-KongenerePCDD- and PCDF-Kongenerewithwith

2,3,7,8-Chlorine substitution pattern2,3,7,8-Chlorine substitution pattern

ChlorineChlorineOxygeneOxygene

““Seveso-Toxin“Seveso-Toxin“

FEFE 77

Equivalence factor of toxicity for PCDD/F according to BGA/UBA andNATO/CCMS

Kongener BGA/UBA-TEF NATO/CCMS-TEF2,3,7,8-TetraCDD 1 11,2,3,7,8-PentaCDD 0,1 0,51,2,3,4,7,8-HexaCDD 0,1 0,11,2,3,6,7,8-HexaCDD 0,1 0,11,2,3,7,8,9-HexaCDD 0,1 0,11,2,3,4,6,7,8-HeptaCDD 0,01 0,01OctaCDD 0,001 0,0012,3,7,8-TetraCDF 0,1 0,11,2,3,7,8-PentaCDF 0,1 0,052,3,4,7,8-PentaCDF 0,1 0,51,2,3,4,7,8-HexaCDF 0,1 0,11,2,3,6,7,8-HexaCDF 0,1 0,12,3,4,6,7,8-HexaCDF 0,1 0,11,2,3,7,8,9-HexaCDF 0,1 0,11,2,3,4,6,7,8-HeptaCDF 0,01 0,011,2,3,4,7,8,9-HeptaCDF 0,01 0,01OctaCDF 0,001 0,001Other TetraCDD/F 0,01 0Other PentaCDD/F 0,01 0Other HexaCDD/F 0,01 0Other HeptaCDD/F 0,001 0

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Waste treatmentWaste treatment

- Recycling not possible due to glass reinforcement and thermoset epoxy- Copper recycling possible- Thermo-treatment possible, if proper flame retarder- Waste uncritical for repository, after copper removal

88

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Environmental aspects on base materialEnvironmental aspects on base materialcannot be converted to PCB´s!cannot be converted to PCB´s!

Solder metalResistDevicesService printNi/Au

99

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Do we really need flameDo we really need flameretarded laminates for allretarded laminates for all

applications?applications?

1010

FEFE 1111

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Base materials without flame retardersBase materials without flame retarders

GradeG-10G-11PDBTCEGigaver

UL-RatingHBHBV-1V-1V-1V-1

1212

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Which compounds can be usedWhich compounds can be usedto obtain a flame retardent effect ?to obtain a flame retardent effect ?

nitrogen compoundsphoshorous compounds

halogen compounds (chlorine, bromine) hydrates (Al(OH)3 xH2O, Mg(OH)2 xH2O)

Reactive components Additives

tetrabromobisphenol AEP-phosphoric acid estersmultifunctional amino-compounds

melaminesphosphatespolybrominated biphenyls*)polybrominated diphenyl ethers*)brominated phthalimideshydrates*) can form dioxins and dibenzofurans

1313

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Mechanism of Flame RetardersMechanism of Flame Retarders

HALOGENES

R + HXR-H + X

HX + OH H2O + X

X = HALOGENES

1414

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Mechanism of Flame RetardersMechanism of Flame Retarders

PHOSPHOROUS COMPOUNDS

+ H3PO4 + CHO

O

P

OH

HO

n

-CH2-CH2-DEHYDRATION

GLASS-LIKEPOLYPHOSPHOROUS

ACID

ORGANICCOMPOUND

PHOSPHOROUSACID

CARBON

-H2O

1515

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Mechanism of Flame RetardersMechanism of Flame Retarders

HYDRATES

Al2O3 + x+3 H2O2 Al(OH)3 xH2O

1616

~ 280oC

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Halogen free base materialHalogen free base material

SC - VO 351(FR-2)

PHOSPHOROUS/NITROGENEADDITIVE

BROMINATEDADDITIVE

IN OUT

1717

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Halogen free base materialHalogen free base material

DURAVER-E-Cu 150(FR-5)

REACTIVE PHOSPHOROUSMODIFIED EPOXY RESIN

REACTIVE BROMINATEDEPOXY RESIN

IN OUT

NITROGENE HARDENER DICY HARDENER

1818

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Halogen free base materialHalogen free base material

DURAVER-E-Cu 156(FR-4)

REACTIVE PHOSPHOROUSMODIFIED EPOXY RESIN

REACTIVE BROMINATEDEPOXY RESIN

IN OUT

1919

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Laminate Requirements UnitsDE-E-Cu 104 DE-E-Cu 156 DE-E-Cu 104 DE-E-Cu 156

1. Peel StrengthStandard profile copper foil

a) after thermal stress N/mm 1,72 1,7 2 2

b) at 125oC N/mm 1,45 1,6 1,9 1,4c) after N/mm 1,71 1,6 2 2 process solutions2. Volume Resistivitya) C-96/35/90 MW x cm 3,20E+07 3,00E+07 - -b) moisture resistance MW x cm - - 8,00E+08 8,00E+08c) at elevated temperature E-24/125 MW x cm 1,70E+07 2,00E+06 8,00E+06 8,00E+063. Surface Resistivitya) C-96/35/90 MW 3,50E+06 2,00E+07 - -b) moisture resistance MW - - 4,00E+06 4,00E+06c) at elevated temperature E-24/125 MW 7,00E+07 2,00E+06 7,00E+04 7,00E+064.Moisture Absorption % 0,5 0,6 - 0,25. Dielectric Breakdown = kV - - 45 756.Permittivity (1MHz) 4,2-4,5 4,5-4,8 4,7 4,87. Loss Tangent (1MHz) 0,024 0,025 0,019 0,028.Flexural Strength

a) Length direction N/mm2 - - 600 670

b) Cross direction N/mm2 - - 480 590

9. Thermal Stress 10 Sek. at 288oCa) unetched s Pass Visual Pass Visual Pass Visual Pass Visualb) etched s Pass Visual Pass Visual Pass Visual Pass Visual10. Electric Strength | V/mm 3,30E+04 4,50E+04 - -11. Flammabilitya) Average burn time, maximum s - 3 3 2b) Individual burn time, maximum s - 5 4 312.Glass Transition Temperature (Tg)

a) DSC oC - - 135 approx. 150

b) DMA oC - - 145 16013. Coefficient of Expansion

a (RT-200oC) TMA ppm/K - - x-16 x-16ppm/K - - y-12 y-12ppm/K - - z-160 z-160

14. T260-Test, thickness: 1,5 mm min - - 15 > 60

thickness < 0,78 mm thickness > 0,78 mm

FEFE 2020

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OutlookOutlook

2121

a) marketsa) markets

- halogen free PCB´s are interesting for the auto- motive industry due to the motor vehicle regulation

- electronic for telecommunication will use halogen free PCB´s for marketing reasons

- with TBBA flame protected PCB´s will be use furthermore in quantities

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OutlookOutlook

2222

b) materialsb) materials

Glass transition

temperature (Tg) Standard Halogen free Standard Halogen free

135 Duraver-E-Cu 104 Duraver-E-Cu 156

150 Duraver-E-Cu 114 under development Isofoil 160 Ecofoil

170 Duraver-E-Cu 117 under development RCC under development

Laminate RCCF