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Halogen free material- Technical necessity or marketing campaign. Dr. M. Cygon Isola AG October 2000. 1. Main components of base materials. Copper foil. Glass fabric. Thermosets. 2. CH 3. CH 2 -CH-CH 2 -O-. -C-. -O-CH 2 -CH-CH 2. O. CH 3. O. Br. CH 3. Br. CH 3. CH 3. -C-.

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Halogen free material-

Technical necessity or

marketing campaign

Dr. M. Cygon

Isola AG

October 2000

1


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Main components of base materials

Copper foil

Glass fabric

Thermosets

2


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CH3

CH2-CH-CH2-O-

-C-

-O-CH2-CH-CH2

O

CH3

O

Br

CH3

Br

CH3

CH3

-C-

-O-

CH2-CH-CH2-O-

-C-

-O-CH2-CH-CH2

CH2-CH-CH2-O-

-C-

-O-CH2-CH-CH2

-O-

CH3

Br

O

CH3

CH3

Br

OH

OH

O

Brominated epoxy resin

Br

CH3

Br

+

2

HO-

-C-

-OH

CH3

Br

Br

DGEBA

TBBA

3


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Hazardous substances (EACEM list)

CFCs and halons

(substances that destroy

the ozone layer)

Acrylonitrile (monomer)

DMA (N,N)-dimethyl acetamide

NMA (N)-methylacetamide

DMF (N,N)-dimethyl formamide

NMF (N)-methyl formamide

Diethylamine

Nitrosamide

Nitrosamine

Ethylene glycol ether

and acetale

Phthalates (all)

Formaldehyde (monomer)

Hydrazine

Picric acid

Halogenated aromatic

hydrocarbons (general

prohibition)

PBD, polybrominated

diphenyls

PBDE, polybrominated

diphenyl ether

PCD, polychlorinated

diphenyls

PCT, polychlorinated

triphenyls

Pentachlorophenol

Dioxins

Dibenzofurans

Halogenated aliphatic

hydrocarbons

Epichlorhydrin (monomer)

Vinyl chloride (monomer)

PVC and PVC mixtures

Antimony and its compounds

Arsenic and its compounds

Beryllium and its compounds

Cadmium and its compounds

Chromium(VI) and its compounds

Cobalt and its compounds

Lead and its compounds

Mercury and its compounds

Metal carbonyl

Organic tin compounds

Selenium and its compounds

Tellurium and its compounds

Thallium and its compounds

Asbestos

Cyanide

Benzene

Phenol (monomer)

Toluene

Xylene

Polycyclical aromatic hydrocarbons

4


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5


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PCDD- and PCDF-Kongenere

with

2,3,7,8-Chlorine substitution pattern

Chlorine

“Seveso-Toxin“

Oxygene

6


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7


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Waste 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

8


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Environmental aspects on base material

cannot be converted to PCB´s!

Solder metal

Resist

Devices

Service print

Ni/Au

9


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Do we really need flame

retarded laminates for all

applications?

10



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Base materials without flame retarders

Grade

G-10

G-11

PD

BT

CE

Gigaver

UL-Rating

HB

HB

V-1

V-1

V-1

V-1

12


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Which compounds can be used

to obtain a flame retardent effect ?

nitrogen compounds

phoshorous compounds

halogen compounds (chlorine, bromine)

hydrates (Al(OH)3 xH2O, Mg(OH)2 xH2O)

Additives

Reactive components

melamines

phosphates

polybrominated biphenyls*)

polybrominated diphenyl ethers*)

brominated phthalimides

hydrates

*) can form dioxins and dibenzofurans

tetrabromobisphenol A

EP-phosphoric acid esters

multifunctional amino-compounds

13


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Mechanism of Flame Retarders

HALOGENES

R-H + X

R + HX

H2O + X

HX + OH

X = HALOGENES

14


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O

HO

O

H

P

OH

n

Mechanism of Flame Retarders

PHOSPHOROUS COMPOUNDS

DEHYDRATION

-CH2-CH2-

H3PO4 + C

+

-H2O

ORGANIC

COMPOUND

CARBON

PHOSPHOROUS

ACID

GLASS-LIKE

POLYPHOSPHOROUS

ACID

15


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Mechanism of Flame Retarders

HYDRATES

~ 280oC

2 Al(OH)3 xH2O

Al2O3 + x+3 H2O

16


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Halogen free base material

SC - VO 351

(FR-2)

IN

OUT

BROMINATED

ADDITIVE

PHOSPHOROUS/NITROGENE

ADDITIVE

17


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DURAVER-E-Cu 150

(FR-5)

Halogen free base material

IN

OUT

REACTIVE

BROMINATED

EPOXY RESIN

REACTIVE PHOSPHOROUS

MODIFIED EPOXY RESIN

NITROGENE HARDENER

DICY HARDENER

18


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DURAVER-E-Cu 156

(FR-4)

IN

OUT

REACTIVE

BROMINATED

EPOXY RESIN

REACTIVE PHOSPHOROUS

MODIFIED EPOXY RESIN

Halogen free base material

19


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20

FE


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Outlook

a) 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

21


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Outlook

b) materials

22


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