Functional migration barrier concept Testing of apolar migrating contaminants – BASF‘s Hexane-test method Barrier functionality for multiple migrating contaminants Heiko Diehl BASF SE 3° Congresso Scientifico Nazionale AIBO - FCE Desenzano, 26-06-14

1. Funct. Barrier
Food
Mineral oil and contaminants: theory and
practical solutions for paper & board
Heiko Diehl
BASF SE
3° Congresso Scientifico Nazionale Food Contact Expert
Desenzano del Garda 25 e 26 giungno 2014

2. Agenda
2
Functional migration barrier concept
Testing of apolar migrating contaminants – BASF‘s Hexane-test method
Barrier functionality for multiple migrating contaminants

3. Migration of contaminants
- only a paper & board problem ?
3
Quelle: Ausmaß der Migration unerwünschter Stoffe aus Verpackungsmaterialien aus Altpapier in Lebensmittel, BMELV Okt. 2012
7/1/2014
Lebensmittel Primärverpackung MOSH <C16 MOSH > C16 Σ MOSH MOAH DIPN
Schoko Spritzgebäck PP-Tray, PP-Acrylat-Folie <0,3 <1 <1,3 <0,1 <0,05
Schoko Waffeln PP-Tray, PP-Acrylat-Folie <0,2 <0,8 <1 0,3 0,1
Schoko Waffelröllchen PP-Tray, PP-Folie 2 2 4 1,9 0,1
Mandel-Nusskonfekt PP-Tray, PP-Folie <0,2 <1 <1,2 0,4 0,1
Butterkeks Vollmilch PP-Tray, PP-Folie 1 4,3 5,3 <0,1 <0,05
Gebäckstangen PP-Folie 1,7 4,2 5,9 0,5 0,3
Dinkelkleie Papier 58 43 101 13 1,7

4. 4
“..[..].For dry, non-fatty foodstuffs having a large surface area (e.g. flour,
semolina, rice, breakfast cereals, breadcrumbs, sugar and salt),
migration of volatile and hydrophobic substances via the gas phase has
to be considered particularly. This could be compensated by the use
of an appropriate additional packaging.”
As of 01.01.2012
 An appropriate packaging should prevent migration
of harmful substances.
 What means volatile, hydrophobic?
Preconditions for the use of recycled fibers
as raw materials for the production of paper
Annex to BfR Recommendation 36

5. Determination of the polar nature
of contaminants
5
Energy of cohesion : Enthalpy of vaporization
R: Gas constant
T: Temperature
Hansen solubility parameter d: dispersive (“hydrophobicˮ)
p: polar
h: hydrogen bonding
Hildebrandt solubility parameter
V: molar volume
Ecoh: energy of cohesion
Hansen Solubility Parameter (HSP) concept

6. Map for Contaminants with Gas Phase
Migration Potential at 25°C
6Source: Hansen Solubility Parameters, A User's Handbook, CRC Press Taylor & Francis Group New York 2007, p. 430ff
Classifying gases, vapors and volatile substances
x
δt [MPa] 0,5
MW [Da]
“polar”
“apolar”
Gases
Liquids, vapor
pressure > 1hPa
Volatile substances with gas phase
migration potential vapor pressure < 1hPa
Vapors
x
25,0
20,0
15,0
10,0
0 50 100 150 200 250 300 350 400 450 500
n – Alances: C5 – C24
Photoinitators:
Benzph., 4 – MBP
Carbondoxide
Phthalates: DMP, DEP,
DBP, DOP, DEHP
BPA
Oxygen

7. How is Regulation for recycl. Plastics ?
7
Exception for
 plastics made from chemical recycling (de – polymerisation)
 Offcuts and scraps from the production of plastic food contact materials,
that has not been in contact with food or otherwise contaminated
Functional migration barrier concept
Recycled plastic used behind a plastic functional barrier
as defined by EU 10/2011

8. “..[..]. is a layer within food contact materials or articles preventing the migration
of substances from behind that barrier into the food. Behind a functional barrier,
non-authorised substances may be used, provided they fulfil certain criteria and
their migration remains below a given detection limit.”
What is a Functional Barrier ?
8
Source: EU 10/2011
Functional barrier requirement fulfilled if:
tb using
b > tShelf life food
t
SML > tShelf life food
tor
SML • mfood
mcont. = P • A • tSML
mcont.
mfoodl
< SML;
tSML
P • A
=
Functional migration barrier concept
tb lag time
SML specific migration limit
mfood mass of packed food
t SML exposure / time period until SML in food is reaches
P Permation rate of contaminant
A surface area of packaging
mcont mass contaminant
m mass transfer
D Diffusion coefficient
K Partition coefficient
„How much of contaminant is
within the food?“

9. BASF – Barrier Design for Food Packaging
e.g.: selective barrier function only to MOSH, MOAH, POSH
9
Functional migration barrier concept

10. Selected Barrier Materials
10
Barrier II
Barrier III
Barrier I
Functional migration barrier concept
ecovio® PS 1606
Polyamide 6 (PA6),
Tradename Ultramid®
New BASF Dispersion
Epotal SP 101 D®

11. Agenda
11
Functional migration barrier concept
Testing of apolar migrating contaminants – BASF‘s Hexane-test method
Barrier functionality for multiple migrating contaminants

12. It has been detected that n-hexane is a suitable simulant to study the barrier
properties of packaging materials against migration contaminants e.g. mineral oil
saturated hydrocarbons (MOSH) in the range of C12 up to C24.
Measuring Barrier Performance by determining
Hexane Vapor transmission Rate (HVTR)
12
Testing of apolar migrating contaminants
Substance
Molar weight
[g/mol]
Melting point
[°C]
Vaporpressure
[hPa]
δd
[MPa1/2]
δp
[MPa1/2]
δhb
[MPa1/2]
n – Pentane
n – Hexane
n – Heptane
n – Octane
n – Nonane
n – Decane
n – Hexadecane
n – Heptadecane
n – Octadecane
n – Eicosane
n – Decosane
n – Tricosane
n – Tetracosane
72
86
102
114
128
142
226
240
254
283
311
324
339
– 130
– 94
– 79
– 57
– 53
– 30
18
22
27
35
48
47
52
570
160
48
14
5
1
<1
<1
<1
<1
<1
<1
<1
14,5
14,9
15,1
15,3
15,5
15,7
16,4
16,5
16,6
16,8
16,9
17,0
17,1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0

13. BASF‘s-Hexane-test method (I)
13
Sealing Barrier sample
Evaporation Cell Closure with barrier
t [hrs]
Semi-quantitative testing method, quantity of hexane vapor that passes under
controlled conditions from an evaporation chamber through the exposed surface
of a packaging sample is determined.
Testing of apolar migrating contaminants
10,000
1000
100
10
1
0 8 16 24
mass n – hexane [g] Card board 300g/m2
Card board 300g/m2
+ Barrier I, 18μm
Card board 300g/m2
+ Barrier II, 15μm
Card board 300g/m2
+ Barrier III, 15μm

14. “Calibrating” BASF‘s-Hexane-test
method (II)
14
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
6,5 8,2 9,4 12,5 17,7 19
HVTR[g/m² d]
The use of the HVTR-method allows a quick and general classification of mineral
oil barrier materials and shows an adequate correlation to Tenax® food migration test
(DIN EN 14338)
Hexane-Test
Auftragsgewicht
[g/m²]
[mg/ dm²]
MOSH C14-C24
MOSH C24-C35
Tenax ®-Test
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
6,5 8,2 9,4 12,5 17,7 19Barrier coating
weight [g/m2]
Testing of apolar migrating contaminants
Hexane vapor transmission rate (HVTR) at various barrier coating
weights, e.g. Barrier II

15. Agenda
15
Functional migration barrier concept
Testing of apolar migrating contaminants – BASF‘s Hexane-test method
Barrier functionality for multiple migrating contaminants

16. 16
Lag time experiment
Barrier Performance Study “Paper Sachet”

17. 17
Paper 60gsm
SP 101-D 5gsm
LDPE 15gsm
Barrier Performance Study “Paper Sachet”
Contaminants
MOSH/MOAH Σ 400ppm
Dry food simulant
Tenax®
Test exposure 50 days at 40°C,
simulating 13 months at 23°C
Migration Test set up according to DIN EN 14338
Actual detection limit
for MOAH (C10-C24): 150ppb

18. 18
Permeation experiment
Barrier Performance Study “Packaging Films vs. Barrier on
Cardboard ”

19. Method: Ewender, J., Welle, F., Franz, R., Permeation of Mineral Oil Components from Cardboard
Packaging Materials through Polymer Films, Packag. Technol. Sci. (2012).
19
P [µg/d dm²]
at 40°C
Mw [Da]
1-Methylnaphthalene
Phenanthrene
Benzophenone
DIPN C16
TXIB
> C16
10000
1000
100
10
1
0,1
0,01
0,001
0 50 100 150 200 250 300 350 400
HDPE 44µm
Barrier I 23µm
OPP 43µm
Barrier Performance Study “Packaging Films vs. Barrier on
Cardboard ”
Permeation rates of typical food contaminant

20. 20
Case Study: Shelf life vs. Permeation
of Contaminants, Food example Cereals
SML > tShelf life food
t
SML • mfood
mcont. = P • A • tSML
mcont.
mfoodl
< SML;
tSML
P • A
=
SML specific migration limit
mfood mass of packed food
t SML exposure / time period until SML in food is reaches
P Permation rate of contaminant
A surface area of packaging
mcont mass contaminant
mCereals = 500g; Acardboard box = 8,9 dm²; shelf life 365 days
tSML at 40°C [d]
Molecular weight SML OPP Ultramid ® Ecovio®
Contaminant [Da] [ppm] [43 μm] [13µm] [23µm]
Hexadecane 226 12 6 13219 13219
Octadecane 254 4 6 2957 22472
Benzophenone 182 0,6 0,3 3371 427
Tetracosane 338 0,6 674 3371 3371
1
1
2
3
1) BfR 2013, 2) BfR XXXVI, 3) worst case JECFA, withdrawn 2012

21. Conclusion
21
Packaging industry and especially paper & cardboard packaging
industry can benefit from using functional migration barriers to overcome
undesired migration of harmful substances.
The use of the HVTR-method (Hexane Test) allows a quick and general
classification of mineral oil barrier materials and shows an adequate
correlation to Tenax® food migration test (DIN EN 14338)
For paper & cardboard packaging effective and efficient barrier solutions
are available against the migration of volatile substances that show
migration potential.
Using recycled paper board protected with functional migration barriers
is a contribution to sustainable packaging of food.

22. Contact
22
November
2012
Heiko Diehl
Global Brand Owner Management
Center for Sustainable Paper Packaging
EP/VB, Paper Chemicals
Phone: +49 621 60-76692
Fax: +49 621 60-6676692
E-Mail: heiko.diehl@basf.com

23. 23