PACKAGING TECHNOLOGY AND SCIENCE

Packag. Technol. Sci. 12, 19±28 (1999)

Component Migration From Adhesives Used

In Paper And Paperboard Packaging For
Foodstuffs
By Anita Gruner* and Otto Piringer

This paper presents the ®rst results of research on the migration of adhesive
components in the paper and paperboard packaging sector. It examines
components that can migrate from a variety of commonly used adhesives in the
framework of a `worst case' scenario in respect of the contents. The report also
explains the methodology used to analyse extraction and migration and the model
used for calculating the transfers. Copyright O 1999 John Wiley & Sons, Ltd.
Received 23 March 1998; Accepted 23 September 1998
KEY WORDS: migration; adhesive; food packaging; evaluation; paperboard

INTRODUCTION in very small quantities or because they do not

Foodstuff packaging can consist of many indivi-
dual components. A single packaging material
(paper, monoplastic, composite plastic, alumi-
nium, tin, etc.) or composite packaging may be
covered with print, varnish, laminate, coatings and
bonded areas. These, in turn, can consist of a
mixture of substances whose individual compo-
nents may contribute to the migration potential of
the packaging.
Packaging must comply with paragraph 31 of
the LMBG (Lebensmittel- und Bedarfsgegenstaen-
degesetz), i.e., it must not affect the smell or
¯avour of the contents. There are numerous
guidelines, recommendations and rules on the
use of individual substances in food packaging.
For many substances there are speci®ed areas of
use and limit values, which establish permissible
limits for transfer into the contents of packages.
There are, however, other substances whose
migration potential has not yet been assessed. This
is mainly because, in packaging, they are used only
come into direct contact with the contents. One
example is adhesives used in paper and board
packaging. Adhesives, in turn, consist of a number
of individual components whose migration poten-
tial is examined in this paper.
The transfer of substances from plastic packa-
ging into foodstuffs is governed by Germany's
LMBG of 10 April 1992, which enacts EU Directive
90/128 (including several amendments). As a
result of these regulations many packaging mate-
rials have already been tested for their migration
potential.
The German Industrieverband Klebstoffe e.V.
has collaborated to select relevant types of adhe-
sives to produce typical packaging samples. The
following adhesives were used:
• EVA hotmelt
• Dextrin adhesive
• Starch adhesive
• PVAc homopolymer dispersion adhesive
• VAE copolymer dispersion adhesive

* Correspondence to: A. Gruner, Fraunhofer-Institut fuÈr Verfahrenstechnik und Verpackung, Giggenhauser Str. 35, D 85354
Freising, Germany
Contract/Grant Sponsor: Industrievereinigung fuer Lebensmitteltechnologie and Verpackung e.V. (IVLV).

Copyright  1999 John Wiley & Sons, Ltd. CCC 0894±3214/99/010019±10 $17.50

TEST DESCRIPTION
Premise
In order to measure or calculate the migration of
components from adhesives into contents, we
must ®rst establish Ð by extraction analysis Ð
the composition of the adhesive, i.e., the type and
quantity of the migratable substances it contains.
Then we must determine Ð by migration tests Ð
the quantity of components actually migrating. We
are then able to calculate migration into the
contents from these test results and from data on
the application quantities and adherend surfaces
used in the bonding process.
Implementation
In order to determine the concentration of migra-
table substances in the adhesives, adhesives were
applied to aluminium foil as the carrier material
and extracted with the FhILV-fast extraction
method using iso-octane and ethanol.1 The quan-
tities applied were higher than commonly used in
commercial manufacture as the production of test
samples on a laboratory scale made it impossible
to achieve a thinner application.
For quanti®cation, the extract solutions were
spiked with an internal standard solution consist-
ing of BHA (3-tert butyl-4-hydroxy-anisole) and
Tinuvin 234, concentrated, and qualitatively and
quantitatively analysed by gas chromatography.
In order to determine the amount of substances,
actually migrating adhesives were applied to
paperboard and analysed with the FhILV tenax
method.2,3 This method was selected as adhesives
do not usually come into direct contact with liquid
foodstuffs and solvent migration is therefore not a
consideration. To simulate migration from paper-
board at room temperature, we chose 24 hours at
60°C as the optimum migration conditions. Pre-
paratory tests had shown that these test conditions
best simulated migration at room temperature
over a longer period. For quanti®cation, the
migration solutions were spiked with an internal
standard solution consisting of BHA (3-tert.-butyl-
4-hydroxy-anisole) and Tinuvin 234, concentrated,
and qualitatively and quantitatively analysed by
gas chromatography.
Copyright O 1999 John Wiley & Sons, Ltd.
A. GRUNER AND O. PIRINGER
Gas chromatography
Equipment: Hewlett Packard model 6890 with
auto sampler.
Column: DB-1; length: 20 m; inner diameter: 0.18
mm; ®lm thickness: 0.18 mm.
Injection: 5 ml; split: 1:20.
Injector temperature: 300°C; detector tempera-
ture: 325°C.
Temperature programme: 50°C (2 minutes)±
340°C/rate 5° C/minute.
Carrier gas: hydrogen.
Test results
1. EVA hotmelt
The chromatograms of the iso-octane and ethanol
extracts (Figure 1) show that the main components
of the hotmelt are non-polar and are, therefore,
extracted better by iso-octane. Oligomer hydro-
carbons and complex paraf®n waxes appear as
undissolved peaks. The resulting pattern is similar
for both mediums of extraction, although with iso-
octane the extraction quantities are higher. How-
ever, only the iso-octane extract produces a typical
distribution pattern of aliphatic paraf®ns, which
are not extracted by the polar ethanol. All relevant
substances appear within a retention period of 20
to 65 minutes which, under these test conditions,
corresponds to a molecular weight range of 200 to
700.
In the chromatogram of the tenax migration, the
less volatile oligomer peaks and the paraf®n
pattern are almost imperceptible. Here the high-
volatile peak groups (4 to 10 minutes and 20 to 28
minutes) are predominant. This corresponds to a
molecular weight range of up to 300. The peaks
marked `i' are the added internal standards.
For the tests a hotmelt ®lm with 470 g/m2 was
used. For a quantitative analysis of the tenax
migration the total retention period of 1 to 50
minutes was integrated as this is the standard
procedure for determining overall migration
values in the tenax method. Because of the
complexity of the chromatogram, a division into
individual peaks was not thought to be a mean-
ingful option. An overall migration value of
300 mg/m2 hotmelt ®lm was found.
20 Packag. Technol. Sci. 12, 19±28 (1999)
COMPONENT MIGRATION FROM ADHESIVES
Figure 1. Gas chromatograms of hotmelt.
2. Starch and dextrin adhesive
As these two types of adhesive consist mainly of
starch and dextrin, respectively, which are not
registered by this method of analysis, the chroma-
tograms of the iso-octane and the ethanol extrac-
tion of both types of adhesive (Figures 2 and 3)
show few peaks. The peaks marked `i' are added
internal standards; the peak appearing at a
retention time of 36 minutes is made up of di-iso-
ethylhexyl-phthalate which, because of its rela-
tively small quantity, is likely to be the result of
solvent contaminations. The very high peak
registering at a retention period of 4 to 14 minutes
in the ethanol extract of the starch adhesive is
glycerine, which makes up 5 per cent of this
sample. Although glycerine also makes up 5 per
cent of the tested dextrin adhesive, the correspond-
ing peak in the ethanol extraction (retention period
4 to 8 minutes) is markedly smaller. It is likely that
here the glycerine has already largely reacted with
Copyright O 1999 John Wiley & Sons, Ltd.
the borax which is also present in this dextrin
adhesive.
The chromatogram resulting from the tenax
method corresponds to the chromatogram of the
paperboard carrier. There is only one conspicuous,
very-high unidenti®ed peak at a retention time of
17 minutes, which appears only in the tenax
chromatogram of the dextrin adhesive.
The starch adhesive was applied to the alumi-
nium foil in a quantity of 72.5 g/m2 for the ethanol
extraction and of 82.4 g/m2 for the iso-octane
extraction. From this an original concentration of
1.8 g/m2 can be calculated for the glycerine peak in
the ethanol extraction. For the tenax migration the
paperboard was coated with 60 g/m2. For the peak
appearing at a retention time of 35.5 minutes the
quantity of migrated substance was calculated as
2.7 mg/m2, and for various smaller peaks as
between 0.3 and 0.6 mg/m2.
The dextrin adhesive was applied to the
aluminium foil in a quantity of 86.4 g/m2 for the
ethanol extraction and of 112.4 g/m2 for the iso-
21 Packag. Technol. Sci. 12, 19±28 (1999)

Figure 2. Gas chromatograms of starch adhesive.
octane extraction. From this an original concentra-
tion of 57 mg/m2 can be calculated for the
glycerine peak in the ethanol extraction. For the
tenax migration the paperboard was coated with
100 g/m2. Here an overall migration value of 41
mg/m2 was found.
3. Dispersion adhesives
3.1 Homopolymer dispersion adhesive. In the
chromatogram for the ethanol extraction of the
softened homopolymer (Figure 4), the high peak of
the softening agent at a retention time of 25
minutes stands out. In addition to the standard
peaks marked `i' there are three larger relevant
peaks that were not identi®ed. This method of
analysis did not detect a silicone-based defoaming
agent which, according to the formula, should
have been present. The declared concentration of
the preservative is so low that this method could
not detect it. The chromatogram for the iso-octane
Copyright O 1999 John Wiley & Sons, Ltd.
A. GRUNER AND O. PIRINGER
extraction is mainly identical to that of the ethanol
extraction.
The three peaks and the softening agent from the
extraction also appear in the tenax chromatogram.
The homopolymer adhesive was applied to the
aluminium foil in a quantity of 105 g/m2 for the
ethanol extraction. This indicates an original
concentration of 15 g/m2 for the softening agent
and of 8 and 32.7 mg/m2, respectively, for the
peaks at the corresponding retention times of 14
and 26.5 minutes.
For the tenax migration the paperboard was
coated with 120 g/m2, which resulted in an overall
migration value of 0.57 g/m2.
3.2 Copolymer dispersion adhesive. In the chro-
matogram for the ethanol extraction of the un-
softened copolymer adhesive (Figure 5) hardly any
peaks were found, apart from the marked stan-
dard peaks. There is a peak at a retention time of 36
minutes and an undissolved peak cluster can be
22 Packag. Technol. Sci. 12, 19±28 (1999)
COMPONENT MIGRATION FROM ADHESIVES
Figure 3. Gas chromatograms of dextrin adhesive.
seen at a retention period of 24 to 40 minutes. The
peak cluster comprises hydrocarbon-containing
components. Here, too, the declared preservative
concentration is so low that this method could not
detect it. The chromatogram of the iso-octane
extraction is largely identical to that of the ethanol
extraction.
The undissolved peak also appears in the tenax
migration.
The copolymer adhesive was applied to the
aluminium foil at 41.6g/m2 for the ethanol extrac-
tion. This indicates an original concentration of
70mg/m2 for the peak at a retention period of 26 to
42 minutes and 2.6 or 1 mg/m2 for the peaks
registering at retention times of 36 and 40.5
minutes, respectively.
For the tenax migration the paperboard was
coated with 60 g/m2, which results in an overall
migration value of 33.3 mg/m2.
Copyright O 1999 John Wiley & Sons, Ltd.
CALCULATION OF
TRANSFER
We selected ®ve packaging samples, bonded with
a variety of adhesives and including inner as well
as outer packaging.
From the analytical test results we calculated the
maximum potential transfer from the packaging to
the contents, taking into account the quantity of
adhesive applied, the adherend surface and the
quantity of contents. Our evaluation of the
calculation results also took account of the differ-
ence between inner and outer packaging and the
fact that bonded areas are usually covered.
Maximal migration quantities: premise
The tenax migration results for the adhesives,
23 Packag. Technol. Sci. 12, 19±28 (1999)

Figure 4. Gas chromatograms of homopolymer dispersion adhesive.
which provided the maximum potential migration
quantities for a given application quantity, were
used as the basis for calculating the transfer into
foodstuffs. Each of the tenax chromatograms had
to be reduced by the reference sample value of the
untreated paperboard. Table 1 shows the corre-
sponding values.
Secondary/outer packaging
Sample 1: outer packaging for pharmaceutical
products. The packaging is bonded with a bead-
line application of copolymer dispersion adhesive
at 50g/m2.
With a bead-line surface of 5 cm2, the maximum
potential migration is 14 mg of substance per
package.
For an 84 g pack containing 90 capsules, the
maximum potential transfer is 167 mg of substance
per 1 kg contents or 0.16 mg of substance per
capsule.
At less than 1 mg/kg, the potential migration
Copyright O 1999 John Wiley & Sons, Ltd.
A. GRUNER AND O. PIRINGER
quantity from the copolymer dispersion adhesive
is relatively small. This is, in any case, the outer
packaging and the contents are additionally
protected by blister packaging, so adhesive com-
ponents have virtually no access to the contents.
Sample 2: outer packaging for chocolates. A see-
through panel is inserted into the packaging with a
bead-line of copolymer dispersion adhesive at 60
g/m2 and the packaging ¯aps are glued down
with spots of hotmelt.
(a) With a bead-line surface of 0.47 dm2, the
maximum potential migration from the copolymer
adhesive is 157.4 mg of substance per pack.
For a 150g package, the maximum potential
transfer is 1 050 mg per 1 kg foodstuff.
(b) With a spot bonding surface of 2 cm2 the
maximum potential migration from the hotmelt is
60 mg of substance per pack.
For a 150g package, the maximum potential
transfer is 400 mg per 1 kg foodstuff.
Again, this is outer packaging, as the chocolates
24 Packag. Technol. Sci. 12, 19±28 (1999)
COMPONENT MIGRATION FROM ADHESIVES
Figure 5. Gas chromatograms of copolymer dispersion adhesive.
are in a covered tray, and transfer is possible only
via the vapour area. A potential migration quantity
of 1 050 mg/kg from the copolymer dispersion
adhesive is not alarming, provided there are no
toxicological restrictions, e.g., speci®c migration
limits, for the individual substances. However,
such an identi®cation and assessment would be
made only if the adhesive was to be added to a
`positive' list. Transfers from the hotmelt are
negligible, as the migration quantity of 400 mg/
kg is below the upper limit for paraf®ns currently
under consideration by the EU.
Sample 3: chocolate bag with see-through/sight
panel. The side seam of the bag is bonded with
bead-lines of hotmelt and copolymer dispersion
adhesives, applied at 50 g/m2 each. The entire
bottom surface is bonded with copolymer disper-
sion adhesive at 50 g/m2 and a sight panel is
inserted into the bag with copolymer dispersion
adhesive at 50 g/m2
(a) With a bonded seam area of 0.22 dm2, the
Copyright O 1999 John Wiley & Sons, Ltd.
maximum potential migration from the hotmelt is
70 mg of substance per bag.
For a 220 g chocolate content, the maximum
potential transfer is 318 mg of substance per 1 kg of
chocolates.
(b) With a side seam adhesive bead surface of
0.22 dm2, a base adherend surface of 0.56 dm2 and
a sight panel adhesive surface of 0.85 dm2, the
maximum potential migration from the copolymer
adhesive is 454.4 mg of substance per bag.
For a 220 g chocolate content, the total maximum
potential transfer is 2 065 mg of substance per 1 kg
of chocolates.
The observations made in connection with
Sample 2, above, apply here too.
Primary/inner packaging
Sample 4: bakery bag. The bag is bonded with an
adhesive bead-line at 50 g/m2. Separate calcula-
tions were made for homopolymer, copolymer and
dextrin adhesives.
25 Packag. Technol. Sci. 12, 19±28 (1999)

Table 1.
Adhesive quantity Applied
EVA-hotmelt 50 g/m2 32 mg/m2
Starch adhesive 50 g/m2 3.3 mg/m2
Dextrin adhesive 50 g/m2 23 mg/m2
PVAc-homopolymer 50 g/m2 239.5 mg/m2
dispersion adhesive
VAE-copolymer 50 g/m2 27.9 mg/m2
dispersion adhesive
(a) With a copolymer adhesive, the maximum
potential migration from a bead-line surface of 0.5
dm2 is 140 mg of substance per bag.
For a 1 kg loaf, the maximum potential transfer
is 140 mg of substance per 1 kg of bread.
(b) With a homopolymer adhesive, the max-
imum potential migration from a bead-line surface
of 0.5 dm2 is 1 198 mg substance per bag, or per 1 kg
of bread.
(c) With a dextrin adhesive, the maximum
potential migration from a bead-line surface of
0.5 dm2 is 115 mg of substance per bag, or per 1 kg
of bread.
Calculations were made for the use of three
different types of adhesive. The bakery bag is
primary packaging, but it is used only for brief
storage or transport periods. A transfer of adhesive
components cannot, however, be ruled out.
The potential transfers for dextrin and copoly-
mer dispersion adhesives are very small. When a
homopolymer dispersion adhesive is used, the
softening agents may transfer at a rate of up to 1
188 mg/kg. Again, in the current example, using a
phthalate softening agent, the transfer quantity
remains below the speci®ed migration limit for
phthalates of 3 mg/kg.
Sample 5: double-layered rusk bag. The bag is
bonded with bead-lines of hotmelt and copolymer
dispersion adhesive, applied at 50 g/m2 each. The
inner bag is ®xed in place with an overall surface
Copyright O 1999 John Wiley & Sons, Ltd. 26
A. GRUNER AND O. PIRINGER
Overall migrate Speci®c migration values
Not determined
2.2 mg/m2 (main substance)
0.7 mg/m2 (unidenti®ed peak)
0.4 mg/m2 (unidenti®ed peak)
20 mg/m2 (main substance)
0.4 mg/m2 (unidenti®ed peak)
0.1 mg/m2 (unidenti®ed peak)
237.5 mg/m2 (softener)
0.7 mg/m2 (unidenti®ed peak)
0.7 mg/m2 (unidenti®ed peak)
27.3 mg/m2 (main substance)
0.3 mg/m2 (unidenti®ed peak)
0.2 mg/m2 (unidenti®ed peak)
0.5 mg/m2 (other peaks)
application of 50 g/m2 copolymer dispersion
adhesive and the bottom surface is bonded ¯at
with 50 g/m2 of hotmelt.
(a) With a bead-line surface of 0.2 dm2 and an
inner bag surface application of 1.2 dm2, the
maximum potential migration from the copolymer
adhesive is 391 mg of substance per bag.
Based on a 225 g rusk content, the maximum
potential transfer is 1 738 mg of substance per 1 kg
of rusk.
(b) With a bead-line surface of 0.1 dm2 and a
base adherend surface of 0.56 dm2, the maximum
potential migration from the hotmelt is 212 mg of
substance per bag.
Based on a 225 g rusk content, the maximum
potential transfer is 938 mg of substance per 1 kg of
rusk.
This sample is primary packaging. Here again
the observations made in Sample 2, above, about a
potential transfer apply. Again, the migration
quantity from the hotmelt remains below the
prescribed upper limit. Because of the low volati-
lity of the paraf®ns and their use at room
temperature, any actual transfer should be limited
to a fraction of the potential transfer quantity.
Use of adhesives in the catering sector
In addition to their typical use in packaging,
adhesives are also used as laminating agents
between the two layers of a composite, for
Packag. Technol. Sci. 12, 19±28 (1999)
COMPONENT MIGRATION FROM ADHESIVES
example, for disposable tableware where several
layers of paper, paper board or cellulose are
laminated together. This inevitably involves a
considerably larger bonded surface than common
for primary or secondary packaging, so a higher
transfer of components cannot be ruled out.
A laminated paper plate, as commonly used at
fast food stands, was chosen for a sample calcula-
tion.
Cellulose paper and paper board are bonded
over the entire surface with 8±11 g/m2 of homo-
polymer PVAc adhesive.
For a plate surface of 2.8 dm2, the maximum
potential migration is 1 463 mg of substance per
plate.
On the standard convention that 1 kg of food-
stuff is packed in 6 dm2 of packaging, the maxi-
mum potential transfer is 3 135 mg of substance per
1 kg of foodstuff (=3.1 mg/kg).
A migration analysis of the paper plate found 6
mg of substance/dm2. For the model calculation,
following the convention, this equates to a transfer
of 36 mg substance per 1 kg of foodstuff.
The discrepancy between the measured and the
estimated transfer value could be due to the fact
that the application quantity used as the basis for
the model was 10 times higher than is common in
practice. In the tenax determination this may have
led to a distribution balance between the adhesive
and the tenax which could have distorted the basis
for the model calculation.
Despite this dif®culty, this transfer is not critical
from the point of view of the overall migration
value which permits a transfer of 60 mg/kg,
provided the migrating substances are not covered
by the prescribed limits for toxicologically relevant
substances.
The substance tested in this case was a phthalate
softening agent for which there is a migration limit
of 3 mg/kg. This limit is just reached in the model
calculation and far exceeded in the migration
analysis. But it is important to recognize that the
test conditions for the migration analysis did not
correspond to conditions in commercial practice,
where a fast-food plate is generally not totally
covered with food and the contact period is very
brief. Tests under more realistic conditions are
likely to result in lower values.
The excessive transfer was caused in this case
not by the laminating adhesive, nor by the
lamination itself, but by the speci®c adhesive
Copyright O 1999 John Wiley & Sons, Ltd.
preparation used. If an unsoftened adhesive is
used, or a softening agent for which there is no
speci®c migration limit value, the maximum
permitted transfer is controlled by the overall
migration limit. It is the packer or laminator's
responsibility to select a suitable adhesive.
CONCLUSIONS
The new LMBG prescribes a limit of 60 mg per 1 kg
on transfers of substances contained in packaging
materials to foodstuffs. Our analysis shows that,
even in a `worst case' scenario, components from
the adhesives tested are well below this limit
value.
In addition to the overall migration, speci®c
migration limits apply to a number of substances.
In our tests of such registered substances, the
measured quantities lay below the speci®c limit
values.
It can be assumed that the migration values in
commercial packaging would be markedly lower,
as adhesives are generally applied to covered
seams or surfaces and direct contact with food-
stuffs is extremely rare.
ACKNOWLEDGEMENTS
We wish to express our thanks to the project's ®nancial
sponsors, the Industrievereinigung fuer Lebensmittel-
technologie und Verpackung e.V. (IVLV) and the
Forschungsgemeinschaft fuer Lebensmitteltechnologie
und Verpackung (FoGe).
We are also grateful to the Industrieverband Kleb-
stoffe e.V. for supplying sample materials, additional
®nancing for the project, and a stimulating discussion of
the topic.
The article was published in The Original German
version in the October 1998 edition of Lebensmittel
Verfahrens-und Verpackungstechnik.
REFERENCES
1. Berghammer, A., Buecherl, T. and Malter, C.
`Schnellextraktionsverfahren zur Bestimmung der
potentiell migrierfaehigen Substanzen aus ¯exiblen
Verpackungen und beschichteten und/oder lack-
27 Packag. Technol. Sci. 12, 19±28 (1999)

ierten Metallen', Verpackungundschau, 45 (7), 41±46
(1994).
2. Piringer, O., Wolff, E. and Pfaff, K. ‘Use of high
temperature-resistant sorbents as simulants for
testing’, Food Additives and Contaminants, 10 (6),
621–629 (1993).
Copyright O 1999 John Wiley & Sons, Ltd.
A. GRUNER AND O. PIRINGER
3. CEN-Entwurf ‘Test methods for the determination
of overall migration at high temperatures (up to 175
Celsius) using modified polyphenylene oxide as an
adsorbant,’ prepared by Fraunhofer Institute, 30
November 1994.
28 Packag. Technol. Sci. 12, 19±28 (1999)