International Journal of Adhesion & Adhesives 22 (2002) 219–226

Lactic acid based polymers as hot melt adhesives for packaging

applications
.
M. Viljanmaaa,b,*, A. Soderg a( rdc, P. Torm.
. al.aa
a
Tampere University of Technology, Institute of Biomaterials, P.O. Box 589, 33101 Tampere, Finland
b
Kiilto Oy, P.O. Box 250, 33101 Tampere, Finland
c
Hycail b.v., Industrieweg 24-1, 9804 Noordhorn, Netherlands
Accepted 22 November 2001

Abstract

The suitability of biodegradable copolymers based on poly(l-lactide) (PLLA) and poly(e-caprolactone) (PCL) with molar ratio of
81:19 for a packaging hot melt adhesive was evaluated. Typical hot melt adhesive properties such as open time, setting time, hot tack
development, viscosity and weight loss were measured for an unstabilized and for two chemically stabilized samples. Mechanical
testing included tensile strength, lap shear strength and elongation measurements. The results show that PLLA/PCL copolymer is a
potential candidate for a biodegradable hot melt adhesive for a packaging application. Most of the measured properties were
comparable to a conventional, non-biodegradable poly(ethylenevinylacetate) (EVA) based hot melt adhesive, which was used as a
typical commercial reference. The stability of the PLLA/PCL copolymer is, however, a limiting factor: mechanical properties change
within few days depending on the geometry of the samples. Also the degradation during processing of the PLLA/PCL copolymers
was severe. The drying of the samples before processing or the use of nitrogen as a protective gas during processing seemed to have
no observable effect on the stability. However, chemically stabilized polymers performed better during processing and also retained
their mechanical properties better than the unstabilized copolymer. r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: A. Hot melt; D. Aging; Polylactic acid

1. Introduction recycling process. Other issues related to adhesives and

Biodegradable hot melt adhesives prepared from
renewable raw materials have a potential for use in
packaging applications. Packaging materials contain in
general only a small amount of adhesives but that can
nevertheless have a significant effect on the repulpability
of the package. Recycled paper from packaging material
waste is used in combination with virgin fibers in the
paper making process and traditional hot melt adhesives
are likely to contaminate the paper made in this way.
Contaminants, or ‘‘stickies’’, can cause pinholes, print-
ing problems or ruin the aesthetics of the paper. They
might even be the reason for undesired interruptions in
the paper production process. It is therefore desirable
that the adhesives used in packages would degrade in the
*Corresponding author. Tampere University of Technology, In-
stitute of Biomaterials, P.O. Box 589, 33101 Tempere, Finland.
Tel.:+358-3-280-8313; fax:+358-3-280-8217.
E-mail address: mikko.viljanmaa@kiilto.com (M. Viljanmaa).
packaging materials are the increasing demands on
compostability and the use of materials from renewable
resources. In compost environments it is important that
the major part of packaging material is degradable in a
certain time [1], which also includes the adhesives used.
Renewability of the adhesive raw materials can be
considered to be an asset compared to petroleum-
derived polymers due to increased environmental
awareness [2,3].
Aliphatic polyesters are known to be susceptible to
degradation processes like for instance hydrolysis [4,5],
and some of them are also derived from renewable raw
materials [6] and could therefore be potential candidates
for a new generation of adhesives. Lactic acid based
polymers (PLA) have been a subject for numerous
studies during the past decades and several attempts
have been made in order to commercialise this polymer
on industrial scale [7]. Lactic acid is the simplest
molecule showing optical activity. The l-stereoform is
the most commonly occurring one in nature, while the

0143-7496/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 3 - 7 4 9 6 ( 0 1 ) 0 0 0 5 7 - 4
220 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226
d-form can be produced either by biological or chemical
methods. Lactic acid based polymers are interesting
because the starting chemical, lactic acid, can be
obtained from renewable sources by fermentation.
PLA is also compostable which means that a CO2-
neutral life cycle can be established for the material.
Lactic acid based homopolymers can be prepared either
by self-condensation reactions of lactic acid, or by ring-
opening polymerisation of lactide, which is the dimer of
lactic acid [8,9]. PLLA homopolymer has a glass
transition temperature in the range 55–601C and a
melting temperature of about 1701C. Tensile strength
and elongation at break are about 50 MPa and 2%,
respectively [10], which means that flexibilizing compo-
nents have to be incorporated in the polymer in order to
make it suitable as an adhesive.
Copolymers of PLLA and PCL are flexible polymers
with low melting points [11–13]. This can be related to
the properties of PCL, which differ significantly from
those of PLLA. PCL has a glass transition temperature
of about –601C and a melting temperature of about
611C [14]. Tensile strength of PCL is about 20 MPa and
elongation at break up to 1000% [15]. Both PLLA, PCL
and copolymers are degradable in biological environ-
ment [8,14,15]. The degradation of aliphatic polyesters
in biological environment is a complicated process,
which can be related to several different factors [4,8].
However, the main mechanism is hydrolysis and this
reaction can be catalysed by carboxyl end groups
initially present or generated during the degradation
process [8,14,15].
A balance between stability and degradation is crucial
for biodegradable materials. For hot melt adhesives in
packages, the material needs to be stable enough during
storage, in the process and in the application, but after
the package has fulfilled its purpose it should preferably
degrade rapidly. Especially the thermal stability of hot
melt adhesives is of major importance. The poor thermal
stability of lactic acid based polymers have been
demonstrated in several publications and different
Table 1
Sample specification and characteristics
Sample No. Sample specification Mwa (g/mol)
1a Unmodified PLLA/PCL 21 800
1b Unmodified PLLA/PCL 44 700
2 Peroxide modified PLLA/PCL 25 500
3 End-capped PLLA/PCL 28 900
4 Reference EVAe n.m.f
a
Measured by GPC.
b
Measured by DSC.
c
In the feed.
d
Measured by 1H-NMR.
e
Sitomelt 1525 supplied by Kiilto Oy, Finland.
f
Not measured.
approaches have been reported to be efficient in the
retarding the thermal degradation of PLLA, e.g.
through pre-drying of the polymer [16], end-capping
the hydroxyl groups with anhydride [17] and peroxide
modification [9]. This paper reports on the stability,
processability and use of a new generation of biode-
gradable hot melt adhesives based on lactic acid based
polymers.
2. Materials and methods
2.1. Adhesive materials
The lactic acid based formulations were prepared and
delivered by Hycail b.v., The Netherlands. Copolyesters
of PLLA and PCL were prepared in a tin-octoate
catalysed polymerization process. The types of samples
and their characteristics are presented in Table 1.
Sample 1a and 1b were PLLA/PCL copolymers
without further modifications with same composition.
Sample 1b was used to investigate the effect of different
processing conditions. Otherwise Sample 1a was used as
a testing material in the experiments. Sample 2 was a
basic PLLA/PCL formulation which was melt-modified
with 0.1 wt% t-butylperoxy benzoate in a Brabender
internal mixer (901C, 5 min). Sample 3 was basic PLLA/
PCL formulation which was allowed to react with about
1.5 wt% acetic anhydride in a round bottom glass flask.
Samples 1a, 2 and 3 were used right after the delivery (in
about 1 week from preparation). Sample 1b was aged
for 5 months before it was studied. All the materials
were packed under dry conditions together with drying
agents and stored in desiccator before the use.
Commercial EVA-based packaging hot melt adhesive
Sitomelt 1525 supplied by Kiilto Oy, Finland, was used
as a reference material in viscosity, mechanical, open
time, setting time, hot tack development and weight loss
measurements.
PDa Tgb (1C) Mp b
(1C) Lactoyl/caproyl ratioc (mol/mol)
1.59 8.9 130–140 81/19
1.33 6.7 130–140 81/19 d
1.53 4.7 130–140 81/19
1.63 3.1 130–140 81/19d
n.m.f n.m.f 100–110 F
 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226
2.2. Molecular weight and polydispersity
Molecular weight (Mw ) and polydispersity (PD)
values were determined by using a Waters GPC
system based on a high-pressure liquid chromato-
graphy pump (Waters 515), three columns (5 mm
particle size) and a differential refractometer detector
(Waters 410 RI). HPLC grade chloroform was used
both as a solvent for the samples and as an eluent.
The sample concentration was 0.1 wt%, injected
volume 150 ml and the eluent flow rates 1 ml/min.
Relative calibration against polystyrene standards was
used and the reported values were averages from two
measurements.
2.3. Glass transition and melting point temperatures
Glass transition (Tg ) and melting point (Mp ) tem-
peratures were determined by differential scanning
calorimetry (DSC) using Perkin Elmer Pyris 1 DSC
equipment. The DSC was calibrated with indium and
results were calculated using the baseline. Experiments
were performed in nitrogen atmosphere with flow rate
20 ml/min. Samples weighed 672 mg and heating rate of
201C/min was used. Samples were heated twice and
before the heating cycle was repeated, samples were
rapidly cooled (2001C/min).
2.4. 1H-NMR studies
1
H-NMR studies were performed with a Varian
500 MHz NMR-apparatus. Deuterated chloroform was
used as a solvent.
2.5. Viscosity measurements
Melt viscosity measurements were performed
with Brookfield RVT (spindel 21), at 20 rpm
and 1601C. Results were average values from two
measurements.
2.6. Mechanical testing
Test specimens for tensile strength and elongation
were prepared by melting the polymers 15 min at 1601C.
Molten samples were poured on a silicone surface and
films were formed with 600 mm applicator, allowed to
cool down to room temperature and cut into test
specimens (15  100 mm). The specimens were stored for
4 h at 231C and 50% RH before the measuring the
tensile properties.
Tensile properties were measured by using a
Lloyd LR 10 K tensile tester according to standard
ISO 527. The gauge length was 50 mm and the crosshead
speed of 100 mm/min was used for measuring tensile
strength and elongation and 50 mm/min for measuring
221
lap shear strength. Results were averages from five
samples.
Lap shear strengths were tested by preparing the
samples from uncoated cardboard. Adhesives were
melted by heating them for 15 min at 1601C and
adhesive strips were poured on the cardboard. Another
piece of cardboard was pressed immediately on the
adhesive strip with a roller (weight 3500 g). After the
adhesive melt was cooled, the test specimens
(30  100 mm) were cut. The cross sectional area of
10  30 mm was attaching two cardboard pieces. The
specimens were stored 4 h in 231C/50% RH before
testing. These conditions were also used in the longer
storage periods.
2.7. Open time, setting time and hot-tack development
Olinger 105-instrument was used to test the hot-tack
development, open and setting times of the samples.
The tester consisted of a horizontally moving
lower sledge and vertically moving upper sledge.
Uncoated cardboard was clamped to both sledges.
When the test started, the lower sledge moved
under nozzle which applied the adhesive on the
cardboard. The width of the adhesive strip was
2.070.5 mm. The lower sledge continued to move
under the upper sledge and after a fixed time was
elapsed (open time) the upper sledge was pressed on
the lower sledge and closed time was activated. After
the closed time elapsed the upper sledge moved up
and separated the bond. The force to separate the
bond could be measured with the strain gauge in
the instrument (hot tack development). The heating
temperature and pressure in the adhesive pot were
1601C and 1 bar, respectively, and the pressure in
vertical cylinder 3 bar.
The open time was defined as a time when some fibres
were still seen on the adhesive strip. The closed time was
set constant at 5 s.
The setting time was defined as a time when clear
cohesive failure between cardboards was produced. The
open time was set constant at 0.5 s.
To measure the hot tack development the pressure in
vertical cylinder was adjusted to 0.8 bar. Open time was
set constant at 0.5 s. Setting times were: 0.3, 0.4, 0.5, 0.6,
0.7, 0.8, 0.9, 1, 2, 3, 4, and 5 s.
The open time and the setting time values were
averages of three and the hot-tack values averages of
two measurements.
2.8. Weight loss
Weight losses were determined by heating 10 g
samples in the Memmert ULE 500-oven at 1701C for
2, 4, 6 and 27 h. The results were the average of two
measurements.
222 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226
2.9. Testing at different processing conditions
When the effect of processing conditions was studied,
Sample 1b was used as a testing material.
Quantities (100 g) from this polymer were heated at
1601C in the 300 ml flask for 35 min. The effect of inert
atmosphere was examined by closing the jar and
applying a nitrogen flow. The effect of elevated
temperature (2001C, without nitrogen) and pre-drying
of the sample (6 h in vacuum at 401C) were also studied.
The degradation of the samples was determined by
molar mass measurements.
3. Results and discussion
3.1. The effect of processing conditions
A series of experiments on different processing
conditions was performed for Sample 1b in order to
verify testing procedure and exclude potential error
factors in the experiments. The processing in inert
atmosphere was compared with processing in presence
of oxygen as well as processing at two different
temperatures (1601C and 2001C). The effect of polymer
pre-drying was also studied in one experiment. The
effect of pre-drying of PLLA has, in some studies been
found important [16], but in other ones not relevant
[9,17]. The processing of polymers in oxygen atmosphere
is in general avoided due to the potential risk for
oxidative degradation [18] but has, on the other hand,
not been found to affect the melt degradation of PLLA
to any larger extent during shorter processing times [9].
In the current study the processing temperature was the
only significant parameter affecting the degradation
50000
44689
45000
40000
35000
30000
g/mol
23315
25000
20000
15000
10000
5000
0
Unprocessed Normal
atmosphere
Fig. 1. The effect of different processing conditions on molecular weights with Sample 1b.
during processing (Fig. 1). The results suggested that
pre-drying and processing at inert atmosphere are not
necessary for these lactic acid formulations, which is of
significant importance for the applicability of the hot
melt adhesives. The possible risk for hydrolysis should
anyway not be neglected for lactic acid based polyesters.
The minor effect of the pre-drying in this study is most
likely related to the handling and storage of the
polymers under dry conditions.
3.2. Thermal stability
The initial melt viscosity values (at time 0) for the
Samples 1a, 2 and 3 were found to be suitable for the
packaging applications (Fig. 2). However, the viscosity
for all the lactic acid based hot melt adhesive formula-
tions decreased more severely than for the reference,
which indicated a significant thermal degradation for the
copolyester based resins. The weight losses for the same
samples verified this observation (Fig. 3). The weight
loss is most likely related to the formation of low molar
mass compounds like lactide and lactoyl lactic acid and
other compounds formed by a thermal degradation and/
or thermohydrolysis. A stabilizing effect of both the
peroxide modification and the end-capping of the lactic
acid copolymer could be noticed in a slower decrease in
the melt viscosity (Fig. 2) as well as in the weight loss
(Fig. 3). Based on the melt viscosity curves the peroxide
modification may be considered as the preferred
stabilization method for shorter processing times (74%
of initial viscosity left after 10 min and 44% after
60 min) and the end-capping more suitable for longer
processing time (70% of initial viscosity left after 10 min
and 56% after 60 min). Similar differences in the weight
loss could not be found, which suggests that the
23917
22311
18951
Nitrogen Higher Pre drying
temperature
 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226 223

3000
Sample 1
Sample 2
2500 2500
Sample 3
Reference
2000
1875
1750 1750
mPas

1500 1550
1400 1400

1125
1000 1000 950 950
825
625
500 525 475

0
0 10 30 60
Minutes

Fig. 2. Viscosity curves of the Samples 1a, 2, 3 and 4 (reference).

35.0

30.0 30.0

25.0
24.0

20.0
%

15.0 Sample 1
Sample 2
10.0 Sample 3
7.9
Reference
5.0 5.2 5.3
3.8
3.0
2.3 3.0
1.0 1.6
0.0 0.7
2 4 6 27
Hours

Fig. 3. Weight losses of the Samples 1a, 2, 3 and 4 (reference).

formation of volatile compounds is proceeding at same
rate, but some differences in the degradation initiating
reactions may be relevant. It should also be noted, that
few hours processing time is normally used at the
maximum for the hot melt adhesives.
3.3. Mechanical testing results
Samples 1a and 3 showed initially rubbery like
elongation (over 800%) and did not break within the
limits in instrument (Fig. 4). Sample 2 (peroxide
modified) showed lower elongation values which may
be caused by of cross-linking or/and due to the bubbles
formed in the film, which might have initiated the
fracture.
After 2 days of storage the unmodified samples
turned brittle with almost no elongation left. This
collapse might be due of degradation of amorphous
segments in polymer [8] or due to crystallization.
Because the samples prepared for elongation tests
were thin films, they had large surface area subjected
to the moisture [19]. However, the end-capped Sample 3
retained some elongation even after 28 days, which
is probably due to the deactivation of the hydroxyl
end-groups. Also the peroxide stabilized Sample 2
was more flexible than the unstabilized Sample 1a,
which could be explained by a slightly different
224 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226

900

800 800
Sample 1
700 Sample 2

600 Sample 3
Reference
500
%

420 417 420 423

400 402
378

300

200

100 100
39 34 25
0 13.6 10.2 5.4 2.6
0 days 2 days 7 days 14 days 28 days

Fig. 4. Elongations of the Samples 1a, 2, 3 and 4 (reference) after storage.

12.0

10.8
10.0 10.1
Sample 1
8.9 8.8
8.6 Sample 2
8.0 7.8
Sample 3
6.9
Reference
MPa

6.0

4.8
4.0

2.9
2.6 2.5 2.5 2.5
2.0 2.2

0.0 0.0 0.0 0.0 0.0

0 days 2 days 7 days 14 days 28 days

Fig. 5. Tensile strengths of the Samples 1a, 2, 3 and 4 (reference) after storage.

polymer structure which might have been formed in
stabilization process. The reference EVA-based Sample
4, remained unchanged.
The loss of elongation was accompanied by an
increase in strength values (Fig. 5), which may be caused
by crystallization. Sample 1a was too brittle for
measurement after 1 week and showed therefore no
detectable strength (no initial values for the Samples 1a
and 3 are shown in Fig. 4 because they did not break).
Sample 2 was also very brittle after 2 weeks (elongation
5.4%) and therefore strength values decreased at this
point.
To simulate the behaviour in the actual packaging
situation, lap shear strengths with uncoated cardboard
were measured. Except for Sample 2 (after 1 week), all
the failures were cohesive in the cardboard and were
similar as with reference EVA-based hot melt (Fig. 6). In
the Sample 2, the peroxide modification caused in-
creased cohesion due to cross-links or entanglements
which might have resulted in poorer adhesion between
cardboard pieces.
In practice, most of the packages do not require
excessive elongation, some flexibility is only needed to
absorb impacts which the packages might be subjected
to. Also especially within the food industry, the lifetime
of the package can be extremely short and therefore long
stability times for the adhesive bonded packages are not
required.
 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226 225

1.6
Sample 1
1.5
1.4 Sample 2
Sample 3
1.2 1.2 Reference
1.1
1.0 1.0 1.0
0.9
MPa

0.8 0.8
0.7
0.6 0.6
0.5
0.4

0.2

0.0
0 weeks 1 weeks 4 weeks

Fig. 6. Lap shear strengths of the simulated packages after storage bonded with the Samples 1a, 2, 3, 4 (reference).

35

30

25
Sample 1
Sample 2
20
Sample 3
N

15 Reference

10

0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 2 3 4 5
Seconds

Fig. 7. Hot tack development curves of the Samples 1a, 2, 3 and 4 (reference).

3.4. Adhesive properties measured with olinger
instrument
Samples 1a, 2 and 3 had almost similar open
and setting time values. Because the method used
to determine the open and setting times is not
very exact it can be said that the Samples 1a, 2
and 3 had open times between 30–35 s and setting
time between 1.2–1.4 s. The reference sample had
slightly shorter setting time (0.7–0.9 s) and also much
shorter open time (10–15 s) than the copolyester
materials.
Hot tack development curves with the samples 1a, 2
and 3 were good and comparable with the reference
material (Fig. 7). The Samples 1a, 2 and 3 had over 10 N
values already after 0.3 s setting time. After the
adhesives started to solidify, very steep increase in the
force values between setting times 0.6–1.0 s could be seen
in Fig. 7. After 1 s, the final level in the force values was
reached. Because the pressure in the vertical cylinder
with the hot tack measurements was lower than in
setting time measurement (0.8 bar instead of 3.0 bar), no
cohesive failure between the cardboard pieces happened.
Lower pressure was used to avoid any compression in
226 M. Viljanmaa et al. / International Journal of Adhesion & Adhesives 22 (2002) 219–226
the cardboard material and to determine only the hot
tack strength of the adhesive.
4. Conclusions
Polylactic acid based hot melt adhesives will offer
significant environmental and technical advantages
compared to traditional petroleum-derived packaging
hot melts. PLLA/PCL hot melts are mostly based on
renewable raw materials, they are biodegradable and
probably decompose rapidly in the paper repulping
process. Additionally, these new generation hot melt
adhesives show interesting adhesive properties e.g.
excellent hot tack and a combination of long open time
with moderate setting time.
Untreated samples degrade rapidly during the proces-
sing and depending on sample geometry also in the
room humidity. However, stability can be increased by
peroxide or acetic anhydride treatment. Acetic anhy-
dride stabilization seems to be most promising technique
according to studied requirements. In the adhesive
bonded samples that resemble e.g. typical food packages,
the degradation does not limit the use of these adhesives.
Acknowledgements
The financial support from Kiilto Oy (Finland) is
greatly appreciated. A. Munneke, H. Westerhof, J. Fijn
and S. Wang are acknowledged for their contribution to
the preparation of lactic acid based adhesive formulations.
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