NOVEL METHOD FOR TESTING THE GREASE RESISTANCE OF

PLASTIC-BASED DRY PET FOOD PACKAGING

Yves Wyser, Chantal Pelletier and Jakob Lange

Packaging Laboratory, Nestlé Research Center, Vers-chez-les-Blanc, 1000 Lausanne 26, Switzerland,
email yves.wyser@rdls.nestle.com

ABSTRACT

For dry pet food packaging, one of the main requirements is a high resistance against staining from or migration of
the fat contained in the product. For both development and quality control, rapid and reliable standardised test
procedures assessing this property are needed. Although a number of tests are available, they either apply only to
certain types of packaging materials and show limited correlation with field behaviour, or employ non-standard
testing substances, long testing times and complicated equipment. In response to this situation, a series of testing
procedures that reflects field behaviour but without the draw-backs of the existing tests has been developed by
Nestlé. The new tests show high reproducibility and good correlation with field performance for a wide range of
multi-wall paper-based bags, folding boxes and multilayer polymer based materials.

INTRODUCTION

Dry pet food is generally packed in either paper-based packaging materials such as folding boxes and multi-wall
bags or, increasingly, in multilayer polymer based materials. In this application, the packaging is required to have a
good resistance against migration through the packaging material of the fat contained in the product. In the case of
paper-based packaging materials, migration will cause staining of the package, whereas for polymer-based
packages, a fatty film forms on the surface of the material. These are in general more of cosmetic than product
quality problems, but are nevertheless issues that have to be addressed. In order to be able to judge the stain
resistance of packaging materials it is necessary to have reliable test procedures that reflect the performance
observed during real use of the packaging. While such procedures have been established for many applications, no
commonly accepted standard procedure for evaluating pet food packaging materials is currently available.

There are two types of paper-based packaging used for dry pet food; paper bags and paperboard folding boxes. The
paper bags generally consist of two layers (plies) of grammage 70 – 100 g/m2 whereas the boxes are made from
paperboard with grammage between 250 and 450 g/m2. At present, the grease resistance is achieved either by
coating the paper or paperboard with a polyethylene (PE) layer or by treating the material with fluorocarbon
chemicals (FC) [1]. For bags, one or both of the plies can be coated or treated, and combinations of PE-coated and
FC-treated materials in one package are commonly observed. For boxes, the paperboard is either PE-coated or FC-
treated. The PE coating works by providing a physical barrier against grease penetration and is thus sensitive to
defects (pinholes) and mechanical abuse. The FC treatment inhibits the wetting of the fibres by the grease, but does
not necessarily stop the grease from penetrating the paper. The FC treatment is less sensitive to mechanical stress
and protects against staining but does not always provide an actual barrier to grease. In the case of plastic packaging
material, the grease resistance is generally given by a barrier layer consisting of a polar polymer.

It is well known that the fat migration mechanism for pet food packaging is complex, and that the transportation and
storage conditions (temperature and humidity) have a major influence on migration and staining behaviour. An in-
depth study of the staining of paper-based packages has been organised by the pet food packaging industry (paper
mills, converters and end-users) and carried out by Pira International, UK. It has shown that the main factors
influencing the staining are the contact pressure between pet food and packaging and the amount of available fat in
the pet food [2].

A wide range of standardised and in-house tests have been developed for assessing the grease resistance of
packaging materials in general and paper-based pet food packaging in particular. The tests are of different types,
ranging from pure lab tests assessing either the barrier function of the material (TAPPI, ISO and 3M tests [3, 4, 5])
or the wettability of the surface (kit test [6]) to more applied tests on finished packages where the actual product or
product components are used as testing substance and evaluation is made in terms of staining. The lab tests all give

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reproducible results for the designated type of materials, but generally show little correlation with field behaviour.
The more applied tests correlate better with field results, but have the draw-backs of being time-consuming,
requiring complicated equipment and employing non-standard testing substances. The problem with using pet food
as testing substance is that its properties vary both with the recipe and with time, which makes it difficult to compare
test results between different test series.

As the use of plastic based materials for dry pet food packaging is relatively recent and still strongly increasing,
there is no test currently available for the testing of such materials, except long-lasting storage tests.

It can thus be seen that there still is a need for a series of tests that reflects field behaviour, but without the draw-
backs of existing tests. Ideally, the tests should be simple to carry out and evaluate, as quick as possible, not involve
expensive equipment, use a standard testing substance, and apply to all types of materials. The present paper
summarises the development of a test method for paper based packaging materials (details available elsewhere [7])
and describes the development of a test method for plastic based material.

TESTING METHOD FOR PAPER-BASED MATERIALS.

The development of this test method is described in details in reference [7].

The tests consist in putting a mixture of chicken fat and silica gel in contact with a folded 10 x 10 cm2 sample of the
packaging material at 60 °C and 65 % relative humidity during 16 hours, using the setup depicted in Figure 1. In
order to reflect the pressure or the absence of pressure acting on the packaging material through the product during
storage, a pressure of approximately 7 kPa is applied to the materials used for the fabrication of multi-wall bags,
while no pressure is applied to folding-box materials.

Weights (for
bag samples)

Fat mix
Ring

Sample

Figure 1. Set-up for test procedure for paper-based materials.

The evaluation of the result of the test is performed by visual observation of the samples (inner and outer side) and
the resistance of the material tested assessed using a scale ranging from 0 (no staining) to 4 (more than 30 % of the
tested surface stained). Due to significant sample to sample variation, 6 specimens are tested and the overall score
given to a material is the worst individual result.

The test conditions described above are the result of an in-depth optimization on temperature, relative humidity,
time, mechanical aggressiveness and fat composition. This optimization could be performed thanks to the use of
packaging materials with known field performance obtained from operating companies.

Chicken fat being a natural product, and therefore subjected to seasonal and geographical variations, the effect of fat
composition was also studied and shown to have no significant effect on the final result.

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TESTING METHOD FOR POLYMER-BASED MATERIALS.

With the increasing use of polymer-based materials for dry pet food packaging, a test method for this type of
materials is desirable. The development aimed at a procedure lying as close as possible to the one used for paper-
based materials, as described above.

Materials

Different types of plastic laminates were used. All materials had been evaluated in terms of stain resistance by
conventional (storage) tests. A list of all packaging material samples with their characteristics is presented in
Table 1. A series of plastic films of non-packaging origin was also used in preliminary testing and during test
development. These samples are listed in Table 2.

Chicken fat with a free fatty acid value (FFA) of <1% and coconut fat was obtained from Nutriswiss, Switzerland.
Oleic acid was purchased from Riedel-de Haen, Switzerland. Poultry fat with a FFA value of 8-13% was obtained
from Prosper de Mulder, UK.

Silica gel with a grain size between 2.5 and 10 mm was obtained from Aldrich, Switzerland. Thin layer
chromatography plates (HPTLC plates, 10 x 10 cm, Silica gel 60 F254) were obtained from Merck, Germany.

Table 1. Packaging material samples.

Total thickness
Sample Composition Storage test
[mm]
Kraft paper with fluorocarbon grease resistance treatment /
Bag 1 Kraft paper / Kraft paper / biaxially oriented Just ok
polypropylene
low density polyethylene / polyethylene terephthalate / low
Bag 2 0.20 Ok
density polyethylene
oriented polypropylene / low density polyethylene /
Bag 3 0.14 Ok
polyamide / low density polyethylene
Bag 4 oriented polypropylene / oriented polypropylene 0.14 Bad
Bag 5 oriented polypropylene / low density polyethylene 0.14 Bad
Bag 6 linear low density polyethylene / polyamide / polyethylene 0.14 Ok
polyethylene terephthalate / linear low density
Bag 7 0.15 Ok
polyethylene
Bag 8 cast polypropylene / polypropylene / polyethylene 0.15 Bad
polyethylene terephthalate / linear low density
Bag 9 0.15 Not tested
polyethylene / HDPE
polyethylene terephthalate / linear low density
Bag 10 polyethylene / high density polyethylene / linear low 0.15 Not tested
density polyethylene
linear low density polyethylene / high density polyethylene
Bag 11 0.19 Not tested
/ linear low density polyethylene
polyethylene terephthalate / high density polyethylene /
Bag 12 0.15 Not tested
linear low density polyethylene

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 Table 2. Plastic film samples.

Sample Composition Thickness

[mm]
PP 1 Polypropylene 0.075
PP 2 Polypropylene 0.14
PET Polyethylene terephthalate 0.023
PE Polyethylene 0.017

Sample preparation

All samples were conditioned at 23°C and 50% relative humidity prior to testing. Squares 10 x 10 cm2 in size were
cut from flat, unfolded areas.

Testing procedure

The samples were placed on a 10 x 10 cm2 glass slide or thin layer chromatography plate, a 60 mm diameter
stainless steel ring positioned at the centre of each sample, and 30 cm3 of testing substance was placed inside the
ring (see Figure 2). In some cases a sheet of standard photocopier paper was placed between the sample and the
glass slide. The testing substance consisted of a blend of grease and silica gel in the proportions of 10 or 25 g grease
to 100 g silica gel. The grease was pure fat (chicken, poultry or coconut), fat with oleic acid added or pure oleic
acid. Two pre-heated 1 kg weights were placed on the testing substance inside the ring. The samples were then
transferred to a climatic chamber at 60 or 70°C and dry air (no humidity control) or 65% relative humidity and left
for 8-60 h.

Weights

Fat mix
Ring

Glass slide or
TLC Plate

Sample

Figure 2. Test set-up.

Evaluation of results

Once removed from the climatic chamber, the sample set-ups were taken apart and the testing substance discarded.
The amount of grease that had permeated through the sample was evaluated in different ways. In some cases,
samples on glass slides were inspected from below in order to see if any grease was present between the sample and
the slide. In other cases the paper placed between the sample and the glass slide was inspected for grease stains.
When thin layer chromatography plates were used, grease migration was either detected directly (as wet stains) or
by inspecting the plates under UV light at 254 nm (Camag 022.91 UV lamp, Camag, Switzerland). For the thin layer

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chromatography plates, the amount of migration was evaluated and each sample assigned a score according to the
criteria in Table 3.

Table 3. Scale for evaluating the results.

It should be noted that the evaluation is carried out on the TLC plate, not the sample itself.

Score Definition Comment

A No migration No colouring visible under UV light

B Limited migration Faint colouring visible under UV light
C Major migration Dark colouring visible under UV light

TEST DEVELOPMENT

Selection of visualisation technique

Various ways of visualizing the presence and amount of fat that has penetrated through the sample after storage at
elevated temperature in the climatic chamber were evaluated. At first it was attempted to see the fat directly on the
glass slide, either by looking at the sample from below or after removal of the sample. Although some fat could be
seen in some cases, in general the amount of fat present on the glass slide was too small to be clearly visible.

Tests were then carried out with a sheet of paper between the sample and the glass slide, the idea being that any fat
would absorb into the paper and create visible stains (wetting). However, it was found that there was not enough fat
that migrated to create a visible stain.

Finally, thin layer chromatography plates, i.e. glass plates covered with a thin layer of highly absorbing silica, were
tried as absorbing media for the fat permeating through the samples. The glass slide under the sample was simply
replaced with a TLC plate and the set-up with grease mix etc. left in the climatic chamber as in the earlier tests.
After the test was completed, the TLC plate was inspected under UV light. The plates exhibit fluorescence, i.e. emit
green light when illuminated with UV light at 254 nm, which is suppressed by UV-absorbing liquids such as fats. It
was found that this technique permitted the detection of quite small amounts of fat, and it was therefore selected for
the remainder of the tests.

Selection of testing substance

The test substances selected were standard chicken fat, a mixed poultry fat and coconut fat. The poultry fat is
produced under more severe conditions (higher temperature and longer time) than the chicken fat, whereas the
coconut fat is composed of shorter chain fatty acids than chicken and poultry fat. Both these factors were believed to
possibly increase the rate of permeation through plastic materials. A free fatty acid, oleic acid, was also tested both
alone and added to the other fats. An overview of the substances can be found in Table 4. As material for the tests
the thin polypropylene film, i.e. PP1, was used as it is known to be a poor barrier to fats. Tests were carried out at
60°C and 65% relative humidity during 16 hours.

The results of the test series are shown in Table 4. As can be seen, coconut fat did not work at all, and poultry fat
was found to be less aggressive than chicken fat. The pure chicken fat was roughly as aggressive as the pure oleic
acid, whereas a mixture of both turned out to be the most aggressive of the substances tested. Based on these
findings, it was decided to use chicken fat with 25% oleic acid as testing substance.

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 Table 4. Results of tests on the PP 1 material using different fats.

Test substance Result Comment

Oleic acid B Some staining
Poultry fat B Some staining, less than with chicken fat
Coconut fat A No staining
Coconut fat with 25% oleic acid A-B Weak staining
Chicken fat B Some staining
Chicken fat with 25% oleic acid B Some staining, more than pure chicken fat

Selection of testing conditions

In order to determine the optimal conditions for testing, a series of experiments were run on the PP 1, PP 2, PE and
PET materials at 60 and 70°C and different humidity conditions for various amounts of time. An overview of the
testing conditions can be found in Table 5.

Table 5 also gives the results of the tests. As can be seen, the PET samples exhibit no migration under any
conditions. Since PET materials are known to be good barriers against grease migration, this result suggests that the
test conditions examined are not unrealistically severe. Table 5 also shows that the PE and PP materials let some
grease through, and that the amount increases with increasing time and temperature. For PE the increase with time is
less pronounced than for PP 1. It can be seen that the PP 1 material lets less grease through under humid than under
dry conditions. Furthermore, Table 5 shows that for the PP materials, a significant amount of migration (i.e. a score
of C) is found only after 24-40 h at 60°C but already after 16 h at 70°C.

Table 5. Results of tests under different conditions of time, temperature and humidity.

Sample ► PET PE PP 1 PP 2
Test conditions▼
60°C dry, 16 h A - B
24 h A - B-C
40 h A - B-C
60 h A - C*
60°C 65% RH, 16 h A B-C* B** A-B
24 h A B-C B-C** B
40 h A B-C B-C** B-C
60 h A - C** -
70°C dry, 16 h A B-C C C
24 h A C C C
40 h A C C C
60 h A - C -
* Less intense staining than at 70°C. ** Less intense staining than at 60°C dry.

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Based on these findings it was decided to choose 70°C, dry air and 16 h as test conditions. 70°C permits a short
testing time while remaining not too severe, whereas working under dry conditions significantly simplifies the
requirements on the testing equipment.

VALIDATION OF THE TEST PROCEDURE

In order to check the validity and relevance of the selected testing conditions, as well as the reliability of the
procedure, a series of tests were carried out on the actual packaging materials. The results are given in Table 6. It
should be noted that Bag 1 is a paper-based material with a polymer layer much thinner than in the other materials.
It can therefore not be directly compared with the other bags. For the other materials, the first observation that can
be made is that the variation between samples is very low.

The second observation that can be made is that the test procedure gives results that correlate quite well with the
grease resistance measured by traditional methods. It can thus be seen that all materials with "bad" resistance
produced a score of C, whereas the materials with "ok" resistance exhibit scores of A or B. It is reminded that the
tested materials include different types of polymers, i.e. polyethylene (PE), polypropylene (PP), polyethylene
terephthalate (PET) and polyamide (PA). It thus appears that the test procedure in general is well suited to evaluate
the grease resistance of different types of plastic materials.

However, here it is worth noting the difference in behavior between the two grease barrier polymers PET and PA.
On the one hand, Table 6 shows that all PET-containing materials gave scores of A, or, in one case, a weak B. This
shows that the test conditions are suitable for this polymer. On the other hand, the polyamide-containing materials
gave scores of A in one case and B in the other (Bags 3 and 6). The reason for these variations in performance is that
polyamide has a glass transition temperature around 60°C and that the test is therefore performed above the glass
transition temperature where the dissolution and diffusion of dissolved species are considerably increased.
Considering the fact that such a temperature will not be achieved in "real-life" means that testing Polyamide at 70°C
may be too severe. The results obtained in this study indicate that it is acceptable (both materials gave scores below
C), but results obtained on polyamide-containing materials should nevertheless be treated with caution. In doubtful
cases it could be useful to re-test the materials at 60°C for longer times.

Table 6. Results of tests on the PP 1 material using different fats.

Sample Composition Result (2 - 6 samples) Grease resistance

Bag 1 FC Paper / PP B, B, B, B, B, B Just ok
Bag 2 PE / PET / PE B*, B*, B*, B*, B*, B* Ok
Bag 3 PP / PE / N / PE B, B, B, B, B, B Ok
Bag 4 PP / PP C, C, C, C, C, C Bad
Bag 5 PP / PE C, C, C, C, C, C Bad
Bag 6 PE / PA / PE A, A, A, A, A, A Ok
Bag 7 PET / PE A, A, A, A, A, A Ok
Bag 8 PP / PP / PE C, C, C, C, C, C Bad
Bag 9 PET / PE / PE A, A
Bag 10 PET / PE / PE / PE A, A
Bag 11 PE / PE / PE C, C
Bag 12 PET / PE / PE A, A
* Very weak staining

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CONCLUSIONS

A test procedure for evaluating the grease resistance of all-plastic dry pet food packaging materials has been
developed. It is based on the recently developed Nestlé test method for paper-based materials (briefly presented in
the paper), employing chicken fat as testing substance under conditions of elevated temperature and pressure. The
modified procedure involves using thin layer chromatography plates under the sample, which makes it possible to
visualize the fat migration under UV light. The test conditions have been modified to give optimum results for the
type of materials in question. The new test conditions are 70°C and dry air as compared to 60°C and 65% relative
humidity for the paper-based materials. The testing time is unchanged, 16 h. A series of tests on different all-plastic
materials with known grease resistance have shown that the test procedure gives correct results for all types of
plastics, although polyamide-containing materials must be treated with caution. It was also found that the test
exhibits minimal sample-to-sample variation.

REFERENCES

1. Deisenroth, E., Jho, C., Haniff, M. and Jennings, J., “The designing of a new grease repellent fluorochemical
for the paper industry”, Surface Coatings International 1998, 440.

2. Sheppard Fiddler, S. and Wood, G., “Test method development – Accelerated grease resistance functionality
test”, Consultancy report, Pira International, 1999.

3. "Paper and board – Determination of grease resistance", ISO 5634-1986, International Organisation for
Standardization, .1986.

4. "Turpentine test for grease resistance of paper", TAPPI official test method T 454 om-89, Trade Association
for the Pulp and Paper Industry, 1989.

5. “Scotchban Performance test No. 1 Paper barrier performance test for pet food applications”, 3M Technical
information, 3M Chemical Group, European Business Centre, Belgium 1997.

6. “Grease resistance test for paper and paperboard”, TAPPI provisional method T 559 pm-96, Trade Association
for the Pulp and Paper Industry, 1996.

7. J. Lange, C. Pelletier and Y. Wyser, "Novel method for testing the grease resistance of pet food packaging",
Packag. Technol. Sci, In press

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