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Larry E. Gwin
Franklin International, 2020 Bruck Street, Columbus, Ohio 43207
Results are reported on a study of the variables controlling the impact that acrylic water-based pressure-
sensitive adhesive (PSA) has on paper recycling operations. Surface, bulk, and performance properties of 25
commercial acrylic water-based PSAs were characterized and compared against their laboratory-measured
screening removal efficiencies. No correlation was discernible. However, the results did indicate that the use
of both vinyl acetate and acrylic acid monomers produced adhesives that readily fragment during repulping
operations, resulting in little or no removal via screening. Study of a model system developed to further
examine this phenomenon demonstrated that replacing these monomers with those possessing greater
hydrophobicities, gauged here with their octanol-water distribution coefficients, produced a substantial increase
in measured removal efficiencies. The improvements correlate with the wet tensile strengths of water-soaked
adhesive films. The measured dependency of removal efficiencies and tensile strengths on soaking times
indicates that the kinetics of water penetration into PSA films is not a controlling factor in determining the
observed behavior; rather the films fragment in their water-saturated form during the repulping process. The
data presented indicate that in formulating benign PSA it is important to avoid the combination of vinyl
acetate and acrylic acid, and in general, increase the residual strength in water-saturated films through a
prudent choice of monomer combinations.
( )
series of commercial water-based PSAs were characterized and
SAFT - TR
exp their removal efficiencies were tested. These results were used
0.1T to guide the development of a model acrylic water-based system
removal efficiency ) 100%
1 + exp
0.1T (
SAFT - TR
) (1)
to better identify controlling variables. Reported data demon-
strate that the behavior of PSAs during recycling operations
have little connection with their dry properties. The information
reviewed here provides guidelines that will allow manufacturers
for which T is the width of the plateau region and the to design environmentally benign PS label systems.
adhesives shear adhesion failure temperature or SAFT is the
inflection point of the sigmoid. Figure 1b shows the fit of Experimental Section
screening removal efficiency data for a commercial hot-melt
PSA using eq 1. This model allows the removal efficiencies of Chemicals and Materials. Acrylic water-based PSAs were
hot-melt PSAs to be predicted based solely on standard adhesive synthesized and formulated at Franklin International (Columbus,
property tests. Thus, the engineering of these properties by a OH). Model water-based PSAs were synthesized using com-
Ind. Eng. Chem. Res., Vol. 46, No. 9, 2007 2755
mercially available monomers including n-butyl acrylate, 2-eth- procedure was described in a previous publication.6 Also
ylhexyl acrylate, styrene, vinyl acetate, methyl methacrylate, described previously is the removal efficiency determination
acrylic acid, and methacrylic acid and commercially available procedure.8 This approach was recently shown to correlate well
sulfated nonylphenol ethoxylate (ammonium salt) and non- with standard government pilot-scale testing for removal ef-
ylphenoxypoly(ethyleneoxy) ethanol emulsifiers. Many of the ficiencies.9
adhesive emulsions utilized sodium persulfate or ammonium
persulfate initiators, tert-butyl hydroperoxide oxidizer, sodium Results and Discussion
formaldehyde sulfoxylate reducer, an ammonia buffer, and
commercial biocides. Emulsions were coated on two-sided Importance of Monomer Composition in Determining
release paper using a draw-down coater and dried in an 82 C Removal Efficiency. The goal of this research is to develop an
oven for 10 min. The film thickness target was 1 mil (25.4 m). understanding of which variables control the fragmentation
Copper(II)-ethylenediamine complex (1 M solution in water) behavior and thus screening removal efficiencies of acrylic
used for the isolation of adhesive rejects was purchased from water-based PSAs. Furthermore, the focus is on adhesive
Acros Organics (Pittsburgh, PA). components that are actually used in label products that may
become part of the recovered paper stream. This requires the
Characterization of Water-Based PSAs. All performance
cooperation of a major manufacturer given that much of what
testing was carried out on 1 mil (25.4 m) thick films at a
is known about the synthesis and formulation of commercial
controlled temperature and humidity of 22 C ((1.5 C) and
PSA is not published in the open literature. During the initial
50% ((2% RH), respectively. Peel strength of water-based
stages of this study, 25 commercial formulations were charac-
PSAs were measured using an IMASS Inc. (Accord, MA) 180
terized and their screening removal efficiencies were tested.
Slip/Peel Tester Model SP101B at a peel rate of 12 in./min.
Unlike hot-melt PSA, which is compounded and coated as a
One inch wide polyethylene terphthalate (PET) backed films
melt, water-based PSA is processed as a colloid with water as
were peeled from PSTC-grade polished stainless steel panels
the continuous phase and is typically coated onto a silicone
(Ryerson Steel, Chicago, IL). Test laminates were rolled with
release liner for drying. This allows for the coalescence of the
a 5.0 lb ASTM quality manual roller. The average peel force
latex particles and formation of the adhesive film. The film,
from three tests was reported for each sample. Shear test strips
backed by the release liner, is then transferred onto a facestock
were prepared with a contact area of 0.5 0.5 in. between
to produce a laminate or PS label stock.
PSTC-grade polished stainless steel panels and PET-backed
As was discussed in previous publications, choice of a paper
films. Samples were rolled with a 4.5 lb ASTM quality manual
facestock can have a significant impact on the fragmentation
roller. Five-hundred gram weights were clipped to the bottom
of the attached PSA.10 Here, a commercially produced electronic
of the test strips. The average time in minutes for the weight to
data processing paper (EDP) is used for all testing. EDP is a
pull the PET-backed films from the plate for three tests was
broad category of uncoated face papers commonly used in PS
reported for each sample. Loop tack strengths of water-based
labels. Properties of this particular EDP were well-characterized
PSA were measured using an Ametek Corporation (Paoli, PA)
and reported in a previous publication. An issue related to
Chatillon with DFM 10 Digit Force meter. PSA was direct-
planning controlled experiments for water-based systems is the
coated onto PET to form 1 5 in. test strips, which were looped
use of formulation additives, in particular, the use of wetting
with the adhesive facing out for testing and used to form a
agents to formulate adhesive emulsions for coating. Given that
contact area of 1 1 in. on PSTC-grade polished stainless steel
silicone release liners typically have surface energies in the range
panels. A dwell time of 1 s and upward travel speed of 12 in./
of 20-25 mJ/m2, a wetting agent is required to produce a
min were used for testing. The average maximum force for three
uniform coating with a water-based adhesive emulsion. Although
tests was reported for each sample.
it was found that the choice of wetting agent was not the
Glass transition temperatures (Tg) were determined using the dominant factor in determining whether a PSA is environmen-
TA Instruments (New Castle, DE) DMA 2980 Dynamic tally benign, it does influence the outcome of removal efficiency
Mechanical Analyzer. Tested samples were composite strips tests. To avoid this, all adhesive emulsions were formulated
formed by dipping a glass support cloth (30 10 0.3 mm) for coating using a sodium polyacrylate rheology modifier. This
into the liquid adhesive emulsion. The sample is dried in a additive allows for the generation of uniform coatings on a
desiccator overnight. The thermal locations of the peaks in the silicone release liner and does not impact the outcome of
loss modulus (E) for scans carried out at 1 Hz were reported removal efficiency testing.
as the Tg. Table 1 lists the physical and performance properties along
Force-displacement curves for PSA films were determined with measured screening removal efficiencies for 25 com-
using an Instron (Norwood, MA) 5542 tensile tester equipped mercial, acrylic water-based PSA emulsions formulated for
with a 10 N load cell. For the dry tests, two pieces of PET coating using the rheology modifier. No connections are
films (1 in. wide 3 in. long strips) were used as sample discernible between removal efficiencies and performance
holders. A 1 mil adhesive film was transferred from a release properties for the adhesives. This is better seen in Figure 2 for
liner over the joint between the two PET films and they were which the measured removal efficiencies are superimposed on
placed in the tensile tester grips. All of the dry tests were made the charted values for various performance properties. There
at 22 C and 50% humidity. For water-submerged testing, the also was no connection found between removal efficiencies and
tensile tester was equipped with an in-house, temperature- the dry tensile properties for PSA films. (Tensile testing of thin
controlled bath. For testing, a crosshead speed of 10 mm/min films will be discussed in greater detail in the next section.)
was used and, unless otherwise indicated, samples were soaked These results contradict previous studies examining commercial
for 1 min prior to the start of the test. At least 16 measurements PSAs that report correlations between screening removal
were made for each sample under both dry and wet conditions, efficiencies of water-based PSAs and tack, peel, and tensile
and the average maximum force was reported for each sample. properties for dry films.11,12
Surface energies of water-based adhesives were determined Our results do indicate a connection between removal
from contact angle measurements for selected liquids. This efficiency and monomer composition. It was previously reported
2756 Ind. Eng. Chem. Res., Vol. 46, No. 9, 2007
Table 2. Structure of Monomers Used in the Model Water-Based Table 3. Monomer Compositions of Model Acrylic Water-Based
PSA Formulations PSA Formulations
monomer components
Figure 4. (a) Maximum tensile force values for model water-based PSAs
Figure 3. (a) Maximum dry tensile force values for the model water-based 1, 5, and 8 as a function of soaking time at 22 C. (b) Removal efficiencies
PSA films (22 C and 50% RH). (b) Maximum tensile force values for the of water-based PSAs 1, 5, and 8 at 50 C as a function of soaking time
model water-based PSAs after soaking in water for 1 min at 22 C (solid prior to repulping.
bars) and 50 C (striped bars). Superimposed on both charts are the removal
efficiencies for the PSA measured at 50 C (solid dots). discernible (e.g., both brittle and ductile behavior is demon-
strated by the PSAs but appears unrelated to removal levels).
films lose their strength more gradually over a broad temperature What is clear from the tensile tests is the impact water has
range. Also, from the results discussed in the previous sections, on strength. Figure 3 shows the maximum force values for the
it appears that the interaction between water-based films and model PSAs that were produced with the same surfactant
water likely plays a significant role in determining their cohesive system. Results are shown for dry films measured at 22 C
strengths during repulping. (Figure 3a) and for wet films (1 min soaking) measured at 22
Acrylic water-based PSA is formulated as an aqueous and 50 C (Figure 3b). (The maximum force may correspond
dispersion often containing polymers of relatively more polar to failure or yielding depending on the behavior of a particular
film.) No correlation between dry film strength and removal
monomers, and their films retain a significant concentration of
efficiency was found and the strength of the films drop
emulsifier and other amphiphilic chemicals. It is likely that these
significantly when exposed to water. The extent of this drop
films will swell and lose strength when placed in water. To
has no relationship to the strength of the films when dry.
gauge the extent to which this occurs, an environmental tensile
Superimposed on the chart is the measured removal efficiency
test was devised. For most solids, cohesive strength is gauged for the PSAs. It would appear that a threshold region exists for
through tensile testing. For PSA films, this is difficult because the wet strength below which the films demonstrate extremely
the films are made to flow under light pressures and yield for low removals and above which the films are benign. This
small deformations. They are also highly viscoelastic. To threshold value is strongly temperature-dependent. Those films
complicate matters further, tensile testing here will be carried that possess wet strengths above about 0.2 N at 22 C and 0.1
out in a temperature-controlled, aqueous environment. As N at 50 C have removal efficiencies above 75%. (This value
described in the Experimental Section, tensile samples are is important because it was previously shown that this is
produced here by coating the PSA film over two separate pieces sufficient to pass standard government pilot tests for benign
of 25 mm wide poly(ethylene terephthalate) (PET) films that adhesives.) The results for both temperatures produce the same
are placed against each other to form a continuous substrate demarcation between the benign and problem formulations.
for the adhesive. All of the films cast for this study are targeted The results above provide for a more general description of
for 1 mil (25.4 m) thickness. The ends of the PET are not what governs the fragmentation of PSAs during paper recycling
coated and serve as gripping tabs. The shapes of the curves operations. It appears that a threshold strength exists below
were repeatable for a particular PSA, but no general trend was which the films readily fragment to a size that is difficult to
Ind. Eng. Chem. Res., Vol. 46, No. 9, 2007 2759
remove via screening. For hot-melt PSAs produced with styrenic concluded that those changes that enhance wet strength, which
block copolymers, strength drops below this threshold near its may include the use of stronger, more water-resistant compo-
SAFT and is therefore primarily temperature-triggered. This is nents, can be used to limit the fragmentation of a PSA film
understood as the movement of temperature toward the hot- during repulping and reduce its impact on paper recycling
melt adhesives styrenic disruption temperature resulting in the operations.
loss of physical cross-linking interactions and increased viscous
behavior by the rubbery phase. Thus, formulating environmen- Acknowledgment
tally benign hot-melt PSA requires that the phase behavior be
properly controlled through choice of base polymer, tackifying This research was supported by the U.S. Department of
resin, and to a lesser extent, plasticizer. For acrylic water-based Energy project number DE-FC36-04GO14309.
PSAs, strength drops when films are exposed to water. If the
strength remains above the threshold value after soaking, the Literature Cited
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Figure 4a shows the maximum force as a function of soaking Benign Stamp Project. 2002 TAPPI Fall Conference and Trade Fair, San
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increases its removal efficiency substantially. Specific demon-
strations of this behavior here included replacing the functional ReceiVed for reView December 14, 2006
monomer AA with MAA and replacing the hard monomer VA ReVised manuscript receiVed February 4, 2007
Accepted February 9, 2007
with either MMA and/or STY. In each case a dramatic increase
in removal efficiency was observed. More generally, it can be IE061610W