International Journal of Adhesion & Adhesives 125 (2023) 103403

Contents lists available at ScienceDirect

International Journal of Adhesion and Adhesives

journal homepage: www.elsevier.com/locate/ijadhadh

Preparation and characterization of high solid content acrylate latex

pressure sensitive adhesives with difunctional cross-linker EGDMA
Cheng Fang *, Chaobo Wu, Xiaoyan Zhao
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037,
China

A R T I C L E I N F O A B S T R A C T

Keywords: Cross-linked acrylate latex pressure sensitive adhesives (PSAs) were synthesized via unseeded semi-batch
Difunctional cross-linker emulsion polymerization processes with butyl acrylate (BA), acrylic acid (AA), 2-hydroxyethyl acrylate (HEA)
Ethylene glycol dimethacrylate and difunctional cross-linker, ethylene glycol dimethacrylate (EGDMA). The influences of EGDMA on the
Emulsion polymerization
comprehensive properties of the acrylate latex PSAs were investigated. The results indicated that both viscosity
Pressure sensitive adhesive
and particle size of the latexes were independent of the amount of EGDMA in the pre-emulsion feed when un­
seeded semi-batch emulsion polymerization process was employed. It was also found that water resistance of the
latex PSA was improved with increasing EGDMA content, further confirmed by water contact angle measure­
ments. DSC and TGA results showed that Tg of the copolymer was elevated, plus thermal stability was increased
with introduction of EGDMA. Besides, with the increase of EGDMA content, the gel content of the polymer
increased. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the
sacrifice of loop tack and peel strength, when compared with the uncross-linked counterparts.

1. Introduction However, as these synthesized acrylic PSAs consist of linear mole­

Pressure sensitive adhesives (PSAs) are viscoelastic materials that
can firmly adhere to a wide range of surfaces by the application of a light
pressure for a short contact time [1,2], and that can be easily removed
from the substrate without any residue [3]. One of the most challenges
in the field of PSA is obtaining a good adhesion-cohesion balance.
Adhesion is characterized by tack and peel resistance, whereas cohesion
is characterized by shear resistance. Both are opposing forces and
therefore when one increases, the other tends to decrease [4]. One
approach to balancing these properties is by controlling the polymer
composition. Acrylic ester monomers are widely used to synthesize
pressure sensitive adhesives (PSAs) through solution or emulsion poly­
merization. In an acrylic PSA, tack and peel strength are imparted by
monomers whose polymers have low glass transition temperatures (Tg)
such as butyl acrylate (BA) or 2-ethylhexyl acrylate (2-EHA), while in­
ternal strength is provided by monomers whose polymers have a higher
Tg such as methyl methacrylate(MMA) or styrene (St). Functional
monomers like acrylic acid (AA) can be incorporated to promote adhe­
sion to specific substrates and to provide reactive sites for cross-linking
reactions [5].
cules that are held together by physical cross-linking, van der Waals
forces, or hydrogen bonding, they have insufficient thermo-mechanical
stability. On the other hand, the environmental disadvantage and high
cost have promoted the replacement of many solvent-borne acrylic PSAs
with emulsion counterparts. Nevertheless, the solvent-borne acrylic
PSAs have been preferred over the emulsion PSAs in high performance
applications which require a high shear holding power together with
high peel and tack. It is known that solvent-borne acrylic PSA films have
a much higher shear-holding power than that of their emulsion coun­
terparts [6]. This is mainly due to the continuous network morphology
formed by the chain entanglements in the solvent-borne adhesive when
the solvent has evaporated [7]. In contrast, microgels were produced
during the process of emulsion polymerization and retain their discrete
morphology in the adhesive film [6]. This morphology decreases the
shear resistance of the emulsion adhesive because of the poor in­
terconnections between the microgels and the linear polymers in the
film.
Cross-linking is one of the key techniques controlling the balance
between cohesive and adhesive strength of the PSA polymer. Insoluble
fractions (related to the degree of cross-linking) in the 50− 70% range

* Corresponding author.
E-mail address: fangcheng533@163.com (C. Fang).

https://doi.org/10.1016/j.ijadhadh.2023.103403
Received 31 July 2022; Received in revised form 4 April 2023; Accepted 18 May 2023
Available online 20 May 2023
0143-7496/© 2023 Elsevier Ltd. All rights reserved.
C. Fang et al.
have been reported as optimal for a good performance in waterborne
adhesives [8–13]. Typical cross-linking methods are based on the
chemical reaction that takes place between the cross-linking agents and
the main chain of the PSA copolymers [14]. The physico-chemical and
mechanical properties of cross-linked PSAs are determined to a large
extent by the type and amount of cross-linking agents added to the
copolymer. On the other hand, multifunctional monomers, often known
as cross-linkers, are usually employed in free-radical polymerization to
produce homopolymers or copolymers (when polymerized with other
vinylic monomers) that lead to polymer networks with applications in
medicine, pharmaceuticals, paints, column packing, optics, polymer
additives, ion exchange resins and diene rubber products [15]. For
example, Kim et al. [16] prepared crosslinked monodisperse spheres
with various crosslinking agents (EGDMA, AMA, HDDA, TMPTMA)
using poly(methyl methacrylate) (PMMA) seed particles in aqueous
alcoholic media by one-step seeded polymerization in the absence of the
swelling process. Qu et al. [17] synthesized novel crosslinked poly
(IBOMA-co-BA) copolymers by free-radical copolymerization from iso­
bornyl methacrylate (IBOMA) and butyl acrylate (BA), using 4,4′ -iso­
propylidenediphenol dimethacrylate (BD) as crosslinking agent and 2,
2′ -azobisisobutyronitrile (AIBN) as thermal initiator. Ghazaly et al. [18]
prepared copolymer latexes of n-BMA and three different crosslinkers
[macromonomer crosslinker (Mac), ethylene glycol dimethacrylate
(EGDMA), and aliphatic urethane acrylate (AUA)] with varying molec­
ular weights. However to our knowledge, no works reporting in the open
literature have examined the application of the difunctional monomer,
Scheme 1. Schematic diagram for the synthesis of acrylate latex PSAs with cross-linker EGDMA.
2
International Journal of Adhesion and Adhesives 125 (2023) 103403
ethylene glycol dimethacrylate (EGDMA), in both emulsion polymeri­
zation and acrylic PSAs. The aim of the present work was to investigate
systematically the effect of the difunctional monomer EGDMA on the
performance properties of the acrylate latex PSA.
In the present study, the cross-linked acrylate PSA latexes were
prepared by unseeded semibatch emulsion polymerization process. The
chemical structure of the resultant polymer and the morphology of the
latex particles were determined by FTIR and TEM, respectively.
Furthermore, the effects of the difunctional monomer EGDMA on the
conversion of monomer and particle size of the latex, as well as on the
thermostability (DSC, TG), water contact angle, water resistance, gel
content and adhesive properties of the polymer films were investigated.
2. Experimental
2.1. Materials
Butyl Acrylate (BA, 99% purity), Acrylic Acid (AA, 99% purity), 2-
Hydroxy ethyl Acrylate (HEA, 96% purity) and Ammonium Persulfate
(APS) were purchased from Shanghai Lingfeng Chemical Co., Ltd.
Ethylene Glycol Dimethacrylate (EGDMA, 98% purity) was purchased
from Shanghai Aladdin Chemistry Co., Ltd. (Shanghai, China). Disodium
butanedioic acid alkyl polyoxyethylene ether monoester sulfonate
(Cytec A-102) and ammonium allyloxtmethylate alkyl alcohol ethox­
ylate sulfate surfactant (Adeka SR-10), which were both purchased
commercially and used as received. Ammonia (25 wt% in H2O) was
C. Fang et al. International Journal of Adhesion and Adhesives 125 (2023) 103403

obtained from Nanjing Chemical Reagent Co., Ltd. All reagents were using a NDJ-8S rotational viscometer (Shanghai Pingxuan, China) at
used without further purification. Distilled deionized water (DI-H2O) 25 ◦ C with 1 # spindle and 30 rpm speed.
was used throughout the study.
2.3.3. TEM analysis
The latex particle morphology was observed by transmission elec­
2.2. Emulsion polymerization
tron microscopy (TEM) (JEOL JEM-1400, Tokyo, Japan). The latex was
diluted in deionized water to a 2 wt% solid content. Then the diluted
The synthetic route and formulation for the acrylate latex pressure
latex was coated and dried on a 400-mesh carbon coated copper grid for
sensitive adhesives with difuctional cross-linker EGDMA were shown in
measurements.
Scheme 1 and Table 1, respectively. The theoretical solid content in the
formulation was 62 wt%. In this study, acrylate latexes were prepared by
2.3.4. FTIR analysis
unseeded semibatch emulsion polymerization process.
The latex was dried in a vacuum oven at 105 ◦ C until it reached a
For a typical experiment, 95 g of BA, 2 g of EGDMA, 1 g of AA, 2 g of
constant weight. Fourier transform infrared (FTIR) spectra of the dried
HEA, 1.5 g of A-102, 0.5 g of SR-10, 0.3 g APS and 25 g of deionized
latex films were recorded with a Bruker VERTEX80 FTIR spectrometer
water were mixed in a 500 mL four-neck round-bottom flask and stirred
(Germany) in the range 4000 to 400 cm− 1.
vigorously to form the pre-emulsion.
Another 500 mL four-neck round-bottom flask with a reflux
2.3.5. DSC analysis
condenser, a thermometer and a mechanical stirrer was filled with 0.2 g
Glass transition temperature (Tg) of the latex film was measured by a
of APS and 37.5 g of deionized water with a stirring rate of 250 rpm at
differential scanning calorimeter (DSC, Model 214 Polyma, NETZSCH
85 ◦ C. Then the pre-emulsion was added dropwise into the reacting
Instruments, Germany). 5–15 mg of dry polymer was weighed into
mixture for 3.5 h. After the feed was completed, the reaction was
standard DSC hermetic alumina crucible. In order to eliminate thermal
allowed to proceed for an additional 1 h to increase monomer conver­
history, two scanning cycles of heating-cooling were performed for each
sion. The latex was then cooled to room temperature and poured into a
sample at a heating rate of 10 ◦ C/min in the temperature range of − 70 to
glass bottle used for further characterization.
100 ◦ C under nitrogen atmosphere. The second heating run was used to
determine the Tg. The theoretical Tg can be estimated by FOX equation:
2.3. Characterization
1 m1 m2 mi
= + + ⋅⋅⋅ + (3a)
2.3.1. Conversion and coagulation Tg Tg1 Tg2 Tgi
The conversion were measured by gravimetric analysis. About 2 g of
where mi is the mass fraction of copolymerized monomer, Tgi is the
latex was weighed into an aluminum foil dish and dried at 105 ◦ C to a
value of Tg of homopolymer.
constant weight. The solid content and the final conversion were
calculated by the following equations, respectively:
2.3.6. Thermal gravimetric (TG) analysis
W3 − W1 TGA was carried out to demonstrate the thermal stability of the latex
Solid content (wt%) = × 100 (1)
W2 − W1 PSA polymers using Q500, TA Instruments, USA. The polymer films
(around 5–10 mg) were heated from ambient temperature to 600 ◦ C at a
where W1 is the weight of the aluminum foil dish, W2 and W3 are the rate of 10 ◦ C/min under nitrogen atmosphere.
weights of latex before and after drying, respectively.
Solid content (wt%) × W4 2.3.7. Gel content
Conversion (wt%) = × 100 (2) The gel content of the acrylic PSA polymers was measured via the
W5
solvent-extraction method. Three samples (around 0.2 g) of the dried
where W4 is the total weight of all the materials added into the glass latex film were weighed and sealed in a PTFE coated membrane pouch.
bottle before polymerization and W5 is the total weight of monomers. This was then placed in a Soxhlet extractor with tetrahydrofuran (THF),
The coagulum was collected from the bottle cap and 100-mesh filter followed by refluxing for 24h. After the extraction process, the mem­
screen and then dried at 105 ◦ C to a constant weight. The coagulation brane pouch was removed and first dried in a fume hood for 3h and then
was described as the weight of coagulum per total weight of monomer in a vacuum oven at 70 ◦ C until it reached a constant weight. The weight
added. of the remaining dry gel was taken and the gel content was calculated
using equation (3):
2.3.2. Particle size and viscosity
Latex particle size and polydispersity index (PDI) were both Gel content = mass of the dry gel/mass of the initial dry polymer (3)
measured using a Dynamic Light Scattering (DLS) instrument (Malvern
NanoS Zetasizer). The analyses were carried out at 25 ◦ C, and every
result was an average of three parallel measurements. The latex was 2.3.8. Water absorption ratio determination
diluted until the solid content was about 1%. The reported diameter is an The weighted latex films were dipped in distilled water at 25 ◦ C for a
intensity-weighted average particle size. Latex viscosity was measured certain time. Then, the free water on the surface of the films was quickly
removed by filter papers and the films were weighed again. The water
Table 1 absorption ratio of the films was calculated by the following formula:
Compositions and amounts employed in the synthesis of the acrylate latex PSA.
W1 − W0
Compositions Amount (g) Water absorption ratio (wt%) = × 100% (4)
W0
Soft monomer BA 93–97
Cross-linker EGDMA 0–4 where Wo and W1 are the weight of the films before and after the films
Functional monomer AA 1 absorb water, respectively.
HEA 2
Emulsifier A-102 1.5
SR-10 0.5 2.3.9. Contact angle analysis
Initiator APS 0.5 Water contact angles on the latex films were determined by a contact
Continuous phase Deionized water 62.5 angle goniometer (Attension Theta, Biolin Scientific, Sweden) at 20 ◦ C

3
C. Fang et al. International Journal of Adhesion and Adhesives 125 (2023) 103403

using sessile drop method. The used injection volume was 4 μL and the
final data of each sample was an average of at least ten readings.

2.3.10. PSA testing [19,20]

The latex was coated with RK (Manchester, UK) KHC.10.5 wire-rod
coater onto 30 μm thickness, 25 mm width poly(ethylene tere­
phthalate) strip to give a film with a dry thickness of 20 μm and dried in
a vacuum oven at 105 ◦ C for 5 min. The PET strips with adhesive coated
on its one side were sticked on release paper for further tests. Before
tests, the PET strips were conditioned for 24 h at standard conditions of
temperature and humidity (23 ± 2 ◦ C and 50 ± 5% Relative Humidity).
A universal BLD-100S electronic stripping tester was used to evaluate
loop tack and peel strength.
For the loop tack test, the strip was formed into a loop with the ad­
hesive side facing outward. Approximately 25 mm at both ends of the
strip was inserted into the upper grip. The instrument moved the upper
grip downward at a speed of 300 mm/min until an area of 25 mm2 came
into contact with the stainless steel substrate mounted into the lower
grip. Next, the tester moved the upper grip upwards at the same speed
while recording the force needed to detach the loop from the substrate.
The maximum force of detachment was reported as loop tack.
For the 180◦ peel test, strips of the adhesive-coated films were
laminated against the stainless steel substrate using a 2 kg rubber roller.
The rubber roller was passed through the PET strip front to back three
times. After 20 min dwell, 180◦ peel off the substrate was done at 300
mm/min. The average force per 25 mm required to peel the strip from
the substrate was recorded and reported as 180◦ peel strength.
For shear holding power, the strips were laminated against stainless
steel using 2 kg rubber roller to make contact areas of 25 mm2. After 20
min dwell, the sample was fixed in the tester vertically with a 1 kg load
suspended in the other hand. Automatic timers were placed below the
weights to count the time of failure. The shear holding power was the
time that elapsed between the application of the load and the completed
separation of the strip from stainless steel.
Every result was an average of five parallel measurements.

3. Results and discussion

3.1. Characterization of latexes

Table 2 summarizes the latexes synthesized in this work as well as
their main properties including conversion, viscosity, particle size and
PDI values. The results indicated that all the experiments were
completed successfully with final conversions exceeding 95% and
negligible coagulums. And all of the latexes produced in this study had
very low viscosity range from 153 to 168 mPa s. Particle size distribution
(PSD) is usually determined over a list of particle size ranges that covers
nearly all sizes present in the sample. Particle dispersity index (PdI) is
used to evaluate the dispersion of PSD [21]. Fig. 1 exhibits the particle
size and particle size distribution curves for the acrylate PSA latexes
with various contents of EGDMA. It can be seen from Table 2 and Fig. 1
that the average particle size of all the latexes is large and distributed in
the range of 348–353 nm, and the particle size distribution is relatively
wide (PDI >0.1). The wider particle size distribution is more conducive
to the stability of high solid content emulsions.
In an effort to identify latex particle morphology, TEM image was
Fig. 1. Particle size and particle size distribution curves for the acrylate PSA
latexes with different content of EGDMA.
collected. Fig. 2 shows the TEM image of the representative latex PSA-
EGDMA-2. It can be obviously seen that the TEM micrograph pre­
sented regular spherical shape and wide dispersion, which was consis­
tent with the particle size and PSD results aforementioned.
3.2. FTIR analysis
FTIR spectrometer was employed to analyze the chemical structures
of the as-prepared acrylate latex PSAs, and the FTIR spectra of PSA-
EGDMA-0 and PSA-EGDMA-4 are displayed in Fig. 3. It can be seen
that both samples have similar peaks at most positions. The observed
peaks at 2958 and 2873 cm− 1 can be attributed to the stretching vi­
bration of –CH3 [22]. The peaks observed at 1729 and 1158 cm− 1 are
– O and C–O–C [23,24]. The
assigned to the stretching vibration of C–

Table 2
Summary and characteristics of the synthesized acrylate PSA latexes with different content of EGDMA.
PSA ID Formulation (wt% monomers) Conversion (%) Viscosity (mPa⋅s) Particle size (nm) PDI

PSA-EGDMA-0 BA/AA/HEA (97/1/2) 95.96 168 350.8 0.181

PSA-EGDMA-1 BA/EGDMA/AA/HEA (96/1/1/2) 96.20 167 351.2 0.179
PSA-EGDMA-2 BA/EGDMA/AA/HEA (95/2/1/2) 96.35 158 348.4 0.184
PSA-EGDMA-3 BA/EGDMA/AA/HEA (94/3/1/2) 96.49 153 352.6 0.182
PSA-EGDMA-4 BA/EGDMA/AA/HEA (93/4/1/2) 96.64 157 349.1 0.177

4
C. Fang et al.
Fig. 2. TEM image of the acrylate PSA latex particles PSA-EGDMA-2.
Fig. 3. FTIR spectra of acrylate latex PSAs without and with EGDMA.
peaks at 1452 and 1378 cm− 1 correspond to the vibration bending of
–CH3 and –CH2 [25]. The absorption at 1063 and 941 cm− 1 are resulted
from characteristic of BA. Moreover, there are no adsorption peak at
1641 cm− 1 which is attributed to the characteristic of C–
– C bonds of the
monomers.
3.3. DSC analysis
Glass transition temperature (Tg) is one of the most important factors
affecting PSA performance. The DSC curves of the acrylate latex PSAs
with different content of difunctional crosslinking agent EGDMA were
illustrated in Fig. 4. The DSC thermograms show that all copolymers
were amorphous (no crystallization/melting events) and exhibit a single
Tg which gives evidence that copolymers with homogeneous composi­
tion were obtained. Meanwhile, it can be clearly seen from Fig. 4 that the
Tg of the acrylate latex PSA raised from − 41.4 to − 35.4 ◦ C with the
concentration of difunctional crosslinking agent EGDMA increased from
0 to 4 wt%. The result was consistent with the work of Trevino [5], who
found that with the amounts of cross-linker TMI increased from 0 to 3 wt
%, the Tg of the water-borne pressure sensitive adhesive increased from
5
International Journal of Adhesion and Adhesives 125 (2023) 103403
Fig. 4. DSC curves of acrylate latex PSAs with different content of EGDMA.
− 44.9 to − 40.6 ◦ C, which was mainly due to the higher crosslinking
density [26]. On the other hand, the data of Tg from theory calculation
and DSC test with different content of EGDMA are shown in Table 3. It
was found that the measured Tg is about 11–13 ◦ C higher than that of the
theory calculation according to the Fox equation [27]. The reason might
be that hydrogen bonds in polymer chain were formed between the
polar carboxyl and hydroxyl groups, which made a contribution to
physical crosslinking [28].
3.4. TG analysis
The effect of EGDMA content on the thermal properties of the ob­
tained acrylate latex PSAs was evaluated using thermogravimetric
analysis (TGA) and the results were plotted in Fig. 5. It is clearly
observed that the samples with different EGDMA contents show
different degradation behavior. At 100–200 ◦ C, the weight loss of the
latex film is caused due to the elimination of unremoved water [23,29].
The main weight loss that occurs between 300 and 450 ◦ C is due to the
decomposition of the polymer carbon chains [30,31]. As seen from Fig. 5
that the initial decomposition temperature (T5) of the latex film
increased from 341 to 360 ◦ C with the amount of EGDMA increased from
0 to 4 wt%. This is probably because that polymer degradation at high
temperature is associated with the initiation of random scission [32].
And the initiation of this random process may be slow after the addition
of the cross-linker EGDMA due to the dense three-dimensional cross-­
linking network formed in the film. This was consistent with the work of
Ha et al. [33] who found that the higher content of EGDMA improves the
thermal stability of poly(St-co-EGDMA) particles due to increased level
of crosslinking between styrene and EGDMA.
3.5. Water absorption and contact angle analysis
In order to explore the influence of the amount of EGDMA on the
water resistance of the acrylate latex film, the 24 h water absorption
ratio of the latex film was tested. The result is depicted in Fig. 6. As
shown in Fig. 6, the water absorption ratio is 6.8 wt% when EGDMA is
not contained in the latex film. As the amount of EGDMA increases, the
water absorption ratio of the latex film decreases. When the amount of
Table 3
Data of Tg from theory calculation and DSC measurement.
PSA-EGDMA-0 PSA-EGDMA-2 PSA-EGDMA-4
Theoretical Tg ( C)
◦
− 52.4 − 50.2 − 48.0
Measured Tg (◦ C) − 41.5 − 38.1 − 35.4
C. Fang et al.
Fig. 5. TG curves of the acrylate latex PSAs with different amounts of EGDMA.
Fig. 6. Effect of EGDMA content on water absorption of the acrylate latex PSAs.
EGDMA is 4 wt%, the water absorption ratio of the latex film reaches a
minimum of 3.0 wt%. The reason is that formation of dense cross-linked
network after the addition of EGDMA, as shown in Scheme 1, can inhibit
water entering the films and hence improve the water resistance. On the
other hand, it can been seen from Fig. 7 that the water contact angles of
the latex films increased from 82◦ (hydrophilic) to 110◦ (lipophilic) with
the increasing EGDMA, which further confirmed the water absorption
results aforementioned.
3.6. Gel content analysis
Gel content is an important parameter contributing to the adhesion
performance of PSAs. The effect of different content of EGDMA on the
final gel content of the acrylate latex PSAs was investigated and the
results are shown in Fig. 8. It can be clearly seen that the gel content was
increased from 63.90% to 71.01% as the amount of EGDMA increased
from 0 to 4 wt%. This phenomenon is well known for the emulsion
polymerization of BA and BA-dominated comonomer systems [20].
When cross-linker was not used, gel was mainly formed by the inter­
molecular chain transfer to polymer plus the bimolecular termination by
combination (propagation to pendant/terminal double bonds formed by
chain transfer to monomer did not contribute much because of the low
amount of pendant/terminal double bonds formed at the low monomer
6
International Journal of Adhesion and Adhesives 125 (2023) 103403
Fig. 7. Effect of EGDMA content on water contact angle of the acrylate
latex PSAs.
Fig. 8. Effect of EGDMA on gel content of the acrylate latex PSA.
concentrations existing in the polymer particles.). However, when the
divinylic monomer EGDMA was used, the crosslinking reaction (prop­
agation to the pendant double bond of the divinylic monomer) was
predominant and the gel was mainly due to crosslinking, thus increasing
the gel content. The result is consistent with the work of Kajtna et al.
[34], who found the amount of gel increases with addition of diacrylic
monomer in the reaction mixture. Different kinds of gel network formed
in the BA-dominated comonomer systems were shown in Fig. 9.
3.7. Adhesive properties
The results of mechanical strength measurements in terms of tack,
peel and shear strength properties are graphically shown in Fig. 10. Tack
refers to the ability of an adhesive to wet a surface and instantaneously
bind to a substrate. In general, tack depends on the polymer chain’s
mobility and its ability to wet the substrate, so any factor that affects this
mobility affects tack [35]. Peel strength evaluation involves the appli­
cation of external pressure to allow the complete wetting of the adhesive
onto the substrate. What is being measured is the ability of the PSA to
resist forces that pull it apart from the substrate. This property is affected
by the same variables that affect tack, but not strictly in the same
manner. Moreover, to some extent, peel strength increases with Tg and
C. Fang et al. International Journal of Adhesion and Adhesives 125 (2023) 103403

Fig. 9. Different kinds of gel network formed in the BA-dominated comonomer systems.

Fig. 10. The mechanical strength results.

gel content, but peel strength will dramatically decreases when the gel
content is very high (>60 wt%) [36]. Shear strength is an evaluation of
the cohesive strength of a material. High shear strength is normally
recorded for samples with high gel content and crosslink density, while
high gel content simultaneously has a deleterious effect on tack and peel
strength [36].
It can be obviously seen from Fig. 10 that the loop tack and peel
strength are considerably reduced, while shear strength is significantly
increased with the amount of EGDMA increasing from 0 to 4 wt%. The
reason was that when the cross-linker EGDMA was introduced, dense
three-dimensional gel network was formed in the latex PSA film (see
Scheme 1 and Fig. 9) and the gel content was increased. Thus, the
resulting lower deformability and flow ability of the PSA weakened the
bonding between the PSA and substrate, causing lower tack and peel
strength and higher shear strength [1]. The result is consistent with the
work of Czech [37], who found that the increase in cross-linker content
affects negatively the adhesiveness and positively the cohesion of the
PSA.
4. Conclusions
A series of high solids cross-linked acrylate latex pressure sensitive
adhesives, consisting of butyl acrylate (BA), acrylic acid (AA), 2-hydrox­
yethyl acrylate (HEA) and difunctional cross-linker, ethylene glycol

7
C. Fang et al.
dimethacrylate (EGDMA), were successfully synthesized via unseeded
semi-batch emulsion polymerization processes. The main conclusions
derived were as follows.
(1) TEM image illustrated that the particles of the high solid content
latex show regular spherical shape and wide dispersion, which
was consistent with the particle size and PSD results obtained
from DLS measurement.
(2) The water resistance of the latex PSA was improved with
increasing EGDMA content, confirmed by water contact angle
measurements.
(3) DSC and TGA results showed that Tg of the copolymer was
elevated, plus thermal stability was increased with introduction
of EGDMA.
(4) The loop tack and peel strength are considerably reduced, while
shear strength is significantly increased with the amount of
EGDMA increasing from 0 to 4 wt%.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The authors are unable or have chosen not to specify which data has
been used.
Acknowledgment
The test supports from the teachers of Advanced Analysis & Testing
Center of Nanjing Forestry University are greatly appreciated.
References
[1] Benedek I. Pressure-sensitive adhesives and applications. In: Revised and
expanded. second ed. CRC Press; 2004.
[2] Satas D. Handbook of pressure sensitive adhesive technology. second ed. 1989.
[3] Callies X, Herscher O, Fonteneau C, et al. Combined effect of chain extension and
supramolecular interactions on rheological and adhesive properties of acrylic
pressure-sensitive adhesives. ACS Appl Mater Interfaces 2016;8:33307–15.
[4] Sun S, Li M, Liu A. A review on mechanical properties of pressure sensitive
adhesives. Int J Adhesion Adhes 2013;41:98–106.
[5] Treviño ME, Dubé MA. Synthesis of self-crosslinkable water-borne pressure
sensitive adhesives. Macromol React Eng 2013;7:484–92.
[6] Tobing S, Klein A. Molecular parameters and their relation to the adhesive
performance of acrylic pressure-sensitive adhesives. J Appl Polym Sci 2001;79:
2230–44.
[7] Anderson C. High strength pressure sensitive adhesives. US Patent 3769254
(1973).
[8] Lee JH, Lee TH, Shim KS, Park JW, Kim HJ, Kim Y, Jung S. Effect of crosslinking
density on adhesion performance and flexibility properties of acrylic pressure
sensitive adhesives for flexible display applications. Int J Adhesion Adhes 2017;74:
137–43.
[9] Lopez A, Reyes Y, Degrandi-Contraires E, Canetta E, Creton C, Keddie JL, Asua JM.
Simultaneous free-radical and addition miniemulsion polymerization: effect of the
chain transfer agent on the microstructure of polyurethane-acrylic
PressureSensitive adhesives. Macromol Mater Eng 2013;298(1):53–66.
[10] Tobing SD, Klein A, Sperling LH, Petrasko B. Effect of network morphology on
adhesive performance. J Appl Polym Sci 2001;81:2109–17.
International Journal of Adhesion and Adhesives 125 (2023) 103403
[11] Aguirreurreta Z, Dimmer JA, Willerich I, Leiza JR. de la Cal JC. Improving the
properties of water-borne pressure sensitive adhesives by using non-migratory
surfactants. Int J Adhesion Adhes 2016;70:287–96.
[12] Alarcia F, de la Cal JC, Asua JM. Continuous production of specialty waterborne
adhesives: tuning the adhesive performance. Chem Eng J 2006;122(3):117–26.
[13] Chauvet J, Asua JM, Leiza JR. Independent control of sol molar mass and gel
content in acrylate polymer/latexes. Polymer 2005;46(23):9555–61.
[14] Czech Z. Solvent-based pressure-sensitive adhesives for removable products. Int J
Adhesion Adhes 2006;26:414–8.
[15] Bouvier-Fontes L, Pirri R, Arzamendi G, Asua JM, Leiza JR. Branching and
crosslinking in emulsion polymerization. Macromol Symp 2004;206:149–64.
[16] Kim D, Lee DY, Lee K, Choe S. Effect of crosslinking agents on the morphology of
polymer particles produced by one-step seeded polymerization. Macromol Res
2009;14(7):250–8.
[17] Qu J, Cheng J, Wang Z, Han X, Zhao M. Synthesis, thermal and optical properties of
crosslinked poly(isobornyl methacrylate-co-butyl acrylate) copolymer films. Opt
Mater 2014;36:804–8.
[18] Ghazaly HM, Daniels ES, Dimonie VL, Klein A, El-aasser MS. Miniemulsion
copolymerization of n-butyl methacrylate with crosslinking monomers. J Appl
Polym Sci 2001;81:1721–30.
[19] Pressure Sensitive Tape Council. Test methods for pressure sensitive adhesive
tapes. Northbrook, Illinois: Pressure Sensitive Tape Council; 2004.
[20] Fang C, Jing Y, Zong Y, Lin Z. Effect of N,N-dimethylacrylamide (DMA) on the
comprehensive properties of acrylic latex pressure sensitive adhesives. Int J
Adhesion Adhes 2016;71:105–11.
[21] Sun YF, Zhao XF, Liu RP, Chen G, Zhou XD. Synthesis and characterization of
fluorinated polyacrylate as water and oil repellent and soil release finishing agent
for polyester fabric. Prog Org Coating 2018;123:306–13.
[22] Ma A, Zhang Q, Zhang H, Shi Y, Liu Y. A novel single component epoxy resin
adhesive with microcapsule latent curing agent of 2-phenylimidazole/polymethyl
acrylic glycidyl ester. J Elastomers Plastics 2013;47(5):439–48.
[23] Jiao C, Shao Q, Wu M, Zheng B, Guo Z, Yi J, Zhang J, Lin J, Wu S, Dong M, Guo Z.
2-(3,4-Epoxy) ethyltriethoxysilane-modified waterborne acrylic resin: preparation
and property analysis. Polymer 2020;190:122196.
[24] Yang Y, Zhang T, Yan J, Fu L, Xiang H, Cui Y, Su J, Liu X. Preparation and
photochromic behavior of spiropyran-containing fluorinated polyacrylate
hydrophobic coatings. Langmuir 2018;34(51):15812–9.
[25] Wang Y, Long J, Bai Y, Zhang C, Cheng B, Shao L, Qi S. Preparation and
characterization of fluorinated acrylic pressure sensitive adhesives for low surface
energy substrates. J Fluor Chem 2015;180:103–9.
[26] Mukhopadhyay SK, Basu D, Banerjee A. DSC, FTIR and TGA studies on crosslinking
and thermal behavior of vinyl acetate-2-ethylhexyl acrylate copolymer and
hexamethoxymethylmelamine blends. J Appl Polym Sci 1997;65:2075–80.
[27] Sperling LH. Introduction to physical polymer science. fourth ed. New Jersey: John
Wiley & Sons, Inc. Publication; 2006. Chap. 3 & 4.
[28] Lu X, Cao G, Niu Z, Pan Q. Viscoelastic and adhesive properties of single-
component thermo-resistant acrylic pressure sensitive adhesives. J Appl Polym Sci
2014;131. https://doi.org/10.1002/APP.40086.
[29] Chen H, Tian X, Liu J. Unsaturated polyester resin nanocomposites containing ZnO
modified with oleic acid activated by N,N-carbonyldiimidazole. Polymers 2018;
362(10):10030362.
[30] Wang W, Kan Y, Pan Y, Yuan Y, Liew KM, Hu Y. Urchinlike shells of TiO2 hollow
spheres for improving the fire safety of epoxy resin. Ind Eng Chem Res 2017;56(5):
1341–8.
[31] Williams BL, Ding H, Hou Z, Paul PO, Lewis FA, Smith AT, Sun L. Highly efficient
polyvinyl alcohol/montmorillonite flame retardant nanocoating for corrugated
cardboard. Adv Compos Hybrid Mater 2021;4(3):662–9.
[32] Daraboina N, Madras G. Thermal and Photocatalytic Degradation of Poly(methyl
methacrylate), Poly(butyl methacrylate), and their copolymers. Ind Eng Chem Res
2008;47:6828–34.
[33] Ha M, Lee K, Choe S. Crosslinkable functional moiety for the formation of highly
crosslinked stable microspheres in the precipitation polymerization. Polymer 2008;
49:4592–601.
[34] Kajtna J, Golob J, Krajnc M. The effect of polymer molecular weight and
crosslinking reactions on the adhesion properties of microsphere water-based
acrylic pressure-sensitive adhesives. Int J Adhesion Adhes 2009;29:186–94.
[35] Aymonier A, Papon E, Castelein G, Brogly M, Tordjeman P. Influence of surface and
bulk structures of acrylic psa films onto their tack properties. J Colloid Interface Sci
2003;268(2):341–7.
[36] Qie L, Dubé MA. The influence of butyl acrylate/methyl methacrylate/2-hydroxy
ethyl methacrylate/acrylic acid latex properties on pressure sensitive adhesive
performance. Int J Adhesion Adhes 2010;30(7):654–64.
[37] Czech Z. Multifunctional propyleneimines-new generation of cross-linkers for
solvent-based pressure-sensitive adhesives. Int J Adhesion Adhes 2004;24:503–11.