2022, 67, nr 7–8 317

Influence of storage time on the useful properties

of silicone pressure-sensitive adhesives*)
Adrian Krzysztof Antosik1), **) (ORCID ID: 0000-0002-3954-6612), Karolina Mozelewska1) (0000-0001-8963-4349)
DOI: https://doi.org/10.14314/polimery.2022.7.4

Abstract: The influence of the storage time on the useful properties (cohesion, adhesion, stickiness) of
silicone pressure-sensitive tapes (Si-PSA) was investigated. Two types of silicone resins PSA 529 and PSA
590 (Momentive, USA) were used and crosslinked with bis (2,4-dichlorobenzoyl) peroxide (DClBPO).
There was no significant effect of tapes long-term storage (7 years) on their properties. The tapes based
on PSA 590 resin were more resistant to aging than PSA 529.
Keywords: pressure-sensitive adhesives, silicone, self-adhesive tape, storage time.

Wpływ czasu przechowywania na właściwości użytkowe silikonowych

klejów samoprzylepnych
Streszczenie: Zbadano wpływ czasu przechowywania na właściwości użytkowe (kohezja, adhezja,
kleistość) silikonowych taśm samoprzylepnych (Si-PSA). Stosowano dwa rodzaje żywic silikonowych
PSA 529 i PSA 590 (Momentive, USA), które sieciowano przy użyciu nadtlenku bis(2,4-dichlorobenzo-
ilu) (DClBPO). Nie stwierdzono istotnego wpływu długotrwałego przechowywania (7 lat) taśm na ich
właściwości. Większą odpornością na starzenie charakteryzowały się taśmy otrzymane na bazie żywicy
PSA 590 niż PSA 529.
Słowa kluczowe: kleje samoprzylepne, silikony, taśmy samoprzylepne, czas przechowywania.

Self-adhesive materials in the international industry are properties, chemical resistance, and exceptional weather
called pressure-sensitive adhesives. Such adhesives adhere resistance [3–4]. In most cases, in comparison with organic
to its surface during a short contact with the substrate, PSA, they show better performance properties. Traditional
without chemical reaction or physical transformation [1]. silicones consist of high molecular weight functional sili-
Polymers like acrylic polymers, SIS and SBS rubbers, cone polymers and siloxane resins. It is well known that
polysiloxanes, polyurethanes, polyesters, polyethers, and the silicone pressure-sensitive adhesives are useful for
EVA polymers are used in the technology of producing special applications. Since the year 2000, there has been
pressure-sensitive adhesives, which many times replace much interest in new uses for silicone PSA, especially in
the standard techniques of joining materials, such as riv- applications such as medical and industrial tapes [5–7].
eting, welding, or drilling. Increased demand for self- Many researchers proved that silicone PSA are able to
adhesive adhesives can be observed both in industry and withstand the high processing temperatures and harsh
everyday practice [2]. conditions of modern industrial operations [5, 8].
Silicone pressure-sensitive adhesives (Si-PSA) exhibit Lin conducted various experiments to investigate the
unique properties such as high flexibility of the Si-O-Si thermal stability of silicone PSA. It was observed that sili-
backbone, low intermolecular interactions, low surface cone polymers, including polydimethylsiloxane (PDMS),
tension, excellent thermal stability, and high UV transpar- methyl silicone, etc., underwent significant thermal deg-
ency, making silicone PSA highly effective in extreme high radation in air at high temperatures. The thermal stabil-
and low temperatures, characterized by excellent electrical ity of the silicone PSA was inherently better than that of
their corresponding silicone polymer components. None
1)
West Pomeranian University of Technology, Szczecin, Facul- of the PSA silicone blends experienced more than moder-
ty of Chemical Technology and Engineering, Department of ate weight loss [9].
Chemical Organic Technology and Polymeric Materials, Pula- Aging tests for selective adhesive compositions were
skiego 10, 70-322 Szczecin, Poland. performed by Antosik et al. and excellent properties were
*) Material contained in this article was presented at the exhibited. With increasing aging of the silicone PSA, low
X Kongres Technologii Chemicznej “X TECHEM”, 11–14 May adhesion and tack were observed. However, aging did
2022, Wrocław, Poland. not affect the cohesion of the adhesive films at 20°C and
**) Author for correspondence: [email protected] 70°C [10].
318 POLIMERY 2022, 67, nr 7–8

In this study, the influence of the storage time of self- stable conditions in an incubator at a temperature of 23°C
adhesive tapes on their self-adhesive and useful proper- and a humidity of 50 without exposure to UV radiation.
ties was investigated. During experiments, the coated Analogously the tape was prepared from silicone pres-
and protected adhesive films were stored at room tem- sure-sensitive adhesive resins’ composition and tested.
perature for 7 years. The properties of tapes were exam-
ined immediately after production and after 7 years of Methods
storage. In the available publications, no research was
conducted so far in time to confirm the uniqueness of The peel adhesion of pressure-sensitive silicone adhe-
silicone pressure-sensitive adhesives. sives was tested using a Zwick-Roell Z1 machine in accor-
dance with the procedures of the international standard
EXPERIMENTAL PART Association des Fabricants Europeens de Rubans Auto-
Adhesifs (AFERA) 4001. A 2.5 cm wide adhesive tape
Materials was sticked to a steel plate under pressure 2 kg of hard
rubber roller. The plate was placed in the jaws of a test-
Commercial silicone resins PSA 529 and PSA 590 ing machine and the free end into the other jaw. The test
(Momentive, USA) were used to obtain the self-adhesive measured the force with which the tape was peeled off
silicone tapes. Bis(2,4-dichlorobenzoyl)peroxide (DClBPO) the plate at a constant speed of 300 mm/min. The result
produced by Peroxid-Chemie (Germany) was used as the was the average of three measurements. The steel plates
crosslinker. To obtain a uniform composition of the adhe- used for the tests should be perfectly flat, 200 mm long,
sive, toluene was added to the resin with the addition of 50 mm wide and about 2 mm thick, made of polished
0–3 wt% DClBPO and stirred until the mixture became stainless steel (of a Brinell hardness ranging from 130 to
homogeneous. Firstly, the appropriate amount of the cross- 200). They should contain the following elements: carbon
linking compound was weighed, and after that toluene <0.12%, nickel >8%, chromium >17% [11–12].
was dosed in such an amount to obtain a 50% solution. Tack was also measured using a Zwik-Roell Z1 testing
After dissolving the crosslinker in toluene, pressure-sensi- machine according to the procedures of the International
tive adhesives PSA 529 or PSA 590 were added and mixed Standard Association des Fabricants Europeens de Rubans
by hand until a homogeneous mixture was obtained. The Auto-Adhesifs (AFERA) 4015. This method measured the
composition containing 50 wt% of the polymer was coated force to detach the tape from a metal plate without pres-
with a polyester film with a thickness of 50 µm using sure. The contact area of the adhesive layer with the sub-
a semi-automatic coater designed at the International strate during the test was 5 cm2 (2.5 × 2 cm) [13–14]. The steel
Laboratory of Adhesives and Self-Adhesive Materials plate had the same parameters as in case of peel adhesion.
at the West Pomeranian University of Technology in The cohesion test was carried out according to the
Szczecin. The films coated in this way were crosslinked method of Fédération Internationale des Fabricants
at a temperature of 110°C for 10 minutes, resulting in self- et Transformateurs d’Adhesifs et Thermocollants sur
adhesive adhesive films with a basis weight of 45 g/m2. Papiers et Autres support (FINAT) FTM 8. A 2.5 × 2.5 cm
The adhesive layer was then secured with a polyester film sample of the tape was glued to a metal plate and then
and cut. One-sided tapes obtained in this way were tested, loaded with a 1 kg weight. During the test, the time
measuring: cohesion at different temperatures, adhesion, needed to detach the tape sample from the metal plate
tack, and the SAFT test. In order to study the aging process
of silicone pressure-sensitive adhesives, all measurements
were carried out after 1 hour and 7 years after receiving
the tape. The tapes tested after 7 years were stored in

Fig. 1. Peel adhesion test at an angle of 90° and 180° Fig. 2. Tack test scheme: a) sample (2) formed into a loop appro-
aches the metal plate (1), b) after contact of the sample (2) with
the plate (1), the plate is separated from the loop.
POLIMERY 2022, 67, nr 7–8 319

Table 2 shows the results of the cohesion at the temper-

ature of 20°C depending on the amount of the compound
used in crosslinking. In case of PSA 529, for all amounts
of crosslinker, the maximum cohesion value of more than
72 hours was obtained immediately after the production
of the tape, as well as after 7 years of storage. Similar
values were also found for adhesive PSA 590. The cohe-
sion value at 20°C was greater than 72 hours. The table
also shows the cohesion results for the adhesives with-
out crosslinker. It can be seen that adhesive PSA 590 had
a higher cohesion value comparing to adhesive PSA 529
(without crosslinker). The obtained results are analogous
to those presented in the literature for tapes examined
immediately after production and stored for a shorter
period of time (up to 9 months) [10, 20–21]. Maintaining
the value for 7 years proves the high resistance of the
materials.
Fig. 3. Cohesion test Figure 4 shows the results of cohesion at 70°C for PSA
529. On the graph, we can observe the dependence of
was measured. This test was carried out at room tempera- the cohesion on the amount of crosslinking compound.
ture and elevated temperature (70°C). The steel plate had The values of cohesion increased with increasing of the
the same parameters as in case of peel adhesion [15–16]. content of crosslinking compound until a maximum at
The SAFT test was also performed in the presented 2.5 wt% was reached. The cohesion results for samples
work. It was performed in a similar way to cohesion, after 7 years of storage are marked in red. They were
except that the test temperature was increasing in time higher comparing to the samples that were tested imme-
(from 20°C to 225°C). The test measured the time required diately after making the tape. Figure 5 shows the results
to detach the sample from the metal plate. It was also of cohesion at 70°C for the second adhesive PSA 590. The
a determination of the maximum operating temperature results for tapes received immediately after preparation
of a given sample of adhesive tape. The starting tempera- are marked in black, and for the content of 1.5 wt% of
ture for the test was room temperature: 22°C. The tem- crosslinking compound and higher they showed the
perature was changing at a rate of 1°C per minute [17–18]. maximum values: over 72 hours. For tapes stored for
The obtained results were presented as an average 7 years, the values were similar, while the maximum
value with standard deviations of at least five replicates. value was obtained for 1 wt% of the crosslinking com-
Where relevant, the data were subjected to one-way anal- pound. It could be seen that adhesive PSA 590 had a better
ysis of variance using ANOVA test. cohesion value than PSA 529. The tests confirmed previ-
ous observations that the PSA 529 resin exhibited lower
RESULTS AND DISCUSSION cohesive properties comparing to the second tested resin.
These results clearly translate into the results of cohesion
Table 1 shows the results for PSA 590 and PSA 529 com- at elevated temperature, both immediately after prepara-
mercial silicone adhesives, without the DClBPO cross- tion and after seven years of storage [10, 20–21].
linking compound. In most cases, the values of the pro- Figures 6 and 7 show the adhesion results for PSA 529
perties tested did not differ significantly between the tape and PSA 590 as a function of the amount of crosslinker.
stored for 7 years and the samples continuously tested In case of PSA 529, it could be observed that the adhe-
immediately after producing. This confirms the informa- sion value increased to the limit value for 2.5 wt%, while
tion about the unique properties of Si-PSA described in for 3.0 wt% the value dropped rapidly. For a tape sample
the literature [5, 8–10, 16–19]. stored for 7 years, the adhesion value increased to the limit

T a b l e 1. Performance of pressure-sensitive adhesives PSA 529 and PSA 590 without crosslinking compound
Cohesion
Peel
Silicone Detach time Detach time SAFT Tack
adhesion
resin at 20°C at 70°C °C N/25 mm
N
h h
Immediately after production 18.03 0.18 77 9.82 3.61
PSA 529
After 7 years 25.45 0.17 89 9.27 6.25
Immediately after production 10.12 0.08 75 7.97 8.85
PSA 590
After 7 years >72 5.6 87 8.29 9.13
320 POLIMERY 2022, 67, nr 7–8

T a b l e 2. Cohesion at 20°C for the tested tapes

Silicone DClBPO Detach time
resin wt% h
0.0 18.03
0.5 >72
1.0 >72
Immediately after production PSA 529 1.5 >72
2.0 >72
2.5 >72
3.0 >72
0.0 25.45
0.5 >72
1.0 >72
After 7 years PSA 529 1.5 >72
2.0 >72
2.5 >72
3.0 >72
0.0 10.12
0.5 >72
1.0 >72
Immediately after production PSA 590 1.5 >72
2.0 >72
2.5 >72
3.0 >72
0.0 15.29
0.5 >72
1.0 >72
After 7 years PSA 590 1.5 >72
2.0 >72
2.5 >72
3.0 >72

30
0 years 0 years
7 years
80 7 years

20 60
Detach time, h
Detach time, h

40

10

20

0 0
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0

DCIBPO, wt% DCIBPO, wt%

Fig. 4. Effect of DCIBPO content of detach time for PSA 529; co- Fig. 5. Effect of DCIBPO content of detach time for PSA 590; co-
hesion at 70°C hesion at 70°C
POLIMERY 2022, 67, nr 7–8 321

17
0 years 15 0 years
16 7 years 7 years
14
15
13

Peel adhesion, N
14
Peel adhesion, N

12
13
11
12
10
11
9
10
8
9
7
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
DCIBPO, wt% DCIBPO, wt%
Fig. 6. Peel adhesion of PSA 529 tapes Fig. 7. Peel adhesion of PSA 590 tapes

12 11
0 years 0 years
10
11 7 jears 7 years
9
10
8
9 7
Tack, N/25 mm
Tack, N/25 mm

8 6
5
7
4
6 3

5 2
1
4
0
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
DCIBPO, %wt DCIBPO, wt%
Fig. 8. Tack of PSA 529 tapes Fig. 9. Tack of PSA 590 tapes

240
0 years 220 0 years
220 7 years 7 years
200
200
180
180
160
SAFT, °C
SAFT, °C

160
140
140

120 120

100 100

80 80

0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0
DCIBPO, wt% DCIBPO, wt%
Fig. 10. Maximum working temperature for PSA 529 Fig. 11. Maximum working temperature for PSA 590
322 POLIMERY 2022, 67, nr 7–8

value for 1.5 wt% and then slightly decreased. With PSA ties (cohesion, adhesion, stickiness). In the case of the con-
590, the results were similar. For the adhesive tested imme- tent of the cross-linking compound above 1.5 wt% the stick-
diately after production, the adhesion value increased to iness of the samples decreased and increased with a smaller
the content of 1.5 wt%, and then decreased quite quickly. one. The self-adhesive tapes based on PSA 590 resin showed
Likewise for a sample stored for 7 years: the value reached higher aging resistance than PSA 529. The unique proper-
a maximum for 1 wt% and subsequent concentrations ties of silicone adhesive tapes have been confirmed.
showed lower values. Two lines are marked in the graphs:
the black line marked with 0 is the adhesion value without ACKNOWLEDGMENT
the DClBPO crosslinker for the sample tested immediately This research was funded by the National Center for Research
after preparation. On the other hand, the red line marked and Development (NCBiR) as part of the LIDER initiative.
with 0 is the initial adhesion value, without the crosslink- Project number LIDER/9/0028/L-11/19/NCBR/2020.
ing compound, for the sample stored for 7 years. In virtu-
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