Viscoelastic Properties of Pressure-Sensitive Adhesives

Recent studies on the correlation of viscoelastic properties of pressure-sensitive adhesive (PSAs) with industry standard performances such as peel, tack and shear are reviewed and discussed. One notewothy feature in these correlations is the separation of the bonding and debonding steps in PSA adhesion, which specifies the characteristic bonding and debonding frequencies of different PSA tests. Viscoelastic windows (VW) for different types of pressure-sensitive adhesives (PSAs) proposed by these workers are also compared and discussed. The observed good correlations reaffirm the importance of bulk viscoelastic properties to PSA adhesion performances.     

PSA performances and viscoelastic properties of SIS‐based PSA blends with H‐DCPD tackifiers

Hotmelt pressure sensitive adhesives (PSAs) usually contain styrenic block copolymers like styrene–isoprene–styrene (SIS), SBS, SEBS, tackifier, oil, and additives. These block copolymers individually reveal no tack. Therefore, a tackifier is a low molecular weight material with high glass transition temperature (T_g), and imparts the tacky property to PSA. The SIS block copolymer with different diblocks was blended with hydrogenated dicyclopentadiene (H‐DCPD tackifier), which has three kinds of T_g. PSA performance was evaluated by probe tack, peel strength, and shear adhesion failure temperature. PSA is a viscoelastic material, so that its performance is significantly related to the viscoelastic properties of PSAs. We tested the viscoelastic properties by dynamic mechanical analysis and the thermal properties by differential scanning calorimeter to investigate the relation between viscoelastic properties and PSA performance. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2839–2846, 2006     

Acrylate Copolymer/Ultraviolet Curable Oligomer Blends as Pressure-sensitive Adhesives

For the blends of acrylate copolymer [poly(2-ethylhexyl acrylate-co-acrylic acid); P(2EHA-AA)] with ultraviolet (UV) curable oligomer [urethane acrylate oligomer; UAO], pressure-sensitive adhesive (PSA) properties, such as peel adhesion, probe tack, and holding power were examined. The values of peel adhesion and probe tack of the P(2EHA-AA)/UAO blends were dramatically reduced by UV irradiation. On the other hand, all blends had a high holding power even if these blends were cured by UV irradiation. The mechanism of reduced PSA properties was investigated via dynamic mechanical properties, DSC, and dynamic contact angle (DCA). The peel adhesion decreased monotonically with increasing storage modulus, E′, and loss modulus, E″, for all non-UV and UV-cured blends. Since modulus values and glass transition temperatures, Tg, of these blends after UV irradiation were higher than those of these blends before UV irradiation, we judged that the reduced peel adhesion and probe tack values were caused by the modulus increase and the Tg increase due to UV irradiation. In other words, the ability of the deformation energy of UV-cured blends to influence the adhesive tests was reduced by the curing process. The DCAs of non-UV-cured blends were the same as those of UV-cured blends. We presumed that the segment mobility of the polymer chain on the surface did not contribute to the reduced peel adhesion and probe tack values.     

Evaluation of natural rubber latex-based PSAs containing aliphatic hydrocarbon tackifier dispersions with different softening points—Adhesive properties at different conditions

Natural rubber latex-based water–borne pressure sensitive adhesives (PSAs) have been formulated with three aliphatic hydrocarbon water-based dispersions (varying softening points) at two different resin addition levels (25% and 50%). Time–temperature superposition analysis using WLF approximations for adhesive peel has revealed that the adhesives formulated with 50% resin addition level show good adhesive behavior. It has also been determined from time–temperature superposition analysis that peel force increases systematically with softening point and peel rate. Correlation of viscoelastic behavior with adhesive properties suggests that at least 50% resin addition level is needed to bring the natural rubber-based formulations into PSA criteria as defined by Dahlquist and others. Adhesive property evaluations performed on a high surface energy substrate (stainless steel) and low surface energy substrate (LDPE) suggested that optimum tack, peel and shear properties at room temperature were obtained for a formulation containing a higher softening point dispersion (95 °C) at 50% resin addition level. Adhesive peel and tack tend to follow softening point trends as well. A 25% tackifier dispersion addition level did not provide any significant adhesion. Humid aging (50 °C and 100% relative humidity) evaluations of the water–borne adhesives seem to correlate well with the room temperature adhesive property observations.     

A review on mechanical properties of pressure sensitive adhesives

The aim of this review is to summarize research works on mechanical properties of pressure sensitive adhesives (PSAs). The mechanical properties of PSAs are usually described by tack, shear resistance and peel strength, which are strongly dependent on bulk viscoelastic properties of adhesive system. Here, we review some typical peeling models and the correlation of bulk viscoelastic properties to peel, shear and tack. Different factors affecting bonding and debonding properties of PSAs are examined in light of their relevance to rheological properties. The effects of substrate surface roughness are also reviewed. At last, some important new characterization methods together with rheology will be discussed.     

Pressure Sensitive Adhesive Properties and Miscibility in Blends of Poly(vinyl ethylene-co-1,4-butadiene) with Hydrogenated Terpene Resin

The pressure sensitive adhesive (PSA) properties of two samples of poly(vinyl ethylene-co-1,4-butadiene) (V-BR) (vinyl content: 47.4 and 60 wt%) blended with hydrogenated terpene resin (CLEARON P125) were measured on blend compositions having CLEARON P125 contents (by weight) of 10%, 30% and 50%. The maximum values of 180° peel adhesion, rolling ball tack and probe tack were observed with a V-BR/CLEARON P125 70/30 blend, whereas the maximum values of holding power were obtained with a 50/50 V-BR/CLEARON P125 blend. In these blends, the miscibility between V-BR and CLEARON P125 was confirmed by means of SEM, DSC and light scattering. The influences of surface tension and dynamic mechanical properties on PSA properties were investigated. The surface tension values were essentially the same in all the V-BR/CLEARON P125 blends. Minimum values of storage modulus G′ and loss modulus G″ at room temperature in V-BR/CLEARON P125 blends were obtained with a 70/30 blend. Thus, it is believed that in V-BR/CLEARON P125 blends, 180° peel adhesion and tack are related to the dynamic mechanical properties.     

The effects of substrate surface properties on tack performance of acrylic Pressure-Sensitive Adhesives (PSAs)

The effects of substrate surface free energy (SFE) and substrate roughness on tack performance of adhesive tapes containing synthesized model acrylic pressure-sensitive adhesive (PSA) have been investigated. In order to study the influence of substrate SFE on tack the adherents with the same surface roughness (expressed by selected amplitude parameters) were used: PTFE, PP, PE, ABS, PC, PMMA, stainless steel and glass. The relationship between substrate roughness and tack was investigated using two polypropylene plates (PP and PP_rough) characterized as having the same wettability (SFE). For tack determination the most common method in the PSA tapes industry was employed (loop tack test). The conducted experiments showed that substrate SFE is a crucial factor governing tack properties of acrylic PSAs. In general, a larger difference between the SFE values of the substrate and adhesive were correlated with greater tack values. The dependence of tack and SFE was significantly influenced by crosslinking degree and layer coat weight of model acrylic PSA. The experiments carried out in the second part of the study revealed that the adhesive׳s viscoelastic properties control the tack properties on rough substrates, however, the final tack performance was found to be strongly affected by the level of substrate roughness and PSA thickness.     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

Unique adhesive properties of pressure sensitive adhesives from plant oils

We report novel insights into the adhesive performance of bio-based pressure sensitive adhesives (PSAs). Three different homopolymers based on renewable fatty acid methyl esters were characterized in terms of their mechanical and adhesive properties. The polymers display the typical dependence of adhesive properties on molecular weight and degree of crosslinking, as quantified by shear modulus, tack and peel measurements. The absolute values of characteristic adhesion parameters are in the range of commercially available petrochemical PSAs. Curing of applied PSA films at elevated temperature results in a pronounced maximum in tack and peel strength at a critical curing time, which corresponds to a change from cohesive to adhesive failure. Thus, demand-oriented tailoring of adhesive properties can be achieved via an appropriate choice of curing time. Moreover, these bio-based adhesives offer improved adhesion on hydrophobic substrates and high water-resistance without any whitening, thus rendering them an attractive alternative to conventional petroleum-based products. These peculiar features are attributed to the high hydrophobicity of the used monomers.     

Adhesion properties of polyacrylic block copolymer pressure-sensitive adhesives and analysis by pulse NMR and AFM force curve

The adhesion strength of a pressure-sensitive adhesive (PSA) is influenced by two factors, the interfacial adhesion and the cohesive strength. A suitable method for the estimation of these two factors was investigated. Blends of triblock and diblock copolymers consisting of poly(methyl methacrylate) (hard) and poly(n-butyl acrylate) (soft) blocks (A) and blends of triblock copolymer and poly(n-butyl acrylate) oligomer (B), both with different blend ratios, were prepared as model PSAs. The peel strength decreased with an increase in the hard block content for B, whereas it was independent for A. The tack increased with a decrease in the hard block content for A, whereas it was independent for B. The influence of the hard block content on the peel strength and tack was thus different. The ¹H pulse nuclear magnetic resonance analysis and force curve analysis showed that the molecular mobility was higher for B than for A. The Young's modulus and adhesive energy calculated by the Johnson–Kendall–Roberts two-point method using the atomic force microscopy (AFM) force curve qualitatively reflected the cohesive strength and the interfacial adhesion, respectively. The Young's modulus and adhesive energy are found to be useful parameters to investigate the adhesion mechanism. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47791.     

Effect of Temperature on Probe Tack Adhesion: Extension of the Dahlquist Criterion of Tack

At a molecular level adhesive joint strength of pressure-sensitive adhesives (PSAs) is governed by the ratio between two generally conflicting factors: high energy of cohesive molecular interactions and large free volume. Increase in temperature leads to domination of the free volume contribution over the cohesive strength, affecting mechanisms of the debonding process, examined with a probe tack test. Linear viscoelastic properties and probe tack adhesion of five types of PSAs have been studied: polyisobutylene (PIB); acrylic, styrene-isoprene-styrene (SIS) triblock copolymer; hydrogen-bonded complex of high molecular weight poly(N-vinyl pyrrolidone), PVP; with oligomeric poly(ethylene glycol), PEG; and plasticized polybase—polyacid polyelectrolyte complex (PEC). The transition from solid-like mechanism of debonding to ductile type of adhesive bond failure with fibrillation of adhesive layer has been established to occur for all examined PSAs under temperature increase within the range from ?20 to 80°C. The Dahlquist criterion of tack, which defines the value of the storage modulus, G′, below 0.1 MPa, featured for all the PSAs demonstrating maximum work of debonding, has been found to have a universal character and holds at corresponding temperatures for all the PSAs examined, including both typical and innovative adhesives. In addition to this adhesion predictor we have also established that for all the PSAs the transition from a solid–like debonding mechanism to a ductile type of debonding is observed in the range of G′ = 0.09–0.34 MPa. The value of the dissipation factor, tan δ, is also included in the analysis of correlation between linear viscoelasticity and probe tack behavior.     

Incorporation of cellulose nanocrystals and reactive surfactants for improved pressure-sensitive adhesive performance

Pressure-sensitive adhesives (PSAs), which achieve instantaneous adhesion with the application of light pressure, are used in a large range of commodity applications. In this work, PSAs enriched with cellulose nanocrystals (CNCs) and stabilized with a reactive surfactant (Hitenol AR-1025, AR) were synthesized via in situ emulsion polymerization. Incorporation of CNCs into AR-stabilized PSAs lead to improvements of peel strength, shear strength, and loop tack with significant increases observed at a CNC concentration of 0.75 parts per hundred monomer (phm). A comparative investigation of PSAs stabilized with reactive (AR) and non-reactive (sodium dodecyl sulfate) surfactant revealed that the enhanced performance can be attributed to the synergistic combination of CNCs and reactive surfactant, as only modest improvements can be attributed to surfactant type. In contrast to previous studies that report a trade-off in adhesive properties, we present a well-rounded PSA with exceptional peel strength, shear strength, and loop tack.     

Preparation and rheological studies on the solvent based acrylic pressure sensitive adhesives with different crosslinking density

On the basis of synthesis of a series of solvent based acrylic pressure sensitive adhesives (PSAs) with different crosslinking density, the thermal and rheological properties were characterized. T_g values were increased after crosslinked with MDI, and the thermal stability was also improved. Rheological studies were performed via frequency sweep, amplitude sweep, temperature sweep patterns, respectively. The creep recovery properties were also researched. In this way, it was proved that the linear viscoelastic (LVE) range was elongated as the feeding MDI increased, the elastic modulus (G′) of the acrylic PSAs was obviously increased after crosslinked with MDI whereas hardly making any change to the viscous modulus (G″). In the frequency sweep pattern, the PSAs samples behave as pseudoplastic non-Newtonian fluid; and zero shear viscosity increased as the feeding MDI mass ratio was increased, after discussing the cross-over frequency (?^?) and the relaxation time t_R, it can be concluded that the addition of MDI would make for the improvement of the elasticity of the PSAs; in the temperature sweep pattern, it could be seen that the cross-over temperatures (where G″=G′) were 34 and 70 °C for the samples crosslinked with 0 wt% and 0.1 wt% MDI, respectively. When the mass ratio of MDI fed was higher than 0.1 wt%, even though the temperature increased to 120 °C, the samples remained elastic (G′>G″). In the creep recovery test, it was noteworthy that as the feeding ratio of MDI was increased, the creep recovery properties of the acrylic PSAs were substantially improved. And for the same sample, as the applied constant stress increased from 200 to 1000 Pa, the recoverable proportion of the materials was principally not changed in that all the experiments were carried out within the linear viscoelastic range of the samples. And the sample crosslinked with 0.5 wt% MDI shows the highest 180° peel stress.     

Acrylate Copolymer/Ultraviolet Curable Oligomer Blends as Pressure-sensitive Adhesives

For the blends of acrylate copolymer [poly(2-ethylhexyl acrylate-co-acrylic acid); P(2EHA-AA)] with ultraviolet (UV) curable oligomer [urethane acrylate oligomer; UAO], pressure-sensitive adhesive (PSA) properties, such as peel adhesion, probe tack, and holding power were examined. The values of peel adhesion and probe tack of the P(2EHA-AA)/UAO blends were dramatically reduced by UV irradiation. On the other hand, all blends had a high holding power even if these blends were cured by UV irradiation. The mechanism of reduced PSA properties was investigated via dynamic mechanical properties, DSC, and dynamic contact angle (DCA). The peel adhesion decreased monotonically with increasing storage modulus, E', and loss modulus, E', for all non-UV and UV-cured blends. Since modulus values and glass transition temperatures, Tg, of these blends after UV irradiation were higher than those of these blends before UV irradiation, we judged that the reduced peel adhesion and probe tack values were caused by the modulus increase and the Tg increase due to UV irradiation. In other words, the ability of the deformation energy of UV-cured blends to influence the adhesive tests was reduced by the curing process. The DCAs of non-UV-cured blends were the same as those of UV-cured blends. We presumed that the segment mobility of the polymer chain on the surface did not contribute to the reduced peel adhesion and probe tack values.     

Molecular design for silane‐terminated polyurethane applied to moisture‐curable pressure‐sensitive adhesive

Moisture‐curable silane‐terminated polyurethanes (SPUs) served as pressure‐sensitive adhesive (PSA) were synthesized based on different soft‐segment materials, silanes and silane end‐capping ratios. Depending on peel strength, tack, and holding power, the characteristic properties for PSA, a proper scheme for the design of the PSA molecular structure could be selected. Completely end‐capped by silane and assembled by poly(propylene glycol), SPU films presented better properties. On the basis of comprehensive considerations, the anilinomethyltriethoxysilane was an excellent silane‐end capper for PSA. Otherwise, the obtained PSAs did not degrade below 250 °C. The glass transition temperature and hydrophobicity of SPU samples with different formulas were also investigated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45292.     

Tack properties and adhesion mechanism of two different crosslinked polyacrylic pressure-sensitive adhesives

Tack properties of cross-linked random poly(n-butyl acrylate-acrylic acid) (A) and poly(2-ethylhexyl acrylate-acrylic acid) (B) copolymers as pressure-sensitive adhesives (PSAs) were compared by a probe tack test to know the optimal application in the industrial field. Tack increased remarkably with temperature, reached a peak, then decreased. The peak of tack appeared at higher temperature for B. Tack increased with increasing contact time and decreasing crosslinking agent level. The fracture energy at higher temperature was higher for B than A. From the observation of debonding behavior, the fibrillation occurred at the edge of probe. The wettability and deformability of PSA were larger for B than A. From a dynamic mechanical analysis, the shear storage modulus (G') in the rubbery plateau region was lower for B than for A. The good wettability and deformability were improved as a result of its lower G'. The relaxation behaviors of PSAs and vulcanized isoprene rubber were measured by ¹H pulsed nuclear magnetic resonance. This technique is found to be useful for estimating the degree of intermolecular interactions. The crosslinking degree hardly influenced. The intermolecular interaction was weaker for B. This was the reason of the lower G' for B.     

Fundamental Understanding in Rolling Ball Tack of Tackified Block Copolymer Adhesives

In the pressure sensitive adhesive (PSA) industry, rolling ball tack is a very common tack test, which is simple, inexpensive and easy to operate. This work attempts to search for key parameter(s), which will affect the rolling ball tack of a PSA based on a blend of styrene-isoprene-styrene triblock copolymer(SIS) and hydrocarbon tackifier(s). We want to better understand whether this particular PSA performance is controlled by the surface or bulk properties of the adhesive.

Firstly, to test the contribution from the surface properties, we employ a model system of SIS/aliphatic tackifier in 1/1 wt. ratio as the control. Part of the tackifier in this PSA is then replaced by various amounts of low molecular weight diluents with different surface tensions. The idea is to vary the surface properties of the PSA because these low surface tension and low molecular weight diluents tend to migrate to the PSA surface. It is observed that the incorporation of a lower surface tension and a lower molecular weight diluent in the PSA tends to produce a larger increase in rolling ball tack compared with the unmodified PSA. On the other hand, the incorporation of a higher surface tension and a more compatible diluent tends to produce a larger increase in loop, peel and quick stick. Each diluent lowers the shear adhesion failure temperature (SAFT) of the diluent-modified PSA. These observations are explained in terms of tackifier molecular weight, and surface tension and compatibility of the various components (polyisoprene, tackifier, diluent and oil) in the adhesive formulation.

Secondly, to test the contribution from the bulk properties, we derive an equation for rolling ball tack in terms of the bulk viscoelastic behavior of the block copolymer PSA. However, experimental values of rolling ball tack do not follow this equation. Also, with increasing tackifier concentration in SIS, rolling ball tack has very different behavior compared with loop, peel, quick stick and probe tack. The latter set of performance criteria is known to be related to PSA bulk viscoelastic behavior. Therefore, these suggest that rolling ball tack is related more to the surface properties than to the bulk properties of the adhesive based on these results and those of the diluent-modified PSA systems.     

Poly(butyl acrylate)/poly(vinylidene fluoride-co-hexafluoroacetone) blends as pressure-sensitive adhesives

The pressure-sensitive adhesive (PSA) properties and dynamic mechanical properties were measured for the poly(butyl acrylate) (PBA)/poly(vinylidene fluoride-co-hexafluoroacetone) [P(VDF-HFA)] blends. The PSA properties of PBA adhesive could be controlled by blending P(VDF-HFA). In order to investigate the relationship between PSA properties and dynamic mechanical properties for PBA/P(VDF-HFA) blends, the master curves of the dynamic mechanical properties, such as storage modulus G′, loss modulus G′′, and dynamic loss tangent tan c, were constructed with the temperature-rate superposition principle. The probe tack and peel strength for PBA/P(VDF-HFA) blends were correlated with G′ and G′′. Since the G′ and G′′ values increased with increasing P(VDF-HFA) content, the holding power of PBA adhesive could be advanced by blending P(VDF-HFA). © 1997 John Wiley & Sons, Inc.     

Effect of organoclay and chain-transfer agent on molecular parameters and adhesion performance of emulsion pressure-sensitive adhesives

Organoclay-reinforced pressure-sensitive adhesives (PSAs) based on poly(butyl acrylate-co-vinyl acetate-co-acrylic acid) were prepared in the presence of an organically modified montmorillonite, that is, Cloisite15A (C15A), via in situ batch emulsion polymerization. The effect of C15A and chain transfer agent (CTA) level on the molecular parameters and adhesion properties of resulting reinforced PSA were investigated. Small-angle X-ray scattering (SAXS), gel permeation chromatography (GPC), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC) were used to determine the characteristics of the neat and reinforced PSAs. The adhesion test results showed that the incorporation of C15A up to 1 wt% considerably increased the peel strength, shear and probe tack due to increasing the entanglement density of the PSA copolymer, while further increase lowered the peal and tack properties. Interestingly, the addition of 0.25 wt% CTA in the presence of 1 wt% C15A silicate layers resulted in PSA nanocomposite with the highest peal strength and probe tack. Although the CTA remarkably decreased the shear resistance of the neat PSA, the existence of C15A layers or tactoids in the reinforced PSAs decreased the rate of shear resistance decay due to the good interaction between the C15A and adhesive copolymer chains.     

Adhesion properties of polyurethane pressure-sensitive adhesive

In this study, the adhesion properties of polyurethane (PUR) pressure-sensitive adhesive (PSA) were investigated. The PUR-PSA was prepared by the cross-linking reaction of a urethane polymer consisting of toluene-2,4-diisocyanate and poly(propylene glycol) components using polyisocyanate as a cross-linking agent. The peel strength increased with the cross-linking agent content and exhibited cohesive failure until the maximum value, after which it decreased with interfacial failure. The PUR-PSA exhibited frequency dependence of the storage modulus obtained from dynamic viscoelastic measurements, but did not show dependence of the tack on the rolling rate measured using a rolling cylinder tack test under the experimental conditions used, which is quite different from the acrylic block copolymer/tackifier system. The PUR-PSA showed strong contact time dependence of tack measured by a probe tack test. The tendency was significantly larger than for the acrylic block copolymer/tackifier system. Therefore, the storage modulus increased, whereas the interfacial adhesion seems to be decreased with increase in the rolling rate for this PUR-PSA system. It was estimated that the influence of rolling rate on the interfacial adhesion and the storage modulus was offset, and, as a result, the rolling cylinder tack did not exhibit rate dependency.