Effects of miscibility and viscoelasticity on shear creep resistance of natural‐rubber‐based pressure‐sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins. Miscibilities of all the blend systems were illustrated as phase diagrams. From these blend systems, we selected 8 systems having typical phase diagrams (completely miscible, immiscible, lower critical solution temperature [LCST] types) and carried out measurements of shear creep resistance (holding power). Holding time was recorded as required time for the pressure‐sensitive adhesive (PSA) tape under shear load to completely slip away from the adherend. Holding time of miscible PSA systems tended to decrease as the tackifier content increased. This is attributable to a decrease in plateau modulus of the PSA with increasing tackifier content. There was rather large difference in holding time by tackifier among the miscible PSA systems; the reason for this is also considered to be a difference in plateau modulus. Holding time of an immiscible PSA system scarcely changed by tackifier content. But in another immiscible system, holding time tended to increase with increasing tackifier content. In fact, in the case of immiscible PSAs, the effect of tackifier content on holding time was different from tackifier to tackifier. This may be caused by difference in extent of phase separation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1535–1545, 2000     

Adhesion behavior of blends of polybutadiene and tackifiers

The adhesion behavior of blends of polybutadiene (PB) and tackifiers was investigated. The peel strength was found to be significantly dependent on blend composition, and a maximum strength behavior was observed for all blend systems. The tack mechanisms were proposed to explain the observed adhesion behavior. The position of the glass transition temperature is related to where the highest tack appears for the miscible blend; for the partially miscible blend the dispersed phase plays an important role in determining the maximum adhesion, and the critical size of the dispersed phase and the Tg of the tackifier phase together determine what concentration of tackifier gives the maximum tack. For the immiscible blends, the maximum adhesion is controlled by both the surface glass transition temperature and the critical diameter of the domains of the tackifier phase.     

Miscibility and Probe Tack of Acrylic Pressure Sensitive Adhesives—Acrylic Copolymer/Tackifier Resin Systems

Miscibility between acrylic copolymers and tackifier resins are investigated in terms of phase diagrams, and the probe tack of the blends are measured as a function of both temperature and rate of separation in order to obtain the master curves. It is found that the probe tack of the pressure sensitive adhesives are closely related to the miscibility between the components. The master curves of the miscible blends shift along the X(rate)-axis according to the change of T_g of the bulk materials with a gradual variation of the peak heights. However, those of the immiscible blends will not shift along the X(rate)-axis, but the magnitude will decrease with increase of a dispersed phase.     

Miscibility between natural rubber and tackifiers. II. Phase diagrams of the blends of natural rubber and petroleum resins

Natural rubber (NR) was blended in various ratios with 12 kinds of tackifiers that were prepared from petroleum. The blends were heated to various temperatures (20–120°C) to investigate their miscibility. The blends were visually observed for transparency or opacity at each temperature and further observed under an optical microscope for any existence of phase-separated structure. Miscibility of the blends is illustrated as phase diagrams in this article. NR/aliphatic resin systems and NR/aliphatic-aromatic copolymer systems showed phase diagrams of the lower critical solution temperature type, wherein the blends turned faintly cloudy over the binodal curves. The NR/hydrogenated petroleum resin system also showed a phase diagram of the lower critical solution temperature type. The miscible range of a blend system tends to become smaller as the molecular weight of a tackifier increases. Resins prepared by polymerization of pure aromatic monomers were completely immiscible with NR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 221–229, 1998     

Miscibility and fracture energy of probe tack for acrylic pressure-sensitive adhesives: acrylic copolymer/tackifier resin systems

The relationship between the miscibility of acrylic pressure-sensitive adhesive (PSA) and the fracture energy (W) (Jm⁻²) of the probe tack was investigated, wherein the master curve of W was compared with that of the maximum force (σ_max) (gf) of the probe tack. It was ascertained that W of acrylic PSA was closely related to the miscibility between the components (acrylic copolymer and tackifier resin). In the case of the miscible blend system, the master curve of W shifted toward the lower rate side and, at the same time, the magnitude decreased as the tackifier resin content increased. The degree of the shift of W was extremely smaller than that of σ_max. In the case of the immiscible blend system, the master curve of W remarkably decreased as the tackifier resin content increased, which suggests the fact that W of the PSA depended on the dynamic mechanical properties of the matrix phase and that the resin-rich phase acted as a kind of filler, thus reducing the practical performance. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 581–587, 1998     

Miscibility and PSA Performance of Acrylic Copolymer and Tackifier Resin Systems

The influence of miscibility of an acrylic PSA and several tackifier resin systems upon PSA performance was investigated. When the acrylic copolymer and the resins were blended in various proportions, three types of mixing state were found: miscible system, partially miscible system and immiscible system. In the case of miscible systems, PSA performance (tack, peel strength and shear resistance) depended upon the viscoelastic properties of the PSA. In the case of completely immiscible systems, the above PSA performance depended primarily upon the viscoelastic properties of a continuous matrix phase, and the separated resin phase acted as a kind of filler. In the case of partially miscible systems, the PSA performance changed discontinuously at the resin concentration where phase separation occurred. It suggests that the phase structure of a PSA greatly influences the PSA's performance.     

Miscibility and pressure‐sensitive adhesive performances of acrylic copolymer and hydrogenated rosin systems

Relationship between the miscibility of pressure‐sensitive adhesives (PSAs) acrylic copolymer/hydrogenated rosin systems and their performance (180° peel strength, probe tack, and holding power), which was measured over a wide range of time and temperature, were investigated. The miscible range of the blend system tended to become smaller as the molecular weight of the tackifier increased. In the case of miscible blend systems, the viscoelastic properties (such as the storage modulus and the loss modulus) shifted toward higher temperature or toward lower frequency and, at the same time, the pressure‐sensitive adhesive performance shifted toward the lower rate side as the T_g of the blend increased. In the case of acrylic copolymer/hydrogenated rosin acid systems, a somewhat unusual trend was observed in the relationship among the phase diagram, T_g, and the pressure‐sensitive adhesive performance. T_g of the blend was higher than that expected from T_gs of the pure components. This trend can be due to the presence of free carboxyl group in the tackifier resin. However, the phase diagram depended on the molecular weight of the tackifier. The pressure‐sensitive adhesive performance depended on the viscoelastic properties of the bulk phase. A few systems where a single T_g could be measured, despite the fact that two phases were observed microscopically, were found. The curve of the probe tack of this system shifted toward a lower rate side as the T_g increases. However, both the curve of the peel strength and the holding power of such system did not shift along the rate axis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 651–663, 1999     

Miscibility between natural rubber and tackifiers. I. Phase diagrams of the blends of natural rubber with rosin and terpene resins

Natural rubber (NR) was blended in various ratios with 17 kinds of tackifiers, which were prepared from rosin and terpenes. The blends were heated to various temperatures (20–120°C) in order to investigate their miscibility. The blends were visually observed for transparency or opacity at each temperature and further observed under an optical microscope for any existence of phase-separated structure. Miscibility of the blends is illustrated as phase diagrams in this article. Phase diagrams of all blends investigated in this study were classified into four types: completely miscible, lower critical solution temperature, upper critical solution temperature, and completely immiscible. The miscible range of a blend system tends to become smaller as the molecular weight of a tackifier increases. The data also indicate that the esters of hydrogenated rosin and of disproportionated rosin show comparatively good miscibility with NR whereas polymerized rosin and its esters have poor compatibility with NR in most cases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2191–2197, 1997     

Miscibility and PSA Performance of Acrylic Copolymer and Tackifier Resin Systems

The influence of miscibility of an acrylic PSA and several tackifier resin systems upon PSA performance was investigated. When the acrylic copolymer and the resins were blended in various proportions, three types of mixing state were found: miscible system, partially miscible system and immiscible system. In the case of miscible systems, PSA performance (tack, peel strength and shear resistance) depended upon the viscoelastic properties of the PSA. In the case of completely immiscible systems, the above PSA performance depended primarily upon the viscoelastic properties of a continuous matrix phase, and the separated resin phase acted as a kind of filler. In the case of partially miscible systems, the PSA performance changed discontinuously at the resin concentration where phase separation occurred. It suggests that the phase structure of a PSA greatly influences the PSA's performance.     

Miscibility and shear creep resistance of acrylic pressure-sensitive adhesives: Acrylic copolymer and tackifier resin systems

The miscibility between an acrylic copolymer and a tackifier resin was investigated in terms of phase diagrams, glass transition temperatures (T_g's), and dynamic mechanical properties of blends. Shear creep resistance (holding power, t_b) of the blends was measured as a function of both temperature and stress (σ₀) in order to obtain the master curves. It was found that the shear creep resistance of the pressure-sensitive adhesives (PSAs) was closely related to the miscibility between the components and viscoelastic properties of the blends. The master curve of the miscible blends shifts toward a longer time scale as the amount of tackifier resin in the blend is increased as a result of the modification of the bulk properties, and their behavior greatly depends on the glass transition temperature (T_g) and storage modulus (G′) of the blends. However, the master curve of immiscible blends where two phases exist in the system does not shift greatly toward a longer time scale, because T_g and the storage modulus of the blend do not change greatly. © 1995 John Wiley & Sons, Inc.     

Surface Property and Compatibility of Poly(styrene-isoprene-styrene) Triblock Copolymer/Tackifier Blend System

The frictional forces between pressure sensitive adhesives (PSAs) and a probe tip were measured with a scanning probe microscopy (SPM). A peak appeared in the scanning rate-frictional force curve shifted to a lower scanning rate with decreasing temperature. In the case of the miscible system of isoprene matrix of SIS base polymer, the tendency of a peak to shift to a lower scanning rate was observed with increasing tackifier content; however, in the case of the immiscible system of styrene domain of SIS base polymer, no remarkable shift was observed. The frictional force is influenced by viscoelastic properties of the PSA which systematically changed with miscibility.

In this study, it is aimed to clarify the correlation between the observation of phase structure and the behavior of surface rheology by using two kinds of tackifiers that have different miscibility with the polyisoprene phase or the polystyrene phase of SIS triblock copolymer.     

Rheological analysis of the adhesion surface with a scanning probe microscope (SPM)

The frictional forces between pressure sensitive adhesives (PSAs), including rosin tackifier resin, and a probe tip were measured with scanning probe microscopy (SPM). A peak that appeared in the scanning rate-frictional force curve shifted to a lower scanning rate with decrease in temperature. The frictional force reflects rheological behavior of the PSA. In the case of the miscible system, the tendency of a peak to shift to a lower scanning rate was observed with increase in tackifier content; however, in the case of the immiscible system, no remarkable shift was observed. The frictional force is influenced by viscoelastic properties of the PSA, which systematically changed with miscibility. The high-scanning rate resulted in the interfacial failure on the surface, while the low-scanning rate resulted in the cohesion failure.     

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.     

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.     

Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier system

The influence of tackifier structure on the temperature dependence of tack for a polystyrene block copolymer/tackifier system was investigated. A blend of polystyrene-block-polyisoprene-block- polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers was used as the base polymer. Four different tackifiers were used: special rosin ester resin (RE), rosin phenolic resin (RP), hydrogenated cyclo-aliphatic resin (HC), and aliphatic petroleum resin (C5). Tack at 20?°C increased with the tackifier content for both RE and HC tackifier systems. Tack is affected by two factors: the work of adhesion at the adherend interface and the viscoelastic properties of the adhesive. The good balance of these two factors brought high tack. The adhesive with 10 wt.% tackifier exhibited the highest tack at 20?°C, whereas those with 30 and 50 wt.% tackifier were lower than those systems with 10 wt.% of the RP or C5 tackifiers. The adhesive with overly high hardness lowered the work of adhesion and the tack was not improved with more than 30 wt.%. A compatibility test in toluene solution and in solid state showed that tackifier RE has good compatibility with both polyisoprene and polystyrene, whereas tackifier RP has lower compatibility. Tackifiers HC and C5 had good compatibility with polyisoprene, but poor compatibility with polystyrene, and that of C5 was poorer. Pulse nuclear magnetic resonance (NMR) analyses indicated that tackifiers RE and HC effectively restrict the molecular mobility of polyisoprene phase.     

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     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Orientation of miscible and immiscible polymer blends

Polystyrene (PS) and poly(vinylmethylether) (PVME) were used to study the orientation of miscible and immiscible polymer blends. A miscible blend containing 60 wt% PS was prepared by casting the sample from a benzene solution. The immiscible blend was made by annealing the initially miscible mixture above its lower critical solution temperature for different times and temperatures. Fourier transform infrared spectroscopy and birefringence were used to measure the orientation of PS and PVME, before and after phase separation. Stress-strain curves were also measured for the two types of systems. It was found that the two polymers orient differently and that phase separation induces an increase in the overall orientation of the mixture, in the modulus and in PS orientation. The differences observed between pure PS and PS in the blend were attributed to changes in specific interactions and density of entanglements. The variations with phase separation were attributed to a change in the morphology of the system.     

Effects of the compatibility of a polyacrylic block copolymer/tackifier blend on the phase structure and tack of a pressure‐sensitive adhesive

Adhesion and viscoelastic properties and morphology of a polyacrylic block copolymer/tackifier blend were investigated. Special rosin ester resins with different weight average molecular weights of 650, 710, 890, and 2160 were used as the tackifier and blended with a polyacrylic block copolymer consisting of poly(methyl methacrylate) and poly(n‐butyl acrylate) blocks at tackifier content levels of 10, 30, and 50 wt %. The compatibility decreased with an increase in molecular weight. From TEM observation, the number of formed agglomerates of the tackifier with sizes on the order of several tens of nanometers increased with increasing tackifier content and molecular weight of the tackifier in the range from 650 to 890. For the tackifier with a molecular weight of 2160, micrometer‐sized agglomerates were observed. The storage modulus at low temperature and the glass transition temperature of adhesive measured by a dynamic mechanical analysis increased dependent on the number of formed nanometer sized agglomerates. Tack was measured using a rolling cylinder tack tester over wide temperature and rolling rate ranges, and master curves were prepared in accordance with the time‐temperature superposition law. Tack and peel strength were optimum at a blend combination of intermediate compatibility, i.e., the molecular weight of 890. These optimum properties were correlated to maximal values of the storage modulus at room temperature and the glass transition temperature. Therefore, it was found that these features of blend properties are strongly affected by the nanometer sized agglomerates of tackifier. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012