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.     

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     

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.     

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.     

配方优选程序设计及在SIS压敏胶配方优选中的应用

SIS压敏胶的配方设计性较强，其性能随配方中各组份用量的变化可在较大范围内变化。该胶可作为装配用接触型胶粘剂至压敏胶粘剂，压敏胶的三大性能指标即剥离强度、持粘时间和快粘性能（也称初粘力）随应用场合变化有不同要求，而这三大性能又与增粘剂和增塑剂的使用量极为密切，因此掌握配方与性能之间的定量规律对于开发SIS压敏胶的应用非常重要。本文提出了胶粘剂性能与组成之间关系的数式化模型，并编制了一套可在微机上运行的配方优选程序，该程序具有数据存贮，数据处理，图形输出的功能，利用这些图形可以根据实际需要进行配方优…     

Pressure Sensitive Adhesives Based on VectorR SIS Polymers I. Rheological Model and Adhesive Design Pathways

Dexco Polymers (a Dow/Exxon partnership) has been manufacturing Vector^R SIS polymers since 1990.¹ This paper describes experiments carried out to study Vector SIS polymers and model pressure sensitive adhesive (PSA) formulations based on Exxon Chemical's Escorez^R 1310LC tackifier. The adhesive behavior of tackified polymers was quantitatively analyzed by applying the rheological principle of time-temperature superposition² and the mapping approach,^3,4 and the pressure sensitive rheological model⁵ developed earlier. This model⁵ was developed by expanding and modifying an equation [adhesive fracture strength = (intrinsic adhesion) × (bulk energy dissipation)] proposed by Gent et al.^6,7 and Andrews et al.^8,9 This study delivers two key results. The first is that the fracture strength of the PSA/steel bond is the multiplication of three terms: the intrinsic (or interfacial) adhesion, the bonding and the debonding terms (Fig. 1). The debonding term is correlated with the logarithm of the loss modulus at the PSA debonding frequency or with the logarithm of the monomeric friction coefficient of the block copolymer/tackifier system. Both the loss modulus and the monomeric friction coefficient measure the energy dissipation in the bulk adhesive. The second is that PSA design pathways can be established by a mapping approach in the rheological space of the plateau modulus versus the loss modulus peak position in the frequency scale (Fig. 2). Plateau modulus is the bonding parameter because it measures the wetting capability of the adhesive with the substrate surface. The loss modulus peak position is the debonding parameter because it corresponds approximately to the time scale (or the frequency scale) in which one deforms the adhesive to maximize energy dissipation. Therefore, the tackifier and oil combination lowers the plateau modulus, but increases the T_g of the polyisoprene phase of the SIS polymer. This increase in T_g is equivalent to the lowering of the rate of local rearrangement (frequency of segment jumps) of the polyisoprene chains of the block copolymer. An optimal “tackification pathway” in this rheological space is achieved by tailoring the tackifier type and T_g, and the amount of oil used in the PSA.

In brief, the PSA rheological model and mapping approach described in this work for Vector SIS polymers give a comprehensive understanding and adhesive design pathways. This concept and approach not only allow raw material suppliers to improve and design better tackifier and polymer products, but also provide PSA formulators a quantitative tool to achieve PSA end property results.     

Effect of Coumarone-Indene Resin on Adhesion Property of SMR 20-Based Pressure-Sensitive Adhesives

The viscosity, tack, and peel strength of a natural rubber (SMR 20)–based pressure-sensitive adhesive (PSA) was studied using coumarone-indene resin as the tackifier. The resin loading was varied from 0–80 parts per hundred parts of rubber (phr). Toluene was used as the solvent throughout the experiment. The viscosity of PSA was measured using a Haake Rotary Viscometer whereas loop tack and peel strength were determined using a Lloyd Adhesion Tester. PSA was coated onto the substrates using a SHEEN hand coater to give a coating thickness of 60 μm and 120 μm. Results show that the viscosity and tack of the adhesive increases with resin content due to the concentration effect of tackifier resin. However, for the peel strength, it increases up to 40 phr of resin for both coating thickness, an observation that is attributed to the wettability of substrates.     

Tack and Shear Strength of Adhesives Prepared from Styrene-Butadiene Rubber (SBR) Using Gum Rosin and Petro Resin as Tackifiers

Tack and shear strength of styrene-butadiene rubber (SBR)-based pressure-sensitive adhesive were studied using gum rosin and petro resin as the tackifiers. The concentration of the tackifying resin was varied from 0 to 100 parts per hundred parts of rubber (phr). Toluene was used as the solvent throughout the experiment. The rolling ball technique was used to measure the tack of the adhesive, whereas, shear strength was determined by a TA-HDi Texture Analyser. Results show that the tack of the adhesive increases with increasing tackifier loadings for both tackifier systems. However, shear strength indicates the reverse behavior with increasing resin content, an observation which is attributed to the decrease in cohesive strength as the tackifier concentration is increased. Both tack and shear strength of the adhesives increases with molecular weight of SBR. Adhesive containing petro resin consistently exhibits higher values than the gum rosin system due to better wettability and compatibility in the former system.     

Effects of hydrocarbon tackifiers on the adhesive properties of contact adhesives based on polychloroprene - III. The effect of the molecular weight of the tackifier

Aromatic hydrocarbon resins with different molecular weights (M_w = 1300-50400 daltons) were added to a solvent-based polychloroprene adhesive. The hydrocarbon resins were characterized using infra-red (IR) and differential scanning calorimetry (DSC) measurements. The properties and compatibility of the polychloroprene/resin blends were studied using mechanical tests, DSC measurements, scanning electron microscopy (SEM), and stress-controlled rheology. Tack measurements were also carried out and the adhesion strength was obtained from T-peel tests on roughened styrene-butadiene rubber/polychloroprene adhesive joints. The addition of low-molecular-weight tackifiers produced a compatible polychloroprene/tackifier system (only one T_g was found in DSC measurements), while the addition of a high-molecular-weight (and broad molecular weight distribution) tackifier produced a partially incompatible system (two Tg's were found in DSC measurements). The compatibility of polychloroprene/tackifier blends was also assessed with stress-controlled rheology and SEM. An increase in the T-peel strength and tack were produced when the molecular weight of the tackifier increased, although the addition of a hydrocarbon resin with a M_w higher than about 50 000 reduced the tack. A broad molecular weight distribution in the tackifier favoured incompatibility with the polychloroprene, resulting in a reduction in the tack and rheological properties.     

Tack and viscoelastic properties of an acrylic block copolymer/tackifier system

The role of tackifier in a pressure sensitive adhesive tape was investigated. For this purpose, a model pressure sensitive adhesive was prepared using an acrylic block copolymer consisting of poly(methyl methacrylate) and poly(butyl acrylate) as base polymer and a tackifier. The poly(butyl acrylate) oligomer was also used as a diluent to compare the effect on the adhesion properties. Tack was measured using a rolling tack tester in wide temperature and rolling rate ranges, and the master curve was made in accordance with the time–temperature superposition law. The tack increased and the failure mode varied from cohesive failure to interfacial failure with an increase in the rolling rate. The tack was higher in the tackifier added system than in the oligomer added system. From a dynamic mechanical analysis, the modulus at high temperature decreased by the addition of both tackifier and oligomer, however, the glass transition temperature of poly(butyl acrylate) and the modulus at low temperature increased only by the addition of tackifier. The dynamic viscoelastic properties were measured in wide temperature and frequency ranges, and the master curve was also made. The viscoelastic properties varied in the order of viscosity, rubbery and glassy with an increase in the deformation rate. It was clarified that the tack value and the failure mode were strongly dependent upon the viscoelastic properties of adhesive. Both tackifier and oligomer improves the mobility of base polymer, whereas, only tackifier increases the cohesive strength of base polymer.     

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     

Rheological and adhesion properties of acrylic pressure‐sensitive adhesives

Different pressure‐sensitive adhesives (PSAs) based on acrylic monomers were synthesized under different reaction conditions. The synthesized PSAs have good adhesive properties and without leaving any residue can be easily peeled off from the surface of a substrate. The relationship between PSAs rheological behavior and its adhesion properties (e.g., peel, tack, and shear resistance) has been studied at constant adhesive thickness. The samples were examined for their surface energy and viscoelastic characteristics. It was observed that increase in reaction temperature and reaction time results in decreased storage modulus due to lowered molecular weight, which finally leads to lower elasticity of the PSA. While the storage (G′) and loss (G″) modulus of samples increase with increased initiator concentration, the elasticity of PSA is increased as well. High G″ at high frequency (100 Hz) represents high peel strength because of higher dissipation of viscoelastic energy during debonding. The tack values increase by lowering storage modulus at 1 Hz due to higher M_e. Shear values are increased by higher storage modulus at low frequency (0.1 Hz) due to hydrogen bonding of the different components. Some parallel investigations on the surface energy of the samples showed that they have different properties because of the nature of different monomeric units with their corresponding orientations. Our results reveal that the peel strength is not affected by surface energy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adhesion properties of pressure-sensitive adhesives prepared from SMR 10/ENR 25, SMR 10/ENR 50, and ENR 25/ENR 50 blends

The adhesion properties, i.e. viscosity, tack, and peel strength of pressure-sensitive adhesives prepared from natural rubber/epoxidized natural rubber blends were investigated using coumarone-indene resin and toluene as the tackifier and solvent respectively. One grade of natural rubber (SMR 10) and two grades of epoxidized natural rubbers (ENR 25 and ENR 50) were used to prepare the rubber blends with blend ratio ranging from 0 to 100%. Coumarone-indene resin content was fixed at 40 parts per hundred parts of rubber (phr) in the adhesive formulation. The viscosity of adhesive was measured by a HAAKE Rotary Viscometer whereas loop tack and peel strength was determined using a Lloyd Adhesion Tester operating at 30 cm/min. Results show that the viscosity of the adhesive passes through a minimum value at 20% blend ratio. For loop tack and peel strength, it indicates a maximum at 60% blend ratio for SMR 10/ENR 25 and SMR 10/ENR 50 systems. However, for ENR 25/ENR 50 blend, maximum value is observed at 80% blend ratio. SMR 10/ENR 25 blend consistently exhibits the best adhesion property in this study, an observation which is attributed to the optimum compatibility between rubbers and wettability of adhesive on the substrate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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.     

Influences of debonding rate and temperature on tack properties and peel behavior of polyacrylic block copolymer/tackifier system

The influences of debonding rate and temperature on the peel behavior of polyacrylic block copolymer/tackifier system were investigated. Poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate) triblock copolymer (MAM) with hard block contents of 23 (MAM-23) and 16 wt.% (MAM-16) and a 1/1 blend with a diblock copolymer (MA) consisting of the same components (MAM-23/MA, total hard block content of 15 wt.%) were used as the base polymer. A special rosin ester was used as a tackifier at various contents in the block copolymer/tackifier system. The peeling process at the probe/adhesive interface during probe tack testing was observed using a high-speed microscope at 23 °C with debonding rate of 10 mm/s. Three different peeling mechanisms were observed. Type A, where peeling progressed linearly from the edge to the center of the probe without cavitation (MAM-23). Type B, where peeling progressed linearly from the edge to the center of the probe with cavitation (MAM-16). Type C, where cavitation occurred over the entire adhesive layer, and peeling initiation was delayed (MAM-23/MA). The peel behavior of MAM-23 changed from Type A to Type B with a decrease of the debonding rate (1 mm/s) or increase of the temperature (40 °C). In contrast, there was no change for MAM-16 and MAM-23/MA. Cavity formation in an adhesive layer restrains peeling; therefore, it is desirable for improvement of the adhesion strength. The tack properties increased with the tackifier content, and the formation of cavitation was less than that for the systems without the tackifier.     

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.     

Synthesis and characterization of hydrogenated sorbic acid grafted dicyclopentadiene tackifier

Hydrocarbon resins, which are defined as low molecular weight, amorphous, and thermoplastic polymers, are widely used as tackifier for various types of adhesives, as processing aids in rubber compounds, and as modifiers for paint and ink products, and for plastics polymers such as isotactic polypropylene. Typically, hydrocarbon resins are non-polar, and thus highly compatible with non-polar rubbers and polymer. However, they are poorly compatible with polar system, such as acrylic copolymer, polyurethanes, and polyamides. Moreover, recently the raw materials of tackifier from naphtha cracking had been decreased because of light feed cracking such as gas cracking. To overcome this problem, in this study, novel hydrocarbon resins were designed to have a highly polar chemical structure. And, it was synthesized by Diels–Alder reaction of dicyclopentadiene monomer and sorbic acid from blueberry as renewable resources. Acrylic resins were formulated with various tackifiers solution including hydrogenated sorbic acid grafted dicyclopentadiene tackifier in acrylic adhesive and rolling ball tack, loop tack, 180° peel adhesion strength, and shear adhesion strength were measured. The properties depend on the softening point and polar content of tackifiers.     

增粘树脂对聚丙烯酸酯压敏胶粘合性能的影响

聚丙烯酸酯乳液和增粘树脂松香、Ｃ_５石油树脂乳液共混，用共混液涂布成压敏胶带。考察了不同增粘树脂用量对压敏胶带粘合性能的影响。结果表明，随松香树脂量增加，１８０℃剥离强度提高，并出现峰值；快粘力不变；持粘力下降。随Ｃ_５石油树脂量增加，１８０°剥离强度，快粘力，持粘力均大幅度下降。     

SIS型热熔压敏胶的粘接性能及动态流变行为研究

以SIS(苯乙烯-异戊二烯-苯乙烯三嵌段共聚物)作为基体树脂制备HMPSA(热熔压敏胶)。研究了不同类型增塑剂与SIS基体的相容性对压敏胶(PSA)性能及动态流变行为的影响,并探讨了PSA性能与动态流变行为之间的关系。结果表明:当增塑剂与SIS中PS(聚苯乙烯)相的相容性较好时,相应HMPSA在低频(1 Hz)时的储能模量较低,初粘力较好;当增塑剂与SIS中PI(聚异戊二烯)相的相容性较好时,相应HMPSA在高频(100 Hz)时的损耗模量较高,剥离强度较大。