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。     

Adhesion and Failure Mechanisms of a Model Hot Melt Adhesive Bonded to Polypropylene

A model hot melt adhesive (HMA) based on an ethylene/vinyl acetate copolymer (EVA), an Escorez® hydrocarbon tackifier, and a wax has been used to bond together polypropylene (PP) films to give equilibrium bonding. Peel strengths were determined over a broad range of peel rates and test temperatures. Contrary to the peel behavior of joints with simple rubbery adhesives [1], peel strengths with this semi-crystalline adhesive are not rate-temperature superposable, and multiple transitions in failure locus occur. The semi-crystalline structure of the HMA also prevents rate-temperature superposition of its dynamic moduli.

At different test temperatures, the dependence of peel strength on peel rate shows some resemblance to the dependence of the loss tangent of the bulk adhesive on frequency. This is consistent with a previous result [2] that the HMA debonding term. D, varies with the loss tangent of a HMA at the T-peel debonding frequency.

This model HMA, similar to block copolymer/tackifier blends [3], consists of two phases: an EVA-rich and a tackifier-rich phase, in its amorphous region. At a low peel rate of 8.33 × 10^-5 m/s, the peel strength shows a maximum at a temperature that corresponds to the transition temperature of the tackifier-rich phase (T₁). At a higher peel rate of 8.33 × 10^-3 m/s, the peel strength rises with increasing test temperature, but becomes essentially constant at temperature T₁'. It is believed that, to optimize the peel strength of a HMA at ambient temperature, it is advantageous to formulate the EVA polymer (or other semi-crystalline polyolefins) with a compatible tackifier that yields a tackifier-rich phase with a transition temperature (T₁') in the vicinity of room temperature.     

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.     

Dynamic mechanical spectra of poly(itaconic acid esters) containing phenyl and cyclohexyl rings

The dynamic mechanical response of a series of poly(itaconic acid esters), in which the ester group, ---COOR, has R = (CH₂)_n ø with n = 0, 1, 2 and ø is either a phenyl or cyclohexyl ring, was studied over the temperature range 90 to 425K. In each case the glass transition temperature T_g, of the cyclohexyl derivative is higher than the corresponding phenyl derivative, and T_g also decreases as n increases. A β-transition, located in both the phenyl and cyclohexyl series, is attributed to motion of the ester groups. In addition the cyclohexyl polymers exhibit a prominant γ-transition caused by cyclohexyl ring movement and there is also a δ-transition in this series which is believed to be a precursor of the γ-transition.     

WATER SORPTION ISOTHERMS AND GLASS TRANSITION PROPERTIES OF GELATIN

The water sorption isotherms of gelatin of different molecular weights (317,700, 228,900, and 197,400) were determined at 50°C using an isopiestic method. The sorption isotherms were modeled using the Brunauer-Emmett-Teller (BET) and Guggenheim-Anderson-deBoer (GAB) equations. The BET and GAB equations were able to predict the equilibrium moisture content (EMC) with a mean relative error of 5.2 and 5.0%, respectively. The BET monolayer moisture content varied from 4.81 to 5.70% (d.b.) while modeling with the GAB equation predicted monolayer moisture content of 6.14-7.58% (d.b.) depending upon molecular weight. The monolayer moisture content increased with increasing molecular weight. Studies on the effect of moisture content on the “rheological glass transition temperature” (T_g) showed a smooth increase in the value of T_g as a function of increasing concentration of gelatin solids. This varied from 7 to 35°C at 75% and 97% solids, respectively for the protein sample with MW = 317,700. Pinpointing of the T_g was implemented with the technique of small deformation dynamic oscillation. It was proposed that the “rheological” T_g is the point between the glass transition region and the glassy state. It acquires physical significance by identifying the transition from free volume phenomena of the polymeric backbone in the glass transition region to an energetic barrier to motions in the glassy state involving stretching and bending of chemical bonds.     

A Study of the Interphase Region in Carbon Fibre/Epoxy Composites using Dynamic Mechanical Thermal Analysis

We have examined the effect of fibre addition on the glass transition temperature (T_g) of two epoxy resin systems (an amine cured and an anhydride cured epoxy system) using dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The presence of fibres changes the glass transition temperature (T_g) of an anhydride cured epoxy resin but does not affect that of an amine cured epoxy. The data suggest that two counteracting mechanisms are responsible for these changes: firstly, the presence of fibres causes a restriction of the molecular motion in the resin system, and secondly, the presence of carboxyi and keto-enol groups on the fibre surface inhibit curing of the resin close to the fibre, i.e. in the interphase region. The former increases the T_g and is a long range effect whereas the latter decreases the T_g and is a localised phenomenon. Changes in the dynamic properties of the interphase region are only detected when the samples are loaded in the longitudinal direction and not in the transverse direction where bulk matrix properties dominate. Sizing the fibres before their incorporation into the epoxy resin eliminates the variation in interfacial properties arising from differences in fibre surface chemistry.     

Conformation of isotactic polystyrene (IPS) in the bulk crystallized state as revealed by small-angle neutron scattering

Neutron scattering experiments have been performed on isotactic polystyrene (IPS) samples in the bulk crystallized state (T_{crystallization} = 185°C). The determination of the conformation of tagged chains ranging from 2.5 × 10⁵ to 7 × 10⁵ has been undertaken on two different hydrogenated IPS matrices. A matrix of usual molecular weight (M_w = 4 × 10⁵) leads to results which do not agree with Flory's model. In this case, measurements on radius of gyration R_g show on the one hand an important increase of this parameter (40%) with increasing crystallinity for the highest molecular weight tagged chains and on the other hand a variation with molecular weight like M^0.78. These results are interpreted with a schematic model involving a long crystalline sequence incorporated in the monocrystal along the 110 plane and two amorphous wings. Such an assumption is confirmed by the scattering behaviours in the intermediate range. On the other hand, by using an IPSH matrix of very high molecular weight (M_w = 1.75 × 10⁶), and the same tagged chains previously considered, a very weak variation of R_g with increasing crystallinity is observed. This leads to consider in this case Flory's conformation which is corroborated by data obtained in the intermediate range.     

Semi-Structural Hot Melt Adhesives Based on Crosslinkable Functionalized Polyolefins

A structural or semi-structural adhesive is usually applied to the substrates as monomers, oligomers, or melts of polymers with reactive groups and is then polymerized or crosslinked in situ in the joint between the substrates. We have been studying a number of crosslinked functionalized polyolefins blended with tackifier used as semi-structural adhesives for bonding to oily galvanized steel surfaces. The functions of takifier, surface properties of adhesive and substrate, geometry effects of lap joints, adhesive T_β, chain end defects, network chain length, and cure kinetics of these systems will be discussed. Our experimental results indicate that lap shear strengths of galvanized steel joints depend on adhesive storage modulus to the power of roughly 1/2. A rough estimate of the fracture energy of the adhesive bond, G_a could be obtained from this relation. Although some estimated G_a values are too low while the others are too high, they seem to be in rough accord with the degree of interfacial bonding and the locus of failure of the lap shear bonds.     

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     

Quantifying the Relationship Between Peel and Rheology for Pressure Sensitive Adhesives

An attempt is made in this work to model quantitatively the peel force vs. rate behavior of a pressure sensitive adhesive (PSA) tape. The approach follows suggestions of previous authors in modeling the deformation of the PSA as uniaxial extension of individual strands. A debonding failure criterion based on stored elastic energy density is used. In this work, experimental measurements of dynamic mechanical master curves are used to provide the mechanical properties of the PSA in the model. The predictions are compared with experimental peel force vs. rate master curves on tapes made from those same adhesives. The only adjustable parameter for the fitting is the quantity related to the debonding criterion. In this set of natural-rubber-based PSAs, the general shape of the peel master curve and the changes in peel behavior associated with tackifier loading and rubber molecular weight are well explained by the model. The effect of changes in substrate chemistry are not well explained.     

Hot Melt Adhesive Model: Interfacial Adhesion and Polymer/Tackifier/Wax Interactions

This work continues our study of the hot melt adhesive (HMA) model published earlier [1]. This HMA model was developed based on the pressure sensitive adhesive (PSA) tack model established previously [2]:

P = P₀BD (1)

where P is the adhesive bond strength, P₀ is the interfacial (intrinsic) adhesion term, B is the bonding term and D is the debonding term. The previous paper [1] describes the B and D terms in detail. However, only a brief discussion of the P₀ term was given. The present paper will provide a more in-depth but still rather qualitative study of the P₀ term within the framework of the adhesion model described in Eq. (1). HMAs studied are ethylene/vinyl acetate copolymer (EVA)/tackifier/wax blends. Substrates studied are untreated and corona-discharge-treated polyolefins such as polypropylene (PP) and polyethylene (PE). First, it has been found that the tackifier surface tension could be roughly correlated with one of its thermodynamic parameters: the solubility parameter dispersion component. Secondly, except for EVA/tackifier binary blends, the compatibility of any two of these three components, the EVA polymer, the tackifier and the wax, in a HMA can be estimated from surface tension and X-ray photoelectron spectroscopy (XPS) measurements. Thirdly, based on the study of the EVA/mixed aliphatic-aromatic tackifier/wax model HMA system, it has been observed that the HMA/polyolefin substrate interfacial composition depends on the wax/substrate compatibility. The cause of an inferior peel strength of a HMA containing a high wax content to a polyolefin substrate is possibly due to the formation of a weak boundary layer (WBL) of wax at the interface and/or low dissipative properties of the HMA.

Also, the relationship between EVA/tackifier/wax interactions and HMA peel strength will be discussed. A correlation between the EVA/tackifier compatibility measured by cloud point and viscoelastic experiments to the debonding term, D, in Eq. (1) has been found.     

The effect of tackifier on phase structure and peel adhesion of a triblock copolymer pressure-sensitive adhesive

The role of tackifier on the adhesive properties of pressure-sensitive adhesive tape was investigated. For this purpose, a model system consisting of polystyrene-b-polyisoprene-b-polystyrene triblock copolymer and a tackifier was prepared. The hydrogenated cyclo-aliphatic resin, such as tackifier, which has poor compatibility with polystyrene increased the peel adhesion significantly. The increase became stronger above 40 wt% tackifier. Nanometer-sized agglomerates of tackifier were found in the polyisoprene matrix and these agglomerates increased in number with an increase in the tackifier content. The higher peel adhesion was obtained in the system with the larger amount of agglomerates of tackifier in the polyisoprene matrix. It was estimated that the tackifier dissolved with initial mixing at the molecular level in the polyisoprene matrix, enhancing the wettability of the adhesive, and separated out in the form of agglomerates over time, developing the cohesive strength. On the other hand, the rosin phenolic resin tackifier had good compatibility with polystyrene, and the peel adhesion increased effectively at the lower tackifier content. However, no significant additional increase at higher tackifier content was observed.     

Mechanical properties of polymers at cryogenic temperatures: relationships between relaxation, yield and fracture processes

Semi-crystalline as well as amorphous polymers generally develop some measure of molecular mobility at temperatures well below their melting temperature, T_m, or their glass transition temperature, T_g. In these polymers, one or more damping or internal friction peaks are usually found to occur in the low temperature region from 4K to 300K. The magnitude and temperature position of these maxima are dependent upon the structure of the polymer, its mode of preparation and past history, and the local environment of the moving units. Various examples are given of polymers that show significant low temperature relaxation processes, and the influence of chemical structure, structural substitution, crystallinity and low molecular weight diluents is illustrated. The extent to which relaxation behaviour can be correlated to macroscopic ductility and fracture toughness is also discussed.     

Resolving lateral variations in the frequency dependence of adhesive properties at the surface of a model pressure sensitive adhesive

A commercial scanning probe microscope may be used to laterally resolve qualitative differences in the frequency dependence of material properties at the surface of a model pressure sensitive adhesive (PSA). In a heterogeneous PSA made from polyisoprene and a wood rosin derivative, both the polymer‐rich matrix and tackifier‐rich domains regions at the surface appear stiffer and show higher adhesive force when increasing the testing frequency from 0.01 to 1 Hz at room temperature. The limited frequency range of the instrument and piezo creep constrain the applicability of the approach. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 400–404, 2002; DOI 10.1002/app.10369     

Heat capacity of copolymers of chlorotrifluoroethylene and vinylidene fluoride

The heat capacities of two copolymers of chlorotrifluorethylene and vinylidene fluoride, one 30:70 mol % and the other 44:56 mol % in composition, were measured in an adiabatic calorimeter from 80 to 340 K. The glass-transition points T_g observed at 256 and 269 K for the 30:70 and 44:56 samples, respectively, closely agree with the prediction of the theory of Flory and Fox; the accompanying jump of heat capacities at these points was found to be 2.2 cal/K ‘per bead’ for both samples, in fair agreement with the ‘constant ΔC_p rule’. A small peak was observed immediately above T_g, and interpreted as a time-dependent effect arising from the lack of equilibrium in the region. The data of the heat capacities were analysed in detail in the framework of the Tarasov model and the principle of additivity, and were found to agree well ( 1–3%) with theory up to the respective glass-transition points in all cases, thus giving support to the validity of the previously published segmental values of heat capacity and of characteristic temperature θ₁.     

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.     

Adhesive and Rheological Properties of Lightly Crosslinked Model Acrylic Networks

The viscoelastic and adhesive properties of a series of model, lightly crosslinked acrylic polymer networks have been investigated. The model networks were statistical copolymers of 2-ethyl-hexyl acrylate and acrylic acid or terpolymers of 2-ethyl-hexyl acrylate, acrylic acid, and stearyl acrylate synthesized in solution. All were lightly crosslinked after the polymerization was completed to obtain typical properties of pressure-sensitive adhesives. The bulk rheological properties of the networks were characterized by dynamical mechanical spectroscopy and in uniaxial extension. Their adhesive properties were tested with an instrumented probe tester fitted with a cylindrical steel probe. The presence of acrylic acid in the copolymer caused an increase in both elastic modulus and resistance to interfacial crack propagation characterized by the critical energy-release rate G_c and the incorporation of stearyl acrylate caused a decrease in both modulus and G_c. In both cases, however, the modification of G_c controlled the overall behavior. The analysis of the nonlinear elastic properties of the adhesives with the Mooney-Rivlin model provided new insights on the role played by the ratio between entanglements and crosslink points in controlling the formation and extension of the bridging fibrils observed upon debonding.     

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.     

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