Modification research on the peel strength of the acrylate emulsion pressure‐sensitive adhesives

Pressure‐sensitive adhesives (PSAs) were produced with latexes synthesized via starved semibatch emulsion polymerization processes with butyl acrylate, three different kinds of hard monomers [styrene (St), methyl methacrylate, and 2‐phenoxy ethyl methacrylate (SR340)], acrylic acid, and 2‐hydroxy ethyl acrylate. The management of both the copolymer composition and the polymerization process allowed us to control the behavior of the PSAs. For the acrylate latexes, the types of hard monomers and their contents, the concentration of buffer [bicarbonate (NaHCO₃)], and three kinds of semibatch processes were manipulated to modify the polymer properties. The performance of the PSA films cast from these latexes was evaluated by the peel strength. The results show that the PSA prepared with St exhibited the highest peel strength among the three hard monomers, and the latex synthesized by SR340 showed the largest gel content compared with the other two hard monomers. With increasing buffer, the latex particle size increased, and the peel strength initially increased to a maximum and then decreased. Nevertheless, the stability of the latexes decreased with increasing buffer concentration. In addition, the effects of the three kinds of semibatch processes on the peel strength of the PSA were also evaluated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40095.     

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     

Acrylic pressure‐sensitive adhesives with nanodiamonds and acid–base dependence of the pressure‐sensitive adhesive properties

A high performance and functional properties in pressure‐sensitive adhesives (PSAs) are attractive in fundamental and industrial fields. To control the performance of PSAs, nanofillers have been loaded into them. In this study, we focused on composites of acrylic PSAs and nanodiamonds (NDs). The loaded NDs reinforced the mechanical properties and increased the performance of the PSAs. NDs in a PSA formed a network structure. In this study, we revealed that the acidic–basic state was a key factor in the control of the dispersion of the NDs. When a PSA emulsions and ND aqueous dispersion was mixed under basic conditions, the composites demonstrated higher PSA properties (tack, holding, and peeling strength). We investigated the effect of the ND loading on the PSA properties from the viewpoints of the nanostructure and acid–base interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46349.     

Sustainable isosorbide‐based transparent pressure‐sensitive adhesives for optically clear adhesive and their adhesion performance

A biomass‐based isosorbide acrylate (ISA) was synthesized in a one‐pot reaction at low temperature with a quite slow dropwise technique using a syringe pump. Using the ISA monomer, UV‐cured transparent acrylic pressure‐sensitive adhesives (PSAs) composed of semi‐interpenetrating networks were prepared. The effect of ISA on the adhesion performance of the resulting acrylic PSAs was investigated by changing the ISA content, while fixing the mole ratio between 2‐ethylhexyl acrylate and 2‐hydroxyethyl acrylate in the PSAs. The prepared acrylic PSAs, with ISA content ranging from 3.2 to 14.3 mol%, were evaluated in terms of 180° peel strength, probe tack, static shear testing and optical properties. Increasing the ISA content in the acrylic PSAs improved the adhesion properties, such as 180° peel strength (0.25–0.32 N/25 mm), shear holding power (0.086–0.023 mm) and probe tack (1.21–2.26 N). Dynamic mechanical analysis indicated that ISA is a good candidate monomer, playing the role of adhesion promoter and hard monomer in the acrylic PSAs. © 2017 Society of Chemical Industry     

Molecular parameters and their relation to the adhesive performance of acrylic pressure‐sensitive adhesives

Model acrylic pressure‐sensitive adhesives (PSAs) based on poly(2‐ethyl‐hexyl acrylate‐stat‐acrylic acid) and poly(n‐butyl acrylate‐stat‐acrylic acid) at 97.5/2.5 wt % were synthesized using semicontinuous emulsion and solution polymerizations. Microgels formed in the lattices retained their discrete network morphology in the film. In contrast, acrylic solution was essentially gel free and crosslinking in the film was provided by the reaction of acrylic acid and post added Al Acetyl Acetonate after solvent evaporation, which led to continuous network morphology. The difference in film network morphology caused significantly lower shear holding power for the film from emulsion PSA compared with that of solvent‐borne film. Unlike shear holding power, loop tack and peel of acrylic PSAs were mainly controlled by the same sol/gel molecular parameters, regardless of emulsion or solution PSAs. The important molecular parameters are sol‐to‐gel ratio, entanglement molecular weight, weight average molecular weight, and to a lesser extent, glass transition temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2230–2244, 2001     

Effect of adhesive thickness on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The effect of adhesive thickness on stringiness behavior during 90° peel testing was investigated for crosslinked poly(n‐butyl acrylate‐acrylic acid) (A) and poly(2‐ethylhexyl acrylate‐acrylic acid) (B) with a constant crosslinker content. The adhesive thickness was varied over the range from 15 to 60 μm. All adhesive thicknesses exhibited sawtooth‐type peeling with a front frame for B, but only the 30‐μm thickness generated a front frame‐type for A. The peel rate decreased from 15 to 45 μm and plateaued above 45 μm under a constant load test. These results indicate that the adhesion strength increases with adhesive thickness, but reaches a constant value at high thicknesses. The stringiness was also analysed for B and the sawtooth interval observed to increase with increasing thickness. This means the sawtooth number decreased. As a result, the concentrated stress per sawtooth induces easier peeling and so this factor tend to increase the peel rate. Conversely, the stringiness width increased with increasing thickness. The stress load over the stringiness region decreased with an increase in thickness, meaning that a decrease in the concentrated stress decreases the peel rate. The actual peel rate is influenced by the contributions of these two factors. The strain rates during constant peel rate tests decreased slightly with increasing thickness, due to a reduction in the apparent modulus. The molecular mobilities near the adherend and the backing surfaces were evidently restrained by these surfaces, and the relative rates of motion of such restrained molecules decrease with increased thickness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42210.     

Novel pyridinium photoinitiators and their applications for the ultraviolet crosslinking of acrylic pressure‐sensitive adhesives

The demand for ultraviolet (UV)‐crosslinkable pressure‐sensitive adhesives (PSAs) has rapidly been increasing. A variety of different PSAs containing new photoreactive pyridinium derivatives have been evaluated for their effectiveness in improving adhesion and cohesion in UV‐crosslinkable PSAs. PSAs have been evaluated with respect to the tack, peel adhesion, and shear strength. This article summarizes the breakthrough technology used to achieve better performances in UV‐crosslinkable acrylic PSAs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crosslinked acrylic pressure‐sensitive adhesives. II. Effect of humidity on the crosslinking reaction

The effect of humidity during storage on the crosslinking reactions of isocyanate groups was investigated with attenuated total reflectance Fourier transform infrared spectroscopy with pressure‐sensitive adhesives composed of poly[ethyl acrylate‐co‐(2‐ethylhexyl acrylate)‐co‐(2‐hydroxyethyl methacrylate)] as a base resin and polyisocyanate as a crosslinker. A peak‐resolving analysis of the amide II region revealed four bands. According to an analysis of the Fourier transform infrared spectra of the model compounds, these four bands were assigned to free urethane linkages, hydrogen‐bonded urethane linkages, free urea linkages, and hydrogen‐bonded urea linkages. As expected, storage under humid conditions led to the formation of free and hydrogen‐bonded urea linkages corresponding to the promotion of isocyanate consumption. Peak resolution of the amide II region was found to be a reasonable way of monitoring urethane and urea linkages during crosslinking reactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3039–3045, 2003     

Viscoelastic and adhesive properties of single‐component thermo‐resistant acrylic pressure sensitive adhesives

Poly(butyl acrylate‐vinyl acetate‐acrylic acid) based acrylic pressure sensitive adhesives (PSAs) were synthesized by solution polymerization for the fabrication of high performance pressure sensitive adhesive tapes. The synthesized PSAs have high shear strength and can be peeled off substrate without residues on the substrate at temperature up to 150°C. The PSAs synthesized in the present work are single‐component crosslinked and they can be used directly once synthesized, which is convenient for real applications compared to commercial multi‐component adhesives. The results demonstrated that the viscosity of the PSAs remained stable during prolonged storage. The effects of the preparation conditions such as initiator concentration, cross‐linker amount, organosiloxane monomer amount and tackifier resin on the polymer properties, such as glass transition temperature (T_g), molecular weight (M_w), surface energy and shear modulus, were studied, and the dependence of the adhesive properties on the polymer properties were also investigated. Crosslinking reactions showed a great improvement in the shear strength at high temperature. The addition of tackifier resin made peel strength increase compared to original PSAs because of the improvement of the adhesion strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40086.     

Crosslinked acrylic pressure‐sensitive adhesives. I. Effect of the crosslinking reaction on the peel strength

For pressure‐sensitive adhesives (PSAs) composed of poly(co‐ethyl acrylate‐2‐ethylhexyl acrylate‐2‐hydroxyethyl methacrylate) as a base resin and polyisocyanate as a crosslinker, the relationship between the crosslinking reaction and peel strength was investigated. A 90° peel test of cured PSA films under various storage conditions was carried out. At the same time, the isocyanate (NCO) consumption in these PSA films was monitored by attenuated total reflectance/Fourier transform infrared spectroscopy. The peel strength of the PSA compounded with the crosslinker decreased as the NCO groups were consumed. The elevation of the aging temperature promoted the crosslinking reaction and increased the decrement in the peel strength. The peel strength of noncrosslinked and crosslinked PSA films increased with the contact time. A high storage temperature made the increment in the peel strength increase. The addition of the crosslinker to the PSA films reduced the increment in the peel strength. Furthermore, PSA films with residual NCO groups possessed stronger peel strengths than fully cured films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1493–1499, 2003     

The viscoelastic properties of natural rubber pressure‐sensitive adhesive using acrylic resin as a tackifier

Acrylic tackifier resins were prepared by free radical polymerization. A natural rubber base was prepared from Standard Malaysian Rubber through mechanical milling. The acrylic tackifier was blended with the rubber base in various ratios. The blends were coated onto strips of paper and tested for shear and peel strengths. Circular samples of the blends were cast onto release paper and their viscoelastic properties studied using DMTA. On plotting storage modulus G′ against frequency, differences between the low frequencies and high frequencies explain the change in pressure‐sensitive adhesive (psa) properties as the percentage of tackifier resin was varied. Blends with good psa have higher loss tangent at higher frequencies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2118–2123, 2003     

UV curable pressure‐sensitive adhesives for fabricating semiconductors. II. The effect of functionality of acrylate monomers on the adhesive properties

In an attempt to control the adhesive properties of acrylic copolymer‐based pressure‐sensitive adhesives, a series of multifunctional acrylate monomers were added and UV cured. The adhesive compound with a difunctional monomer had increased peel strength after UV curing. On the other hand, the compound with a tri‐ or more functional (polyfunctional) monomer had markedly decreased strength after UV curing. Those adhesives containing any polyfunctional monomer also showed much higher storage modulus than an adhesive containing a difunctional monomer. The greater volume contraction of UV‐cured polyfunctional monomer suggested microvoids at the interface between the adhesive layer and the adherent, resulting in poor strength. Estimated values of the peel strength of UV‐cured adhesives according to the theoretical equations proved that the strength is approximately inversely proportional to the elastic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2889–2895, 2004     

Improvement in mechanical properties and thermal stability of solvent‐based pressure‐sensitive adhesives based on triazine heterocyclic monomer

A heat‐resistance monomer denoted as triazine heterocyclic compound (TGIC‐AA) was synthesized and applied into improving the thermal stability of solvent‐based acrylic pressure sensitive adhesives (PSAs) through copolymerization. The modified acrylic PSAs tapes possessed longer holding time at temperature up to 150°C and no large areas of residues could be seen when peeled off on the substrate while the temperature of test was cooled down to room temperature. The thermal stability could be significantly enhanced in PSAs as the content of triazine heterocyclic compounds increased due to the extensive crosslinking networks. This indicated a worthy method to prepared heat resistant acrylic PSAs. An obvious reduction in peel adhesion occurred at the content of crosslinkers range 5 wt %‐7 wt %, while beyond 7 wt % adhesion failure occurred. The influences of crosslinking density on the molecular weight, glass transition temperature and viscosity, etc. for PSAs were also studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43281.     

Solvent‐free radiation‐curable polyacrylate pressure‐sensitive adhesive systems

This article shows radiation‐curable solvent‐free pressure‐sensitive adhesive polyacrylates, their synthesis, chemical modifications, important properties and use after crosslinking with UV‐lamps and UV‐lasers for the production of self‐adhesives tapes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 182–191, 2003     

Effect of adhesive thickness on the wettability and deformability of polyacrylic pressure‐sensitive adhesives during probe tack test

Effect of adhesive thickness on the wetting and deformation behaviors during probe tack test of pressure‐sensitive adhesive (PSA) was investigated. For this purpose, cross‐linked poly(n‐butyl acrylate‐acrylic acid) [P(BA‐AA)] and poly(2‐ethylhexyl acrylate‐acrylic acid) [P(2EHA‐AA)] random copolymers with an acrylic acid content of 5 wt % and thicknesses in the range of ～15–60 μm were used. Tack was measured using the probe tack test and the fracture energy was calculated from the areas under force–displacement curve recorded during debonding process. From contact time dependence of fracture energy, the rising rate of fracture energy with contact time increased with increasing of adhesive thickness and was P(2EHA‐AA) > P(BA‐AA). The fracture energy was P(BA‐AA) > P(2EHA‐AA) at shorter contact time, whereas it reversed at longer contact time. This was caused by two different interfacial adhesions: the physical wetting of PSA molecules to the adherend surface with contact time and the chemical interaction between the acrylic acid units and the adherend surface. From the force–displacement curve measured under the condition of sufficient interfacial adhesion, both maximum force and displacement—namely, the deformability of PSA during debonding process—increased with adhesive thickness. The degree of increase of deformability was P(2EHA‐AA) > P(BA‐AA). The fracture energy was found to depend on the development of interfacial adhesion during contacting process and the deformability of PSA during debonding process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43639.     

Explanation of tackifier effect on the viscoelastic properties of polyolefin‐based pressure sensitive adhesives

The effects of three tackifiers on the glass transition temperature, terminal relaxation time, plateau modulus, and steady shear viscosity of polyolefin‐based pressure‐sensitive adhesives (PSAs) were investigated. Free volume theory and the Gordon‐Taylor equation are used to explain the special effects of tackifiers on the glass transition temperature of the PSA systems. The plateau modulus and zero shear viscosities were determined from which entanglements and monomeric friction coefficients were calculated. The terminal relaxation time (related to the whole molecular chain relaxations) was calculated from the plateau modulus and zero shear viscosity. Explanations were offered as to why tackifiers have “paradoxical” effects on the viscoelastic properties of the polyolefin‐based PSA, such as increasing the glass transition temperature but decreasing the plateau modulus of the base polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of monomer concentration on the adhesive properties of acrylic pressure-sensitive adhesives

2-Ethylhexyl acrylate (2-EHA)-based co- and terpolymers were synthesized using n-butyl methacrylate (nBMA) and acrylic acid (AA) as comonomers. The change in adhesive properties with the change in monomer concentration was studied. The adhesive, cohesive, and tack characteristics were evaluated under standard conditions as specified by ASTM and/or the Pressure-Sensitive Tape Council (PSTC). The 2-EHA-co-nBMA copolymers showed a good balance between these three characteristics at 50% concentration of 2-EHA. It is noteworthy that with the AA concentration at or above 30% in 2-EHA-co-AA, the polyacrylates lose the tack which is necessary for adhesive bond formation. The 2-EHA-co-AA-co-nBMA terpolymers, where the 2-EHA content was kept constant at 50% and the AA content was varied from 1% to 10% with a corresponding variation in nBMA from 49% to 40%, showed an excellent balance between adhesive, cohesive, and tack strength.     

Hydrogenated rosin ester latexes/waterborne polyacrylate blends for pressure‐sensitive adhesives

Diethylene glycol ester of hydrogenated rosin (DGE‐HR) emulsion was prepared via phase inversion method and then blended with waterborne (wb) polyacrylate for pressure‐sensitive adhesives (PSAs). The preparation conditions of DGE‐HR emulsion were studied. DGE‐HR emulsion with an average particle size of about 220 nm was obtained. Furthermore, the thermal, adhesive, and viscoelastic properties and the morphology of DGE‐HR/polyacrylate composite were investigated. Thermal analysis indicated that glass transition temperatures (T_g) of the DGE‐HR/polyacrylate blends became higher as the DGE‐HR content increased and DGE‐HR did not have a significant influence on thermal stability of the blend films. Atomic Force Microscopy (AFM) observation revealed that the DGE‐HR particles added had a good miscibility with acrylic particles. Additionally, for these tackified acrylic PSAs, positive correlations between mechanical performance and viscoelastic response at bonding and debonding frequencies were also found. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42965.     

Molecular parameters and their relation to the adhesive performance of emulsion acrylic pressure‐sensitive adhesives. II. Effect of crosslinking

Acrylic emulsion pressure‐sensitive adhesive (PSA) films generally have much lower shear holding power than that of their solvent‐borne counterparts for the same peel and tack. This is due to their discrete microgel morphology in the film. In contrast, film cast from solution‐polymerized acrylic PSA forms a continuous network as a result of crosslinking acrylic acid and aluminum acetyl acetonate (AAA) in the film following the solvent evaporation. Novel acrylic emulsion PSA was made by copolymerizing ≤1 wt % isobutoxy methyl acrylamide (IBMA) in the polymer backbone. The IBMA grafted the linear portion of the acrylic polymer with the microgels upon heating the film, which resulted in a significant increase in the shear holding power. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2558–2564, 2001     

UV‐curable pressure‐sensitive adhesives derived from functionalized soybean oils and rosin ester

Functionalized plant oils such as epoxidized soybean oil (ESO) are widely used in plastic industries as additives and are available for more value‐added applications. Pressure‐sensitive adhesive (PSA) derived from petroleum feedstocks has a huge market ranging from tapes to packaging. Here we show a sustainable PSA derived from ESO/dihydroxyl soybean oil (DSO)/rosin ester (Sylvalite) via UV‐initiated copolymerization. The ether crosslinks derived from cationic polymerization of ESO and copolymerization between ESO and DSO (or rosin ester) were demonstrated using ¹H NMR, 2D ¹H–¹H COSY NMR, electrospray ionization mass spectrometry and thermal analyses (differential scanning calorimetry and thermogravimetric analysis). The PSA was formulated by modulating the ratio of ESO/DSO/rosin ester to achieve high performance. At a UV dose of 5.1–5.4 J cm^?2 and 0.3–3% (w/w) of a photoinitiator, i.e. [4‐(2‐hydroxy‐1‐tetradecyloxy)‐phenyl]phenyliodonium hexafluoroantimonate, the PSA at a ratio (by weight) of 1:1:0.7 (ESO/DSO/rosin ester) recorded the highest peel and loop tack strength, which was comparable to a commercial PSA, Scotch Magic Tape, and showed much stronger shear strength (>30 000 min) than the commercial tape (10 000 min). The high‐shear rheological behavior and excellent thermal stability of the PSA were also demonstrated. © 2012 Society of Chemical Industry