Effects of surface modification by oxygen plasma on peel adhesion of pressure‐sensitive adhesive tapes

Surfaces of poly(isobutylene) (PIB) and poly(butylacrylate) (PBA) pressure‐sensitive adhesive tapes were treated by oxygen plasma, and effects of surface modification on their adhesive behavior were investigated from the viewpoint of peel adhesion. The peel adhesion between PIB and PBA pressure‐sensitive adhesive tapes and stainless steel has been improved by the oxygen plasma treatment. The surface‐modification layer was formed on PIB and PBA pressure‐sensitive adhesive surfaces by the oxygen plasma treatment. The oxygen plasma treatment led to the formation of functional groups such as various carbonyl groups. The treated layer was restricted to the topmost layer (50–300 nm) from the surface. The GPC curves of the oxygen plasma‐treated PBA adhesive were less changed. Although a degradation product of 1–3% was formed in the process of the oxygen plasma treatment of the PIB adhesive. There are differences in the oxygen plasma treatment between the PIB and PBA adhesives. A close relationship was recognized between the amount of carbonyl groups and peel adhesion. Therefore, the carbonyl groups formed on the PIB and PBA adhesive surfaces may be a main factor to improve the peel adhesion between the PIB and PBA adhesive and stainless steel. The peel adhesion could be controlled by changing the carbonyl concentration on the PIB and PBA adhesive surfaces. We speculate that the carbonyl groups on the PIB and PBA adhesive surface might provide an interaction with a stainless steel surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1392–1401, 2000     

Studies on tack of pressure-sensitive adhesive tapes: On the surface contamination by adhesive mass after peeling

The presence of adhesive residue on the surface of various adherends after peeling has been confirmed using a tracer technique. Adhesive bonding is found to break by a cohesive mechanism, although the unbonding process seems apparently to be due to intersurface failure. This result supports the concept for adhesive bond breaking proposed in the preceding paper: The unbonding proceeds from the viscoelastic deformation of the adhesive mass around the wetted spots on the surface. As the number of spots in a unit area is controlled by surface energy, the tack value is dependent on the critical surface tension of the adherends.     

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.     

Acrylic pressure‐sensitive adhesive for transdermal drug delivery systems

This article describes the development in the area of resin‐free acrylic pressure‐sensitive adhesive (PSA) based on 2‐ethylhexyl acrylate, methyl acrylate, acrylic acid, N‐vinyl caprolactam, and pregnancy transdermal drug delivery systems, and shows the variety of polymer composition, residue monomers content, quality control of peel adhesion level and repeating during the time, biocompatibility of the acrylic PSA layer, and efficacy in clinical medicine. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Studies in the nature of adhesive tack

By measuring tack energy using a modified probe tack testing procedure, the interrelation of bulk energy and surface energy effects in pressure-sensitive adhesives was studied. Tack energy was strongly influenced by the solvent used in the preparation of the adhesive film. A procedure was empirically derived which reduced the number of variables to a single variable, yielding a single master curve in which the independent variable was the speed of probe withdrawal expressed on a logarithmic scale. The form of the curve was a simple exponential function, y = A exp (mx), where A and m are constants and y and x are the dependent and independent variables, respectively. The constant m was found to be a unique function of the type of adhesive used. A theoretical interpretation of the devised procedure was based on bulk viscoelastic effects and a combined activation energy–free volume concept of adhesive bonding. The wider implications of this are briefly discussed.     

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     

Theory of tack of pressure sensitive adhesive. I

If the tack of a pressure-sensitive adhesive is closely related to the rolling motion of a ball on the material, it is more scientific to express tack in terms of the rolling friction coefficient, which depends on the physical properties of the materials, and not on any trivial conditions of measurements. It is shown that the rolling friction coefficient of a pressure-sensitive adhesive can experimentally be determined from the pulling cylinder method much more easily than the rolling ball method and that we can theoretically calculate the rolling friction coefficient by making some assumptions, concerning deformation and failure of a pressure-sensitive adhesive.     

Studies on tack of pressure-sensitive adhesive tapes: On the relationship between pressure-sensitive adhesion and surface energy of adherends

The relationship between wetting and pressure-sensitive adhesion was studied using an adhesive composed of poly(butyl acrylate) and various adherends of different surface tension. The amount of adhesive deposit was determined quantitatively by tracer technique although the unbonding process was apparently observed as interface failure. The adhesive force and amount of deposit were both dependent on the critical surface tension of the adherends. Maximum tack value and contamination were observed with adherends whose critical surface tension was close to that but a little higher than that of the adhesive. The adhesive force obtained was lower than cohesive strength of adhesive. From this evidence, a mechanism for pressure-sensitive adhesion was discussed: the bond breaks in the addesive mass around the very minute spots where interaction is at work between adhesive and adherend. Inasmuch as the density of the minute spots per unit area depends on the surface tension, the adhesive force also depends on the surface tension.     

Effect of molecular weight of epoxidized‐natural rubber on viscosity and tack of pressure‐sensitive adhesives

The effect of molecular weight of rubber on viscosity and loop tack of rubber‐adhesives were studied using two grades of epoxidized‐natural rubber, i.e., ENR 25 and ENR 50. Coumarone–indene resin, gum rosin, and petro resin were used as tackifiers. Toluene was used as the solvent throughout the experiment. The adhesive was coated on polyethylene terephthalate (PET) substrate using a SHEEN hand coater. Viscosity was determined by a HAAKE Rotary Viscometer, whereas loop tack was measured by a Llyod Adhesion Tester operating at 10 cm/min. Results show that viscosity increases gradually upto a critical molecular weight of 6.8 × 10⁴ and 3.9 × 10⁴ for ENR 25 and ENR 50, respectively, before a rapid increase in viscosity is observed. Loop tack indicates maximum value at the respective critical molecular weights for the three tackifiers investigated suggesting the culmination of wettability. For both rubbers, loop tack increases with coating thickness due to the concentration effect of adhesive. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

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     

Synthesis of removable and repositionable water‐borne pressure‐sensitive adhesive acrylics

This publication shows the synthesis of the water‐borne removable pressure‐sensitive adhesive (PSA) based on acrylates and the influence of parameters such as internal emulsifiers on peel adhesion on steel and also the influence of N‐methylol acrylamide and plasticizers on peel adhesion on glass, poly(vinyl chloride), and polypropylene during aging time. Removable and repositionable pressure‐sensitive adhesives based on acrylic polymers are used for the production of removable memo notes, paper and foil labels, double‐sided tapes, carrier‐free tapes to protective films, and manufacturing aids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 886–892, 2005     

Control of structure and tack properties of acrylic pressure‐sensitive adhesives designed by a polymerization process

Free radical emulsion polymerization of methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) results in the synthesis of pressure‐sensitive adhesives (PSAs) with good tack properties. Management of both the copolymer composition and the polymerization process allows one to control the behavior of the PSA. Semicontinuous (SC) processes create polymer particles whose instantaneous composition is close to that of the feed particle The SC Mixture process (continuous feeding with comonomer blends) affords nearly homogeneous latex particles and PSA films. The SC Gradient process (separate feedings at inversely varying rates) affords heterogeneous particles and films. The Batch process leads to somewhat heterogeneous films, but the hard (MMA‐rich) microdomains are made compatible with their soft (EHA‐rich) matrix because of the assumed formation of tapered‐type copolymers. Tack measurements indicate the importance of the particle and film structures. Too much hardness or softness leads to unacceptable lacks of adhesion and cohesion, respectively. Homogeneous structures prove adequate, but their tack properties collapse with rising temperature. Heterogeneous structures, with extensive phase segregation, prove unsatisfactory because they lack adhesion and cohesion. Finally, the association of well‐balanced composition and compatible heterogeneity is the criterion for suitable PSA behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2749–2756, 2003     

Effect of different skin permeation enhancers on tack of a pressure sensitive adhesive

Solutions of an acrylic copolymer pressure sensitive adhesive with different concentrations of propylene glycol (PG) and oleic acid (OA) were cast on a PET film. A rolling ball tack test was carried out on the adhesive coated tapes with different thicknesses. The results were explained on the basis of the surface (energy and roughness) and viscoelastic properties of the copolymer, which were related to the glass‐transition temperature. The 60‐μm PG samples with an approximately equal glass‐transition temperature and surface energy did not have a significantly different tack value. The tack value of the 30‐μm tapes decreased with PG concentrations above 15% (w/w), which was related to an increase in the surface roughness with a more prominent effect at the lower thickness. OA, which improved both the surface and viscoelastic properties, increased the tack value up to 15% (w/w). However, the tack value decreased above 15% (w/w). This was explained on the basis of OA large crystals, which can decrease viscoelastic energy dissipations and form a mechanically weak surface layer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1287–1291, 2005     

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     

耐高温压敏胶粘带的研究进展

综述了近年来国内外在耐高温压敏胶粘带研究开发和应用方面的研究进展,分别对热固型、溶剂型、乳液型、有机硅型、辐射固化型、热熔型等耐热压敏胶粘带作了具体介绍.     

Siloxane‐modified polyacrylate low‐residual pressure‐sensitive adhesive with high peeling strength

A low‐residual siloxane‐modified polyacrylate pressure‐sensitive adhesive (PSA) with a high peeling strength was prepared by seeded semicontinuous emulsion polymerization. 3‐Glycidyloxypropyltrimethoxysilane was introduced into the acrylic (AC) PSA through a thermal posttreatment method to crosslink with AC. To improve the adhesion properties, a polymeric emulsifier, 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid, was introduced into the system with the conventional emulsifier. Several key polymerization conditions, such as the initiator concentration, mass ratio of soft monomer to hard monomer, the content of polymeric emulsifier, and siloxane dosages were examined in detail. Then, the optimal conditions and a proper preparation process were established. The results show that we achieved not only a low repeeling residue with high tack and peeling strength but also excellent properties of high‐temperature aging resistance and water resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42975.     

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     

UV curable pressure‐sensitive adhesives for fabricating semiconductors. I. Development of easily peelable dicing tapes

In order to develop easily peelable dicing tapes from diced wafers, UV curing of various pressure‐sensitive adhesives (PSAs) was studied. After UV irradiation, the adhesive strength of a PSA composition including a diacrylourethane oligomer (UDA) decreased drastically compared with other compositions. Because of network formation via UV irradiation, this composition had a greater volume contraction that might yield microvoids at the interface between the adhesive and the wafer, resulting in the loose adhesion. Its storage modulus increased up to about 1000 times that before UV curing, which was due to the crosslinking of the UDA component. It was suggested that the increased crosslinking density and the high internal coagulant energy of the UDA backbone structure caused a remarkable decrease of the adhesive strength. Furthermore, it was ascertained that the UV‐irradiated UDA adhesives left few residual deposits on the wafer released from the tape. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 436–441, 2003