Influence of the degree of crosslinking on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The stringiness of crosslinked polyacrylic pressure‐sensitive adhesive (PSA) was observed during 90° peeling under the constant peel load. The random copolymer of butyl acrylate with 5 wt % acrylic acid crosslinked by N,N,N′,N′‐tetraglycidyl‐m‐xylenediamine was used as PSA. All observed stringiness upon peeling was sawtooth‐shaped, but it could be classified into three types dependent on the degree of crosslinking. The typical sawtooth‐shaped stringiness with interfacial failure was observed at the relatively higher crosslinker content ranging from 0.008 to 0.016 chemical equivalents (Eq.), where the PSA has high cohesive strength and low interfacial adhesion. The frame formed at the front end of stringiness at the content ranging from 0.002 to 0.004 Eq. Sufficient interfacial adhesion and deformability generate large internal deformation of the PSA layer. Internal deformation occurred preferentially over peeling as a result of front frame formation. The mode of peeling was changed from cohesive failure to interfacial failure in this range of crosslinker content. The sawtooth‐shaped with cohesive failure was observed at the lower content ranging from 0 to 0.001 Eq. The PSA has high interfacial adhesion and low cohesive strength, and thus exhibited cohesive failure. The PSA after peeling remained in the shape of belts. It was found that the shape of stringiness is strongly dependent on the balance between the interfacial adhesion and the cohesive strength of PSA. When the sawtooth‐shaped stringiness with frame formed, the peeling rate was lowest. This means the peel strength should be the maximum in this shape of stringiness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40336.     

Influence of the interfacial adhesion on the stringiness of crosslinked polyacrylic pressure‐sensitive adhesives

The stringiness of crosslinked polyacrylic pressure‐sensitive adhesives (PSA) was observed during 90° peeling under a constant peel rate with various adherends in order to clarify the influence of interfacial adhesion on the stringiness behavior. The crosslinked random copolymer of butyl acrylate with 5 wt % acrylic acid was used as a representative PSA. Poly(methyl methacrylate) (PMMA), polycarbonate (PC), poly(vinyl chloride) (PVC), fused quartz plates and some surface‐modified poly(ethylene terephthalate) films were used as adherends. The films were pasted on a glass plate using a cyanoacrylate adhesive. The 180° peel strength was higher in the order of PVC >> PMMA ≈ PC > other adherends. All observed stringiness was sawtooth‐shaped, but the stringiness width and length were longer in the same order. The number of sub‐branches formed at the tips of the strings was much more for the PVC, PMMA and PC adherends. Frames formed at the front end of the strings in the case of PVC adherend. Sufficient interfacial adhesion generates large internal deformation of the PSA layer. Internal deformation occurred preferentially over peeling as a result of front frame formation. The string length and the peel load required for the constant peel rate have good correlation with the peel strength. The estimation of generated inner stress in the fibrils of the strings was possible by analysis using the string length for various adherends and the stress–strain curve of pure PSA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40869.     

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.     

Stringiness morphology for crosslinked polyacrylic pressure-sensitive adhesives measured by peel testing with constant rate

To clarify the formation mechanism of front frame-type morphology, the stringiness of crosslinked random copolymers of poly(n-butyl acrylate-acrylic acid) during a 180° peel test with a constant tensile rate was examined for various crosslinker contents and rates using a quartz adherend. Cohesive failure occurred for lower crosslinker content and rate, whereas interfacial failure with sawtooth-type stringiness without a frame was observed for higher crosslinker content and rate. Front frame-type stringiness was formed at the boundary of cohesive and interfacial failures. To clarify the formation mechanism, observation was conducted from the start of peel test until the equilibrium state. The sawtooth-type stringiness with branches first formed at the tip. The adjoining branches were connected and the 2D frame was formed only on the adherend surface. The formed 2D frame developed toward the 3D walls and the front frame-type was then completed. This is caused by the surface tension that acts to restrain the increase in the surface area. However, the surface area of the front frame-type morphology was larger than the no frame-type. The larger absorption of peeling stress by the formation of this morphology is expected to contribute to peel strength improvement.     

Surface and Interfacial Structure of Release Coatings for Pressure Sensitive Adhesives I. Polyvinyl N-Alkyl Carbamates

Polyvinyl N-alkyl carbamates belong to the general class of long alkyl side chain polymers. Such polymers are commonly used as release coatings for pressure sensitive adhesive tapes. In this paper the bulk, surface, and interfacial structures of polyvinyl N-alkyl carbamates having either decyl or octadecyl side chains are examined. The bulk structures and thermal transitions were characterized using X-ray scattering and differential scanning calorimetry. Dynamic mechanical thermal analysis was used to investigate thermal transitions and rheology (i.e., segmental mobility) of the polyvinyl N-alkyl carbamates. The surface energies of polyvinyl N-alkyl carbamate coatings were determined using contact angle methods, while X-ray photoelectron spectroscopy and static secondary ion mass spectrometry were employed to characterize the near-surface compositional profiles of the coatings. The peel force provided by the polyvinyl N-alkyl carbamate coatings, as a function of aging time and temperature, was measured for a tape having an acrylic acid containing alkyl acrylate based pressure sensitive adhesive. The changes in peel force with aging time and temperature were related to the ability to maintain a stable interfacial structure between the PSA and polyvinyl N-alkyl carbamate coatings. Changes in the interfacial composition upon aging were characterized by comparing the surface compositions of the PSA and polyvinyl N-alkyl carbamate coatings initially, prior to contact, as well as after aging and peeling them apart. The increase in peel force upon aging can be attributed, in large part, to a restructuring at the PSA/polyvinyl alkyl carbamate interface. Energetically favorable acid-base interactions between the basic urethane and acetate groups in the polyvinyl alkyl carbamates and the acrylic acid groups in the PSA provide a driving force for the restructuring. If the segmental mobility within the polyvinyl alkyl carbamate is sufficient, restructuring can occur, leading to increased concentrations of these groups at the PSA/polyvinyl alkyl carbamate interface, resulting in higher attractive forces and greater adhesion. The propensity for the polyvinyl N-alkyl carbamate coatings to restructure upon contact with a polar medium was also characterized by monitoring the receding contact angle of water, as a function of water contact time and temperature. A good correlation is seen between the ability of the polyvinyl alkyl carbamate coatings to provide a low peel force for the acrylate PSA tape and the ability of the coatings to maintain a high water receding contact angle.     

Effect of Peel Load on Stringiness Phenomena and Peel Speed of Pressure-Sensitive Adhesive Tape

The factors governing interfacial separation in lightly cross-linked polymer adhesives at low pulling rates as demonstrated by their stringiness phenomenon are investigated.

Cohesive failure and adhesive/substrate interfacial separation of uncross-linked polymer adhesives have been adequately explained. However, in lightly cross-linked polymer adhesives, where cohesive failure cannot occur because there is no viscous flow, there are two regions of interfacial separation at low rate and this phemonenon cannot be readily explained by present viscoelastic theories.

Investigation of the stringiness phenomenon of peeling pressure-sensitive adhesive tapes at constant loads shows that two peeling speeds exist for any peeling load up to the vicinity of 200 g/25 mm. Also it is clear that stringiness structure differs greatly at each peeling speed. The stringiness phenomenon of each of these two regions is analyzed using Miyagi's observation apparatus. These two measurements are then reversed and a comparison shows that the two peeling speeds correspond to each steady peeling region.

This field of investigation, when added to the present viscoelastic property studies, should lead to a new peeling adhesive theory which, in turn, may lead to the development of new high peel force pressure-sensitive adhesives.     

偏光片用丙烯酸酯压敏胶粘接性能和老化性能研究

针对偏光片用压敏胶对耐老化性能的特殊要求,采用丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、甲基丙烯酸羟丙酯、丙烯酸等单体通过溶液聚合的方法,制得了不同的丙烯酸酯压敏胶（PSA）。讨论了引发剂、丙烯酸、交联方法等因素对PSA光学性能、粘接性能、热老化及湿热老化性能的影响。当BPO用量为单体总量的为0.6%,AA用量为0.5%,IPDI用量为固含量的3%时,制备的压敏胶具有适宜的粘接性能。湿热老化前后,PET基材压敏胶的剥离强度分别为7.76N/25mm、6.36N/25mm,具有较高剥离强度保持率。该压敏胶用于偏光片和玻璃板贴附时,显示出优良的湿热老化性能。     

Peel adhesion to paper—interpreting peel curves

Peel experiments involving three PSA tapes and three paper substrates were employed to develop a general approach for the analysis of peeling from paper. Plotting the logarithm of the peak peel force (i.e. the maximum value) versus the logarithm of the peel rate yielded a generalized peel curve which illustrated transitions from interfacial to paper failure. The general peel curve consisted of linear segments (on the log/log plots) which intersected when the failure mode changed from interfacial to paper failure. The influence of paper type, PSA type, and peel angle on the generalized peel curve was determined.     

Adhesion performance of PSA–clay nano-composites by the in-situ polymerization and mechanical blending

The synthesis and characterization of acrylic polymer/Na-montmorillonite (Na-MMT) clay nano-composites pressure sensitive adhesives (PSA) are researched. The PSA/clay nano-composites were synthesized by in-situ emulsion polymerization and mechanical blending. And then, different amounts of nanoclay were dispersed in 2-ethylhexyl acrylate (2-EHA)/n-butyl acrylate (BA)/methyl methacylate (MMA)/acrylic acid (AA) monomer mixture, which was synthesized using in-situ emulsion polymerization technique. Morphological observation was carried out using X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM). Viscoelastic properties of PSA/clay nano-composites were analyzed using advanced rheometric expansion system (ARES). The adhesion performances of synthesized PSA/clay nano-composites were determined by measurements of peel strength, probe tack and shear adhesion failure temperature.     

Improvement in wettability of pressure‐sensitive adhesive on silicon wafer using crosslinking agent with siloxane groups

Acrylic copolymers are prepared by radical polymerization of 2‐ethylhexyl acrylate, ethyl acrylate, and acrylic acid followed by crosslinking to manufacture the pressure‐sensitive adhesives (PSAs) for silicon wafer protection. Both higher reliability and wettability are required for the protective acrylic PSAs in the semiconductor processing applications. The siloxane linkages are introduced in the acrylic PSAs via crosslinking with siloxane‐containing crosslinking agent to modify the thermal and wetting properties of PSAs efficiently. The more efficient formation of crosslinked network structure was achieved with higher content of tetra‐functional crosslinking agent, and the surface energy of PSAs decreased significantly with increasing the content of siloxane linkage resulting in the improved areal wetting rate. The thermal stability of PSAs was also improved significantly by incorporation of siloxane linkages. The adhesion properties such as peel strength and probe tack of acrylic PSAs decreased significantly by increasing the content of either crosslinking agent or siloxane linkage. The acrylic PSA with siloxane group showed both satisfactory wetting and clean debonding properties for the optimal protection of thin silicon wafers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

偏光片用压敏胶粘剂的合成及性能研究

采用聚合物共混改性的方法,以高、低分子量共聚物共混,使其分子量分布变宽,在保持较好的持粘力的情况下,改善初粘力和剥离强度。实验以丙烯酸丁酯、丙烯酸乙酯为软单体,甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯等为硬单体,以过氧化苯甲酰BPO为引发剂,甲苯和乙酸乙酯为溶剂,合成了一系列高、低分子量丙烯酸酯共聚物,再通过调节功能性单体丙烯酸AA的含量以及高、低分子量共聚物的共混配比,使压敏胶粘剂的性能得到了很好的改善。     

结合磷阻燃型苯丙共聚乳液胶粘剂的合成及性能研究

以苯乙烯(St)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)和含磷单体为共聚单体,采用预乳化种子乳液聚合法制备PSA(结合磷型苯丙共聚乳液胶粘剂),并在PSA中添加少量无机阻燃剂APP(聚磷酸铵)制备CPSA(复合型阻燃胶粘剂)。系统研究了含磷单体和APP含量对乳液稳定性、胶膜剥离强度、涂层阻燃性和热性能等影响。结果表明:当m(St+BA+EA+MMA+AA)=40 g、m(St)∶m(BA)∶m(EA)∶m(MMA)∶m(AA)=16∶90∶60∶24∶5、w(含磷单体)=4%和w(APP)=12%(相对于单体总质量而言)时,可制成稳定性、剥离强度和阻燃性能俱佳的CPSA。     

Eco-friendly UV-curable pressure sensitive adhesives containing acryloyl derivatives of monosaccharides and their adhesive performances

Two different monosaccharide acrylate monomers were designed and synthesized from glucose and galactose, and were then used to prepare transparent acrylic pressure sensitive adhesives (PSAs) comprised of semi-interpenetrated structured polymer networks. The effects of the monosaccharide architecture in the acrylate monomers on the adhesive performance of the acrylic PSAs were investigated. Prepared UV-curable acrylic PSA syrups were characterized and the optical properties of the acrylic PSAs were also examined. All of the acrylic PSAs exhibited high transparency in the visible wavelength region. With increasing monosaccharide acrylate concentration in the acrylic PSAs, adhesive performances such as the peel strength, cohesion strength, and probe tack were increased. However, there was no difference in their adhesive performances regardless of the different chemical structures of monosaccharide acrylate monomers.     

改性溶剂型聚丙烯酸酯压敏胶的研制

以丙烯酸丁酯(BA)为软单体、丙烯酸甲酯(MA)为硬单体、2-丁酮(MEK)为溶剂和偶氮二异丁腈(AIBN)为引发剂,采用溶液聚合法合成了溶剂型聚丙烯酸酯PSA(压敏胶);然后以交联单体丙烯酸(AA)和丙烯酸羟乙酯(HEA)作为化学交联改性剂、增黏树脂松香作为共混改性剂,考查了各单体用量对PSA综合性能的影响。结果表明:当w(MA)=43.0%、w(AA)=14.0%、w(HEA)=4.9%和w(松香树脂)=18.0%(均相对于BA质量而言)时,PSA胶带的综合性能相对最好,其180°剥离强度为0.917 kN/m、剪切强度为0.651 MPa、初粘力为6#号钢球和持粘力为7.0 h。     

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.     

Buckling instability during the 180°-peeling of brass shim from polychloroprene rubber

The 180°-peel adhesion of brass shim firmly bonded to a steel plate with a rubber interlayer has been studied as a function of rubber thickness, t, and test temperature. At low temperatures, peeling occurs via 'normal' interfacial detachment and the peel force increases to a plateau with rubber thickness. At higher temperatures and with larger values of t, compressive forces during peeling become sufficient to cause buckling of the bonded shim behind the major peel front. This causes a segment of predetachment and results in a unique type of stick-slip peeling pattern, in which alternate bands of cohesive and interfacial failure are formed. The instability is in approximate accord with a model assuming the buckling of a column on an elastic foundation.     

Effect of grafting of acrylic acid onto PET film surfaces by UV irradiation on the adhesion of PSAs

To improve the peel strength between a pressure-sensitive adhesive (PSA) and its substrate, grafting of acrylic acid (AA) onto the surface of poly(ethylene terephthalate) (PET) film was carried out. After AA was coated onto the surface of PET films using a spin coater, the coated PET films were irradiated by UV. To investigate the surface chemistry and topography of the PET-g-AA films, the grafted surface of the PET films was characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM). From these investigations, the effects of grafting of AA at the surface of PET by UV irradiation were discussed. In addition, to determine the effect of grafting on the adhesion between PSA polymer and PET-g-AA films, peel strength was measured after the PSA/PET-g-AA system was cured at various temperatures. As the esterification between PSA polymer and PET-g-AA films occurred in the interfacial region, the peel strength of the PSA/PET-g-AA system generally increased with increasing curing temperature.     

FPC用丙烯酸酯耐高温保护膜的制备和性能研究

以丙烯酸丁酯(BA)和丙烯酸异辛酯(2-EHA)为软单体、醋酸乙烯酯(VAc)为硬单体、丙烯酸(AA)和甲基丙烯酸缩水甘油酯(GMA)为交联单体、三苯基膦为促进剂和偶联剂A/外交联剂B为复合交联剂,采用改进聚合工艺制得溶剂型丙烯酸酯PSA(压敏胶)。研究结果表明:当m(偶联剂A)∶m(外交联剂B)=2∶1、w(偶联剂A/外交联剂B)=0.40%、m(BA)∶m(2-EHA)∶m(VAc)=8∶2∶2、w(三苯基膦)=0.5%和m(GMA)∶m(AA)=2∶1时,该PSA的综合性能相对较好,其耐高温性能(≤180℃)优异、90°耐高温剥离强度适中(2.0 N/25 mm)且不随放置时间延长而增长,并且胶膜经高温处理后从铜箔上剥离时无残胶痕迹,能够满足FPC(柔性印制线路板)用耐高温保护膜的使用要求。     

保护膜用压敏胶剥离强度增幅研究

采用预乳化半连续聚合法合成了保护膜用乳液型压敏胶(PSA),探讨了单体、乳化剂、引发剂、缓冲剂和交联剂等对乳液型PSA剥离强度增幅的影响。结果表明:乳液型PSA剥离强度增幅随丙烯酸丁酯(BA)或复合乳化剂用量的增加呈先降后升的态势,随丙烯酸(AA)或缓冲剂用量的增加而增大,随苯乙烯(St)、丙烯酸-2-羟丙酯(HPA)或引发剂用量的增加而减小;当w(BA)=85%时,剥离强度增幅最小;大分子有机硅和交联剂的加入能明显降低PSA剥离强度增幅,当w(大分子有机硅)=1.0%时,剥离强度增幅最小;当加入相同用量的交联剂GA240或SC-100时,前者使PSA的剥离强度增幅更低。     

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