Effect of the rheological properties of industrial hot-melt and pressure-sensitive adhesives on the peel behavior

Three factors govern the adhesion properties of hot-melt and pressure-sensitive adhesives: (1) thermodynamic interfacial properties (Dupré adhesion energy); (2) interfacial losses due to specific interactions; and (3) viscoelastic losses in the bulk related to the rheological properties of the adhesive. In the present paper, we focus on the main factor in the adhesion properties, which is the viscoelastic factor. We extend in this paper the results obtained on a series of model adhesives to the case of industrial formulations: one SIS triblock copolymer-based PSA formulation and one EVA copolymer-based hot-melt formulation. After studying the rheological properties of these adhesives over a wide frequency range using time-temperature equivalence, we present data obtained on peel tests at various temperatures. As with model adhesives, the peel rate-temperature equivalence leads to the same shift factors as rheology. The experiments demonstrate that there is a one-to-one relationship between the cohesive fracture domain and the terminal region of relaxation exhibited in rheological testing. The first interfacial fracture mode is related to the rubbery plateau, and the brittle interfacial fracture mode observed at high peel rates to the glassy behavior exhibited at very high frequencies in rheological measurements.     

Novel pyridinium derivatives as very efficient photoinitiators for UV-activated synthesis of acrylic pressure-sensitive adhesives

During the development of synthesis of acrylic pressure-sensitive adhesives, newly synthesized pyridinium derivatives were used by the UV-initiated polymerization quarantines of new polymer design for the synthesized self-adhesive acrylics with excellent performance, for which tack, peel adhesion, shear strength and shrinkage were measured. For example, the best tack and peel adhesion performances were achieved after 30 and 60 s UV radiation for 3.0 wt% pyridinium photoinitiator PPP, after 60 and 90 s UV exposure for 4.0 wt% pyridinium photoinitiator HPP and after 90 s UV-crosslinking in the case of 5.0 wt% pyridinium photoinitiator OPP. An increase of novel pyridinium photoinitiators concentration causes in an increase of the monomers conversion. For high photoinitiator content, characterized for each investigated photoinitiator, ranging from about 3.0 (PPP) to 5.0 wt% (OPP), the degree of monomer conversion reaches a maximum value of about 99.6 wt%.Preliminary results are reported illustrating the effectiveness of the acrylic PSA development.     

Power feed synthesis of pressure-sensitive latex adhesives

Latex particles with the same core composition of poly(MMA-co-ALMA) and different shell compositions of poly(BA-co-AA) were prepared by semibatch emulsion polymerization using ‘power feed’ monomer and chain transfer agent addition methods in the shell layers. The seed stage involved formation of seed particles of 111 nm in diameter with a batch process. After that, two growth stages formed the final particle diameter, d_z = 300 nm measured by dynamic light scattering. The gel content and the molecular parameters of the polymer were determined. The adhesive properties including loop tack, peel force and shear resistance were measured according to the FINAT test methods No. 9, 1 and 8. An evaluation was also made for the relationship between pressure-sensitive properties and molecular parameters. Introducing power feed to semibatch emulsion polymerization had no significant effect on the latex preparations and could improve the final conversion and the colloidal stability. The observed particles were grown without significant secondary nucleation. The power feed methods had no effect on the glass transfer temperature (T_g) of the shell layer also. Emulsion polymerization conducted by positive power feed resulted in the formation of longer primary polymer chains at the beginning than that conducted by negative power feed and standard uniform feed, which caused a very high gel fraction. As pressure-sensitive adhesives prepared by using the positive power feed had the highest gel content and strongest core–shell interaction, they exhibited the highest shear resistance, but the lowest tack and peel force.     

Thermal decomposition of polyurethane pressure-sensitive adhesives dispersions

The thermal degradation of polyurethane pressure-sensitive adhesives (PSAs) at temperature 600 °C was investigated by the application of pyrolysis-gas chromatography technique. The present study was undertaken in order to determine the key thermal degradation products of polyurethane PSA based on isophorone diisocyanate (IPDI), polypropylene glycol (PPG), hydroxylated polybutadiene (HTPB), dimethylolpropionic acid (DMPA) and to elucidate the mechanism of the polyurethane PSAs pyrolysis.     

Novel versatile pressure-sensitive adhesives for polarizing film of TFT-LCDs: Viscoelastic characteristics and light leakage performance

One of the main problems in thin film transistor liquid crystal displays (TFT-LCD) is a phenomenon called “light leakage”, seriously affecting black–white contrast and color brightness. It occurs due to a thermal shrinkage of the polarizing film in TFT-LCDs, caused by a heat from the backlight unit. A pressure-sensitive adhesive (PSA) used for assembling of the polarizing film to the TFT-LCD panel can relieve the stress and minimize the light leakage. PSAs are designed specifically for a certain size LCDs, and cannot be used for another size LCD because of poorer light leakage. Obviously, there is a certain necessity to develop a universal PSA applicable simultaneously for LCDs with different sizes, such as mobile phones, digital cameras, navigation systems, computer monitors, HDTVs, etc.In this paper, we introduced N-vinyl pyrrolidone as a comonomer to a conventional copolymer of butyl acrylate, acrylic acid, and 2-hydroxy ethyl methacrylate. It resulted in a higher elasticity modulus and a higher shrinkage resistance of the PSA. A significant reduction of the light leakage to some extend was observed at increase of the hardener content for 2.5 and 7 in samples. However, it was accompanied by deterioration of the peel strength below spec requirements. Lowering molecular weight of the polymers from 626,000 to 205,000 Da resulted in excellent light leakage of both small and large specimens. Dynamic mechanical analysis confirmed that zero light leakage was achieved through a synergy of two mechanisms: high modulus, i.e. resistance to thermo-induced shrinkage, and high stress relaxation of lower molecular weight polymers. The results of this work are perspective for creation of a universal PSA for polarizing film in TFT-LCDs of different sizes.     

Relationship between the fracture energy and the mechanical behaviour of pressure-sensitive adhesives

Mechanical behaviours of two pressure-sensitive adhesives (PSAs) families, composed of elastomer copolymers or polyacrylate/acrylic copolymers, are characterised by peel tests. Fracture energy varies linearly according to the applied contact force between two levels, which depends on tackiness and cohesion of the PSA. Local fracture energies are measured by an original peeling system and they are related with the adhesive deformation. Mechanical behaviours of PSAs depend on their composition but majority of fracture energy is dissipated on the first millimetre near the bending zone where fibrils elongation is maximum. Observations of interfaces between PSAs and glass substrate underline that fracture energy varies linearly according to the contact area.     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

UV固化无溶剂型丙烯酸酯压敏胶的合成与性能表征

以丙烯酸异辛酯(2-EHA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)和四氢化糠基丙烯酸酯(THFA)为主要单体,以丙烯酸(AA)和N,N-二甲基丙烯酰胺(DMAA)为功能性单体,以4-丙烯酰氧基二苯甲酮(ABP)为光引发剂,以十二烷基硫醇(NDM)为链转移剂,通过本体聚合法制备了UV固化无溶剂型丙烯酸酯压敏胶(PSA)。分别探讨了两种功能单体AA和DMAA用量,光引发剂ABP和链转移剂NDM用量对PSA性能的影响。结果表明,当DMAA和AA用量分别为单体总质量的10%和2%时,PSA的120℃熔融黏度适中且粘接性能较优;光引发剂ABP用于PSA体系,且用量为单体总质量的0.2%时,光固化效果最佳;当NDM用量为单体总质量的1.5%时,PSA综合性能最佳。     

TPI/NR力学性能的分子动力学模拟

为研究杜仲胶(TPI)和天然橡胶(NR)之间的相容性、TPI/NR共混物的力学性能,采用分子动力学(MD)法在Compass力场条件下对其进行了模拟。研究结果表明:通过比较溶度参数差值(Δδ)的大小可预测TPI与NR之间的相容性,TPI/NR属于相容体系;与纯TPI相比,TPI/NR共混物的静态力学性能及动态拉伸抗疲劳性能更加优越。     

Adhesion properties of polyurethane pressure-sensitive adhesive

In this study, the adhesion properties of polyurethane (PUR) pressure-sensitive adhesive (PSA) were investigated. The PUR-PSA was prepared by the cross-linking reaction of a urethane polymer consisting of toluene-2,4-diisocyanate and poly(propylene glycol) components using polyisocyanate as a cross-linking agent. The peel strength increased with the cross-linking agent content and exhibited cohesive failure until the maximum value, after which it decreased with interfacial failure. The PUR-PSA exhibited frequency dependence of the storage modulus obtained from dynamic viscoelastic measurements, but did not show dependence of the tack on the rolling rate measured using a rolling cylinder tack test under the experimental conditions used, which is quite different from the acrylic block copolymer/tackifier system. The PUR-PSA showed strong contact time dependence of tack measured by a probe tack test. The tendency was significantly larger than for the acrylic block copolymer/tackifier system. Therefore, the storage modulus increased, whereas the interfacial adhesion seems to be decreased with increase in the rolling rate for this PUR-PSA system. It was estimated that the influence of rolling rate on the interfacial adhesion and the storage modulus was offset, and, as a result, the rolling cylinder tack did not exhibit rate dependency.     

Cellulose nanocrystals (CNCs) reinforced acrylic pressure- sensitive adhesives (PSAs) prepared via miniemulsion polymerization

In this study, poly (n-butyl acrylate-co-2-ethyl hexyl acrylate) (P(nBA-co-2EHA)) pressure sensitive adhesives (PSAs) were successfully synthesized in the presence of cellulose nanocrystals (CNCs) via in-situ miniemulsion polymerization. First, the CNCs were prepared via acid hydrolysis of cellulose microcrystals (CMCs) at various temperatures, 42–54 °C, and characterized using atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) apparatus. The results showed that hydrolysis of MCCs at 45 °C resulted in CNCs with a well-defined aspect ratio, average length of 206 nm and thickness of 3.9 nm, and the highest crystallinity. Adding further CNC to the copolymer adhesive enhanced the mean particle size of the composite latex and decreased the glass-rubber transition temperature (T_g) of the copolymer matrix. Molecular weights and viscoelastic properties of the resultant PSAs were determined using gel permeation chromatography (GPC) and dynamic mechanical thermal analysis (DMTA), respectively. Adhesion performance of the neat and reinforced PSAs containing 1–5 wt% CNCs was evaluated at room temperature. The results showed that the incorporation of CNCs up to 4 wt% in the copolymer adhesive increased the shear resistance by 518%, peel strength by 176% and probe tack by 13%, while further addition, 5 wt%, lowered the adhesion performance due to a lack of surface wettability.     

Tack properties and adhesion mechanism of two different crosslinked polyacrylic pressure-sensitive adhesives

Tack properties of cross-linked random poly(n-butyl acrylate-acrylic acid) (A) and poly(2-ethylhexyl acrylate-acrylic acid) (B) copolymers as pressure-sensitive adhesives (PSAs) were compared by a probe tack test to know the optimal application in the industrial field. Tack increased remarkably with temperature, reached a peak, then decreased. The peak of tack appeared at higher temperature for B. Tack increased with increasing contact time and decreasing crosslinking agent level. The fracture energy at higher temperature was higher for B than A. From the observation of debonding behavior, the fibrillation occurred at the edge of probe. The wettability and deformability of PSA were larger for B than A. From a dynamic mechanical analysis, the shear storage modulus (G') in the rubbery plateau region was lower for B than for A. The good wettability and deformability were improved as a result of its lower G'. The relaxation behaviors of PSAs and vulcanized isoprene rubber were measured by ¹H pulsed nuclear magnetic resonance. This technique is found to be useful for estimating the degree of intermolecular interactions. The crosslinking degree hardly influenced. The intermolecular interaction was weaker for B. This was the reason of the lower G' for B.     

复合填料/聚丙烯酸酯导电压敏胶的制备与性能

针对导电胶黏剂（ECA）在实用中所遇到填料组分单一、易团聚、对基体力学性能影响较大等问题,本文利用不同组分填料间的架桥、插层等“协同”效应,将一定比例的碳黑（CB）、碳纤维（CF）、碳纳米管（CNTs）、纳米石墨微片（NanoG）复合作为导电填料加入到聚丙烯酸酯压敏胶（PSA）中,采用溶液共混法超声分散,得到填料添加量小、导电性能和力学性能良好的导电PSA。运用多种检测手段对导电PSA的电学性质、微观结构、热稳定性和力学性能进行了分析。结果表明,复合填料组成为CF 3%、NanoG 5%、CNTs 5%（均为质量分数）时,导电PSA的电导率达到3.0×10?2S/cm,180°剥离强度为0.38kN/m。     

Molecular dynamics predictions of thermal and mechanical properties of thermoset polymer EPON862/DETDA

We use molecular dynamics (MD) to perform an extensive characterization of the thermo-mechanical response of a thermoset polymer composed of epoxy EPON862 and curing agent DETDA. Our simulations, with no adjustable parameters, show that atomistic simulation can capture non-trivial behavior of amorphous thermosets including the role of polymerization degree, thermal history, strain rate and temperature on the glass transition temperature (T_g) and mechanical response (including ultimate properties) and lead to predictions in quantitative agreement with experiments. We find a significant increase in T_g, Young’s modulus and yield stress with degree of polymerization while yield strain is significantly less sensitive to it. For structures cured beyond the gel point (percolation of a 3D network) conversion degree and temperature affect yield stress in a similar way with yield stress linearly dependent on T−T_g; however, we find non-linear and non-universal relationship below the gel point. Our results show that a relative small variation in polymerization degree (∼5%) can explain the spread in experimental measurements of T_g and elastic constants available in the literature.     

Optical properties and adhesion performance of optically clear acrylic pressure sensitive adhesives using chelate metal acetylacetonate

Optically clear acrylic pressure-sensitive adhesives (PSAs) with different co-monomers were synthesized. This study employed metal chelate aluminum acetylacetonate and zirconium acetylacetonate as curing agents. The optical properties of the acrylic PSAs were examined by UV–visible spectroscopy and a prism coupler. In addition, the adhesion performance was obtained by assessing the peel strength, the tack, and the shear adhesion failure temperature. The decrease in the adhesion performance may be related to a higher crosslinking density, which also resulted in a higher gel content.     

Molecular dynamics study on mechanical cleavage mechanisms of GaAs and experimental verification

Laser bars are fast becoming a key device in a range of specific industrial applications. Mechanical cleavage technology is a new and efficient method for fabricating laser bars. However, there is little detailed analysis of the relationship between scratching step and cleavage step. To close this research gap, a molecular dynamics study on cleavage mechanisms of GaAs are reported investigating surface and subsurface damage, and molecular dynamics method could accurately describe the nano-scale processes in semiconductors at atomic scale. Simulation results show that the scratching depth has a significant effect on the scratch quality as compared with other parameters during the scratching process. Then, a series of cleavage experiments were carried out to verify the simulation results and further explore the influence of key scratching parameters on cleavage plane morphology. Experimental results correlate well with the simulations. Consequently, the achieved optimal combination of parameters have been found to be a scratching load of 10 g, scratching speed of 20 mm/s and scratching length of 0.6 mm, which provides direct guidance for the cleavage processing of GaAs materials. Under optimal conditions, the length and surface roughness of the undamaged area can reach 11.77 mm and 0.43 nm respectively.     

Strengthening the mechanical properties of polysulfide adhesives by introducing polyurethane

Polysulfide adhesives are often subjected to breakage or even fracture caused by highly loaded vibrations and large deformations from the wing, limiting their practical use in aircraft fuel tanks. Inserting polyurethanes into liquid polysulfide systems is a viable approach to strengthening their mechanical properties and avoiding nonuniform dispersion of the curing agent. In this contribution, a series of sulfur-containing curing agents were prepared by liquid polysulfide and trimethylolpropane tris(3-mercapto propionate) (TMPMP) to minimize the effect of the polysulfide-urea (-NHCOS-) groups on water resistance. Subsequently, the two-component polysulfide adhesives were successfully synthesized via the prepolymerization method, and their chemical structure, mechanical properties, and solvent resistance were systematically evaluated. As expected, the large introduction of sulfur linkages and -NHCOS- groups provided excellent oil resistance and strong mechanical properties for polysulfide adhesives. Notably, Samples 2-4 exhibited the highest tensile strength of 1.11 ± 0.02 MPa, the greatest shear strength of 1.87 ± 0.04 MPa, and the best hardness of 81 ± 2 Shore A, with 122.0%, 523.3%, and 170.0% improvement over the control, respectively. Furthermore, the oil absorption rate of all samples was less than 3.0%, and their tensile strength remained almost unchanged after 30 days of immersion than before. We believe our paradigm can provide a valuable guideline for designing high-performance polysulfide adhesives.     

功能性压敏胶的研究进展

综述了功能性压敏胶的研究进展,分别介绍了医用压敏胶、阻燃压敏胶、导电压敏胶和防腐压敏胶的研究概况,并对压敏胶功能材料的发展作了展望。     

Molecular dynamics study of the conformation and dynamics of precisely branched polyethylene

The conformation and dynamics of precisely branched polyethylene, i.e., polyethylene molecules containing regularly spaced, short chain branches along its linear backbone, were studied using molecular dynamics simulation. Models with branch content varying from 0 to 47.6 branches per 1000 backbone carbons were studied over a temperature range of 273–550 K and under a constant pressure of 1 bar. Two types of models were built, one of which contained ethyl branches while the other contained hexyl branches. The results indicated that at a given temperature, the global orientation order parameter decreased almost linearly with increasing branch content up to a value of approximately 38.5 and increased considerably and unexpectedly at a branch content of 47.6. The order parameter was insensitive to the branch length except at high branch contents. The computed packing lengths and activation energy for diffusion are consistent with the above observations.     

Phase structure and adhesion properties of acrylic block copolymer/tackifier blends as nanocomposite-like pressure-sensitive adhesives

In a blend of acrylic block copolymer consisting of poly(methyl methacrylate) and poly(n-butyl acrylate) blocks and a special rosin ester resin (RE) tackifier as a model pressure-sensitive adhesive (PSA), RE exists in two states: as nm-sized agglomerated particles (A) and as dissolved molecules (B). The effect of A and B ratio on the PSA properties were investigated using REs with four different weight-average molecular weights (M_ws) in the range from 680 to 1700. The formation of A increased with increasing of M_w because of lowering of miscibility. The glass transition temperature increased with increasing of M_w. The tack at lower temperatures and the fracture energy were improved by B, whereas the tack at higher temperatures was improved by A. A and B enhanced the cohesive strength and the wettability of PSA, respectively. However, the improvement of cohesive strength by the RE with highest M_w was remarkably low. This seems to be caused by the larger size of agglomerated particles. ¹H pulse nuclear magnetic resonance analysis was useful for estimating the degree of A formation. The model PSA investigated in this study was nanocomposite-like.