压敏胶粘剂的技术发展

对水基（ 丙烯酸酯乳液） 、热熔型和射线固化型３ 类环境友善的压敏胶粘剂近几年国内外的主要技术发展进行了介绍和评述。     

热熔压敏胶的发展动向

美国1965年Shell化学公司将SBSSIS商业化后，HMPSA就有一定程度的发展，到了70年代，此时世界正面临石油危机，能源的缺乏和环保的需要使HMPSA得到了年增长率大干10％的快速发展。到1988年它的用量已上＞7·6万吨，预计1997年的用量为匕．3万吨（表1）。表IHMPSA其美国的用途与用＊（万吨）HMPSA及其产品的生产厂家数目1989年为68个，1992年则为78个，1994年增至96个。70年代后期日本对HMPSA还处于调查阶段，在1978年统计的热熔胶主体聚合物中无SBS‘SIS，11986年热熔胶的生产量已为4万t／a，1992年的用量达到6．5万t八，其…     

Surface Energy and Adhesion Studies on Acrylic Pressure Sensitive Adhesives

The surface energy and adhesion dynamics of pressure sensitive adhesives-like networks (PSA-LNs) as mimics for PSAs were studied using JKR-based contact mechanics and peel tests. Acrylic acid (AA) was co-polymerized with 2-ethyl hexyl acrylate (2-EHA) and 1,6-hexane diol diacrylate (HDDA) to create PSA-LNs. The measured surface energy (27 to 31 mJ/m²) was sensible as surmised from their structure. Acrylic acid content increases the surface energy, threshold adhesion energy and adhesion hysteresis of PSA-LNs. Measurements of adhesion dynamics showed a dependence of adhesion energy to the 0.6–0.8 power of crack speed, depending upon the model chosen for analysis of the data. When compared with actual pressure-sensitive adhesive tape peel tests, the adhesion dynamics data predicted the peel strength. This study shows a direct relationship between threshold adhesion energy, crack propagation mechanics and peel strength measurements.     

Surface Energy and Adhesion Studies on Acrylic Pressure Sensitive Adhesives

The surface energy and adhesion dynamics of pressure sensitive adhesives-like networks (PSA-LNs) as mimics for PSAs were studied using JKR-based contact mechanics and peel tests. Acrylic acid (AA) was co-polymerized with 2-ethyl hexyl acrylate (2-EHA) and 1,6-hexane diol diacrylate (HDDA) to create PSA-LNs. The measured surface energy (27 to 31 mJ/m²) was sensible as surmised from their structure. Acrylic acid content increases the surface energy, threshold adhesion energy and adhesion hysteresis of PSA-LNs. Measurements of adhesion dynamics showed a dependence of adhesion energy to the 0.6-0.8 power of crack speed, depending upon the model chosen for analysis of the data. When compared with actual pressure-sensitive adhesive tape peel tests, the adhesion dynamics data predicted the peel strength. This study shows a direct relationship between threshold adhesion energy, crack propagation mechanics and peel strength measurements.     

A Practical Criterion for Rheological Modeling of the Peeling of Pressure Sensitive Adhesives

The transient extensional viscosity of non-crosslinked pressure sensitive adhesives (PSA's) and physically-crosslinked PSA's is measured and compared with theoretical predictions based on the linear viscoelastic (LVE) properties of the PSA's and the use of linear and quasi-linear constitutive equations. Based on a previously-derived expression for the relative contributions of individual relaxation modes of a polymeric material to its transient extensional viscosity, a criterion for whether large extensional deformations can be modeled on the basis of the LVE spectrum is proposed and evaluated for each PSA. The relevance to adhesion is demonstrated in peel tests, where the deformation of adhesive is quantified in images of the peel front under the assumption of uniaxial elongation and used to obtain theoretical peel forces in excellent agreement with measurements. This demonstrates the applicability of the criterion to the peeling process.     

A Practical Criterion for Rheological Modeling of the Peeling of Pressure Sensitive Adhesives

The transient extensional viscosity of non-crosslinked pressure sensitive adhesives (PSA's) and physically-crosslinked PSA's is measured and compared with theoretical predictions based on the linear viscoelastic (LVE) properties of the PSA's and the use of linear and quasi-linear constitutive equations. Based on a previously-derived expression for the relative contributions of individual relaxation modes of a polymeric material to its transient extensional viscosity, a criterion for whether large extensional deformations can be modeled on the basis of the LVE spectrum is proposed and evaluated for each PSA. The relevance to adhesion is demonstrated in peel tests, where the deformation of adhesive is quantified in images of the peel front under the assumption of uniaxial elongation and used to obtain theoretical peel forces in excellent agreement with measurements. This demonstrates the applicability of the criterion to the peeling process.     

Interfacial Energy and Adhesion between Acrylic Pressure Sensitive Adhesives and Release Coatings

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high – between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.     

Interfacial Energy and Adhesion between Acrylic Pressure Sensitive Adhesives and Release Coatings

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high - between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.     

Rolling Motion of a Ball on Pressure Sensitive Adhesives

Rolling motion of a ball on pressure sensitive adhesives was carefully observed under well-controlled conditions. Rolling distance was measured as a function of time by means of stroboscopic photography, and rollout distance was measured as a function of initial height of a ball. Both rolling distances and rollout distances were analysed according to a unified theory, where rolling friction coefficient (f) of a pressure sensitive adhesive is involved. It is suggested that f depends on viscoelastic properties of the adhesives.     

Rolling Motion of a Ball on Pressure Sensitive Adhesives

Rolling motion of a ball on pressure sensitive adhesives was carefully observed under well-controlled conditions. Rolling distance was measured as a function of time by means of stroboscopic photography, and rollout distance was measured as a function of initial height of a ball. Both rolling distances and rollout distances were analysed according to a unified theory, where rolling friction coefficient (f) of a pressure sensitive adhesive is involved. It is suggested that f depends on viscoelastic properties of the adhesives.     

Adhesive Failure of Model Acrylic Pressure Sensitive Adhesives

An axisymmetric adhesion apparatus was used to characterize the adhesive and viscoelastic properties of acrylic block copolymer layers that behave as model pressure sensitive adhesives. The mechanisms of deformation were summarized and related to the structure and linear viscoelastic response of each model adhesive. In cases where the area between the adhesive layer and adhering surface remained circular and shrunk uniformly during detachment, the adhesive failure criterion can be quantified and compared to predictions from linear elastic fracture mechanics. The nature of adhesive failure can not be reconciled with these traditional, low-strain approaches, but is consistent with models of large strain elasticity, provided that the finite thickness of the adhesive layer is taken into account. A dimensionless ratio involving the adhesive strength, elastic modulus and adhesive layer thickness can be used to define the regime in which the adhesive failure criterion can be quantified with linear elastic fracture mechanics.     

Adhesive Failure of Model Acrylic Pressure Sensitive Adhesives

An axisymmetric adhesion apparatus was used to characterize the adhesive and viscoelastic properties of acrylic block copolymer layers that behave as model pressure sensitive adhesives. The mechanisms of deformation were summarized and related to the structure and linear viscoelastic response of each model adhesive. In cases where the area between the adhesive layer and adhering surface remained circular and shrunk uniformly during detachment, the adhesive failure criterion can be quantified and compared to predictions from linear elastic fracture mechanics. The nature of adhesive failure can not be reconciled with these traditional, low-strain approaches, but is consistent with models of large strain elasticity, provided that the finite thickness of the adhesive layer is taken into account. A dimensionless ratio involving the adhesive strength, elastic modulus and adhesive layer thickness can be used to define the regime in which the adhesive failure criterion can be quantified with linear elastic fracture mechanics.     

偏光片用压敏胶粘剂的研究概况

介绍了偏光片用压敏胶粘剂的组成和性能特点,通过对该胶粘剂的主要生产厂家的专利分析,综述了其在国外的研究概况,并展望其发展前景。     

Pressure Sensitive Adhesives Based on Oleic Acid

Existing pressure sensitive adhesives (PSA) are mostly based on petrochemical‐based polymers. This study reveals a new class of bio‐based polymers that can be used as PSA. The polymers are hydroxyl‐containing polyesters from the step‐growth polymerization of epoxidized oleic acid (EOA), an AB‐type monomer containing both a carboxylic acid group (A) and an epoxy group (B). The monomer is derived from epoxidation of renewable methyl oleate followed by selective hydrolysis of the ester group. The polymers (PEOA) of EOA were characterized for their chemical structure and molecular weight. The PEOA after being cured with a very small amount of a crosslinking agent could serve as a PSA with high peel strength, high tack force, superior shear resistance, excellent aging resistance, and excellent thermal stability. The PSA contains 99 wt% of green renewable materials. The PSA were also characterized for their viscoelastic properties and thermal properties.     

脂肪族聚酯的合成及降解性能研究

通过熔融和溶液结合法合成了脂肪族聚酯—聚丁二酸丁二醇酯(PBS)、丁二酸丁二醇酯-己二酸丁二醇酯共聚物(P(BS-co-BA))和丁二酸丁二醇酯-癸二酸丁二醇酯共聚物(P(BS-co-BSe)),并对其进行了生物降解实验。采用GPC测定了脂肪族聚酯的分子量及其分布,并采用熔点仪测定了聚酯的熔点。得到脂肪族聚酯分子量、熔点以及分子结构对称性和降解之间的关系。     

Emulsion Semi-Batch Terpolymerization Process Using Hybrid Emulsifiers for Synthesizing New Emulsion Pressure Sensitive Adhesives (EPSAs)

In order to obtain a suitable formulation of designing direct synthesis of acrylic latexes to be used as emulsion pressure sensitive adhesives (EPSA), having high shear resistance together with high peel strength and tack, free radical emulsion polymerization of hard monomers, such as styrene (St), vinyl acetate monomer (VAM), methyl methacrylate (MMA) and butyl methacrylate (BMA), and soft monomers, butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA) along with multifunctional monomers, namely acrylic acid (AA), were carried out. The effect of the type of hard and soft acrylic monomers, the type and level of emulsifiers, and the initiator concentration on the emulsion polymer stability and final properties of the EPSA were investigated. The results obtained showed an optimized composition. This composition led to a significant increase in shear strength and peel strength to 909 kPa and 0.45 N/mm, respectively, while the synthesized PSA was still too tacky, 5.5 cm, according to adhesion performance testing. For making this successful balance of the conflicting adhesion properties of PSA, a series of anionic and nonionic emulsifiers were investigated. It was interestingly found out that the hybrid emulsifiers (anionic coupling with nonionic) with the optimized compositions could enhance the stability of the emulsion system and improve the properties of PSA compared with the mono-emulsifier. We also tried to adjust the initiator concentration with the level of the optimized hybrid emulsifier, polyoxyethylene alkyl phenyl ether (K30), dioctyl sulfosuccinate (DOSS), and sodium vinyl sulfonate (SVS) with the ratio 2:1:1, resulting in a highly preferred proportion of the 0.5 part of the initiator versus 1.25 parts of the hybrid emulsifier in terms of the total weight of the monomers.     

Composition and Performance of Styrene-Isoprene-Styrene (SIS) and Styrene-Butadiene-Styrene (SBS) Hot Melt Pressure Sensitive Adhesives

Styrenic block copolymers are widely used in HMPSA formulations, with tackifier resins and oil plasticizer. Although most commercial formulations are based on SIS, mixtures of SIS and SBS are also used to reduce cost. However, the use of SBS is restricted because it generally leads to decrease in tack. In this work, pure SIS and SBS and a SIS/SBS mixture were used in formulations with aliphatic, aromatic, aliphatic hydrogenated, and aliphatic-aromatic copolymer resins, at three different oil contents, according to a 3^3–1 factorial design. Interaction effects among the components were evaluated, showing a strong dependence of the HMPSA final properties on the combination of resin/rubber used. It was found that a blend of aliphatic and aromatic resins is the best tackifier for SIS, while for SBS the best choice is an aromatic-aliphatic copolymer. These results were explained in terms of specific compatibility, which was correlated to the polarizability of the material.     

热熔压敏胶的应用现状及发展

综述了热熔压敏胶的特点及其在欧美等发达国家和我国的应用现状,对改良型热塑性弹性体热熔压敏胶、丙烯酸酯类热熔压敏胶、有机硅类热熔压敏胶和无定形聚烯烃类热熔压敏胶的发展及应用进行了介绍。建议国内企业和科研机构开发多种用途的热熔压敏胶,扩大其使用范围,同时应加快压敏胶性能标准化进程。认为环保型和多功能化是今后热熔压敏胶的发展方向。     

热熔压敏胶粘接性能的流变学研究

研究了苯乙烯嵌段共聚物系热熔压敏胶的动态流变学行为和持粘力之间的联系,主要研究了决定持粘力的流变学参数.研究证明,持粘力受到体系的蠕变过程的控制,可以通过较高温度下得到的持粘力数据来预测室温持粘力的大小.研究了液体树脂含量对持粘力的影响,提出损耗角正切(tan δ)最小值及其对应的温度是决定热熔压敏胶持粘力的关键流变学参数.     

Adhesion Performance and UV-Curing Behaviors of Interpenetrated Structured Pressure Sensitive Adhesives with 3-MPTS for Si-Wafer Dicing Process

Abstract

As Si-wafers, as used in the electronic industry, become thinner and thinner, it is important to investigate the conditions which are suitable for easily peelable acrylic dicing tapes. In the ‘pick-up’ process, the adhesion strength decreased after UV irradiation as a result of polymer network formation. In this study, interpenetrating polymer network (IPN) structured acrylic pressure sensitive adhesives (PSAs) were investigated with two different types of UV irradiation — a steady UV irradiation and a pulsed UV irradiation of 100 mJ/cm². The PSAs binder contained 2-ethylhexyl acrylate (2-EHA), acrylic acid (AA) and 3-methacryloxypropyl trimethoxysilane (3-MPTS). The hexafunctional monomer, dipentaerythritol hexacrylate (DPHA) and 3-methacryloxypropyl trimethoxysilane (3-MPTS) were used as diluent monomers. The adhesion performance as related to the peel strength and the tack properties on the Si-wafer substrates, was examined with increasing UV dose. The effect of UV-curing on the behavior and viscoelastic properties of the ‘pick-up’ acrylic tapes was investigated using Fourier transform infrared — attenuated total reflectance spectroscopy (FTIR–ATR) and an advanced rheometric expansion system (ARES). It is also necessary to consider the contaminants on the Si-wafer substrates left behind after releasing the dicing tapes, because of possible damage to the Si-wafers and subsequent processes. Field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS) analysis revealed little residue on the Si-wafer after removing the tapes and after more than the specific level of UV dose.