Development in the area of UV-crosslinkable solvent-based pressure-sensitive adhesives with excellent shrinkage resistance

Solvent-based UV-crosslinkable pressure-sensitive adhesives (PSA) present a new class of products that offers the potential to produce a novel generation of ultraviolet cured self-adhesive products with excellent shrinkage resistance. A variety of solvent-based pressure-sensitive adhesives were prepared by synthesis in ethyl acetate with solid content on 50 wt.% with 2-ethylhexyl acrylate, methyl acrylate, acrylic acid, N-vinyl caprolactam and unsaturated photoinitiators: 4-acryloyloxy benzophenone, allyl benzoine and phenyl-(1-acryloyloxy)-cyclohexyl ketone. The main emphasis is given to the influence of viscosity and molecular mass of synthesized adhesive on their shrinkage. Further trials show the effect of the UV-crosslinking process with UV-lamp and comparison with acrylics PSA crosslinked with metal chelates aluminium acetylacetonate and titanium acetylacetonate on shrinkage. Further examinations describe the influence of various factors such as UV exposure time and UV dose on very relevant PSA performance such as shrinkage on coated PVC carrier.     

The crosslinking reaction of acrylic PSA using chelate metal acetylacetonates

In this work, metal chelate zirconium acetylacetonate (ZrACA) was added into acrylic polymers with self-adhesive properties. These acrylic polymers, known as acrylic pressure-sensitive adhesives (PSA), were crosslinked with ZrACA to obtain acrylic self-adhesives with which to study the crosslinking reaction between carboxylic groups of the polymer chain and metal chelate crosslinking agent.     

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs—in particular, optically clear adhesives for electronics.     

Development of solvent-free acrylic pressure-sensitive adhesives

The present publication describes a problem to develop solvent-free acrylic pressure-sensitive adhesives (PSA). Solvent-free PSA are established materials for the manufacturing of various self-adhesive products. Only by means of these acrylic PSA was it possible to succeed in drafting the present surprisingly efficient generation of double-sided pressure-sensitive adhesive tapes, medical products, protective masking films, films for the graphics market, and various specialty products. New applications and technical specifications stimulate the continuous development of new methods of polymerization of solvent-free acrylates. New syntheses of solvent-free acrylic PSA include polymerization in the reactor with removal of the solvent and polymerization on the carrier. The polymerization process is connected with UV-crosslinking.     

Thermal degradation of butyl acrylate-methyl acrylate-acrylic acid-copolymers

The thermal degradation of copolymers based on butyl acrylate-methyl acrylate-acrylic acid used as acrylic pressure-sensitive adhesives, especially for bonding of plasticizer containing materials, has been investigated using thermogravimetry and pyrolysis-gas chromatography at 250°C. It was observed that during the pyrolysis of butyl acrylate-methyl acrylate-acrylic acid copolymers unsaturated monomers as methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate were formed. During the side-chain butyl acrylate-methyl-acrylate-acrylic acid-copolymer degradation the presence of methyl alcohol and butyl alcohol was observed.     

Subcritical failure of soft acrylic adhesives under tensile stress

The mechanisms of failure over time of a series of model acrylic pressure-sensitive adhesives under a moderate level of stress has been investigated with a probe method. Two competing mechanisms of failure have been observed: a progressive nucleation of cavities under stress and the propagation of existing cavities at the interface between the probe and the adhesive layer. Homogeneous creep of the adhesive was never observed as the only failure mechanism. In situations where the resistance to crack propagation was good relative to the resistance to cavitation, extensive nucleation of cavities was observed until a material-dependent and stable value of stress was achieved. On the other hand in situations were the resistance to crack propagation was weak, propagation led invariably to a complete failure of the adhesive bond. In addition to the stress relaxation, the energy dissipation was studied allowing to distinguish the different adhesives even further. This allowed determination of the optimal amount of a comonomer (acrylic acid) that had to be added to improve the long-term resistance of the adhesives under study. Further more we investigate the compliance of the confined adhesive layers and compare the obtained results to predictions from theoretical models.     

Photoreactive UV-crosslinkable solvent-free acrylic pressure-sensitive adhesives containing copolymerizable photoinitiators based on benzophenones

The design and development of new, tailor-made, novel photoreactive acrylic pressure-sensitive adhesives, which can cope with both the technical and ecological demands, is therefore a continuing challenge for industrial research and development. Progress in the coating technology and the development of improved photoreactive acrylic adhesive will open the door for new applications and an extended market penetration of UV-crosslinkable acrylic adhesive raw materials containing unsaturated copolymerizable photoinitiators incorporated into the polymer backbone. They are characterized by good tack, good adhesion, excellent cohesion and very high shrinkage resistance. In this paper it is shown the application of H-abstractor such as 4-acryloyloxy benzophenone to obtain of the UV-crosslinked acrylic PSA.The presented novel UV-crosslinkable acrylic hotmelt PSA combines the economic advantages of the hotmelt coating technology with the high performance characteristics of the acrylic chemistry, including an excellent aging resistance, optical transparency and heat resistance.     

Contribution of relaxation processes to adhesive-joint strength of viscoelastic polymers

Relaxation processes accompany all stages of the lifetime of viscoelastic pressure-sensitive polymer adhesives, which can form strong adhesive joints with substrates of various chemical natures under application of a slight external pressure to the adhesive film for a few seconds. This review deals with comparison of the adhesion and relaxation properties of a number of typical pressure-sensitive adhesives based on polyisobutylene, butyl rubber, styrene-isoprene-styrene triblock copolymers, alkyl acrylate copolymers, and silicone adhesives as well as pressure-sensitive adhesives based on blends of high-molecular-mass polyvinylpyrrolidone with oligomeric poly(ethylene glycol). Within all three stages of the lifetime of adhesive joints (under adhesive-bond-forming pressure, upon withdrawal of contact pressure in the course of relaxation of the adhesive material, and under the force detaching an adhesive film from the substrate surface), the strength of adhesive joints has been shown to be controlled by large-scale relaxation processes, which are characterized by long relaxation times in the range 150–800 s. All examined pressure-sensitive adhesives can be arbitrarily divided into two groups. The first group is composed of fluid adhesives that relax comparatively fast and exhibit no residual (unrelaxed) stress. The second group includes elastic adhesives capable storing mechanical energy in the course of deformation that are characterized by appreciably longer relaxation times and display residual stress after relaxation. Conditions of adhesive debonding (e.g., strain amplitude and deformation velocity) significantly affect the relaxation process.     

Waterborne polyurethane-acrylic hybrid nanoparticles by miniemulsion polymerization: applications in pressure-sensitive adhesives

Waterborne polyurethane-acrylic hybrid nanoparticles for application as pressure-sensitive adhesives (PSAs) were prepared by one-step miniemulsion polymerization. The addition of polyurethane to a standard waterborne acrylic formulation results in a large increase in the cohesive strength and hence a much higher shear holding time (greater than seven weeks at room temperature), which is a very desirable characteristic for PSAs. However, with the increase in cohesion, there is a decrease in the relative viscous component, and hence there is a decrease in the tack energy. The presence of a small concentration of methyl methacrylate (MMA) in the acrylic copolymer led to phase separation within the particles and created a hemispherical morphology. The tack energy was particularly low in the hybrid containing MMA because of the effects of lower energy dissipation and greater cross-linking. These results highlight the great sensitivity of the viscoelastic and adhesive properties to the details of the polymer network architecture and hence to the precise composition and synthesis conditions.     

Cooperativity of Catechols and Amines in High-Performance Dry/Wet Adhesives

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino-catechol synergy, polymeric pressure-sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel-inspired lysine- and aromatic-rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM-assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.     

Adhesion of liquid-crystalline polymer systems to substrates of varied roughness

Evolution of the adhesion behavior of a liquid crystalline system under various conditions of the adhesion joint formation was studied. A blend of hydroxypropyl cellulose with propylene glycol was selected as a model liquid crystalline system. Influence of the substrate roughness on the adhesion of the liquid crystalline systems was studied for the first time. It was found out that the roughness influence on the adhesion characteristics of the systems studied was much more pronounced than in case of the common pressure-sensitive adhesives. High values of the debonding energies for the systems studied (up to 280–330 J/m²) were obtained. These values are similar or even exceed the values obtained for the common pressure-sensitive adhesives.     

Properties of single-component acrylic pressure-sensitive adhesives synthesized using <Emphasis Type="Italic">tert</Emphasis>-butyl peroxypivalate initiator

In this work, tert-butyl peroxypivalate initiator was newly used in the solution polymerization of acrylic copolymers with 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate and acrylic acid monomers for application of pressure-sensitive adhesives (PSAs). Its proper dosage was determined to vary from 0.6 to 1.2 wt % when a high monomer conversion (>99%) was ensured. In this amount range, polymer properties and adhesive performance of the PSAs were investigated. The results indicated that with the amount of tert-butyl peroxypivalate increased, the molecular weights of the polymer decreased and the molecular weight distribution became wider. It was also observed that the synthesized PSAs had high interfacial adhesion and low cohesion strength, and thus exhibited cohesive failure during the peel test. So cross-linking agent was employed to improve the shear strength of the PSAs and to eliminate the adhesive residue while at the sacrifice of loop tack and peel strength. As a whole, the optimal performance was obtained by using 1.2 wt % amount of initiator and 0.5 wt % concentration of cross-linker. In this case, the peel and shear strength have achieved the best balance. In addition, for the cross-linked PSA tapes, the peel strength slightly decreased with the dwell time.     

Study on affecting factors of curing rate in ultraviolet curing adhesives containing modified acrylic ester prepolymers

Abstract

Ultraviolet (UV) curing adhesives have been extensively utilized in fields of health care and electronic components due to low energy consumption and solvent pollution. The most used system is modified acrylic ester system whose merits are low cost, high reliability and tensile strength. However, higher UV curing rate is still pursued especially in field of quick dry adhesives as well as influencing factors of curing rate are very complex. For clarifying affecting factors of curing rate as well as achieving higher curing rate, in this work, several UV curing adhesives with acrylic photosensitive resin prepolymers modified by epoxy and polyurethane were prepared. The impacts of class and content of radical photo-initiators, prepolymers and reactive diluents on UV curing rate were deeply researched. Moreover, the influence of oxygen polymerization inhibition on curing rate was discussed as well. The significantly elevated curing rates were obtained in as-prepared adhesives, in comparison with commercial ones. This work might offer a facile and effective strategy to obtain the promising high-performance modified acrylic ester prepolymer bearing UV curing adhesives with a significantly elevated high curing rate by well controlling these investigated affecting factors.     

高效液相色谱-质谱法测定压敏胶及其制品中9种邻苯二甲酸酯

采用高效液相色谱-质谱( HPLC - MS)法,对压敏胶及其制品中的9种邻苯二甲酸酯进行同时测定.以乙酸乙酯为溶剂溶解压敏胶,甲醇沉淀高聚物,以3 000 r/min离心5min,清液定容后,用HPLC -MS分析检测.采用Xterra-Phenyl色谱柱,流动相为乙腈-水,流速为1 mL/min,选择离子监测.在优...     

Comparison between thermal crosslinkers based on melamine-formaldehyde and benzoguanamine resin and their influence on main performance of acrylic pressure-sensitive adhesives as tack,peel adhesion,shear strength and pot-life

An acrylic pressure-sensitive adhesive (PSA) was synthesized in ethyl acetate at about 80 °C by the use of 2-ethylhexyl acrylate, ethyl acrylate, methyl acrylate and acrylic acid at presence of thermal radical initiator AIBN. The synthesized acrylic PSA was crosslinked at relatively low temperatures at about 110–125 °C using thermal crosslinkers selected from melamine-formaldehyde resins and benzoguanamine resins. The crosslinking process runs between carboxylic groups of acrylic PSA and reactive groups from investigated amine resins. The choice of suitable thermal reactive crosslinkers has significant and relevant influence at presence of organic acid catalysts on main performance of crosslinked PSA such as tack, peel adhesion and shear strength.     

Influence of thermal reactive crosslinking agents on the tack,peel adhesion,and shear strength of acrylic pressure-sensitive adhesives

In recent decades, the basic technology of pressure-sensitive adhesive (PSA) acrylics has developed into a sophisticated science. The main properties of acrylic PSAs such as tack, peel adhesion, and shear strength are determined to a large extent by the kind and quantity of crosslinking agents added to the synthesized PSAs. In order to improve their adhesive (tack, peel adhesion) and cohesive (shear strength) properties, a wide range of amino resin thermal crosslinkers are tested. An acrylic PSA based on 2-ethylhexylacrylate, n-butyl acrylate, and acrylic acid was synthesized by performing a radical polymerization in ethyl acetate. After the addition of amino resins to the acrylic PSA and carrying out thermally initiated crosslinking processes to prepare one-sided self-adhesive tapes, their properties were assessed.     

A reversible water-based electrostatic adhesive

Commercial adhesives typically fall into two categories: structural or pressure sensitive. Structural glues rely on covalent bonds formed during curing and provide high tensile strength whilst pressure-sensitive adhesives use physical bonding to provide weaker adhesion, but with considerable convenience for the user. Here, a new class of adhesive is presented that is also reversible, with a bond strength intermediate between those of pressure-sensitive and structural adhesives. Complementary water-based formulations incorporating oppositely charged polyelectrolytes form electrostatic bonds that may be reversed through immersion in a low or high pH aqueous environment. This electrostatic adhesive has the advantageous property that it exhibits good adhesion to low-energy surfaces such as polypropylene. Furthermore, it is produced by the emulsion copolymerization of commodity materials, styrene and butyl acrylate, which makes it inexpensive and opens the possibility of industrial production. Bio-based materials have been also integrated into the formulations to further increase sustainability. Moreover, unlike other water-based glues, adhesion does not significantly degrade in humid environments. Because such electrostatic adhesives do not require mechanical detachment, they are appropriate for the large-scale recycling of, e.g., bottle labels or food packaging. The adhesive is also suitable for dismantling components in areas as varied as automotive parts and electronics.     

Use of α‐diketones as visible photoinitiators for the photocrosslinking of waterborne latex paints

The efficiency of several α‐diketones as visible light photoinitiators for the crosslinking of waterborne latex dispersions in the presence of acrylic monomers was evaluated. Among the eight α‐diketones studied, camphorquinone allows the fastest curing speed, and the curing of the acrylic waterborne coating is not affected by the presence of oxygen. The properties of the sunlight‐cured volatile organic compound (VOC)‐free pigmented paints prepared from the waterborne latex are as good or better than the equivalent conventional paint containing VOCs. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3171–3181, 2002     

Bio-based and Degradable Block Polyester Pressure-Sensitive Adhesives

A new class of bio-based fully degradable block polyesters are pressure-sensitive adhesives. Bio-derived monomers are efficiently polymerized to make block polyesters with controlled compositions. They show moderate to high peel adhesions (4–13 N cm⁻¹) and controllable storage and loss moduli, and they are removed by adhesive failure. Their properties compare favorably with commercial adhesives or bio-based polyester formulations but without the need for tackifier or additives.