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.     

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.     

Photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives containing type-II photoinitiators

UV-crosslinking is an established technology used in many industrial manufacturing processes. New applications and technical specifications of UV technologies stimulate the continuous development of photoinitiators that can efficiently meet specific requirements. A typical class of radical-reactive type-II photoinitiators has been used for the UV-initiated crosslinking of acrylic pressure-sensitive adhesives (PSAs).The activity of type-II photoinitiators such as: benzophenone derivatives, thioxanthone derivative, antraquinone derivative and fluorenone (without tertiary amine as a co-initiator) in the photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives was described. The effect of the type-II photoinitiators on the acrylic PSA properties (tack, peel, and shear strength) was summarized.     

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.     

SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH) ACRYLATES WITH HIGH-SOLID CONTENT: EFFECT OF THE OPERATION CONDITIONS

The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA),2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate(HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solidcontent. The effects of monomer emulsion feed rates (R_a) and (R/E)_E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E),on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,T_g and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.     

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.     

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.     

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.     

Probing particle structure in waterborne pressure-sensitive adhesives with atomic force microscopy

There is a need to know the nanostructure of pressure-sensitive adhesive (PSA) films obtained from waterborne polymer colloids so that it can be correlated with properties. Intermittent-contact atomic force microscopy (AFM) of an acrylic waterborne PSA film identifies two components, which can be attributed to the polymer and the solids in the serum (mainly surfactant). It is found that when the average AFM tapping force, F(av), is relatively low, the polymer particles appear to be concave. But when F(av) is higher, the particles appear to have a convex shape. This observation is explained by a height artefact caused by differences in the indentation depths into the two components that vary with the tapping amplitude and F(av). To achieve the maximum contrast between the polymer and serum components, F(av) should be set such that the indentation depths are as different as possible. Unlike what is found for the height images, the phase contrast images of the PSA do not show a reversal in contrast over the range of tapping conditions applied. The phase images are thus reliable in distinguishing the two components of the PSA according to their viscoelastic properties. At the surface of films dried at room temperature, the serum component is found in localized regions within permanent depression into the film.     

Influence of surface and bulk structures of acrylic PSA films onto their tack properties

PSA films are obtained by coalescence of latices synthesized by free-radical emulsion polymerization of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (EHA). For the same overall 50/50 molar composition, the polymer particles have well-defined structures when the feed composition and the feed mode (using batch or semicontinuous processes) are adjusted. The characterizations of the film structures by surface (tapping mode AFM) and bulk (DSC, rheology) analyses argue for the conservation of the initial particle structure when coalescence occurs. The influence of the chemical heterogeneity on the tack properties of the films is investigated to extend the study of these original acrylic PSA films up to relevant structure-property correlations.     

Unique thermal behavior of acrylic PSAs bearing long alkyl side groups and crosslinked by aluminum chelate

An acrylic pressure-sensitive adhesive (PSA), bearing octadecyl acrylate, methyl acrylate and acrylic acid groups, and crosslinked by aluminum acetylacetonate (AlACA), displayed behavior unique among acrylic PSAs in that its adhesion, which decreases with an increase in temperature, began to increase again from around 150 °C. In order to understand this behavior, the structure and thermal properties of the PSA were investigated in detail, along with another PSA crosslinked by a covalent crosslinking agent (Az). From thermal mechanical analysis, the PSA with ionic crosslinks (AlACA) showed three softening points at 20, 60, and 160 °C. In comparison, the PSA covalently crosslinked by Az only exhibited two softening points (at 20 and 60 °C). The softening point at 160 °C is clearly related to ionic chelate crosslinking. DSC measurements indicated that the softening point at 20 °C resulted from melting of the ordered octadecyl group, and the softening point at 60 °C was due to an increase in the mobility of the main chain. The temperature dependence of viscoelastic measurements revealed that the viscosity of the PSA crosslinked by AlACA increased at around 160 °C. From these results, we considered that the distinctive adhesion of the PSA crosslinked by AlACA could be due to ligand exchange at the aluminum crosslinking points, which are chelated by carboxy groups built in the main chain.     

Influence of Particle Nucleation in Pressure Sensitive Adhesive Properties: Miniemulsion versus Emulsion Polymerization

Miniemulsion polymerization is a promising approach to produce and tailor pressure sensitive adhesives (PSAs). In this paper, a systematic comparison of the adhesive properties of latexes produced by miniemulsion and conventional emulsion polymerization is presented. Specifically, the influence of the total surfactant concentration, chain transfer agent concentration and chemical composition on the final adhesive properties of the polymer 2-ethyl hexyl acrylate/methyl methacrylate/acrylic acid was discerned using a 2³ factorial design for each polymerization method. In addition to the adhesive properties (i.e., loop tack, peel strength and shear strength), molecular weight distribution, particle size distribution (PSD) and glass transition temperature were analyzed. The results show that under the conditions used in this work, it is possible to produce PSAs using miniemulsion polymerization, a process wherein monomer droplet nucleation is the dominant particle nucleation mechanism. The use of a miniemulsion polymerization process, as opposed to the conventional emulsion technique, produced several differences such as larger particles sizes and narrower molecular weight distributions. Focusing on the PSA films that exhibited adhesive rather than cohesive failure, the PSA films generated via miniemulsion polymerization displayed higher values of loop tack and peel strength compared to those produced via conventional emulsion polymerization. Shear strength results were strongly dependent on the amount of gel content and sol molecular weight for both cases.     

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.     

Assessing the effect of latex particle size and distribution on the rheological and adhesive properties of model waterborne acrylic pressure-sensitive adhesives films

The adhesive and rheological properties of model acrylic pressure-sensitive adhesive (PSA) films prepared from high solid emulsions with different particle sizes and distributions have been investigated with a customized probe tack apparatus. For each emulsion, the monomer composition and gel content were kept constant but different average particle sizes and distributions were used. Adhesive films 100 microm thick were then prepared from these emulsions and their rheological properties in the linear regime and adhesive properties were systematically characterized. Surprisingly, both the rheological and adhesive properties were found to be very dependent on the initial latex particle size distribution. A series of experiments were carried out to assess the adhesive properties of films made from blends of small- and large-particle-size latexes. Using the probe tack test, a maximum in adhesion energy of the dry films was found for 60% of small particles in the blend, a composition clearly different from that giving a minimum viscosity of the latex implying that optimizing for properties may not be equivalent to optimizing for processing in these adhesive applications. Finally, the adhesive properties of two multimodal latexes with different particle size distributions were investigated. Both gave significantly higher adhesion energies and clear evidence of a fibrillar detachment process. This important result suggests that the spatial distribution of gel domains in the dry film and the molecular connectivity between those gel domains also play an important role in controlling its adhesive properties.     

Polymerizable Solvent-free Organic Liquids: A New Approach for Large Area Flexible and Foldable Luminescent Films

The high demand for light-emitting and display devices made luminescent organic materials as attractive candidates. Solvent-free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large-area device applications. Herein, we functionalized solvent-free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole-based solvent-free liquid emitters enabled on-surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non-sticky, flexible, foldable, and free-standing large-area films with reasonably high quantum yield. Our demonstration of the tunable and white light-emitting films using polymerizable solvent-free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.     

The Effect of Polymer Microstructure and Thermal Post-Treatment on Latex-Based Pressure Sensitive Adhesive Performance

Summary: Butyl acrylate/acrylic acid/2-hydroxyl methacrylate (BA/AA/HEMA, weight ratio: 96/2/2) latexes were produced via starved seeded semi-batch emulsion polymerization. The microstructure of the latex polymers was controlled by varying the amount of chain transfer agent (1-dodecanethiol). The latexes were characterized for gel content, M_c (molecular weight between two adjacent cross-linking points), M_w (molecular weight of sol polymers) and M_e (molecular weight between entanglements). From these latexes, PSA films were cast, dried, conditioned and then thermally post-treated at 120 °C to react the carboxyl and hydroxyl groups from the AA and HEMA units. Tack, peel strength and shear strength of the PSA films were then measured. The thermal post-treatment was shown to be an effective way to improve latex-based PSA performance. The effectiveness of the post-treatment was observed to depend on the polymer microstructure (M_c relative to M_e relative to M_w) of the untreated latex-based PSAs and on the gel content.     

Phospho sulfonic acid as an efficient and recyclable solid acid catalyst for the solvent-free preparation of acylals

Phospho sulfonic acid (PSA) acts as a highly effective and reusable catalyst for the chemo-selective protection of aldehydes with acetic anhydride under solvent-free conditions. The desirable features of this new catalytic methodology include its sustainability, effectiveness in the absence of solvent, a facile work-up procedure, and economic viability. PSA is fully characterized by Fourier transform infrared spectroscopy, wide-angle X-ray scattering analysis, and scanning electron microscopy with energy dispersive X-ray spectroscopy. The catalyst can be reused several times without significant loss of activity. In addition, no chromatographic separations are needed to obtain the desired products.     

Patterned immobilization of biomolecules by using ion irradiation‐induced graft polymerization

A new method for biomolecular patterning based on ion irradiation‐induced graft polymerization was demonstrated in this study. Ion irradiation on a polymer surface resulted in the formation of active species, which was further used for surface‐initiated graft polymerization of acrylic acid. The results of the grafting study revealed that the surface graft polymerization using 20 vol % of acrylic acid on the poly(tetrafluoroethylene) (PTFE) film irradiated at the fluence of 1 × 10¹⁵ ions/cm² for 12 h was the optimum graft polymerization condition to achieve the maximum grafting degree. The results of the fluorescence microscopy also revealed that the optimum fluence to achieve the maximum fluorescence intensity was 1 × 10¹⁵ ions/cm². The grafting of acrylic acid on the PTFE surfaces was confirmed by a fluorescence labeling method. The grafted PTFE films were used for the immobilization of amine‐functionalized p‐DNA, followed by hybridization with fluorescently tagged c‐DNA. Biotin‐amine was also immobilized on the acrylic acid grafted PTFE surfaces. Successful biotin‐specific binding of streptavidin further confirmed the potential of this strategy for patterning of various biomolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6124–6134, 2009     

Functionalization of Poly[Ethylene Terephthalate) by Means of Glow-Discharge-Initiated Polymerization of Acrylic Acid

Glow-discharge-initiated polymerization of acrylic acid incorporated in poly(ethylene terephthalate) (PET) films was investigated. An increase in polymerization yield with plasma treatment duration and power was found. Polymerization was not confined to the film surface. At high power and long treatment time, polymerization in the bulk of the PET also took place. Water regain and contact angle of the PET-treated films were affected by the presence of poly(acrylic acid) (PAA). The carboxyl groups of the PAA chains incorporated in the PET matrix were utilized for further chemical modification of the PET film. Poly(ethylene glycol) (PEG) was grafted onto PAA by esterification. DSC studies showed the presence of both PAA and PEG in the PET matrix and shed light on the morphology of the multicomponent polymeric system. Free isocyanate groups were introduced into the PET matrix by reacting PAA carboxyl groups with hexamethylene diisocyanate.     

Photo-induced Alignment Behavior of Azobenzene-containing Polymer Films with Different Cross-linking Degree

Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree (from 0 to 32%, which was monitored by FT-IR spectra measurement). Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated "writing" and "erasing" cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.