UV-crosslinkable Pressure-sensitive Adhesives Research Articles

2-Methylbenzothiazolium derivatives as cationic photoreactive crosslinker for acrylic pressure-sensitive adhesives containing oxirane groups from glycidyl methacrylate

UV crosslinking technology is well established in the market and allows the production of a wide range of UV-crosslinkable pressure-sensitive adhesives (PSA) based on acrylics with interesting performance. The balance between adhesive and cohesive strengths after the crosslinking process is very important and critical for the properties of acrylic PSAs in the form of self-adhesive layers. The cationic UV-crosslinking of an acrylic PSA containing oxirane groups in the structure and additionally with the cationic photoinitiator 1,10-bis[N,N’-(2-methylbenzothiazolium)]decane diiodide, designed to promote properties such as tack, peel adhesion and shear strength of self-adhesive polymer layers, has been investigated using a UV-lamp as an ultraviolet source. An acrylic PSA synthesized from 55wt% of butyl acrylate, 30wt% of 2-ethylhexyl acrylate and 15wt% of glycidyl methacrylate was studied. The application of 1,10-bis[N,N’-(2-methylbenzothiazolium)]decane diiodide as a photoreactive crosslinker allows the manufacture of high quality PSA products with interesting properties, such as high tack, high peel adhesion, and excellent shear strength.

Application of selected 2-methylbenzothiazoles AS cationic photoreactive crosslinkers for pressure-sensitive adhesives based on acrylics

Since their introduction half a century ago, acrylic pressure-sensitive adhesives have been successfully applied in many fields. They are used in self-adhesive tapes, label signs, marking films and protective films as well as in medical pharmaceutical applications for plaster, in dermal dosage systems and in a wide range of biomedical electrodes. In the last 15 years or so, the UV technology, especially UV-crosslinking, is well established in the market and allows the production of UV-crosslinkable pressure-sensitive adhesives (PSA) based on acrylics with interesting performance. So much so that the larger manufacturers of pressure-sensitive adhesive materials and their suppliers now use very expensive equipment to study pressure-sensitive adhesive behavior: tack, peel adhesion and shear strength. The balance between adhesive and cohesive strength after the crosslinking process is very important and critical for properties of acrylic PSA in form of self-adhesive films. In this work the cationic UV-crosslinking of acrylic PSA containing epoxy groups in their structure and additionally cationic photoinitiators based on 2-methylbenzothiazoles as photoreactive crosslinkers have been investigated using UV-lamp as ultraviolet sources. The investigated acrylic PSA were synthesized from 80wt% of butyl acrylate, and 20wt% of glycidyl methacrylate. The use of selected photoreactive crosslinkers: 1,5-bis[N,N׳-(2-methylbenzothiazolium)]pentane diiodide and 1,10-bis[N,N׳-(2-methylbenzothiazolium)]decane diiodide allows manufacturing of high quality PSA materials with interesting properties, such as high tack, high peel adhesion, and excellent shear strength.

Synthesis and dynamic mechanical analysis of nanocomposite UV crosslinkable 100% solid acrylic pressure sensitive adhesives

A synthesis and characterization of nanocomposite solventless acrylic UV crosslinkable pressure sensitive adhesives is presented. Different prepolymers were synthesized using bulk polymerization procedure. The reaction mixture consisted of acrylic monomers (2-ethylhexyl acrylate, acrylic acid and t-butyl acrylate), azobisisobutyronitrile initiator, chain transfer agent n-dodecylmercaptan and unsaturated UV photoinitiator 4-acryloyloxybezophenone. Different formulations with different amounts of modified and unmodified montmorillonite (MMT) clays were tested and the prepolymer was characterized by viscosity measurements. UV crosslinking process was monitored using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Gel phase amount in crosslinked samples was determined by Soxhlet extraction. Clay dispersion in polymer matrix was investigated by X-ray diffraction analysis (XRD). Three basic adhesive properties, the tack, peel and shear strength were measured and the viscoelastic properties of crosslinked adhesive films were characterized using dynamic mechanical analysis (DMA). Results of the study showed high increase in prepolymer viscosity, when hydrophobic types of MMT clays were added in the reaction mixture. The addition of clay had a negative effect on UV crosslinking process. XRD analysis confirmed complete exfoliation and/or intercalation of modified clays in polymer matrix, depending on modifier amount and type. Results of adhesive properties testing showed a major influence of clay addition on adhesive properties, especially on shear strength. DMA analysis showed an increase in storage modulus (G′) and a decrease of tanδ values for adhesives synthesized with clay what also concurs with higher shear strength and implies an improved cohesion of adhesive.

Photocrosslinking of solvent-based acrylic pressure-sensitive adhesives (PSA) by the use of selected photoinitiators type I

This study investigated the photocrosslinking of solvent-based acrylic pressure-sensitive adhesives (PSA) containing selected photoinitiators type I, known as α-cleavage photoinitiators. Photocrosslinking of PSA, especially of acrylic PSA, is well established crosslinking process using the UV radiation technology. UV-initiated crosslinking of acrylic PSA allows the synthesis of the wide range of UV-crosslinkable PSA with the interesting features. Especially, the important balances of properties such as adhesive and cohesive strength which are typically critical for the application performance can be achieved by this technology. The selection of suitable photoinitiator plays an important role to obtain the optimum properties of acrylic PSA including tack, peel adhesion, and shear strength. In this study, the investigations on different saturated conventional photoinitiators of type I for solvent-based PSA were carried out. The effects of photoinitiator concentration, UV crosslinking time and UV dose on the tack, peel strength, and shear strength were explored in detail for guiding the choice of photoinitiators to fabricate advanced PSA for industrial usage.

Photoreactive UV-Crosslinkable Pressure-Sensitive Adhesives Based on Butyl Acrylate and 4-Acryloyloxy Benzophenone Copolymers

It has been previously shown that copolymers synthesized from n-butyl acrylate and unsaturated photoinitiator 4-acryloyloxy benzophenone can be used as pressure-sensitive adhesives (PSA). This paper presents synthesis and application of solvent-borne copolymer system for the preparation of photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives comprising n-butyl acrylate/ benzophenone copolymers, characterized by molecular mass in the range of 180 000 to 480 000 Dalton. These copolymers were tacky but possessed insufficient cohesive strength after UV-crosslinking to be useful as PSA. They resulted in materials having a balance of cohesive and adhesive characteristics required of good PSA. Some of the parameters affecting the pressure-sensitive adhesive properties of the copolymer are: amount of the 4-acryloyloxy benzophenone, molecular mass of the polymeric components, UV-reactivity and properties, such as tack, peel adhesion and shear strength.

“Design of experiments” analysis in study of solventless UV crosslinkable acrylic pressure sensitive adhesives

A 24 full factorial design was employed in the study of solventless acrylic UV crosslinkable pressure sensitive adhesives. The effect of four different factors (acrylic acid, t-butyl acrylate azobisisobutyronitrile initiator, and chain transfer agent) on different responses (prepolymer viscosities, final overall monomer conversion, tack, peel, and shear strength) was studied. Prepolymers were synthesized using a batch bulk polymerization procedure. The reaction mixture consisted of acrylic monomers (2-ethylhexyl acrylate, acrylic acid, and t-butyl acrylate), azobisisobutyronitrile initiator, chain transfer agent n-dodecylmercaptan, and unsaturated UV photoinitiator 4-acryloyloxybezophenone, which was copolymerized into the polymer backbone. The adhesive properties of the acrylic coatings were evaluated using tack, peel, and shear strength tests. Results showed that statistical analysis of the studied factors on polymer properties meets theoretical expectations. Analysis showed that the acrylic acid and the chain transfer agent (CTA) had the greatest effect on the prepolymer viscosity. None of the factors had a major impact on the final conversion of the synthesized products. The acrylic acid had a significant impact on the adhesive properties of the coating, i.e. tack and peel strength due to molecular hydrogen bonding. The impact of the studied factors could not be ascertained for the shear resistance of the adhesive coating.

Influence of the unsaturated photoinitiators kind on the properties of uv-crosslinkable acrylic pressure-sensitive adhesives

UV-crossinkable pressure-sensitive adhesives (PSA) materials are called, in the adhesives trade photoreactive self-adhesive. UV-crosslinkable PSAs are designed after the UV-initiated crosslinking reaction to stick to almost any surface by a simple contact under light pressure. This special class of adhesives does not undergo any physical transformation or chemical reaction during the bonding process. Because of the rheological properties the adhesive must be fi nely tuned for the application, combining a carefully chosen polymer architecture and monomer composition with the proper addition of small additives called photoinitiators. The best way is using the unsaturated copolymerizable photoinitiators and their direct incorporation into polymer chain during the polymerization process. Progress in the coating technology and the development of novel photoreactive acrylic adhesives will open the door to new applications and an extended market penetration of UV-crosslinkable acrylic adhesive raw materials containing unsaturated copolymerizable photoinitiators incorporated into the polymer backbone. Photoreactive UV-crosslinkable acrylic PSA are characterized by good tack, good adhesion, excellent cohesion and very low shrinkage.

Solventless UV crosslinkable acrylic pressure sensitive adhesives

The synthesis and characterization of solventless acrylic UV crosslinkable pressure sensitive adhesives are presented. Different prepolymers were synthesized using bulk polymerization procedure. The reaction mixture consisted of acrylic monomers (2-ethylhexyl acrylate, acrylic acid and t-butyl acrylate), azobisisobutyronitrile initiator, chain transfer agent n-dodecylmercaptan and unsaturated UV photoinitiator 4-acryloyloxybezophenone, which was copolymerized into polymer backbone. Different formulations were tested and the prepolymer was characterized by viscosity measurements and final monomer conversions. The prepolymers were coated onto PET foil and crosslinked by application of UV light source. Peel adhesion at 180° on glass plate was measured. Gel phase was determined using the Soxhlet extraction and copolymer glass transition temperatures ( T g ) were analyzed by differential scanning calorimetry (DSC). Results showed that the final monomer conversions in highly exothermic bulk polymerization reached a level between 75% and 90%. Prepolymer viscosity was highly influenced by change in polymer molecular weight and by addition of acrylic acid as a comonomer. On the other hand, the viscosity remained at the low level when t-butyl acrylate was used. The amount of gel phase for all adhesives was above 60 wt.%. Peel strength measurements showed decrease in peel strength with decreasing polymer molecular weight and increase of peel, when acrylic acid was used as a comonomer. All adhesive coatings with t-butyl acrylate comonomer showed cohesive failure.

Butyl acrylate/4-acryloyloxy benzophenone copolymers as photoreactive UV-crosslinkable pressure-sensitive adhesives

Butyl acrylate/4-acryloyloxy benzophenone copolymers as photoreactive UV-crosslinkable pressure-sensitive adhesives It has previously been shown that copolymers of butyl acrylate with 4-acryloyloxy benzophenone can be used as pressure-sensitive adhesives (PSAs). This paper presents the synthesis and application of a solvent-borne polymer system for the preparation of photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives. Butyl acrylate/benzophenone copolymers with molecular mass in the range 180 000 to 480 000 Dalton were prepared by carrying out free-radical solution polymerization. These copolymers were found to be tacky but in some cases to possess insufficient cohesive strength after UV-crosslinking to be useful as PSAs. The other copolymers resulted in materials with the balance of cohesive and adhesive characteristics required of good PSAs. Some of the parameters affecting the pressure-sensitive adhesive properties of the copolymers are the concentration of 4-acryloyloxy benzophenone, the molecular mass of the polymeric components, the UV-reactivity, and properties such as tack, peel adhesion, and cohesion.

2-Ethylhexyl acrylate/4-acryloyloxy benzophenone copolymers as UV-crosslinkable pressure-sensitive adhesives

It has been previously shown that copolymer of 2-ethylhexyl acrylate with an 4-acryloyloxy benzophenone can be used as PSA. This paper presents synthesis and application of solvent-based polymer system for the preparation of acrylic pressure-sensitive adhesives (PSA). 2-Ethylhexyl acrylate benzophenone copolymers, having molecular mass in the range of 120 000 to 380 000 Dalton were prepared by free-radical solution polymerization. These copolymers were tacky but possessed insufficient cohesive strength after UV-crosslinking to be useful as PSAs. These copolymers resulted in materials having a balance of cohesive and adhesive characteristics required of a good PSA. Some of the parameters affecting the pressure-sensitive adhesive properties of the copolymer are: amount of the 4-acryloyloxy, molecular mass of the polymeric components, UV-reactivity and such properties like tack, peel adhesion and cohesion.

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.

Method for electrodepositing metal-carbon alloys

The synthesis and characterization of solventless acrylic UV crosslinkable pressure sensitive adhesives are presented. Different prepolymers were synthesized using bulk polymerization procedure. The reaction mixture consisted of acrylic monomers (2-ethylhexyl acrylate, acrylic acid and t-butyl acrylate), azobisisobutyronitrile initiator, chain transfer agent n-dodecylmercaptan and unsaturated UV photoinitiator 4-acryloyloxybezophenone, which was copolymerized into polymer backbone. Different formulations were tested and the prepolymer was characterized by viscosity measurements and final monomer conversions. The prepolymers were coated onto PET foil and crosslinked by application of UV light source. Peel adhesion at 180° on glass plate was measured. Gel phase was determined using the Soxhlet extraction and copolymer glass transition temperatures (Tg) were analyzed by differential scanning calorimetry (DSC). Results showed that the final monomer conversions in highly exothermic bulk polymerization reached a level between 75% and 90%. Prepolymer viscosity was highly influenced by change in polymer molecular weight and by addition of acrylic acid as a comonomer. On the other hand, the viscosity remained at the low level when t-butyl acrylate was used. The amount of gel phase for all adhesives was above 60 wt.%. Peel strength measurements showed decrease in peel strength with decreasing polymer molecular weight and increase of peel, when acrylic acid was used as a comonomer. All adhesive coatings with t-butyl acrylate comonomer showed cohesive failure.