Epoxy acrylate UV/PU dual‐cured wood coatings

For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation,characterization of UV‐Curable Waterborne Polyurethane‐Acrylate and the application in metal iron surface protection

Hydroxyethyl methyl acrylate (HEMA) capped waterborne polyurethane‐acrylate (WPUA) oligomer was firstly prepared from isophorone diisocyanate (IPDI), polyether polyol (NJ‐220), dimethylolbutanoic acid (DMBA), HEMA via in‐situ and anionic self‐emulsifying method. Ultraviolet (UV) curable WPUA coating was obtained from HEMA‐capped oligomer, butyl acrylate (BA) and multifunctional acrylates (TPGDA) as reactive diluents, and Darocur 1173 as photoinitiator. The physical properties of WPUA oligomers, such as particle size, apparent viscosity, and surface tension were investigated. Some mechanical properties of UV‐WPUA films, such as contact angles, thermal properties, and solvent (water, HCl, NaOH, NaCl, and ethanol) resistance of UV‐WPUA coating films were measured. The surface morphologies were measured by scanning electron microscope and atomic force microscope. The surface free energy of the UV‐cured film was calculated from contact angle measurements using the Lewis acid–base three liquids method. The specific UV‐WPUA coating was selected to protect the iron materials that observed the effect of the protection. The results indicate that the prepared UV‐WPUA coating has excellent protective behavior to metal iron materials and may offer some contributions to protect iron cultural relics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3142–3152, 2013     

Influence of a long‐side‐chain‐containing reactive diluent on the structure and mechanical properties of UV‐cured films

The dimethacrylate reactive diluent (HEMA‐DDSA), a long‐side‐chain‐containing reactive diluent, was prepared by reacting 2‐dodecen‐1‐ylsuccinic anhydride with two equivalents of hydroxyethyl methacrylate. Its structure was characterized by IR and ¹H NMR spectroscopy. This new diluent was added into the formulation of UV‐curable epoxy acrylate networks. Results show that the formulation with the addition of HEMA‐DDSA has massively reduced viscosity and shows several attractive properties of epoxy acrylate oligomers. The mechanical resistance of the films is dramatically enhanced with the incorporation of long alkyl groups derived from HEMA‐DDSA, the plastic deformation zone expands, thus decreasing the inner stress of the polymer structure. Moreover, the cured coatings have a higher glass transition temperature as the percentage of HEMA‐DDSA is increased up to 5 wt%. Due to the excellent integrated performance of the polymeric films, HEMA‐DDSA proved to be an effective reactive diluent, which is of potential interest for applications in high performance materials. © 2016 Society of Chemical Industry     

Preparation and properties of UV‐curable waterborne polyurethane–acrylate emulsion

Polyurethane–acrylate oligomer terminated with multiple unsaturated bonds was prepared using isophorone diisocyanate, (IPDI), methylene diphenyl diisocyanate, and polyols as monomers, using 2,2‐dimethylol propionic acid as hydrophilic chain extender, together with pentaerythritol triacrylate (PETA) as end‐capper. The UV‐curable waterborne polyurethane–acrylate (UV‐WPUA) composite emulsion was obtained by mixing the PUA oligomer with certain content of reactive diluents and then dispersing the mixture in water. The molecular structure of the polyurethane prepolymer, PUA oligomer, and UV‐cured polymer was investigated by Fourier transform infrared spectroscopy. The influence of the composition and content of the diluents and end‐capper on UV‐WPUA properties, including the emulsion stability, thermal property, water resistance, adhesion, hardness, glossiness of polymer film were studied. The results show that the WPUA emulsion has excellent stability, and the UV‐cured film features good hardness and remarkable water resistance when PETA is used as end‐capper and the end‐capping ratio of the polyurethane prepolymer is 70% and dipentaerythritol hexaacylate/dipropylene glycol diacrylate (mass ratio 1:1) is used as diluent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45208.     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates

A series of UV‐curable polyurethane acrylates (PUA0, FPUA3, FPUA6, FPUA 9 FPUA12, FPUA15, where the numbers indicate the wt % of perfluoroalkyl acrylate), were prepared from a reactive oligomer [4,4 ?‐dicyclohexymethanediisocyanate(H12MDI)/ poly(tetramethylene glycol)(PTMG)/2‐hydroxyethyl methacrylate (HEMA): 2/1/2 molar ratio, prepolymer:40 wt %] and diluents [methyl methacrylate (MMA, 20 wt %)/ isobornyl acrylate (IBOA, 40–25 wt %)/heptadecafluorodecyl methacrylate (PFA, 0–15 wt), total diluents: 60 wt %]. This study examined the effect of PFA/IBOA weight ratio on the properties of the UV‐curable polyurethane acrylates for antifouling coating materials. The as‐prepared UV‐curable coating material containing a 15 wt % PFA content in diluents (MMA/IBOA/PFA) form a heterogeneous mixture, indicating that a PFA content of approximately 15 wt % was beyond the limit of the dilution capacity of diluents for the oligomer. In the wavelength range of 400–800 nm, the UV‐cured PUA0 film sample was quite transparent (transmittance%: near 100%). On the other hand, the transmittance% of the FPUA film sample decreased markedly with increasing PFA content. XPS showed that the film‐air surface of the UV‐cured polyurethane acrylate film had a higher fluorine content than the film‐glass dish interface. As the PFA content increased from 0 to 12 wt %, the surface tension of the UV‐cured urethane acrylates decreased from 26.8 to 15.6 mN/m, whereas the water/methylene iodide contact angles of the film–air surface increased from 90.1/63.6° to 120.9/87.1°. These results suggest that the UV‐curable polyurethane acrylates containing a PFA content up to 12 wt % have strong potential as fouling‐release coating materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40603.     

Synthesis and kinetic studies of UV‐curable urethane‐acrylates

The UV‐curable urethane‐acrylates based on 2‐hydroxyethyl methacrylate (HEMA)‐terminated polyurethane (PU) for lithographic and coating applications are investigated in this study. Series of PU prepolymers were made from 4,4‐diphenyl methane diisocyanate (MDI), poly(propylene oxide) glycol (PPG 400), poly(butylene adipate)glycol (PBA 500), or poly(tetramethylene oxide) glycol (PTMO 1000) and are terminated with HEMA. The 2,2‐azobisisobutyronitrile (AIBN) was used as a UV‐initiator under air atmosphere. The curing kinetics of HEMA‐terminated PU film were studied. The curing analysis, using FTIR and reaction kinetics, indicate the reaction rate equation correlates well with the film thickness [T], initiator concentration [I], unreacted double bond concentration [C?C], and exposed energy [E] of the reaction system. The kinetic rate equation for the UV‐curable reaction can be written as © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3162–3166, 2004     

UV‐curable coatings with nano‐TiO2

Nano‐TiO₂ particles were first milled into butyl acetate or trimethylolpropane triacrylate (TMPTA) to obtain TSB and TST slurries, then embedded into epoxy acrylate to obtain UV‐curable coating. The influence of nano‐TiO₂ particles on the photopolymerization kinetics, tack free time, thermal and optical properties of UV‐curable coatings was investigated. It was found that TST‐based coating had a decreasing but TSB‐based coating had an increasing UV cured rate in comparison with the pristine epoxy acrylate. Nevertheless, the TST‐based coating occupied shorter tack free time, good thermal property and UV absorbance than their corresponding TSB‐based coating. POLYM. ENG. SCI. 46:1402–1410, 2006. © 2006 Society of Plastics Engineers.     

Dual‐Curing of Waterborne Urethane‐Acrylate Coatings by UV and Thermal Processing

A waterbased dual‐cure urethane‐acrylate oligomer has been synthesized by polycondensation of monomers bearing hydroxyl, isocyanate and acrylate groups. To obtain a stable aqueous dispersion, carboxylate groups were grafted on the oligomer chain and the isocyanate groups were protected by a blocking agent. After water release by a brief heating, the dry films were cured either by a short UV exposure in the presence of a photoinitiator to induce the polymerization of the acrylate double bonds, or by heating up to 150 °C to release the isocyanates and promote the polycondensation by reaction with the hydroxyl groups, but mainly by a combination of UV and thermal cure. Both processes have been followed quantitatively by infrared spectroscopy to evaluate the influence of the temperature on the reaction rate and on the cure extent. The newly developed waterbased dual‐cure coatings were found to be quite resistant to accelerated weathering because of their aliphatic structure and their high crosslink density. Their light stability was substantially improved by the addition of a hydroxyphenyltriazine UV absorber and a hindered amine radical scavenger.

Thermal curing of the dual‐cure waterborne PUA formulation at a temperature of 150 °C.     

Role of sand on curing of partex surface by UV radiation

A partex surface was modified by a UV‐curing system with epoxy acrylate (EB‐600). A set of formulations was prepared with oligomer and the trifunctional monomer trimethylol propane triacrylate in different combinations of percentages (1–5%) of sand to study the role of sand in various physical properties of UV‐cured thin films, as well as partex surfaces. Increased pendulum hardness (PH), gloss, adhesion, and abrasion values were obtained by the addition of sand into the partex surfaces. The best results were obtained with the formulation containing 3% sand. An enhanced PH and a decreased percentage of gel content of the UV‐cured film was observed with an increase of the sand concentration. A simulated weathering test was performed with partex surfaces cured by a formulation containing 3% sand in the base coat. The losses of the physical properties were found to be lower over the surface treated with the formulation containing sand. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2385–2392, 2002     

Mechanical properties study of photocured paperboard surface treated with aliphatic epoxy diacrylate

In order to improve the quality of paperboard (a well‐known packing material) surface by photocuring method, different formulations were developed with aliphatic epoxy diacrylate (EA‐1020) oligomer along with reactive monomers of various functionalities. The reactive monomers are tripropylene glycol diacrylate (TPGDA), a difunctional monomer, and trimethylol propane triacrylate (TMPTA), a trifunctional monomer. 2‐Benzyl‐2‐dimethylamino‐1(4morpholinophenyl) butanone‐1 (Irgacure 369), a photoinitiator (2%), was incorporated into the formulations to initiate photocuring reaction. The formulated solutions were coated on clean glass plate and irradiated under UV radiation of different intensities. Different physical properties like pendulum hardness and gel content of the cured films were studied. The formulation containing TMPTA showed better properties. After characterization of the films, these formulations were applied on paperboard surfaces and cured under the same UV radiation. Various physicomechanical properties such as pendulum hardness, tensile properties, surface gloss, adhesion, abrasion, and water uptake were studied. The best performance was obtained at 12 passes of radiation with 18% TMPTA‐containing formulation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1774–1780, 2003     

A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.     

Flame retardation improvement of aqueous‐based polyurethane with aziridinyl phosphazene curing system

Aziridinyl phosphazene (NPAZ) was introduced to aqueous‐based polyurethane (PU) as a flame retardant and a postcuring agent, mainly because of the presence of phosphorus compositions, as well as the reactive aziridinyl groups on NPAZ. This dual‐function NPAZ was prepared from the substitution reaction of hexachlorocyclotriphosphazene with aziridine. Aqueous‐based PU was treated with NPAZ and its curing reaction took place upon drying. The performance properties of this NPAZ cured PU (NPAZ‐PU) were improved and better than those of the original PU. The phosphorus composition from NPAZ was evenly distributed on this NPAZ‐PU film, which was identified by the phosphorus mapping on the energy dispersion spectrum. The physical and mechanical properties of NPAZ‐PU were evaluated by the measurements of the gel content, water uptake, ethanol swelling, and tensile stress. The thermal properties of NPAZ‐PU were investigated by thermogravimetric analysis (TGA), TG analyzer‐interfaced FTIR, and dynamic mechanical thermal analysis. Furthermore, its combustion behaviors were demonstrated with the data of a cone calorimeter measurement. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 662–673, 2001     

Allyl ether‐modified unsaturated polyesters for UV/air dual‐curable coatings. I: Synthesis and characterization of the oligomers and their cured films

Allyl ether (AE)‐modified unsaturated polyester oligomers were synthesized from polyethylene glycol (PEG), maleic anhydride (MAH), and trimethylolpropane mono allyl ether (TMPAE), and characterized by Fourier transform infrared (FTIR) spectra. The UV/air dual‐curable coatings were prepared from the oligomers using vinyl ether (VE) as a reactive diluent. FTIR spectra showed that C?C bonds in the coating composition had polymerized partially after cured by UV or air. The investigation of rheological behavior of the dual curable composition suggested that all the systems belonged to pseudoplastic fluid, and the increasing allyloxy content in oligomer resulted in a higher viscosity. Differential scanning calorimetry (DSC) analysis showed that the increasing TMPAE‐PEG molar ratio resulted in lower T_g, and all samples had the same glass transition temperature irrespective of the type of curing. The results of TGA for cured films indicated that UV‐cured film had better thermal stability than the air‐cured one. The air‐cured film showed superior pencil hardness, impact strength, and flexibility to the UV‐cured counterpart. However, the air‐cured film had poor adhesion and electric resistance properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2765–2770, 2004     

Effect of lamp cycling on conversion and stress development in ultraviolet‐cured acrylate coatings

In radiation‐cured acrylate coatings, a high conversion of monomer is generally desired to improve hardness, prevent further slow reaction upon aging, and avoid surface toxicity; however, shrinkage and, consequently, stress in coatings tend to increase with conversion. One route to achieve high conversion while maintaining low coating stress is to promote stress relaxation. In this study, acrylate coatings were cured with a UV lamp that was cycled on and off, varying the period from 2 to 60 min while keeping the total dose constant. All samples reached nearly the same conversion, between 46 and 48% conversion of functional groups, as measured by FTIR spectroscopy. The coating stress (measured with cantilever deflection) at the end of the exposure cycles, however, was lowered from 8 MPa (tension) to less than 3 MPa (tension) as the period was decreased from 60 to 2 min. The cycling had no significant effect on either the coating hardness or the modulus, as measured by a Hysitron triboscope. Stress relaxation and/or slower reaction during the dark periods are the likely causes for the lower coating stress. It was advantageous to introduce dark periods early in the processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2784–2793, 2002     

Ultraviolet curing of epoxy coating on wood surface

Different formulations were developed with EB-600 (Ebcryl-600), an epoxy acrylate oligomer in the presence of N-vinylpyrrolidone and trimethylol propane triacrylate. Thin films were prepared with these formulated solutions under ultraviolet (UV) radiation. These solutions were coated on a low-grade wood substrate (simul) and cured under UV light. Both UV-cured thin films and surface coatings were characterized, and the best formulations for coating wood surface were evaluated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1997–2004, 1997     

Ultraviolet‐curing behavior and mechanical properties of a polyester acrylate resin

Ultraviolet (UV) curing technology has been widely used in many applications because it has several distinct advantages compared to solvent‐based processes or thermal‐curing technology. The effects of photoinitiator types and their contents as well as reactive diluent types and their contents on the UV‐curing behavior and mechanical properties of a UV‐curable polyester acrylate resin were investigated in this study. Three photoinitiators, Irgacure 184, Darocur 1173, and benzophenone, were used in this study. Hexanediol diacrylate, tripropylene glycol diacrylate, and trimethylol propane triacrylate were used as reactive diluents to modify the properties of the acrylate resin. The change of chemical structure during UV curing was monitored by FTIR. A universal testing machine was used to measure the tensile properties of various UV‐cured acrylate films of different compositions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3921–3928, 2004     

Light cured fluoride filled denture‐coating materials

Light cured denture‐coating materials were prepared by formulating an acrylate monomer with a photoinitiator system (camphorquinone and dimethylaminoethyl methacrylate) using one of three base monomers [bisphenol A glycerolate diacrylate (Bis‐GDA), glycerol 1,3‐diglycerolate diacrylate (GDA), and diurethane dimethacrylate (DU‐DMA)] each with four diluents [triethylene glycol dimethacrylate (TEGDMA), di(ethylene glycol) methyl ether methacrylate, 2‐hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA)] at a fixed 1 : 1 molar ratio of base monomer to diluent. The twelve formulations were then evaluated for their surface hardness and water sorption as coating materials. The DU‐DMA/MAA, DU‐DMA/HEMA, Bis‐GDA/HEMA, and GDA/MAA based coatings provided a high level of both surface hardness and water sorption properties. When sodium fluoride (NaF) or calcium fluoride (CaF₂) was incorporated into those formulations, the fluoride ion release rate from all four NaF containing coating materials was extremely high in the first week, decreasing sharply in the second week and then decreasing in the later 2 weeks. In contrast, the CaF₂ containing coating materials showed a slower sustained rate of fluoride ion release over the 4‐week test period, with the DU‐DMA/HEMA based coating having a fluoride ion release pattern that meets the requirements for dental use. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An UV‐curable epoxy acrylate oligomer with high refractive index containing fluorene: Preparation,characterization, and application

In this article, a novel UV‐curable epoxy acrylate oligomer (BPEFPGMA) with high refractive index is successfully prepared through semi‐esterification reaction of 9,9‐bis[4‐(2‐hydroxyethoxy)phenyl]fluorene and phthalic anhydride, followed by end‐caping of glycidyl methacrylate. After 15 times’ repetitions, the process and properties of this oligomer are stable and reliable. The resulting BPEFPGMA exhibited low solvent content (≤1600 ppm), low viscosity (1900–2500 mPa s at 60°C), high refractive index (1.587 ± 0.003 at 20°C), and normal M_w (2550–3536 g/mol). The coating formulations of 1.57 UV‐curable glue are mixed with BPEFPGMA as reactive oligomer. Through the technology of UV‐curing forming, the corresponding brightness enhancement films are obtained. The resulting films exhibit normal structure, excellent adhesion (5B), good scratch resistance (50 g), and good abrasion resistance (50 g). They show excellent performance, and have reached the quality standard for use in liquid crystal display industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42386.     

Photopolymerization and thermal behavior of phosphate diacrylate and triacrylate used as reactive‐type flame‐retardant monomers in ultraviolet‐curable resins

Tri(acryloyloxyethyl)phosphate (TAEP) and di(acryloyloxyethyl)ethyl phosphate (DAEEP) were used as reactive‐type flame‐retardant monomers along with commercial epoxy acrylate and polyurethane acrylate oligomers in ultraviolet (UV)‐curable resins. The concentrations of the monomers were varied from 17 to 50 wt %. The addition of the monomers greatly reduced the viscosity of the oligomers and increased the photopolymerization rates of the resins. The flame retardancy and thermal degradation behavior of the UV‐cured films were investigated with the limiting oxygen index (LOI) and thermogravimetric analysis. The results showed that the thermal stability at high temperatures greater than 400°C and the LOI values of the UV‐cured resins, especially those containing epoxy acrylate, were largely improved by the addition of the monomers. The dynamic mechanical thermal properties of the UV‐cured films were also measured. The results showed that the crosslink density increased along with the concentrations of the monomers. However, the glass‐transition temperature decreased with an increasing concentration of DAEEP because of the reduction in the rigidity of the cured films, whereas the glass‐transition temperature increased with the concentration of TAEP because of the higher crosslink density of the cured films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 185–194, 2005     

紫外光固化涂料的研究进展

紫外光固化涂料由于固化速度快、涂膜质量高、环境污染少以及能耗低等优点,已经成为涂料工业中的一支重要生力军。本文介绍了紫外光固化涂料的固化原理,同时也对紫外光固化涂料中的光引发剂、活性单体、齐聚物、助剂等的发展现状进行了综述,重点介绍了混杂齐聚物、水性齐聚物、超支化齐聚物的研究进展。详细介绍了环氧丙烯酸酯、聚酯丙烯酸酯、聚氨酯丙烯酸酯类齐聚物的研究。紫外光固化涂料的水性化和粉末化将是紫外光固化涂料未来的发展方向。