Photo-cured 3D architectures are successfully printed using the designed waterborne polyurethane-acrylate (WPUA) formulation. A WPUA series is synthesized in the presence of polycaprolactone diol (PCL) and 4,4′-methylene dicyclohexyl diisocyanate (H₁₂MDI) as the soft segment part, dimethylolbutanoic acid (DMBA) as the emulsifier, and triethylamine (TEA) as the neutralizer, as a function of prepolymer molecular weight. The compatibility of WPUA and the photo-activating acryl monomer is as a key factor to guarantee the high resolution of 3D digital light processing (DLP) printing. The optimized blending formulations are tuned by using triacrylate monomers instead of diacrylate derivatives. For the high-accuracy and fine features of 3D DLP printing, WPUA are designed to be a suitable molecular structure for a 385 nm wavelength source, and the target viscosity is achieved in the range from 150 to 250 Cp. Photo-cured 3D architectures based on WPUA exhibit good flexural strength and high resolution.

Polyurethane pressure-sensitive adhesives (PU-PSAs) with satisfactory tack, cohesion, and removability were newly developed through the synthetic process by reacting methylene diisocyanate, poly(ethylene glycol) (PEG), and a 1,4-butanediol chain extender based on the different HDI/HDI trimer ratios. The sticking properties of PU-PSAs depended on both the HDI/HDI trimer ratio and crosslinking-agent composition in the formulation. The molecular weight (MW) dependence of adhesion in PU-PSA was observed in the range of 1000 < Mn < 3000, suggesting that the increase in MW limits the pressure-sensitive adhesion of these samples. The differences in the crosslinking-density significantly affected the cohesion, adhesion, and tack in PU-PSA. The formulation of 50 wt.% 600PEG and 50 wt.% crosslinking-agent and an HDI/HDI trimer ratio of 1.0 led to the optimal balance between the adhesion and cohesion properties owing to the sufficient tack, high 180-peel strength, and good cohesion.

An acryl-functionalized polyurethane (PU) series was successfully synthesized using poly(tetramethylene ether) glycol-methylene diphenyl diisocyanate (PTMG-MDI) oligomer based on urethane methacrylates to control the flexibility of photo-cured 3D printing architectures. The mass ratio of acryl-urethane prepolymer: 1,4-butanediol (BD) chain-extender: diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) photoinitiator was 10:0.25:1. To produce suitably hard and precisely curved 3D architectures, the optimal UV absorbance and exposure energy of the acryl-PTMG-MDI resin were controlled precisely. Owing to the optimized viscosity of the acryl-PTMG-MDI resins, they could be printed readily by digital light processing (DLP) to form precisely curved 3D architectures after mixing with 1,6-hexanediol diacrylate (HDDA). The acryl-PTMG-MDI formulations showed much better flexural resolution than the neat resins. The printed 3D structure exhibited high surface hardness, good mechanical strength, and high elasticity for flexible applications in consumer/industrial and biomedical fields.

A thermoplastic polyurethane (TPU) series for automotive panels with high durability have been newly synthesized using the reacting process based on polyester polyol (BTG), polycaprolactone triol (PCL), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 1,4-butanediol chain extender as a function of NCO/OH ratio (NCO index). The dependence of varying NCO index of synthesized TPUs on tensile strength and hardness have evaluated. To form PU foams with suitable rigidity and uniform skin-pores, the optimal synthetic process was controlled precisely by the amount of solvent, foaming agent, silicone surfactant, and catalysts content. A considerable NCO index dependence was observed in the range of 0.96 ≤ NCO index ≤ 0.99 at almost same molecular weight. When NCO index of TPU was 0.98, mechanical properties achieved maximum value due to the uniform open cell structure of molding PU foam. With the ratio of NCO/OH increasing, the hardness of PU foam also increased until 0.98 NCO index while the hardness of 0.99 NCO index decreased. The designed TPU with 0.98 NCO could be a promising formulation for molding foams of automotive skin panels and seating.

In the current study, an acrylic polymer binder applicable to road signs was successfully developed by mixing various acrylic, acrylate-type, and photoinitiator-based monomer species at different acrylate series/silicone acrylate ratios. An amorphous acrylic monomer was used, and the distance between the polymers was increased to improve transparency. The binder was designed with the purpose of reducing the yellowing phenomenon due to resonance by excluding the aromatic ring structure, which is the main cause of yellowing. The optical properties of the binder were determined according to the content of n-butyl methacrylate/methyl methacrylate and the composition of the crosslinking agent in the formulation. Allyl glycidyl ether and dilauroyl peroxide were used to improve the yellowing problem of benzoyl peroxide, an aromatic photoinitiator. Adding a silicone-based trivalent acrylic monomer, 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), was also found to have a significant effect on the transparency, shear properties, and water resistance of the binder. When 15 wt% TMSPMA was added, the best water repellency and mechanical properties were exhibited. The surface morphology of the improved binder and the peeling part were confirmed using field emission scanning electron microscopy. The acrylic polymer developed in this study can be applied in the coating and adhesive industries.