An acrylic resin was synthesized with several monomers, styrene(St), 2-hydroxyethyl methacrylate(2-HEMA), n-butyl acrylate, methyl methacrylate, and acetoacetoxyethl methacrylate(AAEM) to prepare a high-solid coatings. Then, a high-solid acryl/melamine coatings was prepared by curing the acrylic resin with a curing agent, hexamethoxymethylmelamine(HMMM). The curing behavior of the acrylic resin with HMMM was investigated by the Ozawa method using DSC. For AAEM/HMMM and 2-HEMA/HMMM curing reactions, activation energies were 33.01 and 27.12 kcal/mol and frequency factors were 9.54×1015 and 1.53×1013 min-1, respectively. From the results, it was found out that 2-HEMA showed higher reactivity with the curing agent than AAEM.