The color performances of disperse dye washing-free printing have tight connections with the solubility parameters of polymer binders. Based on the solubility parameter theory, ethylhexyl acrylate (EHA) and methyl methacrylate (MMA) were selected as monomers. A series of polyacrylate (PA) binders were prepared by mini-emulsion polymerization. The effects of the mixed emulsifiers and the EHA-MMA mass ratios on PA properties were investigated. Results showed that PA emulsion remained more stable, the particle size and distribution were smaller, and the film possessed better tensile performances at the mass ratio of sodium lauryl sulfate (SDS):fatty alcohol polyoxyethylene ether (O-10):propylene oxide propyl alkyl phenyl polyether ammonium sulfate (V-20S) of 1.5:1:1 at 6 wt %. The larger solubility parameter differences between monomers and disperse dyes could improve color yield of the washing-free printed polyester fabric to a greater extent. At the mass ratio of EHA and MMA of 11:9 (55 wt % EHA), PA achieved the best mechanical and washing-free printing properties and surpassed the commercial binders.