The thermodynamic behavior of phenolic resin was investigated to verify the relation between the properties of porous ceramics with $ZrO_2$-C system for submerged entry nozzle and the characteristics of phenolic resin with various relative humidity. The green and the sintered density were decreased between 25% and 50% relative humidity, whereas they were gradually enhanced above 50% relative humidity. The highest value of apparent porosity was 20.1% and the minimum compressive strength was 69MPa in the specimen using the powder exposed to 50% relative humidity. As a result of thermal analysis for phenolic resin, the shift of endothermic peak to low temperature and the reduction of exothermic peak were observed, and the peaks corresponded to melting and curing of phenolic resin, respectively. The melting and the curing of phenolic resin generate the change of green density, and it can affect the properties of submerged entry nozzle.