新規水溶性リン原料の開発およびリン酸塩機能材料の高機能化

本年度进行了新型水溶性磷酸酯的合成和表征，并通过合成LiCaPO_4：Eu^2+磷光体证实了它们的优点。以聚乙二醇300、五氧化二磷和多聚磷酸为原料，合成了一种稳定的水溶性磷酸酯。多聚磷酸、聚乙二醇300和P_2O_5在N_2气氛中混合。记录<31>制备的磷酸酯低聚物的13 P{^1H}NMR谱。磷酸和磷酸酯的比例取决于回流条件。采用<097>可聚合络合物法（PC）合成了掺Eu的LiCa_ PO_4：0.03Eu^&lt;2+&gt;。此外，还进行了SSR方法的合成。比较了荧光粉的激发光谱和发射光谱。在三种样品中，在使用磷酸酯的PC法合成的样品中观察到最强的发射强度。采用磷酸酯法制备的Eu分布均匀。因此，通过使用磷酸酯的PC方法制备的样品显示出最高的发射强度。最后，成功地开发了用于溶液法的磷酸盐源，并通过合成LiCaPO_4：Eu^2+荧光粉证实了磷酸酯的优越性，利用所开发的PC法合成了<1-x>NaBa_Ca_xPO_4固溶体，并研究了其光致发光性能和晶体结构。在320 nm激发下，随着Ca取代量的增加，发光强度降低，发射中心从438 nm红移到455 nm。X射线衍射分析表明，<0.5><0.5>x = 0.5时的NaBa_Ca_PO_4和x = 1/3时的Na_3Ba_2CaPO_4是它们的固溶体。最后，我们发现了两种新的化合物，并确定了它们的晶体结构。

In this year, synthesis and characterization of novel water soluble phosphate ester and confirmation of their advantages by synthesis of a LiCaPO_4 : Eu^2+ phosphor were conducted. A stable and water soluble-phosphate ester was synthesized from reaction among polyethylene glycol 300, P_2O_5, and Polyphosphoric acid. Polyphosphoric acid, polyethylene glycol 300, and P_2O_5 were mixed in N_2 atmosphere. ^<31>P{^1H}NMR spectra of the prepared phosphate oligomers were recorded. The proportion of phosphoric acid and phosphate ester was depended on the reflux condition. The amount of H_3PO_4 was around 12%, while around 45% H_3PO_4 was unreacted using the previous method.Eu-doped LiCa_<097> PO_4:0.03Eu^<2+> was synthesized by the polymerizable complex (PC) method employing a prepared phosphate ester. In addition, the synthesis by the SSR method was conducted. Excitation and emission spectra of phosphors were compared. The strongest emission intensity among three samples was observed at the sample synthesized by PC method employing phosphate ester. PC method using phosphate ester could produce homogeneous Eu distribution. Therefore, the sample prepared by PC method employing phosphate ester showed the highest emission intensity. Finally, development of the phosphate source to use for solution based method was successfully conducted and the advantage of phosphate ester was proved by synthesis of LiCaPO_4 : Eu^2+ phosphor.Using the developed PC method, we synthesized NaBa_<1-x>Ca_xPO_4 solid solutions via PC method, and investigated their photoluminescence properties and crystal structures. As increase of Ca substitution, emission intensity decreased and the red shift of emission center was observed from 438 nm to 455 nm under excitation at 320 nm. XRD measurements of the samples revealed that NaBa_<0.5>Ca_<0.5>PO_4 at x = 0.5 and Na_3Ba_2CaPO_4 at x = 1/3 were solid solutions of them. Finally, we found two kinds of new compositions and determined their crystal structures.