本研究運用溶液法聚合來製備聚氨酯鞋底塗料；並藉由改變軟硬鏈段的種類和比例，試圖從中找出解決目前聚氨酯鞋底塗料所遇到夏天容易沾黏包裝紙和冬天容易龜裂的問題；另一方面利用脂肪或脂肪環來取代苯環類的二異氰酸鹽來改善聚氨酯塗料經過陽光照射後會變黃的情形。本研究利用黏度儀、DMA、DSC、RDAII、拉伸機、GPC、自動螢光比色計及比色標來測量材料的性質以尋找能解決上述問題的鞋底塗料基質。研究結果發現，添加分子量1000的聚四亞甲基二醇(PTMG1000)和異佛爾酮二異氰酸酯(IPDI)可以改善聚氨酯鞋底塗料的沾黏情形，但PTMG1000會增加聚氨酯在丁酮中的黏度而不利於噴塗；聚合之加料順序會影響基質的性質，當加料順序為先讓硬鏈段反應完全後再加入軟鏈段，可以使T2升高、降低殘留比；當NCO和OH的莫耳比為1.15時有T2為83.93℃、殘留比為4.48時有最好的效果。利用六亞甲基二異氰酸酯(HDI)和異佛爾酮二異氰酸酯(IPDI)確實不會發生材料的變黃情形，當添加30%甲苯二異氰酸酯(TDI)來取代HDI和IPDI時樣品之比色等級為3-4達到可接受的變黃效果。 This work prepared polyurethanes based sole coating materials by solution polymerization with different compositions and types of hard and soft segment in order to resolve the problem that the sole coating cracks in the cold winter and sticks back to wrapping paper in the summer. To improve the yellowing resistance of the polyurethanes, aliphatic and cycloaliphatic isocyanates were used to replace aromatic isocyanates. The polyurethanes were analyzed by rheometry, dynamic mechanical analysis, differential scanning calorimetry, tensile test, spectrophotofluorometry and color matching guide in order to find an appropriate formulus that can resolve the problem mentioned above. The polyurethanes were constituted of polytetramethylene oxide(PTMG) as the soft segment, isophrone di-isocyanate (IPDI), hexamethylene di-isocyanate (HDI) or toluene di-isocyanate (TDI) as the source of NCO and neopentyl alcohol (NPG) as the chain extender. The results showed that the addition of PTMG of molecular weight 1000 and IPDI resolved the back-stuck problem, but the addition of PTMG1000 enhanced the viscosity of the binder solution in methyl ethyl ketone. When the ratio of NCO/OH was 1.15 the sticking test showed a residue of 4.48% and T2 of the polymer reached 83.93℃and gave better sticking resistance. For the yellowing test, the polyurethanes with IPDI or HDI as the hard segment had a better yellowing resistance. The acceptable yellowing level is 3-4 when 30% of HDI or IPDI was replaced by TDI.
