臺灣博碩士論文加值系統

本研究係以丙酮萃取生漆之主成分漆酚（Urushiol）後作為原料，添加環氧氯丙烷（Epichlorohydrin）合成環氧漆酚（Epoxy urushiol, EU），以降低漆酚之過敏性，並藉由添加具有胺基之矽氧烷與EU反應後，再加入鹽酸水溶液使其行溶膠-凝膠反應，製備有機-無機混成木材塗料。依不同胺基/環氧基（莫耳比）於EU中添加3-胺基丙基三乙氧基矽烷（3-Aminopropyltriethoxysilane, APTES）在60oC中，反應1 h製備含矽氧烷漆酚環氧樹脂，再添加鹽酸水溶液調配成木材塗料。試驗結果顯示，各塗膜僅具一個玻璃轉移溫度（Glass transition temperature, Tg），顯示改善漆酚添加矽氧烷易產生不均質塗膜之缺點，其中又以APTES-1.50（APTES之胺基/EU之環氧基=1.50/1.00）者具有最佳之塗膜硬度、玻璃轉移溫度、質量保留率、拉伸強度及耐熱性，但其可使用時間太短。進一步在EU中分別添加APTES及N-2-胺乙基-3-胺丙基三乙氧基矽烷（N-(2-aminoethyl)-3-aminopropyltriethoxysilane, AAPTS），並提高反應溫度至100oC，反應時間1.5 h，可製備出具有三級胺結構之含矽氧烷漆酚環氧樹脂（EU-APTES與EU-AAPTS），進而降低塗料鹼性，並成功增加可使用時間至24 h以上；再將EU-APTES與EU-AAPTS以不同質量比例摻合，即可製得含矽氧烷漆酚環氧樹脂混成塗料，其可使用時間可增加至24 h以上，且以APTES-25-AAPTS-75（EU-APTES/EU-AAPTS=25/75）者具有最佳的耐磨性及耐光性，而其他塗膜性質則較為均衡。本研究將APTES-25-AAPTS-75以不同質量比與生漆摻合成混成木材塗料，其中以OL-90-Silane-10（生漆/APTES-25-AAPTS-75＝90/10）者具最短乾燥時間18.5 h，同時塗膜亦具最佳之拉伸強度、破壞伸長率、耐磨性、附著性及耐光性，顯示添加矽氧烷可以明顯改善生漆之乾燥性與耐光性。

Urushiol, the main component of oriental lacquer, was extracted by acetone as raw material. The epoxy urushiol (EU) can be successfully synthesized by adding epichlorohydrin reacted with urushiol for reducing the allergenicity of urushiol. The organic-inorganic hybrid wood coatings were prepared by adding amino silane to react with EU and adding HCl(aq) as catalyst through sol-gel reaction. The 3-aminopropyltriethoxysilane (APTES) was added to EU to form the silane-containing urusgiol epoxy resin and the was added to prepare the wood coating. The results showed that only a glass transition temperature of all films, so EU could improved that urushiol easily produced heterogeneous films with silane. And according to the molar ratio of amino groups/epoxy groups, the APTES-1.50 with molar ratio of 1.50/1.0 had the best hardness, glass transition temperature, mass retention, tensile strength and heat resistance of film, however the pot-life of coating was too short. Furthermore, by adding APTES and N-2-aminoethyl-3-aminopropyltriethoxysilane (AAPTS) in the EU respectively, and increasing the reaction temperature to 100oC, the reaction time was 1.5 h for preparing silane-containing urushiol epoxy resin (EU-APTES and EU-AAPTS) with tertiary amine structure. Then, the EU-APTES and EU-AAPTS were blended with different weight ratios to obtain silane-containing urushiol epoxy hybrid resin coatings, which pot-life could be extending to more than 24 h, and APTES-25-AAPTS-75 (EU-APTES/EU-AAPTS=25/75 with weight ratio) had the best abrasion resistance, lightfastness, and more balances among the other film properties. Moreover, APTES-25-AAPTS-75 was also blended with oriental lacquers by different weight ratios to obtain hybrid wood coatings. The results showed that the OL-90-Silane-10 (oriental lacquer/APTES-25-AAPTS-75=90/10 with weight ratio) has the shortest drying time of 18.5 h, and had the best tensile strength, elongation at break, abrasion resistance, adhesion and lightfastness of films, the drying and lightfastness of oriental lacquer could be improved significantly by adding the silane resin.

摘要.......................................i
Summary...................................ii
目錄.......................................iv
表目次......................................vi
圖目次......................................ix
第一章 前言..................................1
第二章 文獻回顧...............................5
一、天然生漆及其組成...........................5
二、生漆之乾燥機制、致敏性與耐光性...............9
三、生漆之改質.................................12
（一）生漆之精製...............................13
（二）摻合不同樹脂及硬化劑......................15
（三）添加不同乾燥劑及催化劑....................16
（四）添加光引發劑.............................19
四、生漆之有機-無機混成塗料.....................20
（一）矽氧烷之溶膠-凝膠反應機制..................21
（二）水含量對溶膠-凝膠反應之影響................22
（三）不同pH值對溶膠-凝膠反應之影響...............23
（四）以溶膠-凝膠法製備有機-無機混成材料實例......23
第三章 含矽氧烷漆酚環氧樹脂木材塗料..............29
一、材料與方法.................................29
（一）試驗材料.................................29
（二）試驗方法.................................31
二、結果與討論.................................37
（一）樹脂與塗料性質............................37
（二）塗膜性質.................................44
第四章 含不同矽氧烷漆酚環氧混成樹脂木材塗料.......54
一、材料與方法.................................54
（一）試驗材料.................................54
（二）試驗方法.................................56
二、結果與討論.................................59
（一）樹脂與塗料性質............................59
（二）塗膜性質.................................67
第五章 添加含不同矽氧烷漆酚環氧樹脂之生漆混成塗料..78
一、材料與方法.................................78
（一）試驗材料.................................78
（二）試驗方法.................................80
二、結果與討論.................................82
（一）樹脂與塗料性質............................82
（二）塗膜性質.................................84
第六章 結論....................................97
參考文獻.......................................99

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