臺灣博碩士論文加值系統

本研究以大豆油製成之油變性醇酸樹脂與油溶性胺基樹脂混合成酸硬化胺基醇酸樹脂(AA)，再將AA與硝化纖維素(NC)摻合而成半互穿聚合體網狀結構物(Semi-IPNs)，期能提昇AA之性能，並降低AA塗料之游離甲醛釋出量，更期望藉此摻合而導入NC的優良特性，進而探討其應用於木器塗料之可行性。
由試驗結果得知，胺基樹脂/短油性醇酸樹脂重量混合比30/70之AA塗料，其胺基樹脂以三聚氰胺樹脂(MF)/尿素樹脂(UF)為25/75及0/100者塗料與塗膜性質最為均衡。在各種配方之AA-NC semi-IPNs塗料均可明顯縮短AA塗料之乾燥時間，其中以AA/NC 重量比為25/75的AA-NC semi-IPNs之塗料與塗膜性質最為均衡，能提升AA塗膜之硬度、耐磨耗性及拉伸強度等機械性質，且耐光性亦可獲得改善，並可降低塗膜之游離甲醛釋出量；由耐溶劑性試驗可證明AA與NC確有互穿效果產生，而由FT-IR分析亦可獲知AA與NC兩者僅以物理性之纏繞互穿而結合。
不同油長醇酸樹脂所調配之AA-NC semi-IPNs塗料中，以短油性者之塗膜游離甲醛釋出量為最少，但以中油性者之塗料與塗膜性質較為均衡。AA-NC semi-IPNs各組成分之添加順序以胺基樹脂 NC
醇酸樹脂 酸催化劑的方法A之AA-NC semi-IPNs，其塗料與塗膜性質較方法B者及方法C者為均衡。

In this study, the semi-interpenetrating polymer networks (semi-IPNs) which were made from soybean oil modified amino-alkyd resin (AA) and nitrocellulose (NC) were prepared for wooden coatings and would be expected to improve the properties of AA coatings and films and reduce the released formaldehyde from AA. The effects of several factors such as components of AA, AA/NC weight ratios, oil length of alkyd and addition sequence of semi-IPNs on properties of coatings and films were investigated.
Both AA coatings were prepared from melamine-formaldehyde resin (MF)/urea-formaldehyde resin (UF)/alkyd = 7.5/22.5/70 and UF/alkyd = 30/70(by wt. %) respectively, had a better compatible system and balance on properties of coatings and films. While, AA made from UF/alkyd = 30/70 had more released formaldehyde than that of MF/UF/alkyd = 7.5/22.5/70.
AA and NC were compatible on all of AA-NC semi-IPNs formulations and the drying time of AA could be shortened significantly by interpenetrating with NC. The formulation of AA-NC semi-IPNs with MF/UF/alkyd = 7.5/22.5/70 and AA/NC = 25/75(by wt. %) had an excellent performance system and balance on properties of coatings and films. Meanwhile, the released formaldehyde of the semi-IPNs could be reduced significantly. The results also indicated that the AA-NC semi-IPNs had only a physical interpenetrating between AA and NC by solvent resistance test and FT-IR spectra analysis.
Among all of various oil length alkyds, the short oil AA-NC semi-IPNs had the least released formaldehyde. However, the medium oil AA-NC semi-IPNs had a better balance on properties of coatings and films than those of short and long oil length AA-NC semi-IPNs. In addition, the properties of films by the addition sequence of amino resin
NC alkyd resin acid catalyst were better than those of amino resin alkyd resin acid catalyst NC and all components mix together at the same time of AA-NC semi-IPNs.

目錄
目錄 I
圖目次 IV
表目次 VI
摘要 IX
SUMMARY X
一、前言 1
二、文獻回顧 5
三、試驗材料與方法 20
(一)試驗材料 20
(二)試驗方法 21
1.大豆油性質之測定 21
2.油變性醇酸樹脂合成及性質測定 24
3.油溶性胺基樹脂合成及性質測定 28
4.塗料的調配 29
(1)不同MF/Alkyd比例之AA塗料 29
(2)不同MF/UF比例之AA塗料 31
(3)不同AA/NC摻合比之AA-NC semi-IPNs 31
(4)不同油長之AA-NC semi-IPNs 32
(5)不同組成分添加順序之AA-NC semi-IPNs 32
5.試材塗裝 34
6.塗料性質測定 35
(1)黏度 35
(2)指觸乾燥 35
(3)乾燥乾間 36
(4)可使用時間 36
7.塗膜性質測定 37
(1)物理性質 37
A.硬度 37
B.抗彎曲性 37
C.耐磨耗性 37
D.耐衝擊性 37
E.拉伸強度 38
F.破壞伸長率 38
(2)光澤度 39
(3)冷熱循環試驗 39
(4)附著性 40
(5)不黏著性 41
(6)游離甲醛含量 41
(7)耐光性 42
(8)耐溶劑性 43
(9)傅立葉轉換紅外線光譜分析 43
四、結果與討論 44
(一)合成樹脂之基本性質 44
1.油變性醇酸樹脂 44
2.胺基樹脂 47
(二)酸硬化胺基醇酸樹脂塗料 48
1.不同MF/alkyd重量比對AA塗料與塗膜性質之影響 48
2.不同MF/UF重量比對AA塗料與塗膜性質之影響 51
(三)AA/NC摻合比對AA-NC semi-IPNs性質之影響 57
(四)不同油長對AA-NC semi-IPNs性質之影響 71
(五)組成分添加順序對AA-NC semi-IPNs性質之影響 75
五、結論 85
六、參考文獻 87

1. 呂孔文 (1993) 高分子紅外線光譜分析。高分子紅外線光譜分析技術講習會講義，工業技術研究院、化學工業研究所 pp.1-1 ~ 1-91。
2. 吳宗嶽譯著， Clive H. Hare et al. 原著 (1980) 塗料工藝講座。pp.61 ~ 100、pp.162 ~ 191 國立編譯館 台北。
3. 林阿英 (1986) 低甲醛尿素膠之合成及性能之研究。國立中興大學森林學研究所碩士論文 pp.1 ~ 5。
4. 洪純仁譯著，三原一幸原著 (1995) 解說塗料學。pp.50 ~ 56 復漢出版社 台南。
5. 張上鎮 (1984) 木材用透明塗料的耐光性。林產工業 3(4)：31 ~ 41。
6. 張上鎮 (1987) 木材用塗料耐久性之研究。林業試驗所研究報告季刊 2(4)：303 ~ 318。
7. 張上鎮 (1989) 硝化纖維素塗料光劣化後之表面化學性質變化分析。林業試驗所研究報告季刊 4(3)：123 ~ 136。
8. 張上鎮 (1995) 透明塗料抑制木質材料光劣化效能之評估。中華林學季刊 28(2)：117 ~ 137。
9. 張上鎮 (2001) 淺談木材塗料之組成份與乾燥原理。木材塗料，林產工業叢書 17 pp.17 ~ 24。
10. 張上鎮、周佰隆 (1995) 透明塗料之耐候性改善及其天候變色與光變色之比較。林產工業 14(3)：374 ~ 390。
11. 張上鎮、周佰隆 (1999) 胺基甲酸酯變性壓克力紫外光硬化塗料之研製與耐久性之改善。林產工業 18(3)：311 ~ 320。
12. 張上鎮、蕭雅芳 (1998) 塗裝木材人工加速劣化與自然暴露試驗之相關性（I）表面性質變化。林產工業 17(1)：123 ~ 137。
13. 陳劉旺、童欽文 (1981) 塗料製造化學。pp.111 ~ 114 高立圖書有限公司 台北。
14. 陳劉旺 (1997) 工業塗料與高分子化學。pp.1 ~ 40 高立圖書有限公司 台北。
15. 陳麗玉 (1989) 粒片板各種甲醛釋出量測定之相關性及甲醛之消除法。國立中興大學森林學研究所碩士論文 pp.1 ~ 5。
16. 黃金城 (1988) 桐油製造油變性合成樹脂塗料之研究。國立中興大學森林學研究所碩士論文。
17. 黃金城、劉正字 (1995a) 高固形份胺基醇酸樹脂應用在木材塗料之研究。林產工業 14(1)：95 ~ 115。
18. 黃金城、劉正字 (1995b) 氣乾型水性胺基醇酸樹脂之研究－塗料之分子量、粘度、穩定性、乾燥時間及硬化動力學。林產工業 14(2)：120 ~ 148。
19. 黃金城、劉正字 (1995c) 水性胺基醇酸樹脂應用在木材塗裝之研究。林產工業 14(4)：565 ~ 581。
20. 黃金城、盧崑宗、劉正字 (1997) 硝化纖維素種類對拉卡性質之影響。林產工業 16(3)：423 ~ 436。
21. 劉正字 (1997) 木器塗料之種類及特性。木材塗裝及塗膜性能檢驗研習會講義，行政院農委會、國立中興大學 pp.I-1 ~ I-23。
22. 劉正字 (2001) 常用木器塗料。木材塗料，林產工業叢書 17 pp.1 ~ 15。
23. 劉正字、盧崑宗 (1984) 烏桕種子油製造塗料之研究(第二報)－油變性胺系醇酸樹脂之研究。林產工業 3 (4)：2 ~ 21。
24. 劉正字、盧崑宗、江燕秋 (2001) 多羥基樹脂種類對PU-NC Semi-IPNs木器塗料性質之影響。林產工業 20(3)：237 ~ 246。
25. 盧崑宗 (1987) 木製家具之塗料。塗料與塗裝技術 2：68 ~ 78。
26. 盧崑宗、劉正字 (1997) PU-NC semi-IPNs應用於木器塗料之研究（I）NCO/OH莫耳比與PU/NC組成對塗料及塗膜性質之影響。林產工業 16(4)：731 ~ 748。
27. 盧崑宗、劉正字 (1999) 木工家具塗料I.概論。木工家具雜誌179：74 ~ 80。
28. 盧崑宗、劉正字 (2000) 木工家具塗料 VI.硝化纖維拉卡。木工家具雜誌 191：112 ~ 130。
29. 盧崑宗、劉正字 (2001) 木工家具塗料 VII.酸硬化胺基醇酸樹脂塗料。木工家具雜誌 206：89 ~ 106。
30. 蘇文清 (1990) 樹脂變性對硝化纖維素塗料之改善效應。國立中興大學森林學研究所碩士論文。
31. 山下晉三、金子東助 (1981) 架橋劑ハンドブツク。pp.223 ~ 226大成社，高立圖書有限公司印行 台北。
32. 長倉 稔 (1991) コーテイング用ビヒクルの材料設計第21回。塗裝技術 30(9) : 161 ~ 168。
33. 長倉 稔 (1993) コーテイング用ビヒクルの材料設計第45回。塗裝技術 32(10) : 153 ~ 158。
34. 鐮田賢一 (1995) 木工製品の木を生かした塗裝。塗料工學30(10)：4 ~ 12。
35. Aigbodion, A.I. and F.E. Okieimen (1996) Kinetics of rubber seed oil alkyds. Eur. Polym. J. 32(9) : 1105 ~ 1108.
36. Aigbodion, A.I. and F.E. Okieimen (2001) An investigation of the utilization of African locustbean seed oil in the preparation of alkyd resins. Industrial Crops and Products 13 : 29 ~ 34.
37. Ajithkumar, S., N.K. Patel, and S.S. Kansara (1998) Sorption behaviour of interpenetrating polymer networks based on polyurethane and unsaturated polyester. Polymer Gels and Networks 6 : 137 ~ 147.
38. Ajithkumar, S., N.K. Patel, and S.S. Kansara (2000) Sorption and diffusion of organic solvents through interpenetrating polymer networks(IPNs) based on polyurethane and unsaturated polyester.
Eur. Polym. J. 36 : 2387 ~ 2393.
39. Athawale, V. and S. Kolekar (1998) Interpenetrating polymer networks based on polyol modified castor oil polyurethane and polymethyl methacrylate. Eur. Polym. J. 34(10) : 1447 ~ 1451.
40. Bobalek, E.G. and M.T. Chiang (1964) Synthesis and properties of some alkyds of more complex carboxyl functionality. J. Appl. Polym. Sci. 8 : 1147 ~ 1168.
41. Bobalek, E.G., E.R. Moore, S.S. Levy, and C.C. Lee (1964) Some implication of the gel point concept to the chemistry of alkyd resins.
J. Appl. Polym. Sci. 8 : 625 ~ 657.
42. Byun, J., Y.M. Lee, and C.S. Cho (1996) Swelling of thermosenstive interpenetrating polymer networks composed of poly(vinyl alcohol) and poly(acrylic acid). J. Appl. Polym. Sci. 61 : 697 ~ 702.
43. Chen, C.H., W.J. Chen, M.H. Chen, and Y.M. Li (2000) Simultaneous full-interpenetrating polymer networks of blocked polyurethane and vinyl ester : Part I. Synthesis, swelling ratio, thermal properties and morphology. Polymer 41 : 7961 ~ 7967.
44. Derrough, S.N., C. Rouf, J.M. Widmair, and G.C.Meyer (1993) Investigations for obtaining semi-interpenetrating polymer networks base on monomers of different reactivity toward radicals. J. Appl. Polym. Sci. 48 : 1183 ~ 1188.
45. Frish, H.L., L. Wan , W. Huang, and Y.H. Hua (1991) Interpenetrating polymer networks from polyurethanes and poly(methyl Acrylate). J. Appl. Polym. Sci. 43 : 475 ~ 479.
46. Gallagher, J.A. (1982) Urethane bonded particleboard. For. Prod. J. 32(4) : 26 ~ 29.
47. Goldsmith, H.A. (1948) Alpha- and beta-hydroxyls of glycerol in preparation of alkyd resins. Ind. Eng. Chem. 40 : 1205 ~ 1211.
48. Hsine, K.H. and J.L. Han (1980) Graft interpenetrating polymer networks of polyurethane and epoxy. I. Mechanical behavior. J. of Appl. Polym. Sci. 28 : 623 ~ 630.
49. Hourston, J.D. and M.G. Huson (1992) Semi- and fully interpenetrating polymer networks based on polyurethane-polyacrylate systems. XI. The influence of polymerization temperature on morphology and properties. J. Appl. Polym. Sci. 45 : 1753 ~ 1762.
50. Jeevananda, T., M. Begum, and Siddaramaiah (2001) Studies on polyaniline filled PU/PMA interpenetrating polymer networks. Eur. Polym. J. 37 : 1213 ~ 1218.
51. Kienle, R.H. (1949) Alkyd resins : development of and contributions to polymer theory. Ind. Eng. Chem. 41 : 726 ~ 729.
52. Loew, G., and H.I. Sachs (1979) Isocyanate as a binder for particleboard. Proceeding-W.S.U. particleboard 17 : 273 ~ 491.
53. Lu, S.P., H.X. Xiao, and K.C. Frisch (1996) Crosslinking kinetics studies on interpenetrating polymer networks powder coatings.
Polym. Adv. Technol. 7 : 323 ~ 328.
54. Mallu, P. S., and A. Varadarajulu (1999) Interpenetrating polymer networks from castor oil-based polyurethane and polystyrene. Polym. Degrad. Stabil. 36 : 305-309.
55. Myers, G.E. (1984) How mole ratio of UF resin affects formaldehyde emission and other properties : A literature critique. For. Prod. J. 34(5) : 34 ~ 35.
56. Nuanphun, C., F. Nawee, K. Kantima, and E. Anucha (2000) Application of bis-(3-allyloxy-2-propanol) diphenylolpropane as a crosslinking agent in the preparation of polyurethane-polystyrene interpenetrating polymer networks. Eur. Polym. J. 36 : 95-100.
57. Roffael, E. (1978) Progress in the elimiation of formaldehyde delibration from particleboards. Proceeding-W.S.U. particleboard 12 : 233 ~ 249.
58. Schulza, U., G. Ponipe, E. Meyer, A. Janke, A. Fiedlerova, and E. Borsig (1995) IPN-like systems based on polyethylene and methacrylates. Polymer 36 (17) : 3393~3398.
59. Sperling, L.H. and V. Mishra (1996) The current status interpenetrating polymer networks. Polym. Adv. Technol. 7：197 ~ 208.
60. Susheela, B., D.V. Khakhar, and V.M. Nadkarni (1997) Mechanical properties of simultaneous interpenetrating polymer networks of castor oil based polyurethane and polystyene. Polymer 38(17) : 4319-4323.
61. Suthar, B., H.X. Xiao, D Klempner, and K.C. Frisch (1996) A review of kinetic studies on the formation of interpenetrating polymer networks. Polym. Adv. Technol. 7 : 221 ~ 233.
62. Yin, W., J. Li, and J. Wu(1997) Design and systhesis of conducting secondary crosslinked interpenetrating polymer network. J. Appl. Polym. Sci. 63 : 13 ~ 16.