Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/89315
標題: Development of Vegetable Oil-based Waterborne Wood Coatings
以植物油為基質水性木材塗料之研發
作者: Chia-Wei Chang
張家偉
關鍵字: 木材塗料
植物油
水性紫外線乾燥塗料
水性雙重硬化塗料
二液型水性聚胺基甲酸酯塗料
光引發劑
wood coating
vegetable oil
waterborne ultraviolet curing coating
waterborne dual curing coating
2-package waterborne polyurethane coating
photoinitiator
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摘要: 為改善傳統溶劑型塗料中含有揮發性有機化合物(volatile organic compounds,VOCs)之 缺點, 本研究以植物油為基質製備水性木材塗料 (waterborne woodcoatings),包括二液型水性聚胺基甲酸酯(waterborne polyurethane, WPU)、水性紫外線乾燥(waterborne ultraviolet curing, WUV)及水性雙重硬化(waterborne dualcuring)木材塗料,並探討其樹脂合成、塗料與塗膜性質。 二液型 WPU 塗料中,探討四種不同硬化劑對於以蓖麻油為基質之二液型WPU 塗料之影響。先將蓖麻油與甘油以莫耳比 2 進行酯交換反應,得到蓖麻仁油甘油酯(castor oil glyceride, COG),再與二羥甲基丙酸(2,2-dimethylolpropionicacid, DMPA)、異佛爾酮二異氰酸酯(isophorone diisocyanate, IPDI)以丙酮法合成含有羧基之預聚合體(prepolymer),此預聚合體再以三乙胺(triethylamine, TEA)中和得到離子體(ionomer),並以水分散,再經減壓蒸餾去除丙酮後得到水分散 PU 多元醇 (waterborne polyurethane dispersed polyol, PUDp),將其與四種不同硬化劑分別為 IPDI 單體、六亞甲基二異氰酸酯(hexamethylene diisocyanate, HDI)單體、經過聚乙二醇(polyethylene glycol, PEG)改質之多異氰酸酯 PEG-PIPDI 及經過 PEG改質之 PEG-PHDI 硬化劑等 以 NCO/OH 莫耳比為 1.5 混合並調配成二液型 WPU,塗料,結果顯示,以 PUDp 混合 IPDI 硬化劑之塗膜具有高硬度及光澤度﹔而以PEG-PHDI 混合者具有高破壞伸長率、耐磨、耐衝擊性,但硬度低﹔以 HDI 作為硬化劑者具有適中塗膜硬度、破壞伸長率及最高之拉伸強度與耐水性,但光澤度低﹔而使用 PEG-PIPDI 為硬化劑者具有高光澤度、適中硬度及拉伸強度,並具有良好耐熱性,適合一般木材塗裝使用。 又 WUV 木材塗料之試驗中,則先以 COG、DMPA、2-甲基丙烯酸羥乙酯(2-hydroxyethyl methacrylate, HEMA)與 HDI 及 IPDI 合成出具有羧基及丙烯醯基之預聚合體,經過 TEA 中和、水分散並去除丙酮後,得到水性丙烯醯化聚胺酯分散液(waterborne acrylated polyurethane dispersion, APUD),並於 APUD 中分別添加 1、3 及 5 wt.% Irgacure 2959 或 Irgacure 184 光引發劑,調配成 WUV 塗料,再於不同光源包括水銀燈、鹵素燈及兩者併用下硬化﹔結果顯示添加 3 wt.%Irgacure 2959 光引發劑並以水銀燈照射 18 sec 所得到之塗膜具有最高之拉伸強度及玻璃轉移溫度(glass transition temperature, Tg),但其硬度較低﹔而以 IPDI 及季戊四醇三丙烯酸酯(pentaerythritol triacrylate, PETA)合成 WUV 塗料之塗膜硬且脆,不適合作為木材塗料使用﹔為改善塗膜硬度,以 IPDI 部分代替 HDI 所合成之WUV 塗料中,其以 HDI/IPDI 莫耳比為 3/1 者具有優良塗膜硬度、破壞伸長率與附著性,適合作為一般木材塗料使用。 此外,以亞麻仁油為基質合成 WUV 分散液,並作為雙重硬化塗料,並探討不同硬化程序之塗料及塗膜性質。首先將亞麻仁油甘油酯(linseed oil glyceride,LOG), DMPA, IPDI, HDI 及 HEMA 以丙酮法合成具有丙烯醯基及脂肪酸雙鍵之溶劑型預聚合體,再以 TEA 中和並分散於水中,並經減壓蒸餾後得到 WUV 分散液。再將 WUV 分散液單獨添加光引發劑成為 UV 硬化型塗料(UV)、單獨添加金屬乾燥劑成為空氣乾燥型塗料(Air),及同時添加光引發劑與金屬乾燥劑之UV/Air 及 Air/UV 雙重硬化型塗料。結果顯示以先照射 UV 光再進行空氣乾燥之UV/Air 雙重硬化型塗膜較單獨 UV 硬化者具有較高的耐久性及耐光性,且能改善 UV 塗料附著性不佳之缺點,其高效率、高品質且對環境友善之特性,具有作為木材塗料之潛力。
For solving the defect of VOCs in traditional solvent-borne coatings, the synthesis, coating properties and film performance of three vegetable oil based waterborne wood coatings including 2-package waterborne polyurethane (WPU) coating, waterborne UV curing (WUV) coating and waterborne dual curing coating were examined. The effects of four kinds of hardener on the properties of castor oil based 2-package WPU coatings were evaluated. Castor oil glyceride (COG) was first prepared by transesterification of glycerin and castor oil (CO) at the molar ratio of 2.0. The waterborne polyurethane dispersed polyols (PUDp) was first synthesized from COG, dimethylol propionic acid (DMPA) and isophorone diisocyanate (IPDI) by the acetone process to provide a prepolymer with a carboxyl and hydroxyl groups. Then the prepolymer was neutralized by triethylamine (TEA) to obtain an ionomer and was dispersed into water. After vacuum distillation to remove acetone, the PUDp was obtained and then mixed with four different hardeners: IPDI, hexamethylene diisocyanate (HDI), polyethylene glycol (PEG) modified PIPDI (polymeric IPDI), named PEG-PIPDI and PEG-modified PHDI (polymeric HDI), named PEG-PHDI. The NCO/OH molar ratio of 1.5 was used and a 2-package WPU coating was obtained. The results showed that the film of the 2- package coatings obtained from IPDI hardener had excellent hardness and gloss. On the contrary, the film containing PEG-PHDI had low hardness but had high tensile strength, elongation at break, abrasion resistance and impact resistance. The film containing HDI hardener showed the best tensile strength, superior water resistance, and higher elongation at break and hardness, however it had the worst gloss among four WPU coatings. The film with PEG-PIPDI hardener had the best heat resistance, high gloss and optimal hardness and tensile strength, and it was suitable for wood coatings among four WPU coatings. The WUV coating for wood finishing was investigated. First, urethane acrylate prepolymers were synthesized from COG, DMPA, 2-hydroxyethyl methacrylate (2- HEMA) and HDI. And then the prepolymer was neutralized with TEA and dispersed in water. A waterborne acrylated polyurethane dispersion (APUD) was obtained after removing the acetone. The WUV coatings were formulated by mixing the APUD with 1, 3, or 5 wt.% photoinitiator Irgacure 2959 or Irgacure 184, repectively, and were cured by different UV light sources including mercury lamp (H), halogen lamp (C) and both of C+H lamps. The results indicated that the coating containing 3wt.% Irgacure 2959 photoinitiator and cured by mercury lamp for 18 sec showed the best tensile strength and glass transition temperature (Tg), but it had the lowest hardness. The WUV coatings synthesized by IPDI and pentaerythritol triacrylate (PETA) showed hard and brittle film, and was not suitable for wood finishing. For improving the poor hardness which containing HDI alone, the HDI was partially replaced by IPDI. The results showed that a WUV coating with an HDI/IPDI molar ratio of 3/1 had superior film hardness, elongation at break, and adhesion, and it would be suitable for wood finishing. In the chapter Ⅴ, the synthesis of linseed oil based WUV dispersion as a dual curing wood coatings using different curing processes, as well as their coating and film properties were examined. The prepolymer was synthesized first from linseed oil glyceride (LOG), DMPA, IPDI, HDI and HEMA using an acetone process to prepare a solvent-borne prepolymer with double bonds derived from methacrylic acid and fatty acids. The prepolymer was subsequently neutralized with TEA and dispersed in water. After removing acetone, WUV dispersion was obtained. Wood coatings were formulated by mixing WUV dispersion with photoinitiator (Irgacure 2959) for UV curing alone, named UV or by mixing WUV dispersion with metal driers for air drying alone, named Air or by combining WUV dispersion with the two formulations as UV/Air and Air/UV dual curing systems. The results showed that the durability and the colo of films prepared using the UV/Air dual curing process (i.e., first UV curing, followed by air drying) were better than those of the coatings cured using UV alone. Furthermore, the poor adhesion of the films cured using UV alone was significantly improved through the use of the UV/Air dual curing system. In conclusion, the linseed oil based waterborne UV/Air dual curing coatings possess the potential to provide high- efficiency, high-performances and environmentally friendly coatings for wood furniture finishing.
URI: http://hdl.handle.net/11455/89315
其他識別: U0005-2306201515072400
文章公開時間: 2017-07-16
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