TW201329154A - 用於複合結構之表面膜及其製備方法 - Google Patents

用於複合結構之表面膜及其製備方法 Download PDF

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TW201329154A
TW201329154A TW101146253A TW101146253A TW201329154A TW 201329154 A TW201329154 A TW 201329154A TW 101146253 A TW101146253 A TW 101146253A TW 101146253 A TW101146253 A TW 101146253A TW 201329154 A TW201329154 A TW 201329154A
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surface film
paint
resin
epoxy
epoxy resin
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TW101146253A
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TWI558759B (zh
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Junjie Jeffrey Sang
Dalip Kumar Kohli
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Cytec Tech Corp
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    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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Abstract

本發明係關於自可固化樹脂組合物形成之表面膜，該組合物含有環氧酚醛樹脂、三官能基或四官能基環氧樹脂、陶瓷微球體、基於胺之固化劑、顆粒無機填料及韌化組份。該表面膜在固化後呈現高Tg及高交聯密度，以及對油漆剝離劑溶液之高抗性。該表面膜適於與纖維強化樹脂複合材料共固化。該表面膜可視情況含有導電添加劑，以為雷擊保護(LSP)或電磁干擾(EMI)屏蔽提供足夠導電性。

Description

用於複合結構之表面膜及其製備方法
本發明概言之係關於複合表面膜。更具體而言，本發明係關於用於纖維強化聚合物基質複合結構之表面膜。
纖維強化聚合物基質複合物(PMC)係常用於需要抗侵襲性環境、高強度及/低重量之應用的高性能結構材料。該等應用之實例包括飛機組件(例如，機尾、機翼、機身及螺旋槳)、高性能汽車、艇的外殼及自行車框架。
航天工業中所用之習用複合結構通常包括表面膜以在塗漆之前為複合結構提供所需性能特徵。該等表面膜用於改良結構零件之表面品質，同時減少人力、時間及成本。在結構零件之製造期間，通常使表面膜與聚合物基質複合材料共固化。然而，出於油漆剝離目的，習用表面膜對市售油漆剝離溶液(例如基於苯甲醇之溶液)之抗性並不高。彼等油漆剝離劑可引起表面膜溶脹及/或浮泡且可使得重新塗漆製程更麻煩。因此，業內需要可使用習用油漆剝離溶液耐受再油漆剝離以在使用壽命內允許再塗漆複合結構及耐久油漆附著且亦可耐受紫外(UV)輻射暴露的表面膜。
本發明提供自包括以下之可固化組合物形成的表面膜：具有超過1之環氧官能度之環氧酚醛樹脂；三官能基或四官能基環氧樹脂；陶瓷微球體；潛在的基於胺之固化劑；作為流動控制劑之顆粒無機填料；及至少一種選自由以下 組成之群之韌化劑：(a)藉由環氧樹脂、雙酚及彈性體之反應形成之預反應加合物；(b)聚醚碸(PES)及聚醚醚碸(PEES)之共聚物；(c)核-殼橡膠(CSR)粒子；及其組合。在固化後，所得熱固性表面膜具有180℃之玻璃化轉變溫度(Tg)及如根據ASTM D-3363量測為大於7H之表面鉛筆硬度。
本發明亦提供纖維強化基於樹脂之複合基板上形成有表面膜之複合結構，以及製造複合結構之方法。可於250℉至355℉(或120℃至180℃)範圍內之溫度下使表面膜與基於樹脂之複合基板共固化。
根據本揭示內容之各個態樣之以下詳細說明結合繪示本揭示內容之各個實施例之附圖將更容易理解本揭示內容之特徵。
與航天複合零件一起使用之典型基於環氧樹脂之表面膜在暴露於習用基於醇之油漆剝離劑(例如基於苯甲醇之溶液)及紫外(UV)輻射時經常受影響。改良之表面膜經設計以克服該等問題。改良之表面膜組合物經調配以便產生高Tg及高交聯密度。已發現高Tg與高交聯密度之組合使得表面膜對基於醇之油漆剝離劑溶液(例如基於苯甲醇之溶液)具有高度抗性。為達成該等性質，表面膜組合物係基於以下之組合：某些多官能基樹脂、用於韌化樹脂基質之聚合物韌化組份、潛在的基於胺之固化劑、作為流體障壁組份之陶瓷微球體及作為流變性改良組份之顆粒無機填料。多 官能基樹脂及陶瓷微球體佔總組合物之50重量%以上，較佳60重量%以上。表面膜組合物之組份的詳細說明現將如下。
多官能基樹脂
表面膜組合物含有至少兩種多官能基環氧樹脂，其中一種係具有大於1之環氧官能度之環氧酚醛樹脂。第二環氧樹脂係非酚醛多官能基環氧樹脂、較佳四官能基或三官能基環氧樹脂(即每分子具有三個或四個環氧官能基之環氧樹脂)。
適宜環氧酚醛樹脂包括苯酚-甲醛酚醛樹脂或甲酚-甲醛酚醛樹脂之聚縮水甘油基衍生物，其具有以下化學結構(結構I)：
其中n=0至5，且R=H或CH3。在R=H時，樹脂係苯酚酚醛樹脂。在R=CH3時，樹脂係甲酚酚醛樹脂。前者係以DEN 428、DEN 431、DEN 438、DEN 439及DEN 485自Dow Chemical公司購得。後者係以ECN 1235、ECN 1273及ECN 1299自Ciba-Geigy公司購得。其他可使用之適宜酚醛樹脂包括來自Celanese Polymer Specialty公司之SU-8。在一較佳實施例中，環氧酚醛樹脂具有於25℃下4000-10,000 mPa．s之黏度及190-210 g/eq之環氧化物當量重量(EEW)。
適宜四官能基環氧樹脂係每分子具有四個環氧官能基及至少一個縮水甘油基胺基團之四官能基芳香族環氧樹脂。作為實例，四官能基芳香族環氧樹脂可具有以下一般化學結構(結構II)，即亞甲基二苯胺之四縮水甘油醚：
顯示結構II中之胺基團在芳香族環結構之對位或4,4'位，然而，應瞭解，其他異構體(例如2,1'、2,3'、2,4'、3,3'、3,4')係可能替代。適宜四官能基芳香族環氧樹脂包括以Araldite® MY 9663、MY 9634、MY 9655、MY-721、MY-720、MY-725由Huntsman Advanced Materials供應之四縮水甘油基-4,4'-二胺基二苯基甲烷。三官能基環氧樹脂之實例包括胺基苯酚之三縮水甘油醚，例如由Huntsman Advanced Materials供應之Araldite® MY 0510、MY 0500、MY 0600、MY 0610。
在一較佳實施例中，基於表面膜組合物之總重量，環氧酚醛樹脂與多官能基環氧樹脂(三官能基及/或四官能基)之組合佔至少30重量%。在某些實施例中，基於表面膜組合物之總重量，環氧酚醛樹脂與多官能基環氧樹脂之組合佔約30重量%至約60重量%，且在其他實施例中約40重量%至約50重量%。環氧酚醛樹脂與多官能基環氧樹脂之相對量可變，但環氧酚醛樹脂之量較佳在80-100份/100份多官 能基環氧樹脂範圍內。環氧酚醛樹脂與多官能基環氧樹脂以指定比例之組合在固化後促進高Tg及經調整交聯密度。
聚合物韌化組份
為韌化基於上文論述之多官能基樹脂之混合物的樹脂基質，向表面膜組合物中添加一或多種聚合物韌化劑。聚合物韌化劑選自由以下組成之群：(i)藉由環氧樹脂、雙酚與彈性體聚合物之反應形成之預反應加合物；(ii)聚醚碸(PES)與聚醚醚碸(PEES)之共聚物；及(iii)核-殼橡膠粒子；及其組合。在一較佳實施例中，使用來自此群之兩種韌化劑之組合。基於表面膜組合物之總重量，韌化劑之量總共係約10重量%至約20重量%。
關於預反應加合物，適宜環氧樹脂包括雙酚A之二縮水甘油醚、四溴雙酚A之二縮水甘油醚、雙酚A之氫化二縮水甘油醚或雙酚F之氫化二縮水甘油醚。環脂族環氧樹脂(其包括每分子含有至少一個環脂族基團及至少兩個環氧乙烷環之化合物)亦適宜。具體實例包括由以下結構代表之環脂族醇、氫化雙酚A(EpalloyTM 5000、5001，由CVC Thermoset Specialties供應)之二環氧化物：
該環脂族環氧樹脂之實例係自CVC Thermoset Specialties購得之EPALLOY® 5000(藉由氫化雙酚A二縮水甘油醚製備之環脂族環氧樹脂)。適用於預反應加合物中 之其他環脂族環氧化物可包括EPONEX環脂族環氧樹脂，例如由Momentive Specialty Chemicals供應之EPONEX Resin 1510。
預反應加合物中之雙酚起直鏈或環脂族環氧樹脂之鏈延長劑的作用。適宜雙酚包括雙酚A、四溴雙酚A(TBBA)、雙酚Z及四甲基雙酚A(TMBP-A)。
適於形成預反應加合物之彈性體包括(但不限於)橡膠，例如胺封端之丁二烯丙烯腈(ATBN)、羧基封端之丁二烯丙烯腈(CTBN)、羧基封端之丁二烯(CTB)、碳氟化合物彈性體、聚矽氧彈性體、苯乙烯-丁二烯聚合物。在一實施例中，預反應加合物中所用之彈性體係ATNB或CTBN。
在一個實施例中，使環氧樹脂與雙酚鏈延長劑及彈性體聚合物在觸媒(例如三苯基膦(TPP))存在下在約300℉(或148.9℃)下預反應以鏈連接環氧樹脂並形成高黏度、膜形成高分子量環氧樹脂預反應加合物。隨後使預反應加合物與表面膜組合物之剩餘組份混合。
聚合物韌化組份之第二選擇係熱塑性韌化材料，其係平均分子量為8,000-14,000之聚醚碸(PES)與聚醚醚碸(PEES)之共聚物。在一實施例中，堅韌劑係聚(氧基-1,4-伸苯基磺醯基-1,4-伸苯基)，其具有約200℃之Tg。
聚合物韌化組份之第三選擇係粒度為300 nm或更小之核-殼橡膠粒子。核-殼橡膠(CSR)粒子可為軟核由硬殼包圍之任何核-殼粒子。較佳CSR粒子係彼等具有聚丁二烯橡膠核或丁二烯-丙烯腈橡膠核及聚丙烯酸酯殼者。然而， 亦可使用具有由軟殼包圍之硬核之CSR粒子。CSR粒子可以分散於液體環氧樹脂中之CSR粒子的25-40重量%供應。具有橡膠核及聚丙烯酸酯殼之CSR粒子係自Kaneka Texas公司(Houston,Tex.)以商品名Kane Ace MX購得。較佳但不必須地，將核-殼橡膠粒子以存於適宜液體環氧樹脂中之粒子之懸浮液形式添加至表面膜組合物中。Kane Ace MX 411係25重量%核-殼橡膠粒子存於MY 721環氧樹脂中之懸浮液且係核-殼橡膠粒子之適宜來源。Kane Ace MX 120、MX 125或MX 156(其含有25-37重量%分散於DER 331樹脂中之相同核-殼橡膠粒子)亦係核-殼橡膠粒子之適宜來源。亦可使用核-殼橡膠粒子之其他適宜來源，例如MX 257、MX 215及MX 451。核-殼橡膠粒子之另一市售來源係來自Dow Chemical公司之ParaloidTM EXL-2691(平均粒度為約200 nm之甲基丙烯酸酯-丁二烯-苯乙烯CSR粒子)。
陶瓷微球體
將陶瓷微球體添加至表面膜組合物中以改良膜之表面光滑度。在一個實施例中，使用由惰性二氧化矽-氧化鋁陶瓷材料製得之中空陶瓷微球體。陶瓷微球體之抗壓強度可為60,000 psi以上，介電常數為約3.7-4.6，軟化點在1000℃至1100℃(或1832℉至2012℉)範圍內，且粒子直徑在0.1微米至50微米或1-50微米範圍內。陶瓷微球體之高軟化點使得其不能夠吸收溶劑、不可燃且對化學品具有高度抗性。已發現直徑在約0.1微米至約20微米、且較佳約1微米至約15微米範圍內之微球體尤其適宜。尤其適用於本發 明表面膜組合物中之市售陶瓷微球體之實例係由Zeelan Industries公司以商品名Zeeospheres®(例如G-200、G210及W-200)銷售。該等微球體係具有厚壁、無味且顏色為淺灰色之中空二氧化矽-氧化鋁球體。在一較佳實施例中，多官能基樹脂與陶瓷微球體之組合佔表面膜組合物之50重量%以上、較佳60重量%以上。在某些實施例中，基於表面膜組合物之總重量，陶瓷微球體之量係至少20重量%、較佳至少25%或至少30重量%。在一些實施例中，陶瓷微球體之量可在20重量%至40重量%、或25重量%至35重量%範圍內。
固化劑
可由多種在高溫(例如高於150℉(65℃)之溫度)下活化之潛在的基於胺之固化劑來固化多官能基環氧化物樹脂。適宜固化劑之實例包括二氰二胺(DICY)、鳥糞胺、胍、胺基胍及其衍生物。亦可使用咪唑及胺複合物類別之化合物。在一實施例中，固化劑係二氰二胺。基於胺之固化劑係以基於表面膜組合物之總重量1重量%至5重量%範圍內之量存在。
固化加速劑可與基於胺之固化劑結合使用，以促進環氧樹脂與基於胺之固化劑之間之固化反應。適宜的固化加速劑可包括烷基及芳基取代之脲(包括芳香族或脂環族二甲基脲)；基於甲苯二胺或亞甲基二苯胺之雙脲。雙脲之一個實例係4,4'-亞甲基雙(苯基二甲基脲)(以Omicure U-52或CA 152自CVC Chemicals購得)，其係二氰二胺之適宜加速 劑。另一實例係2,4-甲苯雙(二甲基脲)(以Omicure U-24或CA 150自CVC Chemicals購得)。固化加速劑可以0.5重量%至3重量%範圍內之量存在。
流動控制劑
將呈顆粒形式(例如粉末)之無機填料作為流變性改良組份添加至表面膜組合物中以控制樹脂組合物之流動並防止於其中聚集。可用於表面膜組合物中之適宜無機填料包括滑石粉、雲母、碳酸鈣、氧化鋁及發煙二氧化矽。在一個實施例中，使用疏水性發煙二氧化矽(例如Cab-O-Sil TS-720)作為無機填料。基於表面膜組合物之總重量，無機填料之量可在1重量%至5重量%範圍內。
可選添加劑
表面膜組合物可進一步包括一或多種可選添加劑，該等添加劑影響固化或未固化表面膜之機械、電、光學、阻燃性及/或熱性質中之一或多者。添加劑可包含以化學方式與上面形成表面膜之複合基板之環氧樹脂反應或可不與其反應的材料。該等添加包括(但不限於)紫外(UV)穩定劑、顏料/染料及導電材料。在使用該等添加劑時，基於表面膜組合物之總重量，其總量小於5重量%。
可添加至表面組合物中之UV穩定劑之實例包括丁基化羥基甲苯(BHT)、2-羥基-4-甲氧基-二苯甲酮(UV-9)、2,4-雙(2,4-二甲基苯基)-6-(2-羥基-4-辛基氧基苯基)-1,3,5-三嗪(CYASORB® UV-1164光吸收劑)、3,5-二-第三丁基-4-羥基苯甲酸、正十六烷基酯(CYASORB® UV-2908光穩定 劑)、異戊四醇丙酸四(3-(3,5-二-第三丁基-4-羥基苯基)酯(IRGANOX 1010)。來自Ciba Specialty Chemicals之液體位阻胺光穩定劑，例如2-(2H-苯并***-2-基)-4,6-二第三戊基苯酚(TINUVIN 328)、1,2,2,6,6-五甲基-4-六氫吡啶基癸二酸甲酯(TINUVIN 292)。亦可使用癸二酸、雙(2,2,6,6-四甲基-1-(辛基氧基)-4-六氫吡啶基酯(TINUVIN 123)作為適宜UV穩定劑。另外，亦可使用奈米級氧化鋅(n-ZnO)(例如NanoSunGuard 3015)及氧化鈦奈米粒子(n-TiO2)作為UV穩定劑。
可將業內已知用於為樹脂系統增加顏色之顏料及/或染料添加至表面膜組合物中。顏料及/或染料之實例包括(但不限於)紅氧化鐵、綠鉻、碳黑及氧化鈦。在一實施例中，顏料係氧化鈦(白色)顏料。在另一實施例中，顏料係碳黑。
亦可將呈顆粒形式之導電材料(例如粒子或薄片)添加至表面膜組合物中以賦予最終表面膜導電性。適宜導電材料之實例包括呈薄片或粒子形式之金屬，例如銀、銅、鎳、銅、鋁及其合金。亦可使用基於碳之奈米級材料(例如碳奈米管(單壁奈米管或多壁奈米管)、碳奈米纖維、石墨烯、巴克紙(bucky-paper))作為導電成份以賦予樹脂膜導電性。奈米纖維可具有70奈米至200奈米範圍內之直徑及約50微米至200微米之長度。奈米管之外徑為約10奈米，長度為約10,000奈米，且縱橫比(L/D)為約1000。
表1顯示本發明之表面膜組合物之各個實施例。所有百 分比(%)均係重量百分比。
在一個實施例中，表面膜組合物具有以下調配物：以基於組合物之總重量之重量百分比表示，20%-25%環氧苯酚酚醛樹脂；20%-25%四官能基環氧樹脂；10%-15%預反應加合物、1%-3% PES-PEES共聚物、25%-35%陶瓷微球體；1%-5%潛在的基於胺之固化劑；0.5%-3%固化加速劑；1%-3%無機填料；及視情況0.1-1%彩色顏料。
表面膜及複合結構之形成
可將表面膜組合物之組份添加至配備用於混合、加熱及 /或冷卻組份之混合容器中。此外，若需要，亦可將一或多種有機溶劑添加至混合物中，以有利於組份之混合。該等溶劑之實例包括(但不限於)甲基醚酮(MEK)、丙酮、二甲基乙醯胺及N-甲基吡咯啶酮。隨後使用習用膜形成方法自表面膜組合物形成表面膜。端視預定用途而定，如此形成之表面膜可具有介於約0.01至0.45 psf(磅/平方英尺)之間之膜重量。
為有利於表面膜之操作，將表面膜組合物施加至載體上。載體之非限制實例可包括由熱塑性聚合物纖維或碳纖維製得之纖維片、金屬屏幕或箔、非織造墊、無規墊、針織載體、金屬塗佈之碳面罩及諸如此類。金屬屏幕或箔之實例可包括膨脹金屬屏幕或箔及金屬塗佈之面罩。該等屏幕及箔可包含銅、鋁、銀、鎳及其合金。非織造墊、織造或針織背襯之實例可包括碳墊、聚合物墊、及金屬塗佈之碳、玻璃或或聚合物玻璃面罩。非織造墊、織造或針織背襯可塗佈有銅、鋁、銀、鎳及其合金。
如此形成之表面膜亦可以未固化狀態儲存直至其準備使用為止。舉例而言，表面膜可以冷儲存形式儲存以抑制表面膜固化並延長其有用存架壽命。可將可移除背襯紙施加於表面膜之一或多個表面以抑制表面膜在其預定使用之前附接至不期望表面。
表面膜經設計以與纖維強化樹脂基質複合基板於高於150℉(65℃)、更具體而言250℉至350℉(或120℃至175℃)範圍內之溫度下共固化。纖維強化樹脂基質複合基板包括 經基質樹脂浸漬或輸注之強化纖維。基質樹脂可包括一或多種可熱固化之樹脂，例如環氧樹脂。複合基板可為預浸材片層或預浸材疊層。預浸材片層包括呈織物形式之強化纖維或經樹脂(例如環氧樹脂)浸漬之在方向上對準之連續纖維。在方向上對準之纖維可為單向或多向纖維。預浸材疊層包括複數個以堆疊順序佈置之預浸材片層。一般而言，可將未固化表面膜施加至呈未固化或部分固化狀態之纖維強化樹脂基質複合基板上，之後共固化以形成鍵結有熱固性表面膜之完全固化複合基板。
在一個實施例中，在層疊過程中納入表面膜以形成複合結構。如圖1中所示，首先使表面膜10與模製工具20之模製表面接觸，且將預浸材片層依序一個在另一個頂部上層疊於表面膜10上以形成預浸材疊層30。或者，可將預浸材片層組裝於不同位置處且隨後放置於表面膜10上。可將一或多個核(例如發泡體或蜂窩狀結構)插在預浸材疊層之片層之間，如業內已知。隨後使整個總成經受熱及壓力以將預浸材疊層及表面膜固化成具有選擇形狀之最終複合結構。在自模製工具移出複合結構時，表面膜成為複合結構之最外層。
在一個實施例中，可將表面膜施加(藉由塗佈或層壓)至單一預浸材片層以產生自身表面化預浸材膠帶。該自身表面化預浸材膠帶適用於配備有構件之自動膠帶分層(Automated Tape Laying，ATL)或自動纖維佈置(AFP)系統中，該構件用於將預浸材狹縫膠帶直接分配並壓縮至模製 表面(例如芯軸表面)上以形成複合部分。
在固化後，所得固化表面膜係具有高交聯密度、180℃之高玻璃化轉變溫度(Tg)、根據ASTM D-3363為7H或更高之鉛筆硬度的熱固性膜。該等性質使得固化表面膜能夠對習用油漆剝離劑(例如基於苯甲醇之油漆剝離溶液)，以及UV輻射及微裂開具有高抗性。已發現，在環境溫度(20℃至25℃)下與基於苯甲醇之油漆剝離溶液接觸7天後，表面膜呈現小於0.5%之流體吸收，且鉛筆硬度降低不超過2H鉛筆等級。此外，已發現固化表面膜在經受2000×介於-55℃與71℃之間之熱循環測試後呈現小於0.3個裂縫/in2之微裂縫密度。表面膜進一步對常用於塗漆航天結構之油漆塗層呈現高附著力。表面膜對油漆塗層之附著力應使得經塗漆表面在乾燥條件或潤濕條件(於75℉下在去離子水中浸沒7天)下根據ASTM D3359經受油漆附著測試、經受或不經受1000 KJ/m2 UVA輻射暴露後呈現實質上0%之油漆損失。
實例
以下實例用於給出根據本發明形成之表面膜之具體實施例，但並不意欲以任何方式限制本發明之範疇。
基於表2中所示調配物(1-9)製備9個表面膜試樣。所有量均係以重量百分比表示。
藉由將表2中揭示之組份添加至混合容器中並使用高速剪切實驗室混合器混合該等組份來製備每一表面膜。首先添加環氧樹脂。若需要，將作為溶劑之MEK添加至環氧樹脂混合物中，以調節組合物之流變性及固體含量。隨後，將韌化劑(預反應加合物及/或PES-PEES共聚物)添加至環氧樹脂中。在某些表面膜(調配物4及5)中，亦將導電添加劑(銀薄片或Ag-Cu薄片)添加至混合容器中。進一步將陶 瓷微球體、發煙二氧化矽及UV穩定劑(在一些調配物中)添加至混合容器中。若需要，添加MEK溶劑以將上述混合物之黏度控制為約80 wt.%固體且以約1000-3000 rpm將組合物之組份混合約50至70分鐘。將組合物之溫度保持低於約160℉。若需要，添加額外MEK以抑制混合物隨混合軸攀升。
隨後將混合物冷卻至低於約120℉並將固化劑(二氰二胺(Dicy)及雙脲)添加至組合物中。隨後混合組合物直至近似均質為止。將固化劑添加期間之混合物溫度維持低於約130℉。
為自上述組合物形成表面膜，使每一組合物經應變、脫氣且沈積為膜。經由過濾介質EP-15實施應變。實施脫氣以使組合物之固體含量係約80 wt.%。隨後藉由膜塗佈器將經應變及脫氣之組合物塗佈為具有約0.020-0.030 psf之膜重量之膜，且隨後乾燥以使揮發物小於約1重量%。在輕壓力下將所選非織造聚酯或玻璃無規墊載體或導電載體壓製至膜中，以將墊包埋至膜中。
藉由納入自表2之調配物形成之表面膜來製作複合面板。對於每一面板，將表面膜放置於工具上，隨後層疊預浸材片層(來自Cytec Industries公司之CYCOM 5276-1，碳纖維/基於環氧之預浸材)以形成預浸材疊層。隨後於約350℉之溫度下在80 psi及高壓釜條件下固化預浸材疊層2小時。
表面膜評價
藉由在氮下以10℃/min之斜度在30℃至230℃溫度範圍內使用經調節DSC(TA 2910)或熱機械分析儀(TMA 2940,TA Instruments)測定固化表面膜之玻璃化轉變溫度(Tg)。
在固化後，檢查經表面膜表面化之複合面板的表面外觀缺陷(凹陷、銷孔)。隨後評價複合面板之油漆剝離劑抗性、具有或無UV暴露下乾燥及濕油漆附著及微裂縫抗性。
油漆剝離劑抗性測試
藉由量測在用於航天複合結構油漆剝離過程中之基於苯甲醇之油漆剝離劑溶液(自McGean購得之Cee Bee 2012A或自Henkel購得之Turco 1270-6)的浸沒時段(於環境室溫下高達168小時)內油漆剝離劑流體攝取及表面鉛筆硬度變化來量測未經塗漆之表面化複合面板(2"×2"樣品大小，厚度為0.15 mm)之油漆剝離劑抗性。在油漆剝離劑浸泡之前及之後以24小時、48小時及高達168小時(7天)之間隔量測每一測試面板之重量。以高達168小時(7天)浸沒之相同測試間隔量測測試面板之油漆剝離劑流體攝取(在浸沒時間內之重量變化，以wt.%表示)。
於環境室溫下將每一未經塗漆測試面板之表面浸沒於基於苯甲醇之油漆剝離劑溶液中高達168小時，且隨後根據ASTM D3363測試浸沒時段期間之鉛筆硬度變化。ASTM D3363係指用於測定基板上之透明且有顏色之塗佈膜之表面硬度的標準測試方法。鉛筆硬度標度係如下：6B(最軟)、5B、4B、3B、2B、B、HB、F、H、2H、3H、4H、 5H、6H、7H、8H、9H(最硬)。在油漆剝離劑中浸泡之前及之後以24小時、48小時及高達168小時(7天)之間隔量測測試面板之鉛筆硬度。在24小時浸沒後變化超過2H量之鉛筆硬度視為不具有良好油漆剝離劑抗性。
具有或無UV暴露之乾燥及濕油漆附著
根據ASTM D3359量測在具有或無UV暴露下在塗漆之前經表面膜表面化之經塗漆複合面板(呈以下形式：3"×6"樣品大小，厚度為0.15 mm)的乾燥及濕劃線油漆附著。ASTM D3359係指藉由在膜中製得之切口上施加並移除壓敏性膠帶評定塗佈膜與基板之表面附著之標準測試方法(交叉陰影劃線膠帶測試)。根據AATCC測試方法16之選項3將固化測試面板暴露於零(無UV)、200 kJ/m2或1000 kJ/m2紫外(UV-A)輻射。用於UV測試之儀器係Xeno o型耐候計(例如Atlas CI3000 FadeoMeter)。準備每一測試面板表面(利用及不利用磨砂清潔)並施加有航天塗漆中所用之外部裝飾性油漆塗層(環氧油漆引物、之後基於聚胺基甲酸酯之頂部塗層)。隨後，根據ASTM D3359實施乾燥油漆附著測試。對於實施濕油漆附著，對UV暴露之測試面板進行塗漆且隨後於75℉下於去離子水中浸沒7天。隨後根據ASTM D3359實施濕油漆附著測試。
含有導電添加劑之表面膜之導電量測
切割具有固化表面膜之測試面板以形成約6×5英吋之測試試件且使用四點探針AVO® Ducter® DLRO10X數位低電阻率歐姆計(Digital Low Resistivity Ohmmeter)量測其導電 率或表面電阻率(以Ohm/平方或百萬歐姆/平方表示)。
表3顯示具有基於表2之調配物1-9之表面膜的測試面板之表面性質及測試結果。測試面板編號對應於表面膜調配物編號。
基於調配物8及9之表面膜不含三官能基或四官能基環氧 樹脂，因此，在浸沒時段內其對油漆剝離劑之抗性並不與針對其他表面膜所觀察到者一樣好。然而，所有表面膜均呈現良好油漆附著(10+意指0%之油漆損失)。
微裂縫抗性測試
亦量測經塗漆及表面化複合測試面板(呈以下形式：4"×6"樣品大小，厚度為0.15 mm)之微裂縫抗性。使經塗漆測試面板經受介於-55℃與71℃之間之高達2000×循環之熱循環。在顯微鏡下檢驗熱循環後在暴露於400×、800×、1200×、1600×及2000×熱循環後每一測試面板之表面的微裂縫出現。使用裂縫密度(測試面板大小區域中所示表面油漆裂縫之數目)量測表面化複合測試面板之微裂縫抗性。裂縫之最大長度可小於0.1英吋。2000×熱循環後之微裂縫測試結果示於表4中。
基於調配物6及7之表面膜不含存於其他調配物中之韌化劑。因此，測試面板6及7之微裂縫抗性並不與其他測試面板之微裂縫抗性一樣好。
術語「第一」、「第二」及諸如此類在本文中並不表示任何次序、量或重要性，而是用於將元素彼此區分，且術語「一」(「a」及「an」)在本文中並不表示限制量，而是表示存在所提及項目中之至少一者。與量連用之修飾詞 「約」(「approximately」及「about」)涵蓋所述值且具有由上下文指定之含義(例如，包括與特定量量測相關之誤差度)。如本文所用後綴「(s)」意欲包括單數及複數個其修飾之項，藉此包括該項中之一或多種(例如，金屬包括一或多種金屬)。本文中揭示之範圍具涵蓋性且可獨立組合(例如，「高達約25 wt%、或更特定而言約5 wt%至約20 wt%」之範圍包括該範圍之終點及所有中間值，例如「1 wt%至10 wt%」包括1%、2%、3%等)。
儘管本文闡述各種實施例，但自說明書應瞭解，可由彼等熟習此項技術者作出要素之各種組合、其中之改變或改良，且此在本發明範疇內。另外，為適應特定情況或材料亦可對本發明之教示實施多項改良，此並不背離本發明之基本範疇。因此，本文並非意欲將本發明限制於所揭示之作為實施本發明最佳設想模式之特定實施例，而係意欲使本發明包括所有屬於隨附申請專利範圍範疇內之實施例。
10‧‧‧表面膜
20‧‧‧模製工具
30‧‧‧預浸材疊層
圖1示意性顯示根據本發明實施例具有在模製工具上形成之表面膜的複合結構。
10‧‧‧表面膜
20‧‧‧模製工具
30‧‧‧預浸材疊層

Claims (16)

  1. 一種表面膜，其對油漆剝離劑具有高抗性，該表面膜具有180℃之玻璃化轉變溫度(Tg)及根據ASTM D-3363為7H或更高之鉛筆硬度，其中在20℃至25℃範圍內之溫度下與基於苯甲醇之油漆剝離溶液接觸7天後，該表面膜呈現小於0.5%之流體吸收，且該鉛筆硬度降低不超過2H鉛筆等級，且其中該表面膜係自包含以下組分之可固化樹脂組合物形成：具有超過1之環氧官能度之環氧酚醛樹脂；三官能基或四官能基環氧樹脂；陶瓷微球體；潛在的基於胺之固化劑；顆粒無機填料；及至少一種選自由以下組成之群之韌化劑：(a)藉由環氧樹脂、雙酚及彈性體之反應形成之預反應加合物；(b)聚醚碸(PES)及聚醚醚碸(PEES)之共聚物；(c)核-殼橡膠(CSR)粒子；及其組合。
  2. 如請求項1之表面膜，其在經受2000×介於-55℃與71℃之間之熱循環測試後呈現小於0.3個裂縫/英吋2之微裂縫密度。
  3. 如請求項1之表面膜，其中該環氧酚醛樹脂具有以下結構： 其中R=H且n=0至5，該四官能基環氧樹脂係四縮水甘油基4,4'-二胺基二苯基甲烷，且該三官能基環氧樹脂係胺基苯酚之三縮水甘油醚。
  4. 如請求項1之表面膜，其中該至少一種韌化劑包括藉由四溴雙酚A之二縮水甘油醚、雙酚A及ATBN或CTBN彈性體之反應形成的預反應加合物。
  5. 如請求項1之表面膜，其中該至少一種韌化劑包括該預反應加合物及PES-PEES共聚物。
  6. 如請求項3之表面膜，其中該等陶瓷微球體係由二氧化矽-氧化鋁陶瓷材料製得且具有1微米至50微米範圍內之粒度的中空微球體。
  7. 如請求項1之表面膜，其中該等環氧樹脂及該等陶瓷微球體佔該表面膜組合物之總重量之60重量%以上。
  8. 如請求項1之表面膜，其進一步包含足量的呈顆粒形式之導電材料以提供表面電阻率小於100 mΩ之導電表面膜，其中該表面膜能夠提供雷擊保護(LSP)或電磁干擾(EMI)屏蔽。
  9. 如請求項1之表面膜，其係由選自聚酯墊、玻璃墊或導電載體之非織造載體支撐。
  10. 如請求項1之表面膜，其中該可固化樹脂組合物進一步包含雙脲作為固化加速劑。
  11. 一種複合結構，其包含上面形成有表面膜之複合基板，其中該複合結構包含基質樹脂及強化纖維，且該表面膜具有180℃之玻璃化轉變溫度(Tg)及根據ASTM D-3363為7H或更高之鉛筆硬度，其中在20℃至25℃範圍內之溫度下與基於苯甲醇之油漆剝離溶液接觸7天後，該表面膜呈現小於0.50%之流體吸收，且該鉛筆硬度降低不超過2H鉛筆等級，且其中該表面膜係自包含以下組分之可固化樹脂組合物形成：具有超過1之環氧官能度之環氧酚醛樹脂；三官能基或四官能基環氧樹脂；陶瓷微球體；基於胺之固化劑；顆粒無機填料；及至少一種選自由以下組成之群之韌化劑：(a)藉由環氧樹脂、雙酚及彈性體之反應形成之預反應加合物；(b)聚醚碸(PES)及聚醚醚碸(PEES)之共聚物；(c)核-殼橡膠(CSR)粒子；及其組合。
  12. 如請求項11之複合結構，其中該複合基板包含預浸材疊層，該預浸材疊層包括複數個逐層疊加佈置之預浸材層，每一層包含經基質樹脂浸漬之強化纖維，且該表面膜係在該預浸材疊層之外表面上形成。
  13. 如請求項11之複合結構，其進一步包含施加於該表面膜上之油漆塗層，其中該表面膜對該油漆塗層之附著力係 使得經塗漆表面在以下處理後呈現實質上0%之油漆損失：(a)在乾燥條件下根據ASTM D3359經受油漆附著測試或(b)於75℉下於去離子水中浸泡7天，隨後根據ASTM D3359經受油漆附著測試。
  14. 如請求項11之複合結構，其中該表面膜對該油漆塗層之附著力係使得該經塗漆表面呈現如藉由以下程序測定之實質上0%之油漆損失：使未經塗漆之表面膜經受1000 KJ/m2 UVA輻射暴露，隨後使該經塗漆表面在乾燥條件下根據ASTM D3359經受油漆附著測試。
  15. 如請求項13之複合結構，其中該表面膜對該油漆塗層之附著力係使得該經塗漆表面呈現如藉由以下程序測定之實質上0%之油漆損失：使該未經塗漆之表面膜經受1000 KJ/m2 UVA輻射暴露，隨後使該經塗漆表面經受於75℉(23.9℃)去離子水中浸泡7天且隨後根據ASTM D3359進行油漆附著測試。
  16. 一種用於製造複合結構之方法，其包含：(a)提供包括複數個以堆疊配置佈置之預浸材層的可塑形預浸材疊層，每一預浸材層包含未經固化或部分固化之樹脂基質樹脂及強化纖維；(b)自包含以下組分之可固化樹脂組合物形成表面膜：具有超過1之環氧官能度之環氧酚醛樹脂；三官能基或四官能基環氧樹脂；陶瓷微球體；潛在的基於胺之固化劑； 顆粒無機填料；及至少一種選自由以下組成之群之韌化劑：(a)藉由環氧樹脂、雙酚及彈性體之反應形成之預反應加合物；(b)聚醚碸(PES)及聚醚醚碸(PEES)之共聚物；(c)核-殼橡膠(CSR)粒子；及其組合；(c)使該表面膜與該預浸材疊層接觸；及(d)於250℉至350℉(120℃至175℃)範圍內之溫度下共固化該表面膜及該預浸材疊層，藉此該固化表面膜具有180℃之玻璃化轉變溫度(Tg)及根據ASTM D-3363為7H或更高之鉛筆硬度，且其中在20℃至25℃範圍內之溫度下與基於苯甲醇之油漆剝離溶液接觸7天後，該固化表面膜呈現小於0.5%之流體吸收，且該鉛筆硬度降低不超過2H鉛筆等級。
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