TW201429704A - 用於複合物結構之傳導性表面材料 - Google Patents
用於複合物結構之傳導性表面材料 Download PDFInfo
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- TW201429704A TW201429704A TW102144263A TW102144263A TW201429704A TW 201429704 A TW201429704 A TW 201429704A TW 102144263 A TW102144263 A TW 102144263A TW 102144263 A TW102144263 A TW 102144263A TW 201429704 A TW201429704 A TW 201429704A
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- resin
- surface material
- electrically conductive
- conductive surface
- resin film
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Abstract
本發明揭示一種可為雷擊保護(LSP)及/或電磁干擾(EMI)屏蔽提供充份傳導性之電傳導性表面材料。該傳導性表面材料係多層結構,其具有極薄傳導性層(例如固體金屬箔)及形成於該傳導性層之至少一表面上之樹脂膜。該樹脂膜係由可固化樹脂組合物形成,該組合物含有環氧酚醛清漆樹脂、三官能團或四官能團環氧樹脂、陶瓷微球、基於胺的潛性固化劑、粒狀無機填料及韌化組分。視情況地,該樹脂膜另外包括可提升該表面材料之導電性之傳導性添加劑。該樹脂膜呈現高Tg及對脫漆劑溶液之高耐性。此外,該傳導性表面材料適合與纖維增強樹脂複合物基板進行共固化。
Description
纖維增強聚合物基質複合物(PMC)係常用於需要抵抗侵蝕環境、高強度及/或低重量的應用中之高性能結構材料。此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、船殼及自行車骨架。
用於航太應用之複合物結構部件通常包括表面膜,以在上漆前為複合物結構提供所需的性能特性。該等表面膜係用以提升結構部件之表面品質,同時減少勞力、時間及成本。該等表面膜通常係在製造結構部件的過程中與纖維增強聚合物基質複合物材料進行共固化。習知基於環氧的複合物預浸體及表面膜因其絕緣性質而對電磁能(EME)事件(諸如雷擊(LS)、靜電放電(ESD)及電磁干擾(EMI))呈現較差抵抗性。環氧樹脂所展現的相對高電阻率(低導電率)會抑制雷擊能量之適當消散,從而導致蒙皮刺穿及底層複合物結構剝離。另外,複合物表面上所生成的電荷可殘留很長時間,從而提升低相對濕度環境中之ESD風險(其會損傷電子系統)及燃油箱蒸汽空間點火之風險。此外,基於環氧的表面膜之不良導電率會抑制電荷載體遷移,其可削弱複合物結構提供EMI屏蔽之能力。為了儘可能減小雷擊對複合物結構之損傷,需提升複合物結構之導電率,為飛機上的複合物部件提供LS/ESD/EMI保護。然而,不希望併入會顯著增加飛機總重量之傳導
性材料。此外,習知表面膜對用於脫漆目的之商業脫漆溶液(諸如基於苯甲醇的溶液)之耐性非常不足。彼等脫漆劑可導致表面膜隆起及/或起泡,從而使得重漆過程更為麻煩。正因如此,需要一種重量輕,可耐受使用習知脫漆溶液反覆脫漆,且亦可耐受曝露至紫外(UV)輻射之多功能傳導性表面材料。
本發明提供一種電傳導性表面材料,其係多層結構,該多層結構係由厚度等於或小於3密耳(76.2μm)之極薄傳導性層及形成於該傳導性層之至少一表面上之樹脂膜組成。該樹脂膜係由基於環氧的可固化組合物形成,藉以在固化時,該固化樹脂層具有180℃之玻璃轉化溫度(Tg),及根據ASTM D-3363測量之大於7H之表面鉛筆硬度。
該傳導性表面材料可與纖維增強聚合複合物基板在於250℉-355℉(120℃-180℃)範圍內之溫度下共固化形成複合物結構。此外,該傳導性表面材料可用以形成適用於自動化鋪帶(ATL)或自動化鋪絲(AFP)之狹窄線帶。
11‧‧‧第一樹脂膜
12‧‧‧釋離紙襯底
13‧‧‧金屬箔
14‧‧‧第二樹脂膜
20‧‧‧三層結構
30‧‧‧複合物基板
由以下本發明各態樣之詳細描述連同描繪本發明各實施例之附圖將更輕易理解本發明之特徵。
圖1示意性顯示根據一項實施例之三層傳導性表面材料之組裝。
圖2示意性顯示根據一項實施例之複合物結構,其上具有三層傳導性表面材料。
本文揭示一種重量輕,可提供LS/ESD/EMI保護,可耐受使用習知脫漆溶液反覆脫漆,且亦可耐受曝露至紫外(UV)輻射之多功能電傳導性表面材料。與用於LS/ESD/EMI保護之習知傳導性層壓板相比,本文所揭示的傳導性表面材料可顯著節省重量(比一些習知傳導性層
壓板之重量降低50%-80%)。
該傳導性表面材料係一種多層結構,其包括極薄傳導性層及形成於該傳導性層之兩個相對表面之至少一者上之可固化樹脂膜。該傳導性層可為固體金屬箔或層或者碳層。在本說明書內,碳包括石墨。該傳導性層較佳具有小於10mΩ,較佳小於5mΩ之電阻率。此外,該傳導性層較佳具有3密耳(76.2μm),較佳為3μm-38μm之厚度。該樹脂膜每一面具有小於0.1psf(或500gsm)之膜重量,例如,0.01-0.03psf(或50-150gsm)。在一項實施例中,該傳導性表面材料係一種三層結構,其包括夾於兩樹脂膜間之傳導性層。該等兩樹脂膜可能具有相同樹脂組成份或不同樹脂組成份。在該三層結構之一項實施例中,該傳導性層係厚度為3μm-5μm之微米薄金屬箔,且該形成於該金屬箔每一面上之樹脂膜具有0.01-0.03psf(或50-150gsm)之膜重量。舉例而言,金屬層/箔可由金屬(諸如銅、鋁、青銅或其合金)形成。
該傳導性表面材料可藉由使用習知塗覆技術將可固化液體樹脂組合物塗覆於傳導性層(例如固體金屬箔)之一個或兩個表面上而製得。
或者,該傳導性表面材料可藉由將預製樹脂膜層壓至傳導性層之一面上,形成雙層結構或將兩面預製樹脂膜層壓至該傳導性層之相對表面上以形成三層結構而製得。
圖1示意性圖示說明如何根據一項實例製造三層傳導性表面材料。將藉由可剝離之釋離紙襯底12承載之第一樹脂膜11層壓至金屬箔13之一表面上,並將第二樹脂膜14層壓至金屬箔13之相對表面,以形成三層結構20。該層壓製程可藉助施加壓力及熱來進行。釋離紙襯底12可在層壓後剝離。為了形成雙層結構,可省略第二樹脂膜14,且金屬箔係藉由其本身的可剝離載體承載。
本文所揭示的傳導性表面材料係設計為與纖維增強聚合複合物基板在高於150℉(65℃)(更特定言之,介於250℉-350℉(或120℃-175℃)之範圍內)之溫度下進行共固化。該纖維增強聚合複合物基板係由經過可固化基質樹脂浸漬或灌注的增強纖維組成。在一些實施例中,該複合物基板可為預浸體層片或預浸體疊層。該預浸體疊層係由複數個以堆疊順序配置之預浸體層片組成。各預浸體層片係由經過基質樹脂(例如環氧樹脂)浸漬/灌注之呈織物或定向排列的連續纖維形式之增強纖維組成。該等定向排列的纖維可為單向或多向纖維。一般而言,可將可固化傳導性表面材料施加至處於未固化或部份固化狀態之纖維增強聚合複合物基板,隨後共同固化,以形成完全固化的複合物結構,其上黏合有硬化表面膜作為最外層。
參考圖2,為形成複合物結構,使三層結構20與複合物基板30接觸,使得樹脂膜14與複合物基板30直接接觸。在一項實施例中,複合物基板30為預浸體疊層。在該實施例中,紙襯底12被剝離,並使樹脂膜11與工具表面接觸,及然後將複數個預浸體層片以堆疊配置疊合於樹脂膜14上。該工具表面可為平面或非平面(例如曲線表面或一些其他三維組態)。隨後可將該等預浸體層片逐一往上疊合於該工具上。或者,該等預浸體層片可在不同位置組裝,隨後再置於樹脂膜14上。可將一或多種核心結構(例如:發泡體或蜂巢結構)插入預浸體疊層的層片之間,其係如此項技術中已知。在完全真空下減少整個組件之積層厚度後,即可對該整個組件進行加熱或加壓,讓該預浸體疊層及該表面材料之該等樹脂膜固化成最終具有選定形狀之硬化複合物結構。當將該複合物結構移出模塑工具後,原來與該工具表面接觸之樹脂膜11成為該複合物結構之最外層。
可藉由省略第二樹脂膜14修改圖2中之組件,使金屬箔13與該複合物基板接觸。
該傳導性表面材料可用於形成適用於自動化鋪帶(ATL)或自動化鋪絲(AFP)製程中之連續預浸體線帶,進而形成最外層為該傳導性表面材料之可固化複合物結構。就ATL/AFP應用而言,該傳導性表面材料可呈原樣使用或層壓至由可固化基質樹脂及呈單向纖維或織造織物形式之纖維增強體組成之預浸體層片上。將該傳導性表面材料或層壓預浸體層片分割成具有適宜AFP寬度(例如,0.125英吋-1.5英吋或3.17mm-38.1mm,包括0.25英吋-0.50英吋或6.35mm-12.77mm)或ATL寬度(例如6英吋-12英吋或152mm-305mm)之狹窄線帶。
ATL及AFP係係利用電腦控制機器人將一層或若干層纖維帶或纖維束放置於模具表面(例如心軸)上以產生複合物部件或結構之方法。示例性應用包括飛機機翼蒙皮及機身。ATL/AFP製程涉及將一或多條線帶並列分配於心軸表面上,以產生具有所需寬度及長度的層,及然後將額外層累加於前一層上,以提供具有所需厚度的疊層。ATL/AFP系統配備有分配預浸體線帶及將其直接壓至心軸表面上之構件。
AFP自動將許多單根預浸漬纖維束或狹窄切割線帶(例如,0.125英吋-1.5英吋)置於心軸上,以組成指定的總預浸體帶寬。材料係以高速度放置,其在放置期間使用數值控制放置頭分配、固定、切割每根纖維束,並重新啟動。ATL機器鋪疊預浸體單向線帶或連續織物條,其等比用於AFP中之單根纖維束或切割線帶更寬。通常,就兩種方法而言,材料係透過機器人控制頭施加,該機器人控制頭含有進行材料放置所必需的機制。AFP傳統上係用在極為複雜表面上。
航太複合物部件所用的典型表面膜通常係基於環氧樹脂,且在曝露到紫外(UV)輻射及習知基於醇的脫漆劑(諸如基於苯甲醇的溶液)時,會造成不利影響。本文所揭示的多官能傳導性表面材料之設計係用於克服此等問題。為此,已調配樹脂膜組合物之樹脂組分,以產生高Tg及高交聯密度。已發現,高Tg及高交聯密度之組合使得該樹脂膜
高度耐受基於醇的脫漆劑溶液(諸如基於苯甲醇的溶液)。為達成此等性質,樹脂膜組合物係基於以下成份之組合:某些多官能樹脂、使樹脂基質韌化的聚合性韌化組分、基於胺的潛性固化劑、作為流體屏障組分之陶瓷微球及作為流變性改質組分之粒狀無機填料。多官能樹脂及陶瓷微球佔總組合物之超過35重量%,較佳超過45重量%。
多官能樹脂
該多層表面材料中之樹脂膜係由熱可固化組合物形成,其含有至少兩種多官能環氧樹脂,較佳地,其中一種為具有超過一個環氧官能基之環氧酚醛清漆樹脂。第二種環氧樹脂為非酚醛清漆型多官能環氧樹脂,較佳為四官能團或三官能團環氧樹脂(亦即每分子具有三個或四個環氧官能基之環氧樹脂)。
適宜的環氧酚醛清漆樹脂包括具有以下化學結構(結構I)之苯酚-甲醛酚醛清漆樹脂或甲酚-甲醛酚醛清漆樹脂之聚縮水甘油基衍生物:
其中n=0至5,且R=H或CH3。當R=H時,該樹脂為苯酚酚醛清漆樹脂。當R=CH3時,該樹脂為甲酚酚醛清漆樹脂。前者係可自Dow Chemical Co購得之DEN 428、DEN 431、DEN 438、DEN 439及DEN 485。後者係可自Ciba-Geigy Corp購得之ECN 1235、ECN 1273及ECN 1299。其它可使用的適宜酚醛清漆樹脂包括來自Celanese Polymer Specialty Co之SU-8。在較佳實施例中,該環氧酚醛清漆樹脂在25℃下之黏度為4000-10,000mPa.s,且環氧化物當量(EEW)為190-210g/eq。
適宜的四官能團環氧樹脂為每分子具有四個環氧官能基及具有至少一個縮水甘油胺基之四官能團芳族環氧樹脂。例如,該四官能團芳族環氧樹脂可具有以下一般化學結構(結構II),亦即二苯胺基甲烷之四縮水甘油基醚:
結構II中之胺基係示於芳族環結構之對位或4,4’位上,然而,應瞭解,其它異構體(諸如2,1’、2,3’、2,4’、3,3’、3,4’)亦係可行替代物。適宜的四官能團芳族環氧樹脂包括四縮水甘油基-4,4’-二胺基二苯基甲烷,其可購得Huntsman Advanced Materials所供應之Araldite® MY 9663、MY 9634、MY 9655、MY-721、MY-720、MY-725商品。三官能團環氧樹脂之實例包括胺基苯酚之三縮水甘油基醚,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,基於該樹脂膜組合物總重量計,環氧酚醛清漆樹脂及多官能性環氧樹脂(三官能團及/或四官能團)之組合佔至少15重量%。在某些實施例中,基於該樹脂膜組合物總重量計,環氧酚醛清漆樹脂及多官能性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,佔約15重量%至約25重量%。環氧酚醛清漆樹脂及多官能性環氧樹脂之相對含量可能有變化,但環氧酚醛清漆樹脂之含量較佳係於80-100份/100份多官能性環氧樹脂之範圍內。呈指定比例之環氧酚醛清漆樹脂與多官能性環氧樹脂之組合有助於在固化時達到所需高Tg及指定的交聯密度。
聚合性韌化組分
為了使基於上述多官能性樹脂混合物之樹脂基質韌化,將一或多種聚合性韌化劑添加至該樹脂膜組合物中。該等聚合性韌化劑係選自由下列各物組成之群:(i)藉由環氧樹脂、雙酚及彈性聚合體反應所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-殼橡膠顆粒;及其組合。在一較佳實施例中,使用兩種來自該群組的韌化劑之組合。基於表面膜組合物總重量計,韌化劑(群)之含量總計佔約10重量%至約20重量%。
就該預反應加合物而言,適宜的環氧樹脂包括雙酚A之二縮水甘油基醚、四溴雙酚A之二縮水甘油基醚、雙酚A之氫化二縮水甘油基醚或雙酚F之氫化二縮水甘油基醚。環脂族環氧化物亦適合,其包括每個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。具體實例包括環脂族醇氫化雙酚A之二環氧化物(由CVC Thermoset Specialties供應之EpalloyTM 5000、5001),其係由以下結構表示:
此種環脂族環氧樹脂之實例為可自CVC Thermoset Specialties購得之EPALLOY® 5000(藉由氫化雙酚A二縮水甘油基醚所製得之環脂族環氧化物)。其他適用於預反應加合物中之環脂族環氧化物可包括由Momentive Specialty Chemicals供應之EPONEX環脂族環氧樹脂,例如EPONEX樹脂1510。
該預反應加合物中之雙酚充當線性或環脂族環氧化物之鏈延長劑。適宜的雙酚包括雙酚A、四溴雙酚A(TBBA)、雙酚Z及四甲基雙酚A(TMBP-A)。
適用於形成該預反應加合物之彈性體包括(但不限於)橡膠,諸
如,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)、氟碳彈性體、聚矽氧彈性體、苯乙烯-丁二烯聚合物。在一項實施例中,用於該預反應加合物中之彈性體為ATNB或CTBN。
在一項實施例中,使環氧樹脂在約300℉(或148.9℃)下與雙酚鏈延長劑及彈性體聚合物在觸媒(諸如三苯基膦(TPP))存在下反應,以將該等環氧樹脂連成鏈,並形成高黏度、形成膜之高分子量環氧樹脂預反應加合物。然後將該預反應加合物與該表面膜組合物之其餘組分混合在一起。
聚合性韌化組分之第二選擇為熱塑性韌化材料,其係聚醚碸(PES)與聚醚醚碸(PEES)之共聚物,其平均分子量為8,000-14,000。在一項實施例中,該韌化劑為聚(氧-1,4-伸苯基磺醯基-1,4-伸苯基),其由示差掃描熱量儀(DSC)測得之Tg為約200℃。
聚合性韌化組分之第三選擇係粒度為300nm或更小之核-殼橡膠顆粒。該等核-殼橡膠(CSR)顆粒可係以堅硬外殼包圍柔軟核心之任何核-殼顆粒。較佳的CSR顆粒係彼等具有聚丁二烯橡膠核心或丁二烯-丙烯腈橡膠核心及聚丙烯酸酯外殼之顆粒。然而,亦可使用以柔軟外殼包圍堅硬核心之CSR顆粒。該等CSR顆粒可呈25-40重量%的CSR顆粒分散於液態環氧樹脂中供應。具有橡膠核心及聚丙烯酸酯外殼之CSR顆粒可自Kaneka Texas Corporation(Houston,Tex.)購得名稱為Kane Ace MX之商品。該等核-殼橡膠顆粒較佳(但並非必需)係呈含該等顆粒之適宜液態環氧樹脂之懸浮液添加至表面膜組合物中。Kane Ace MX 411係含25重量%核-殼橡膠顆粒之MY 721環氧樹脂之懸浮液,且係核-殼橡膠顆粒之適宜來源。含有25-37重量%的相同核-殼橡膠顆粒分散於DER 331樹脂中之Kane Ace MX 120、MX 125或MX 156亦係核-殼橡膠顆粒之適宜來源。亦可使用核-殼橡膠顆粒之其他適宜
來源,諸如MX 257、MX 215、MX217及MX 451。核-殼橡膠顆粒之另一商業來源係來自Dow Chemical Co.之ParaloidTM EXL-2691(平均粒度為約200nm之甲基丙烯酸酯-丁二烯-苯乙烯CSR顆粒)。
陶瓷微球
將陶瓷微球添加至該樹脂膜組合物中,以提升該膜之表面光滑度。在一項實施例中,使用由惰性二氧化矽-氧化鋁陶瓷材料製成之中空陶瓷微球。該等陶瓷微球可具有超過60,000psi之抗壓強度,約3.7-4.6之介電常數,於1000-1100℃(或1832-2012℉)範圍內之軟化點及介於0.1微米至50微米(或1-50微米)範圍內之粒子直徑。陶瓷微球之高軟化點可使其等不吸收溶劑,不可燃,且對化學品具有高度耐受性。已發現,直徑介於約0.1μm至約20μm,及較佳約1μm至約15μm範圍內之微球尤其適宜。尤其適用於本發明樹脂膜組合物之市售陶瓷微球之實例係由Zeelan Industries,Inc.以商品名Zeeospheres ®銷售的微球,例如,G-200、G210及W-200。此等微球為具有厚壁、無臭且顏色為淺灰色之中空二氧化矽-氧化鋁球。在較佳實施例中,多官能性樹脂與陶瓷微球之組合佔該樹脂膜組合物之超過50重量%,較佳超過60重量%。在某些實施例中,基於該樹脂膜組合物總重量計,該等陶瓷微球之含量為至少20重量%,較佳至少25重量%或至少30重量%。在一些實施例中,陶瓷微球之含量可介於20重量%-40重量%或25重量%-35重量%之範圍內。在其他實施例中,陶瓷微球之含量可介於3重量%-15重量%或5重量%-10重量%之範圍內。
固化劑
多官能性環氧樹脂可藉由各種在高溫(例如超過150℉(65℃)的溫度)下活化的基於胺的潛性固化劑固化。適宜固化劑之實例包括雙氰胺(DICY)、三聚氰二胺、胍、胺基胍及其衍生物。亦可使用屬於咪唑及胺複合物類的化合物。在一項實施例中,該固化劑為雙氰胺。基於
該樹脂膜組合物總重量計,該基於胺的固化劑之含量係佔1重量%-5重量%範圍內。
固化促進劑可與該基於胺的固化劑結合使用,以促進該環氧樹脂與該基於胺的固化劑間之固化反應。適宜的固化促進劑可包括經烷基及芳基取代的脲(包括芳族或脂環族二甲基脲)及基於甲苯二胺或二苯胺基甲烷的二脲。二脲之一實例係4,4’-亞甲基雙(苯基二甲基脲),其可自CVC Chemicals購得Omicure U-52或CA 152之商品,其係雙氰胺之適宜促進劑。另一實例係2,4-甲苯雙(二甲基脲),其可自CVC Chemicals購得Omicure U-24或CA 150之商品。基於該樹脂膜組合物總重量計,該固化促進劑之含量可介於0.5重量%至3重量%範圍內。
流動控制劑
將呈微粒形式(例如粉末)的無機填料添加至該樹脂膜組合物中作為流變性改質組分,以控制該樹脂組合物之流動,及防止在其中聚結。可用於該樹脂膜組合物中之適宜無機填料包括滑石、雲母、碳酸鈣、氧化鋁及發煙矽石。在一項實施例中,使用疏水發煙矽石(例如Cab-O-Sil TS-720)作為無機填料。基於該樹脂膜組合物總重量計,該無機填料之含量可介於1重量%-5重量%範圍內。
可選添加劑
該樹脂膜組合物可另外包括一或多種可影響固化或未固化樹脂膜之機械性質、電性質、光學性質、阻燃性及/或熱學性質中之一或多項性質之可選添加劑。該等添加劑可包括可與複合物基板(其與樹脂膜接觸)之環氧樹脂進行化學反應之材料或不會與其等反應之材料。此等添加劑包括(但不限於)紫外線(UV)穩定劑、色素/染料及傳導性材料。當使用此等添加劑時,基於該樹脂膜組合物總重量計,其總含量係低於5重量%。
可添加至該樹脂組合物之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(例如UV-9);2,4-雙(2,4-二甲基苯基)-6-(2-羥基-4-辛氧基苯基)-1,3,5-三嗪(例如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(例如CYASORB ® UV-2908光穩定劑);季戊四醇肆(3-(3,5-二-第三丁基-4-羥苯基)丙酸酯(例如IRGANOX 1010)。來自Ciba Specialty Chemicals之液態位阻胺光穩定劑(諸如2-(2H-苯并三唑-2-基)-4,6-二-第三戊基苯酚(例如TINUVIN 328)、1,2,2,6,6-五甲基-4-哌啶基癸二酸甲酯(例如TINUVIN 292))。癸二酸雙(2,2,6,6-四甲基-1-(辛氧基)-4-哌啶基酯(例如TINUVIN 123)亦可用作適宜UV穩定劑。此外,奈米尺寸的氧化鋅(n-ZnO)(例如NanoSunGuard 3015)及二氧化鈦奈米顆粒(n-TiO2)亦可用作UV穩定劑。
可將此項技術中已知用於向樹脂系統添加顏色之色素及/或染料添加至該樹脂膜組合物中。色素及/或染料之實例包括(但不限於)紅色氧化鐵、綠色鉻、碳黑及二氧化鈦。在一項實施例中,將二氧化鈦(白色)色素添加至該樹脂膜組合物中。在另一項實施例中,添加碳黑色素。
亦可將呈微粒(例如顆粒或薄片)形式的傳導性材料添加至該樹脂膜組合物中,以賦予最終樹脂膜導電性。已發現,金屬層(或箔)與其中分佈有傳導性顆粒或薄片之樹脂膜之組合可產生類似於純金屬層之傳導性。例如,具有一層或兩層與金屬層/箔組合之傳導性樹脂膜之多層結構可達到小於20mΩ之表面電阻率,在有些情形下為5mΩ。適宜傳導性材料之實例包括呈薄片或顆粒形式之金屬(諸如銀、金、鎳、銅、鋁、青銅及其合金)。基於碳之材料(諸如碳奈米管(單壁奈米管或多重壁奈米管)、碳奈米纖維及石墨烯)亦可用作賦予樹脂膜導電性之傳導性添加劑。奈米纖維可具有介於70至200奈米之範圍內之直徑及約50-200微米之長度。奈米管可具有約10奈米之外徑,約10,000
奈米之長度,及約1000之縱橫比(L/D)。此外,傳導性添加劑亦可包括碳黑顆粒(諸如來自DeGussa之Printex XE2)。
在某些實施例中,具有與傳導性樹脂膜(有傳導性添加劑分散其中)組合之金屬層/箔之多層傳導性表面材料可呈現類似金屬之傳導性,其比單獨傳導性樹脂膜高1至2個數量級。因此,該多層傳導性表面材料提供正如金屬一樣的三維均一之高傳導性,其可顯著改善複合物在LSP及EMI屏蔽方面的EME保護。
表1A及1B顯示樹脂膜組合物之各種實施例。
表1A
表1B
在一項實施例中,該樹脂膜組合物具有如下調配物,以基於該組合物總重量之重量百分比計:20%-25%的苯酚酚醛清漆環氧樹脂;20%-25%的四官能團環氧樹脂;10%-15%的預反應加合物、1%-3% PES-PEES共聚物、25%-35%的陶瓷微球;1%-5%的基於胺的潛性固化劑;0.5%-3%的固化促進劑;1%-3%的無機填料;及視情況選用0.1-1%的著色色素。
在另一項實施例中,該樹脂膜組合物具有如下調配物,以基於該組合物總重量之重量百分比計:5%-15%的苯酚酚醛清漆環氧樹脂;5%-15%的四官能團環氧樹脂;10%-20%的預反應加合物、1%-3%的PES-PEES共聚物、25%-35%的陶瓷微球;1%-5%的基於胺的潛性固化劑;0.5%-3%的固化促進劑;1%-3%的無機填料;及視情況選用45%-70%的傳導性添加劑,諸如銀薄片或銀-銅薄片或者上文所述的基於碳之奈米尺寸的材料。
該樹脂膜組合物之組分可添加至配備用於混合、加熱及/或冷卻該等組分之混合容器中。此外,必要時亦可將一或多種有機溶劑添加至該混合物中,以便於混合該等組分。此等溶劑之實例可包括(但不限於)甲基乙基酮(MEK)、丙酮、二甲基乙醯胺及N-甲基吡咯啶酮。隨後使用習知膜形成製程,由該樹脂膜組合物形成樹脂膜。
為便於該樹脂膜之加工,將該樹脂膜組合物施加至載體上。載
體之非限制性實例可包括由熱塑性聚合物纖維或碳纖維製成之纖維片材、非織造氈、無序氈、針織載體、經金屬塗覆的碳膜等。非織造氈、織造或針織襯底之實例可包括碳氈、聚合物氈及經金屬塗覆的碳、玻璃或聚合物玻璃膜。非織造氈、織造或針織襯底可經銅、鋁、銀、鎳及其合金塗覆。固化後,所得固化樹脂膜呈現高交聯密度、由DSC測量之180℃之高玻璃轉化溫度(Tg)、根據ASTM D-3363測量之7H或更高的鉛筆硬度。此等性質可使該固化樹脂膜對習知脫漆劑(例如基於苯甲醇的脫漆溶液)及UV輻射具有高耐受性及抗微裂性。已發現,在環境溫度(20℃-25℃)下與基於苯甲醇的脫漆溶液接觸7天後,該表面膜的流體吸收量小於0.5%,且鉛筆硬度下降不超過2H鉛筆等級。此外,已發現,該固化樹脂膜在-55℃與71℃之間接受2000次熱循環測試後,具有小於0.3個裂紋/平方英吋之微裂紋密度。該固化樹脂膜另外對常用於塗刷航太結構之塗料層具有高黏著性。該樹脂膜對塗料層之黏著性使得經過塗刷之表面在依據ASTM D3359下,在乾燥條件或濕潤條件(在75℉之去離子水中浸泡7天後)下接受油漆黏著力測試後,在接受或不接受1000KJ/m2 UVA輻射曝露下,均呈現實質上0%的塗料損失。
實例
以下實例係針對根據本發明之傳導性表面材料提出具體實施例,並無意以任何方式限制本發明範圍。
基於表2中所示調配物(1-9)製備九種樹脂膜。所有用量均係以重量百分比計。
表2
各樹脂膜係藉由將表2中所揭示的組分添加至混合容器中,並使用實驗室高速剪切混合機混合該等組分而製得。首先添加環氧樹脂。必要時,MEK係作為溶劑添加至該環氧樹脂混合物中,以調整該組合物之流變性及固形物含量。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4-7)中,亦將傳導性添加劑(銀薄片或Ag-Cu薄片)添加至混合容器中。另外,將陶瓷微球、發煙矽石及UV穩定劑(在有些調配物中)添加至該混合容器中。必要時添加MEK溶劑,以將上述混合物之黏度控制為約80重量%固形物,並使組合物之組分以約1000-3000rpm混合約50-70分鐘。將該組合物之溫度維持在低於約160℉。必要時添加額外的MEK,以抑制該混合物黏附在混合軸上。
隨後將該混合物冷卻至低於約120℉,並將固化劑(雙氰胺(Dicy)
及二脲)添加至該組合物中。然後混合該組合物,直至大體上均勻。在添加固化劑期間,將該混合物之溫度維持在低於約130℉。
為了自以上組合物形成表面樹脂膜,對各組合物進行粗濾,除氣,並沉積成為膜。粗濾係透過過濾介質EP-15進行。進行除氣,以使得該組合物之固體含量為約80重量%。然後,藉由膜塗覆機將該經粗濾及除氣的組合物塗覆成膜重量為約0.020-0.030psf之膜,然後乾燥,以達到低於約1重量%的揮發物。在低壓力下將選定的非織造聚酯或玻璃無序氈載體或傳導性載體壓入樹脂膜中,讓該載體包埋在該膜中。
為了形成多層傳導性表面材料,在適當溫度及壓力下,藉由膜/箔層壓製程,將由表2樹脂組合物形成的樹脂膜與各種金屬箔組合在一起,形成三層結構(如圖1中所示)。然後,藉由將該多層傳導性表面材料與預浸體疊層組合在一起,製得複合物面板。就各面板而言,將該三層傳導性表面材料置於工具上,隨後疊合預浸體層片(來自Cytec Industries Inc.的CYCOM 5276-1,碳纖維/基於環氧樹脂之預浸體),以形成預浸體疊層。然後,在80psi高壓釜中,使該具有該傳導性表面材料之預浸體疊層在約350℉之溫度下固化2小時。
表面膜評估
固化樹脂膜之玻璃轉化溫度(Tg)係藉由使用調控式DSC(TA 2910)或熱機械分析儀(TMA 2940,TA Instruments),在氮氣下,依10℃/min之升溫速率,於30℃-230℃溫度範圍內測定。
複合物層壓面板評估
檢查以該多層傳導性表面材料作表面的複合物面板之表面外觀缺陷(凹陷、針孔)。然後,評估該等複合物面板之脫漆劑耐性、在經過或未經過UV曝露後之乾漆黏著力及濕漆黏著力、及抗微裂性。
脫漆劑耐性測試
由未上漆的表面複合物面板(2”x 2”試樣尺寸,厚度為0.15mm)在浸沒於用於航太複合物結構脫漆製程之基於苯甲醇的脫漆劑溶液(可自McGean購得之Cee Bee 2012A或可自Henkel購得之Turco 1270-6)期間(在環境室溫下浸沒至多168小時),測定脫漆劑流體吸收量及表面鉛筆硬度變化,測定其脫漆劑耐性。在浸泡脫漆劑之前及之後間隔24小時、48小時及至多168小時(7天)測量各測試面板之重量。以相同測試間隔直到浸沒至多168小時(7天)測量測試面板之脫漆劑流體吸收量(在浸沒期間之重量變化,以重量%表示)。
在環境室溫下將各未上漆測試面板表面浸沒於基於苯甲醇的脫漆劑溶液中,歷時至多168小時,然後根據ASTM D3363,測試浸沒期間之鉛筆硬度變化。ASTM D3363係指用於測定基板上之透明及著色有機塗膜之表面硬度之標準測試方法。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)。在浸泡於脫漆劑中之前及之後間隔24小時、48小時及至多168小時(7天)測量測試面板之鉛筆硬度。在浸沒24小時後若鉛筆硬度變化超過2H等級,則視為不具有良好脫漆劑耐性。
經過或未經過UV曝露之乾漆黏著力及濕漆黏著力
根據ASTM D3359測量以多層傳導性表面膜作表面,在上漆前經過或未經過UV曝露之上漆的複合物面板(呈3”x 6”試樣尺寸之形式,厚度為0.15mm)之乾劃線及濕劃線塗漆黏著力。ASTM D3359係指藉由在膜上所形成的切口上施加及移除感壓性膠帶評估塗膜對基板之表面黏著力之標準測試方法(交叉刻劃法附著力試驗(cross-hatch scribe tape test))。按照AATCC測試方法16,第3項,將固化測試面板曝露至零(無UV)、200kJ/m2或1000kJ/m2紫外(UV-A)輻射。用於UV測試之儀器係Xeno Weather-o-meter,諸如Atlas CI3000 Fadeo Meter。製備各
測試面板表面(經過清潔,經過砂紙打磨及未經過砂紙打磨),並施加用於航太塗漆之外部裝飾性塗料(環氧樹脂塗料底漆,繼之為基於聚胺基甲酸酯之面漆)。隨後,按照ASTM D3359進行乾漆黏著力測試。為進行濕漆黏著力測試,在經過UV曝露的測試面板上塗漆,然後浸沒於75℉去離子水中7天。然後,依據ASTM D3359進行濕漆黏著力測試。
導電率測量
取具有傳導性表面材料之測試面板切割成約6 x 5英吋的試樣,並使用四點探針AVO® Ducter® DLRO10X數位低電阻率歐姆計測量其導電率或表面電阻率(以歐姆/平方或毫歐姆/平方計)。
表3及4顯示以三層表面材料(樹脂膜/金屬箔/樹脂膜)作表面之測試面板之表面性質及測試結果,該等三層表面材料係依據表2之樹脂膜調配物及如表3及4中所指定之固體金屬箔(銅或鋁)。
如表3及4中所示,該等測試面板呈現極佳脫漆劑耐性及高表面硬度(>7H)。此等面板亦在各種測試條件(乾燥及潮濕,經過或未經過UV曝露)下呈現極佳之塗漆黏著力(10+意指0%塗料損失)。
參考表3,已發現,以三層傳導性表面材料作為表面之複合物面板(測試面板1-2及5-7)呈現意想不到的類金屬導導性(小於5mΩ/sq),其比單獨傳導性樹脂膜(沒有金屬箔)高1至2個數量級。因此,該等三層傳導性表面材料提供正如同金屬一樣的三維均一性、高傳導性。該等三層傳導性表面材料之類金屬傳導性使其可提供良好LSP保護及EMI屏蔽。
抗微裂性測試
為表3及4中所揭示的測試面板上漆,且亦測量經塗漆測試面板(呈4”x 6”試樣尺寸之形式,厚度為0.15mm)之抗微裂性。使該等經塗漆測試面板在-55℃至71℃之間進行熱循環,至多進行2000次循環。在顯微鏡下檢查進行熱循環後的各測試面板表面,以得到曝露至400次、800次、1200次、1600次及2000次熱循環後出現的微裂紋。採用裂紋密度(測試面板尺寸面積中所顯現之表面塗漆裂紋數量)來衡量表面複合物測試面板之抗微裂性。裂紋之最大長度應小於0.1英吋。2000次熱循環後之微裂紋測試結果示於表5中。
如表5中所示,以多層傳導性表面材料作表面之測試面板顯示良好抗微裂性,且裂紋密度小於0.3個裂紋/平方英吋。
本文的術語「第一」、「第二」等並不表示任何順序、用量或重要性,而是用以區分不同元素,且本文的術語「一」並不表示限制數量,而是表示存在至少一個引用項。與數量連用的修飾語「大約」及
「約」包含所述數值,且具有上下文所決定的含義,(例如,包括與測量特定數量有關的誤差度)。如本文中所使用的後綴「(群)」意欲包括單個及複數個其所修飾術語,因此其包括一個或多個該術語(例如,金屬(群)包括一或多種金屬)。本文所揭示的範圍具有包容性,且可獨立組合(例如,「至多大約25重量或更具體言之,大約5重量%至大約20重量%」之範圍包含該等範圍之端點及所有中間值,例如,「1重量%至10重量%」包括1%、2%、3%等)。
雖然本文已描述各種實施例,但從該說明書中可瞭解,熟習此項技術者可得到其元素、變體或改良之各種組合,且係在本發明範圍內。此外,可在不脫離其基本範圍內,在符合本發明教義下對特定情形或材料進行許多修改。因此,希望本發明並不限於以預期用於實施本發明之最佳模式所揭示之特定實施例,而是本發明將包括落於隨附申請專利範圍之範圍內之所有實施例。
11‧‧‧第一樹脂膜
12‧‧‧釋離紙襯底
13‧‧‧金屬箔
14‧‧‧第二樹脂膜
20‧‧‧三層結構
Claims (25)
- 一種可提供雷擊保護或電磁干擾屏蔽之電傳導性表面材料,該表面材料係多層結構,其包括:(a)電傳導性層,其具有兩個相對表面,及小於3密耳之厚度及小於10mΩ之電阻率;(b)樹脂膜,其係形成於該傳導性層之至少一個表面上,其中該樹脂膜係由可固化組合物形成,該組合物包含:具有超過一個環氧官能基之環氧酚醛清漆樹脂;三官能團或四官能團環氧樹脂;陶瓷微球;基於胺的潛性固化劑;粒狀無機填料;及至少一種選自由下列組成之群之韌化劑:(i)由環氧樹脂、雙酚及彈性體反應形成的預反應加合物;(ii)聚醚碸(PES)與聚醚醚碸(PEES)之共聚物;(iii)核-殼橡膠(CSR)顆粒;及其組合,且固化後,該樹脂膜具有180℃之玻璃轉化溫度(Tg),及如根據ASTM D-3363測得大於7H之表面鉛筆硬度。
- 如請求項1之電傳導性表面材料,其中該樹脂膜具有於0.01至0.03psf範圍內之膜重量。
- 如請求項1之電傳導性表面材料,其中該傳導性層具有於3μm至38μm範圍內之厚度。
- 如請求項1之電傳導性表面材料,其中該傳導性層為具有於3μm至5μm範圍內之厚度之金屬箔。
- 如請求項1之電傳導性表面材料,其中該金屬箔包括選自銅、鋁、青銅或其合金之金屬。
- 如請求項1之電傳導性表面材料,其中該樹脂膜在於20℃至25℃範圍內之環境溫度下與基於苯甲醇的脫漆溶液接觸7天後,呈現小於0.5%的流體吸收量,且硬度下降不超過2H鉛筆等級。
- 如請求項1之電傳導性表面材料,其中該樹脂膜另外包含分佈遍及該樹脂膜之傳導性顆粒或薄片。
- 如請求項7之電傳導性表面材料,其中該等傳導性顆粒或薄片係由選自下列之傳導性材料形成:銀、金、鋁、銅、青銅、碳及其組合。
- 如請求項7之電傳導性表面材料,其中該多層結構之表面電阻率係低於5mΩ。
- 如請求項1之電傳導性表面材料,其中將兩樹脂膜形成於該金屬層之相對表面上,以使該金屬層被夾在該兩樹脂膜之間。
- 如請求項10之電傳導性表面材料,其中該兩樹脂膜之組成不同。
- 如請求項10之電傳導性表面材料,其中該兩樹脂膜之組成相同。
- 如請求項1之電傳導性表面材料,其中第一樹脂層在-55℃至71℃之間接受2000次熱循環測試後呈現少於0.3個裂紋/平方英吋之微裂紋密度。
- 如請求項1之電傳導性表面材料,其中該可固化組合物中之該環氧酚醛清漆樹脂具有以下結構:
- 如請求項1之電傳導性表面材料,其中該熱固化組合物中之該至少一種韌化劑包括由四溴雙酚A之二縮水甘油基醚、雙酚A與胺封端之丁二烯丙烯腈(ATBN)或羧基封端之丁二烯丙烯腈(CTBN)彈性體反應形成之預反應加合物。
- 如請求項1之電傳導性表面材料,其中該可固化組合物包含該預反應加合物及PES-PEES共聚物作為韌化劑。
- 如請求項1之電傳導性表面材料,其中該等陶瓷微球係由二氧化矽-氧化鋁陶瓷材料製成並具有於1至50微米範圍內之粒度之中空微球。
- 如請求項1之電傳導性表面材料,其中該等環氧樹脂及該等陶瓷微球佔該熱固化組合物總重量之超過35重量%。
- 如請求項1之電傳導性表面材料,其中該可固化組合物另外包含二脲作為固化促進劑。
- 一種適於自動化鋪帶(ATL)或自動化鋪絲(AFP)之傳導性預浸體線帶,其係衍生自如請求項1之電傳導性表面材料。
- 如請求項20之傳導性預浸體線帶,其具有於0.125英吋至1.5英吋範圍內之寬度。
- 如請求項20之傳導性預浸體線帶,其具有於6至12英吋範圍內之寬度。
- 一種製造複合物結構之方法,其包括:在自動化鋪帶(ATL)或自動化鋪絲(AFP)製程中,使用配備有用於分配預浸體線帶及將其直接壓至模塑表面上之構件之自動化系統疊合預浸體線帶,形成複合物結構;將如請求項20之傳導性預浸體線帶併入該ATL或AFP製程中, 以致將該傳導性預浸體線帶放置成最終複合物結構中之最外層。
- 一種複合物結構,其包括:複合物基板,其包含經基質樹脂浸漬之增強纖維;及如請求項1之電傳導性表面材料,其係形成於該複合物基板之表面上,以使得該金屬層置於該樹脂膜與該複合物基板之間。
- 如請求項24之複合物結構,其中該複合物基板係預浸體疊層,其包括複數個配置成堆疊配置之預浸體層片,各預浸體層片包含經基質樹脂浸漬之增強纖維。
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TWI711055B (zh) * | 2019-04-25 | 2020-11-21 | 國立虎尾科技大學 | 高電壓介電層結構與其製造方法 |
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RU2605131C1 (ru) | 2016-12-20 |
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BR112015012619A2 (pt) | 2017-07-11 |
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CN104853910B (zh) | 2017-03-22 |
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BR112015012619B1 (pt) | 2021-06-01 |
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MX2015006452A (es) | 2015-08-14 |
CA2893646A1 (en) | 2014-06-12 |
EP2900468B1 (en) | 2016-09-07 |
US20140154496A1 (en) | 2014-06-05 |
MY176165A (en) | 2020-07-24 |
KR20150091480A (ko) | 2015-08-11 |
JP2016508077A (ja) | 2016-03-17 |
US10256618B2 (en) | 2019-04-09 |
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