TWI519586B - Thermosetting resin composition, thermosetting sheet and thermosetting sheet - Google Patents
Thermosetting resin composition, thermosetting sheet and thermosetting sheet Download PDFInfo
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Description
本發明係關於一種含有丙烯酸系共聚物、環氧樹脂及環氧樹脂用之硬化劑之熱硬化性樹脂組成物、熱硬化性接著片及熱硬化性接著片之製造方法。本申請案係基於2010年12月1日在日本提出申請之日本專利申請2010-268081號而主張優先權者,藉由參照該申請案而援用至本申請案中。
於用於可撓性印刷配線板(Flexible Printed Circuits,以下稱作「FPC」)用途之接著材料中,將環氧樹脂與環氧樹脂之硬化劑之混合物作為硬化成分,為改善剝離強度或賦予可撓性而摻合丙烯腈丁二烯橡膠(NBR:Nitril-Butadiene Rubber)(以下稱作「NBR」)等。為獲得良好之焊接耐熱性,廣泛使用含有可與環氧樹脂交聯之羧基之樹脂系組成物作為該NBR(參照專利文獻1)。
用於FPC用途之接著組成物含有大量環氧樹脂,故有於加熱加壓成形時未反應之環氧樹脂等大量地滲出,堵塞設置於覆蓋層或加強板等上之開孔部之問題。
於專利文獻2中,提出藉由使接著組成物中含有紫外線(UV)硬化樹脂,對開孔部照射紫外線使其硬化,而防止接著組成物自開孔部滲出之方法。
然而,於專利文獻2所記載之技術中,由於追加紫外線照射之步驟,故而需要用於該紫外線照射步驟之設備投資、及保管時用以避開紫外線之特殊之保管狀態。
[專利文獻1]日本特開平04-370996號公報
[專利文獻2]日本特開昭62-85941號公報
本發明係鑒於以上先前之實際情況而提出者,其目的在於提供一種無需進行紫外線照射等而於加熱加壓成形時未反應之環氧樹脂等之滲出性良好之熱硬化性樹脂組成物、熱硬化性接著片及熱硬化性接著片之製造方法。
本發明之熱硬化性樹脂組成物係含有丙烯酸系共聚物、環氧樹脂及該環氧樹脂用之硬化劑,該丙烯酸系共聚物含有含環氧基之(甲基)丙烯酸酯單體,且上述丙烯酸系共聚物之環氧基部分經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺(polyamideamine)而部分地交聯。
本發明之熱硬化性接著片於基材膜上形成有由上述熱硬化性樹脂組成物構成之熱硬化性接著層。
本發明之熱硬化性接著片之製造方法包括:交聯步驟,係將溶解於有機溶劑中之含有含環氧基之(甲基)丙烯酸酯單體之丙烯酸系共聚物、及具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺加以混合,使該丙烯酸系共聚物之環氧基部分經由該液狀之聚胺或聚醯胺胺而部分地交聯;製備步驟,係於含有上述環氧基部分經交聯之丙烯酸系共聚物之有機溶劑中溶解環氧樹脂、及含有有機酸二醯肼之該環氧樹脂用之硬化劑,藉此製備熱硬化性接著層形成用塗料;及熱硬化性接著層形成步驟,其係將上述熱硬化性接著層形成用塗料塗佈於基材膜上,並進行乾燥,藉此形成熱硬化性接著層。
根據本發明,丙烯酸系共聚物之環氧基部分經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而部分地交聯,故可使加熱加壓成形時之未反應環氧樹脂等之滲出性良好。
以下,一面參照圖式,一面依照以下順序對應用本發明之熱硬化性樹脂組成物、熱硬化性接著片及熱硬化性接著片之製造方法的具體實施形態之一例進行說明。
1.熱硬化性樹脂組成物
1-1.丙烯酸系共聚物
1-2.環氧樹脂
1-3.硬化劑
1-4.具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺
2.熱硬化性樹脂組成物之製造方法
3.熱硬化性接著片
4.熱硬化性接著片之製造方法
5.其他實施形態
6.實施例
<1.熱硬化性樹脂組成物>
本實施形態之熱硬化性樹脂組成物含有丙烯酸系共聚物、環氧樹脂及環氧樹脂用之硬化劑,該丙烯酸系共聚物含有含環氧基之(甲基)丙烯酸酯單體。
<1-1.丙烯酸系共聚物>
丙烯酸系共聚物係用以使膜成形時具有成膜性,對硬化物賦予可撓性、強韌性者。丙烯酸系共聚物係例如使含環氧基之(甲基)丙烯酸酯單體、丙烯腈單體、不含環氧基之(甲基)丙烯酸酯單體共聚合而成者。
<含環氧基之(甲基)丙烯酸酯單體>
含環氧基之(甲基)丙烯酸酯單體係用於與環氧樹脂用硬化劑反應,而於熱硬化性樹脂組成物之硬化物中形成三維交聯結構。若形成三維交聯結構,則可提高硬化物之耐濕性及耐熱性。例如,即使對由以熱硬化性樹脂組成物之硬化物接著固定於可撓性印刷配線板上之加強樹脂片構成之加強可撓性印刷配線板進行260℃以上之焊接處理(例如回焊處理)之情形時,亦可防止其接著固定部產生因吸濕而引起之膨脹現象。
作為此種含環氧基之(甲基)丙烯酸酯單體,可自應用於電子零件領域之先前之丙烯酸系熱硬化性接著劑所使用者中適當選擇而使用。例如,作為含環氧基之(甲基)丙烯酸酯單體,可列舉:丙烯酸縮水甘油酯(GA)、甲基丙烯酸縮水甘油酯(以下稱作「GMA」)。於該等含環氧基之(甲基)丙烯酸酯單體之中,就安全性、容易於市場上之獲得之觀點而言,較佳為使用GMA。再者,含環氧基之(甲基)丙烯酸酯單體可單獨使用1種,亦可併用2種以上。
若製備丙烯酸系共聚物時使用之總單體中含環氧基之(甲基)丙烯酸酯單體之量過少,則耐熱性降低,若過多,則有剝離強度降低之傾向,故而較佳為3~15質量%。
<丙烯腈單體>
丙烯腈單體係用以提高耐熱性。例如作為丙烯腈單體,可列舉:丙烯腈、甲基丙烯腈。丙烯腈單體可單獨使用1種,亦可併用2種以上。
若製備丙烯酸系共聚物時使用之總單體中丙烯腈單體之量過少,則耐熱性降低,若過多,則變得難以於溶劑中溶解,故而較佳為20~35質量%,更佳為25~30質量%。
<不含環氧基之(甲基)丙烯酸酯單體>
作為不含環氧基之(甲基)丙烯酸酯單體,可自應用於電子零件領域之先前之丙烯酸系熱硬化性接著劑所使用者中適當選擇而使用。作為不含環氧基之(甲基)丙烯酸酯單體,例如可列舉:丙烯酸甲酯(MA)、丙烯酸乙酯(EA)、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸正己酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸2-乙基己酯、丙烯酸異壬酯、丙烯酸硬脂酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸正己酯、甲基丙烯酸正辛酯、甲基丙烯酸異辛酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異壬酯、甲基丙烯酸正十二烷基酯、甲基丙烯酸異十二烷基酯、甲基丙烯酸硬脂酯等。於該等不含環氧基之(甲基)丙烯酸酯單體之中,較佳為使用丙烯酸丁酯、丙烯酸乙酯。該等不含環氧基之(甲基)丙烯酸酯單體可單獨使用1種,亦可併用2種以上。
若製備丙烯酸系共聚物時使用之總單體中不含環氧樹脂之單體之量過少,則基本特性降低,若過多,則有耐熱性降低之傾向,故而為60~75質量%,更佳為65~70質量%。
<重量平均分子量>
若丙烯酸系共聚物之重量平均分子量過小,則剝離強度及耐熱性降低,若重量平均分子量過大,則有溶液黏度上升而使塗佈性變差之傾向。因此,丙烯酸系共聚物之重量平均分子量較佳為50萬~70萬,更佳為55萬~65萬。
<1-2.環氧樹脂>
構成熱硬化性樹脂組成物之環氧樹脂係用以形成三維網狀結構,使接著性良好。
環氧樹脂可自應用於電子零件領域之先前之環氧樹脂系熱硬化性接著劑所使用的液狀或固體狀之環氧樹脂中適當選擇而使用。例如可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AD型環氧樹脂、氫化雙酚A型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聚伸烷基多元醇(新戊二醇等)聚縮水甘油醚、四縮水甘油基二胺基二苯基甲烷、三縮水甘油基-對胺基苯酚、三縮水甘油基-間胺基苯酚、四縮水甘油基-間二甲苯二胺、鄰苯二甲酸二縮水甘油酯、六氫鄰苯二甲酸二縮水甘油酯、四氫鄰苯二甲酸二縮水甘油酯、二氧化環己烯乙烯(vinyl cyclohexene dioxide)、3,4-環氧環己烷甲酸3,4-環氧環己基甲酯、己二酸雙(3,4-環氧-6-甲基己基甲基)酯等。該等環氧樹脂可單獨使用1種,亦可併用2種以上。
若環氧樹脂之使用量過少,則耐熱性降低,若過多,則有接著性降低之傾向,故而相對於丙烯酸系共聚物100質量份,較佳為5~30質量份,更佳為5~20質量份。
<1-3.硬化劑>
熱硬化性樹脂組成物含有有機酸二醯肼作為環氧樹脂之硬化劑。藉由使用有機酸二醯肼作為硬化劑,可提高常溫下為固體之熱硬化性樹脂組成物之常溫保管性。
較佳為有機酸二醯肼之平均粒徑為0.5~15 μm,並且均勻地分散。若有機酸二醯肼之平均粒徑未達0.5 μm,則有於使用用以塗佈熱硬化性樹脂組成物之有機溶劑之情形時,有機酸二醯肼粒子溶解之可能性提高,常溫保管性降低之虞。若有機酸二醯肼之平均粒徑大於15 μm,則有熱硬化性樹脂組成物之塗佈性降低,由於粒度較大導致與丙烯酸系聚合物或環氧樹脂熔融時無法充分地混合之虞。
有機酸二醯肼可自先前用作環氧樹脂之硬化劑之有機酸二醯肼中適當地選擇。例如可列舉:乙二酸二醯肼、丙二酸二醯肼、丁二酸二醯肼、亞胺基二乙酸二醯肼、己二酸二醯肼、庚二酸二醯肼、辛二酸二醯肼、壬二酸二醯肼、癸二酸二醯肼、十二烷二酸二醯肼(dodecane dihydrazide)、十六烷二酸二醯肼、順丁烯二酸二醯肼、反丁烯二酸二醯肼、二甘醇酸二醯肼、酒石酸二醯肼、蘋果酸二醯肼、間苯二甲酸二醯肼、對苯二甲酸二醯肼、2,6-萘甲酸二醯肼、4,4'-雙苯醯肼、1,4-萘甲酸二醯肼、Amicure VDH、Amicure UDH(商品名,味之素股份有限公司製造)、檸檬酸三醯肼、7,11-十八碳二烯-1,18-二碳醯肼等。有機酸二醯肼可單獨使用1種,亦可併用2種以上。於該等有機酸二醯肼之中,就熔點相對較低、硬化性之平衡優異、容易獲得之觀點而言,較佳為使用己二酸二醯肼或7,11-十八碳二烯-1,18-二碳醯肼。
若硬化劑之使用量過少,則未反應之環氧基殘餘,交聯不充分,故而耐熱性、接著性降低。又,若硬化劑之使用量過多,則有過量之硬化劑未反應而殘留因而耐熱性、接著性降低之傾向。因此,硬化劑之使用量相對於丙烯酸系共聚物及環氧樹脂之合計100質量份,較佳為2~15質量份。
<1-4.具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺>
於熱硬化性樹脂組成物中,丙烯酸系共聚物之環氧基部分經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而部分地交聯。如此般,藉由使熱硬化性樹脂組成物中丙烯酸系共聚物之環氧基部分地交聯,可調整熱硬化性樹脂組成物之滲出性,使加熱加壓成形時之未反應環氧樹脂等之滲出性良好。此處,所謂滲出性良好,例如係指加熱加壓成形時之未反應環氧樹脂之滲出量較少。就與環氧樹脂於常溫下發生硬化之觀點而言,具有一級胺基及二級胺基之至少一者之聚胺或聚醯胺胺較佳為液狀者。
具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺,例如可列舉作為脂肪族聚胺之鏈狀脂肪族聚胺、環狀脂肪族聚胺等。鏈狀脂肪族聚胺例如可列舉:二伸乙三胺、三伸乙聚胺(triethylene polyamine)、四伸乙五胺、三伸乙四胺、二丙二胺、二乙基胺基丙胺。作為環狀脂肪族聚胺,例如可列舉薄荷烷二胺、異佛爾酮二胺。此處,具有三級胺基之聚胺或聚醯胺胺難以控制交聯時之反應速度,進而對環氧樹脂發揮作為陰離子聚合型硬化劑之作用而引起環氧樹脂本身之聚合,故而難以控制交聯量,根據上述理由,不適合於本實施形態之熱硬化性樹脂組成物中使用。
本實施形態之熱硬化性樹脂組成物較佳為丙烯酸系共聚物之環氧基部分的1%以上、更佳為丙烯酸系共聚物之環氧基部分的3~12%經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而交聯。於丙烯酸系共聚物中經交聯之環氧基部分未達1%之情形時,加熱加壓成形時之未反應環氧樹脂等之滲出性無法達到充分良好之狀態。又,於丙烯酸系共聚物中經交聯之環氧基部分多於12%之情形時,儘管滲出性方面不存在問題,但硬化反應過度進行而使常溫保管性變得不良。再者,環氧基經交聯之比例雖然難以進行嚴格之測定,但可例如藉由觀察DSC(示差掃描熱析法,Differential Scanning Calorimetry)測定之發熱量而算出大致之比例。
如此般,本實施形態之熱硬化性樹脂組成物特佳為丙烯酸系共聚物之環氧基部分的3~12%經由具有一級胺基及二級胺基之至少一者之聚胺或聚醯胺胺而交聯。藉此,可調整接著劑之滲出量,使加熱加壓成形時之未反應環氧樹脂等之滲出性良好,並且可長期表現良好之膜之常溫保管性。
又,本實施形態之熱硬化性樹脂組成物藉由含有有機酸二醯肼作為硬化劑,可使常溫保存穩定性優異,無需冰櫃等設備,而使運輸、保管等之操作變得非常容易。
進而,本實施形態之熱硬化性樹脂組成物具有優異之接著強度,故而可對聚醯亞胺膜、金屬板保持較高之接著性。又,本實施形態之熱硬化性樹脂組成物由於吸濕焊接耐熱性優異,故而即使於例如夏季等高濕度下亦可使安裝時之耐無鉛回焊性良好。
<2.熱硬化性樹脂組成物之製造方法>
本實施形態之熱硬化性樹脂組成物可藉由利用常法將丙烯酸系共聚物、環氧樹脂、硬化劑、具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺均勻地混合而製備。熱硬化性樹脂組成物之形態例如可列舉糊狀、膜、分散液狀。
熱硬化性樹脂組成物例如可藉由以下方法進行製造。一面使用攪拌機將溶解於有機溶劑中之丙烯酸系共聚物、及具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺進行混合,一面使該等反應。混合後,於該有機溶劑中投入規定量之環氧樹脂及硬化劑,從而可製作成為熱硬化性樹脂組成物之接著劑溶液。
<3.熱硬化性接著片>
熱硬化性接著片係例如於基材膜(剝離基材)上形成由上述熱硬化性樹脂組成物構成之熱硬化性接著層而成。基材膜可列舉聚對苯二甲酸乙二酯膜、聚醯亞胺膜等。就保管性或使用時之操作性等觀點而言,熱硬化性接著片較佳為使由熱硬化性樹脂組成物構成之熱硬化性接著層以10~50μm之厚度成形於視需要以聚矽氧等對聚對苯二甲酸乙二酯膜、聚醯亞胺膜等進行剝離處理而成之基材膜上。
<4.熱硬化性接著片之製造方法>
熱硬化性接著片例如可藉由以下方法進行製造。熱硬化性接著片之製造方法包括:交聯步驟,係使丙烯酸系共聚物之環氧基部分之1~15%經由液狀之聚胺或聚醯胺胺而交聯;製備步驟,係製備熱硬化性接著層形成用之塗料;及熱硬化性接著層形成步驟,係形成熱硬化性接著層。
於交聯步驟中,使溶解於有機溶劑中之含有含環氧基之(甲基)丙烯酸酯單體之丙烯酸系共聚物、及具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺混合。藉此,使丙烯酸系共聚物之環氧基部分經由液狀之聚胺或聚醯胺胺而部分地交聯。丙烯酸系共聚物及液狀之聚胺或聚醯胺胺可使用上述化合物。
於製備步驟中,以達到適於有機溶劑之黏度之方式投入熱硬化性樹脂組成物,並於有機溶劑中分散硬化劑,使丙烯酸系共聚物及環氧樹脂於有機溶劑中溶解,藉此製備熱硬化性接著層形成用塗料。作為有機溶劑,例如可使用甲基乙基酮、甲苯等。於製備步驟中,較佳為總有機酸二醯肼粒子之70質量%於室溫下以固體粒子之形式分散於熱硬化性接著層形成用塗料中。藉此,可提高硬化性接著片之常溫保管性。
於熱硬化性接著層形成步驟中,利用棒式塗佈機、輥式塗佈機等將於製備步驟中製備之熱硬化性接著層形成用塗料以乾燥厚度成為10~50 μm之方式塗佈於基材膜上,利用常法使其乾燥而形成熱硬化性接著層。藉此,可獲得熱硬化性接著層片。
上述熱硬化性樹脂組成物及熱硬化性接著片例如可較佳地應用於電子零件領域。尤其是,熱硬化性接著片可較佳地用以接著固定可撓性印刷配線板之端子部等、與用作其襯裏之聚對苯二甲酸乙二酯、聚醯亞胺、環氧玻璃、不鏽鋼、鋁等厚度50 μm~2 mm之加強用樹脂片。藉此,可獲得可撓性印刷配線板之端子部與加強用樹脂片藉由本實施形態之硬化性接著層片之去除基材膜的熱硬化性接著層之熱硬化物進行接著固定而成之加強可撓性印刷配線板。
<5.其他實施形態>
本實施形態之熱硬化性樹脂組成物除上述成分以外,亦可於不損及本發明之效果之範圍內視需要摻合不促進有機酸二醯肼之溶解之金屬減活劑、消泡劑、防銹劑、分散劑等公知之添加劑。
[實施例]
以下對本發明之具體實施例進行說明。再者,本發明之範圍並不限定於下述實施例。
(材料)
‧丙烯酸系共聚物
丙烯酸丁酯(BA)、丙烯酸乙酯(EA)、丙烯腈(AN)、甲基丙烯酸縮水甘油酯(GMA)
‧環氧樹脂
JER828、JER1001
‧硬化劑
4,4'-二胺基二苯基碸(DDS)、7,11-十八碳二烯-1,18-二碳醯肼(UDH)
‧具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺
三伸乙四胺及其改質物之混合物
‧含有羧基之NBR
Nipol 1072J
(熱硬化接著層形成用塗料之製備)
準備由表1所示單體構成之丙烯酸系共聚物。以成為表1之組成之方式稱量溶解於有機溶劑中之丙烯酸系共聚物、三伸乙四胺及其改質物之混合物,一面利用攪拌機混合一面使其反應2小時,使丙烯酸系共聚物之環氧基部分經由三伸乙四胺及其改質物之混合物而部分地交聯。混合後,投入規定量之環氧樹脂、硬化劑,製作成為表1之組成之熱硬化性接著層形成用塗料(接著劑溶液)。再者,於比較例1中,未混合三伸乙四胺及其改質物之混合物。
(熱硬化性接著片之製作)
將所獲得之熱硬化性接著層形成用塗料塗佈於實施有剝離處理之聚對苯二甲酸乙二酯膜上,於50~130℃之乾燥爐中乾燥而形成35 μm厚之熱硬化性接著層,藉此製作熱硬化性接著片。
於表1中,「BA」表示丙烯酸丁酯,「EA」表示丙烯酸乙酯,「AN」表示丙烯腈,「GMA」表示甲基丙烯酸縮水甘油酯,「DDS」表示4,4'-二胺基二苯基碸,「UDH」表示7,11-十八碳二烯-1,18-二碳醯肼。又,於表1中,丙烯酸系共聚物、環氧樹脂、硬化劑、一級或二級之液狀胺及含有羧基之NBR之添加量的單位分別為質量份。
於表1中,所謂「一級或二級之液狀胺之實際摻合量」係表示實際添加之三伸乙四胺及其改質物之量(質量份)。
於表1中,所謂「丙烯酸系橡膠中之環氧基之交聯比例」係表示丙烯酸系共聚物之環氧基部分經由三伸乙四胺及其改質物之混合物而交聯之比例(%)。
(滲出性評價)
滲出性之評價係以如下方式進行。如圖1A所示般準備接著片4,其係加工成於膜化為35 μm之熱硬化性接著層1之表面設置有輕剝離型之剝離膜(以下稱作「輕面側膜」)2及重剝離型之剝離膜(以下稱作「重面側膜」)3之兩面剝離(double separate)型者。如圖1B所示般,剝離接著片4之輕面側膜2,如圖1C所示般,以100℃、1 m/min、5 kg/cm之條件對175 μm之聚醯亞胺膜5進行層壓。如圖1D及圖1E所示般,對於層壓於聚醯亞胺膜5上之接著片4,使用圖2所示之整緣模具6自聚醯亞胺膜5側衝壓接著片4。如圖1F所示般,將自聚醯亞胺膜5側衝壓之接著片4之樣品之重面側膜3剝離,層壓由銅7及聚醯亞胺膜8構成之CCL(copper clad laminate,覆銅箔層壓板)9。藉此,製成試片10。如圖1G及圖3所示般,試片10之短邊為50 mm,長邊為100 mm,於試片10之短邊方向(厚度方向)上形成有直徑10 mm、直徑5 mm及直徑3 mm之滲出性測定用之孔。
滲出性係以170℃、2 MPa、1分鐘之條件對試片10進行壓製,利用光學顯微鏡測定壓製後之熱硬化性接著層1自衝壓剖面之滲出量。將滲出性之測定結果示於表1。表1中,所謂滲出性為「○」,係表示自設置於試片10之孔滲出之熱硬化性接著層1之凸出寬度為50~100 μm。滲出性為「△」係表示自設置於試片10之孔滲出之熱硬化性接著層1之凸出寬度為100~200 μm。滲出性為「×」係表示滲出之熱硬化性接著層1之凸出寬度為200 μm以上。
(剝離強度之評價)
剝離強度之評價係以如下方式進行。將剛獲得之熱硬化性接著性片切割為規定大小之短條(5 cm×10 cm),利用設定為80℃之貼合機將該熱硬化性接著層暫時貼附於175 μm之聚醯亞胺膜(175AH,Kaneka股份有限公司製造)後,去除基材膜而使熱硬化性接著層露出。對於露出之熱硬化性接著層,從上方重疊同樣大小之50 μm厚之聚醯亞胺膜(200H,DUPONT公司製造),於170℃以2.0 MPa之壓力加熱加壓60秒之後,於140℃之烘箱中保持60分鐘。
又,將切割為短條(5 cm×10 cm)之熱硬化性接著片之熱硬化性接著層抵壓而暫時貼附於0.5 mm之SUS304板或厚度1 mm之玻璃環氧板上後,去除基材膜而使熱硬化性接著層露出。對於露出之熱硬化性接著層,從上方重疊短條狀之厚度50 μm之聚醯亞胺膜(5 cm×10 cm),於170℃以2.0 MPa之壓力加熱加壓60秒後,於140℃之烘箱中保持60分鐘。
於烘箱中保持後,以剝離速度50 mm/min對聚醯亞胺膜進行90度剝離試驗,測定剝離所需要之力。將測定結果示於表1。期待剝離強度於實際應用中為10 N/cm。
(吸濕回焊接耐熱性試驗)
吸濕回焊接耐熱性試驗係以如下方式進行。利用設定為80℃之貼合機將切割為短條(2 cm×2 cm)之熱硬化性接著性片之熱硬化性接著層暫時貼附於175 μm厚之聚醯亞胺膜(Apical 175AH,Kaneka股份有限公司製造)。自熱硬化性接著性片去除剝離基材而使熱硬化性接著層露出。對於露出之熱硬化性接著層,從上方重疊同樣大小之厚度50 μm厚之聚醯亞胺膜(Kapton 200H,DUPONT公司製造),於170℃以2.0 MPa之壓力加熱加壓60秒後,於140℃之烘箱中保持60分鐘。將加熱硬化之試片於40℃、90 RH之濕熱烘箱中放置96小時。
使剛經濕熱處理後之試片通過設定為最高溫度260℃-30秒之回焊爐,目視觀察通過後之試片有無膨脹、剝落等外觀異常。將觀察結果示於表1。表1中,吸濕回焊接耐熱性為「A」係表示外觀完全不存在問題之情況。吸濕回焊接耐熱性為「C」係表示於試片上觀察到由發泡引起之膨脹之情況。
(關於常溫保管性)
常溫保管性係以如下方式進行評價。表1中,所謂常溫保管性為「○」,係表示剝離強度之值相比初始降低率為30%以內,且吸濕回焊性無變化。又,所謂常溫保管性為「×」,係表示剝離強度之值相比初始降低率為30%以上或吸濕回焊性變化之情況。
於實施例1~實施例5所獲得之熱硬化性接著片中,丙烯酸系共聚物之環氧基部分之0.5~18%經由三伸乙四胺及其改質物之混合物而交聯。因此,於實施例1~實施例5所獲得之熱硬化性接著片中,加熱加壓成形時之未反應環氧樹脂等之滲出性良好。
尤其是實施例3~實施例5所獲得之熱硬化性接著片於熱硬化性接著層中含有有機酸二醯肼,且丙烯酸系共聚物之環氧基部分的3~12%經由三伸乙四胺及其改質物之混合物而交聯。因此,於實施例3~實施例5所獲得之熱硬化性接著片中,加熱加壓成形時之未反應環氧樹脂等之滲出性、膜之常溫保管性、剝離強度、吸濕回焊接耐熱性試驗之評價均良好。
比較例1所獲得之熱硬化性接著片於熱硬化性接著層中不含有有機酸二醯肼,並且丙烯酸系共聚物之環氧基部分未經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而交聯。因此,於比較例1所獲得之熱硬化性接著片中,加熱加壓成形時之未反應環氧樹脂等之滲出性、膜之常溫保管性、剝離強度、吸濕回焊接耐熱性試驗之評價均不良。
1...熱硬化性接著層
2...輕剝離型之剝離膜(輕面側膜)
3...重剝離型之剝離膜(重面側膜)
4...接著片
5...聚醯亞胺膜
6...整緣模具
7...銅
8...聚醯亞胺膜
9...CCL
10...試片
圖1A至圖1G係用以說明試片之製作方法之步驟圖。
圖2係示意地表示於滲出性之測定方法中使用的整緣模具之一例之平面圖。
圖3係示意地表示滲出性測定用之試片之一例的立體圖。
Claims (7)
- 一種熱硬化性樹脂組成物,含有丙烯酸共聚物、環氧樹脂及該環氧樹脂用之硬化劑,該丙烯酸共聚物含有含環氧基之(甲基)丙烯酸酯單體,且該丙烯酸共聚物之環氧基部分的1%~12%經由具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而交聯。
- 如申請專利範圍第1項之熱硬化性樹脂組成物,其中,該丙烯酸共聚物之環氧基部分的3~12%經由該具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺而交聯。
- 如申請專利範圍第2項之熱硬化性樹脂組成物,其中,該硬化劑含有有機酸二醯肼。
- 如申請專利範圍第3項之熱硬化性樹脂組成物,其中,該含環氧基之(甲基)丙烯酸酯單體的摻合比率為該丙烯酸共聚物的3~15質量%。
- 如申請專利範圍第3或4項之熱硬化性樹脂組成物,其中,該有機酸二醯肼之平均粒徑為0.5~15μm,且均勻地分散。
- 一種熱硬化性接著片,於基材膜上形成有由申請專利範圍第1至5項中任一項之熱硬化性樹脂組成物構成之熱硬化性接著層。
- 一種熱硬化性接著片之製造方法,具有以下步驟:交聯步驟:係將溶解於有機溶劑中之含有含環氧基之 (甲基)丙烯酸酯單體的丙烯酸共聚物、及具有一級胺基及二級胺基之至少一者的液狀聚胺或聚醯胺胺混合,使該丙烯酸共聚物之環氧基部分的1%~12%經由該液狀之聚胺或聚醯胺胺而交聯;製備步驟:係將環氧樹脂、及含有有機酸二醯肼之該環氧樹脂用硬化劑溶解於含有該環氧基部分經交聯之丙烯酸共聚物的有機溶劑中,藉此製備熱硬化性接著層形成用塗料;以及熱硬化性接著層形成步驟:係將該熱硬化性接著層形成用塗料塗佈於基材膜上,並進行乾燥,藉此形成熱硬化性接著層。
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