TWI617441B - 於基板上製備圖案化覆蓋膜之方法 - Google Patents
於基板上製備圖案化覆蓋膜之方法 Download PDFInfo
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- TWI617441B TWI617441B TW106111471A TW106111471A TWI617441B TW I617441 B TWI617441 B TW I617441B TW 106111471 A TW106111471 A TW 106111471A TW 106111471 A TW106111471 A TW 106111471A TW I617441 B TWI617441 B TW I617441B
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- Prior art keywords
- polyimide
- alkyl
- dry film
- film
- present
- Prior art date
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- H05K1/02—Details
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- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
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- H05K3/007—Manufacture or processing of a substrate for a printed circuit board supported by a temporary or sacrificial carrier
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
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Abstract
本發明係關於一種於基板上製備圖案化聚醯亞胺覆蓋膜之方法。該方法包含:提供一聚醯亞胺乾膜,其包含支撐體及位於該支撐體上之非感光型聚醯亞胺層,該非感光型聚醯亞胺層包含(i)聚醯亞胺前驅物或可溶性聚醯亞胺及(ii)溶劑;於該聚醯亞胺乾膜形成預定圖案;將該已形成預定圖案之聚醯亞胺乾膜以非感光型聚聚醯亞胺層之面與基板進行壓合;及加熱形成圖案化聚醯亞胺覆蓋膜。
Description
本發明係關於一種於基板上製備圖案化覆蓋膜之方法,尤其係於軟性印刷電路板上製備圖案化覆蓋膜之方法。
近年來由於電子產品強調輕、薄、短、小,各種電子零組件之尺寸也必須跟著越做越小。在這種發展趨勢下,具有輕、薄及耐高溫等特性並可大量生產的軟性印刷電路板(flexible printed circuit,FPC),便有了更多的發展空間。目前熱門的電子產品如行動電話、液晶顯示器及有機發光二極體等都可見到軟性印刷電路板的蹤跡。軟性印刷電路板係將線路及其他電子元件布置於軟性銅箔基板(FCCL)上而得,相較於使用傳統矽基板或玻璃基板之印刷電路板具有較佳的可撓性,因此又可稱為軟板。軟板表面上通常會加上一層覆蓋膜(coverlay),可作為絕緣保護層,來保護軟板表面之銅製線路並增加線路耐彎折能力。合適的覆蓋膜材料必須具備較佳的耐熱性、尺寸安定性、絕緣特性及耐化學性。聚醯亞胺(PI)絕緣性佳且在延展性、熱膨脹係數(CTE)值、耐熱能力及化學穩定性等物理性質較優,因此是常用的覆蓋膜材料。
圖1係技術領域中習知施加覆蓋膜以保護軟板表面之銅線路的方法:(a)首先係提供一包含絕緣材料層11、黏合劑層(adhesive)12及離
型層13之膜片10;(b)將其加工成預定形狀;(c)移除離型層13並對準至軟板50的相應位置;(d)進行壓合,將絕緣材料層11壓合至軟板50上作為覆蓋膜。上述絕緣材料層11通常係使用已合成且經加工之薄膜,例如經單軸或雙軸拉伸之聚醯亞胺薄膜(PI film)。上述聚醯亞胺薄膜因製備時需經過拉伸,厚度不能太薄,否則韌性度會大大的降低,拉伸性也不好。再者,聚醯亞胺薄膜與常用作軟板50的軟性銅箔基板間密著不佳,所以必須使用黏著劑,例如環氧膠或壓克力膠,這也會增加覆蓋膜的厚度,故傳統的覆蓋膜的厚度較厚(一般大於20μm),不符合目前要求輕薄的製程。又,軟板表面因具備銅線路係呈圖案化表面之形式,因此,為能有效覆蓋銅線路,黏著劑層至少必須能在特定條件下產生流動性,以填覆至軟板表面之凹槽處。常用之黏合劑材料包含環氧系樹脂,例如,US2006/0234045(A1)或US2012/0015178(A1)所揭示者,惟,相較於聚醯亞胺而言,黏著劑層中的環氧系樹脂耐熱及耐折性較差。
上述方法中,由於必須使用具強密著力之黏著劑,因此,發生對位錯誤時,難以將黏著劑溶解去膠,無法進行重工。再者,基於黏著劑層、絕緣材料層及軟板間熱膨脹係數之差異,易有翹曲問題。此外,為使黏著劑層產生所需之流動性,圖1之壓合步驟(d)通常係在高溫高壓條件,例如85~100kg/cm2之壓力及150~190℃之溫度下進行,但卻因此易有黏著劑溢膠(adhesive bleeding)問題。另一個常見問題是,膜片壓合至圖案化表面時,可能有不欲之氣體殘存於兩者間,此將影響最終產品之可靠度及品質。使用真空壓膜設備(例,真空壓膜機(vacuum laminator)或真空熱壓機(vacuum hot press))將空氣排出後再加壓貼合,可避免此問題。然而,使用真空壓膜設備之方法大多僅能以單片方式進行壓合,亦即片對片(sheet by sheet)方式,在每次壓合步驟完成後需暫停一段時間,移除已完成壓合之試片並替換上另一
試片,不僅耗時、無法達到連續製程和快速生產之目標,且真空壓膜設備成本昂貴,不符成本效益。
有鑑於此,技術領域需要一種加工步驟簡單、符合電子產品輕薄要求,且能解決黏著劑所造成之溢膠及無法重工等問題之覆蓋膜。
本發明提供一種於基板上製備圖案化聚醯亞胺覆蓋膜之新穎方法,可有效解決前述問題。
本發明之方法包含:(a)提供一聚醯亞胺乾膜,該聚醯亞胺乾膜包含支撐體及位於該支撐體上之非感光型聚醯亞胺層,其中該非感光型聚醯亞胺層包含:(i)聚醯亞胺前驅物或可溶性聚醯亞胺;及(ii)溶劑;(b)於該聚醯亞胺乾膜上形成一預定圖案;(c)將該已形成預定圖案之聚醯亞胺乾膜以非感光型聚醯亞胺層之面與基板進行壓合;及(d)進行加熱,以形成圖案化聚醯亞胺覆蓋膜。
本發明之方法係於聚醯亞胺乾膜上預製開口(預先圖案化)後進行貼合,因此不涉及曝光、顯影等繁複的步驟,故製法簡單且具經濟效益。再者,本發明之方法利用聚醯亞胺前驅物或可溶性聚醯亞胺與基(軟)板密著性佳,所以本發明之聚醯亞胺乾膜不需要使用黏著劑,也不會產生溢膠現象,且該非感光型聚醯亞胺層厚度可調整,可有效降低覆蓋膜的厚度,達到薄型化要求,所得產品亦具有較佳之低翹曲、耐熱及耐折性。
A‧‧‧基板捲
B‧‧‧產品捲
1‧‧‧乾膜捲
2‧‧‧上滾輪
3‧‧‧下滾輪
10‧‧‧膜片
11‧‧‧絕緣樹脂層
12‧‧‧黏合劑層
13‧‧‧離型層
20‧‧‧聚醯亞胺乾膜
21‧‧‧保護膜
22‧‧‧聚醯亞胺層
23‧‧‧支撐體
50‧‧‧軟板/基板
22'‧‧‧圖案化聚醯亞胺覆蓋膜
H1‧‧‧厚度
H2‧‧‧厚度
圖1為習知施加覆蓋膜以保護軟板表面銅線路之方法的示意圖。
圖2為根據本發明一實施態樣之於基板上製備圖案化聚醯亞胺覆蓋膜之方法之示意圖。
圖3為捲對捲製程之示意圖。
為便於理解本文所陳述之揭示內容,茲於下文中定義若干術語。
術語「約」意謂如由一般熟習此項技術者所測定之特定值的可接受誤差,其部分地視如何量測或測定該值而定。
在本發明中,術語"烷基"係指飽和直鏈或支鏈烴基,較佳具有1至30個碳原子,更佳具有1至20個碳原子;其實例包括(但不限於)甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、戊基、己基及其類似基團。
在本發明中,術語"烯基"係指具有至少一個碳-碳雙鍵之不飽和直鏈或支鏈烴基,較佳具有2至30個碳原子,更佳具有10至20個碳原子;其實例包括(但不限於)乙烯基、丙烯基、甲基丙烯基、異丙烯基、戊烯基、己烯基、庚烯基、1-丙烯基、2-丁烯基、2-甲基-2-丁烯基及其類似基團。
在本發明中,術語"炔基"係指具有至少一個碳-碳參鍵之不飽和直鏈或支鏈烴基,較佳具有2至30個碳原子,更佳具有10至20個碳原子;其實例包括(但不限於)乙炔基、炔丙基、3-甲基-1-戊炔基、2-庚炔基及其類似基團。
在本發明中,術語"芳基"或"芳香族化合物"係指6-碳單環、10-碳二環-或14-碳三環之芳環體系,舉例言之,芳基之實例包括(但不限於)苯基、甲苯基、萘基、芴基、蒽基、菲基及其類似基團。
在本發明中,術語"鹵烷基"係指經鹵素取代之烷基,其中"鹵素"意謂氟、氯、溴或碘,較佳為氟及氯。
在本發明中,術語"烷氧基"係指附著於氧原子上之烷基,其實例包括(但不限於)甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、異丁氧基、戊氧基、己氧基、苯甲氧基、芴甲氧基及其類似基團。
在本發明中,術語"雜環基"係指由碳原子及至少一個選自N、O或S之雜原子所組成之飽和、部分飽和(例如以字首二氫、三氫、四氫、六氫等命名者)或不飽和之3至14員環基,較佳為4至10員環基,更佳為5或6員環基;較佳具有1至4個雜原子,更佳具有1至3個雜原子。該雜環基可為單環、雙環或三環形環系統,其包含稠合環(例如與另一雜環或另一芳族碳環一起形成之稠合環)。除非特別指明,在本發明中,"雜環基"可經取代或未經取代。取代基例如但不限於:鹵素、羥基、側氧基(oxo)、烷基、羥烷基、-NO2等。
在本發明中,術語"含氮雜環基"係指至少一個環碳原子被N原子置換之3至14員雜環基,較佳為4至10員含氮雜環基,更佳5或6員含氮雜環基。其實例包含但不限於:吡咯基(pyrrolyl)、咪唑基(imidazolyl)、吡唑基(pyrazolyl)、嘧啶(pyrimidinyl)基、噻唑基(thiazolyl)、吡啶基(pyridyl)、吲哚基(indolyl)、異吲哚基(isoindolyl)、苯並咪唑(benzimidazolyl)、苯並噻唑基(benzothiazolyl)、喹啉基(quinolyl)、喹啉基(isoquinolyl)等。除非特別指明,在本發明中,"含氮雜環基"可經取代或未經取代。取代基係如上述關於"雜環基"所定義者。
在本發明中,除非特別指明,術語"聚醯亞胺層"則指含尚未環化或固化之聚醯亞胺前驅物或含可溶性聚醯亞胺樹脂之樹脂層,前述"聚醯亞胺"亦包含聚醚醯亞胺(polyetherimide,PEI)。"聚醯亞胺"可為聚醯亞胺均聚物或共聚物。
在本發明中,術語"乾膜"係技屬領域中之慣用語,係指將含溶劑之樹脂係以表面成膜之形式施加於支撐體上,視需要進行乾燥後所製
得之膜片。乾膜中的樹脂層可視需要含有溶劑。不同於液態樹脂材料,乾膜上之樹脂材料可藉由壓合之方式轉印至基板上,而一般液態材料是將可流動的材料以塗佈方式施加於基板上。
感光型聚醯亞胺乾膜可用作感光型覆蓋膜(photo-imageable coverlay,簡稱PIC)保護軟板表面的銅製線路。然而,感光型聚醯亞胺乾膜在壓合至軟板後,必須進行諸如曝光、顯影、蝕刻等繁複的加工步驟製備所欲之開口,製程繁複且成本較高。
本發明之方法不涉及感光製程,因此,本發明之聚醯亞胺乾膜並不特別限於感光型或非感光型聚醯亞胺乾膜,在本發明之較佳實施例中係使用非感光型聚醯亞胺乾膜。
本發明方法所使用之聚醯亞胺乾膜包含支撐體和位於該支撐體上之非感光型聚醯亞胺層,其中該非感光型聚醯亞胺層包含:(i)聚醯亞胺前驅物或可溶性聚醯亞胺;及(ii)溶劑。
本發明使用之支撐體,可為任何本發明所屬技術領域具有通常知識者所已知者,例如玻璃或塑膠。上述塑膠支撐體並無特殊限制,其例如但不限於:聚酯樹脂(polyester resin),如聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)或聚萘二甲酸乙二酯(polyethylene naphthalate,PEN);聚甲基丙烯酸酯樹脂(polymethacrylate resin),如聚甲基丙烯酸甲酯(polymethyl methacrylate,PMMA);聚醯亞胺樹脂(polyimide resin);聚苯乙烯樹脂(polystyrene resin);聚環烯烴樹脂(polycycloolefin resin);聚烯烴樹脂(polycycloolefin resin);聚碳酸酯樹脂(polycarbonate resin);聚胺基甲酸酯樹脂(polyurethane resin);三醋酸纖維素(triacetate cellulose,TAC);或彼等之混合物。較佳為聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚環烯烴樹脂、三醋酸纖維素
或其混合物,更佳為聚對苯二甲酸乙二酯。支撐體之厚度通常取決於所欲得電子產品的需求,其較佳介於約16μm至約250μm之間。
在本發明之較佳實施例中係使用非感光型聚醯亞胺乾膜,上述乾膜中包含非感光性聚醯亞胺層,上述非感光性聚醯亞胺層可包含聚醯亞胺前驅物或可溶性聚醯亞胺,亦即,聚醯亞胺前驅物或可溶性聚醯亞胺不具感光性基團。
本發明乾膜中之聚醯亞胺層之厚度可依產品需求去做調整,,一般係介於約5μm至約60μm之間,較佳介於約10μm至約50μm之間,更佳介於約15μm至約40μm之間。
聚醯亞胺層之流平性受其玻璃轉換溫度高低影響,較高之玻璃轉換溫度導致聚醯亞胺層之流平性差,難以壓合,且在壓合過程中易產生無法溶解之氣泡,而較低之玻璃轉換溫度,使聚醯亞胺層在壓合過程中易產生沾黏現象,操作性差。根據本發明之一實施態樣,本發明之聚醯亞胺層具有較有益之介於-10℃至20℃間之玻璃轉換溫度,較佳係介於0℃至15℃間之玻璃轉換溫度。
本發明所用之聚醯亞胺前驅物並無特殊限制,且可為本發明所屬技術領域中具有通常知識者所熟知者,例如聚醯胺酸、聚醯胺酯、任何可經由反應生成聚醯亞胺之材料或其混合物。技術領域中已開發出多種不同聚醯亞胺前驅物,例如中華民國發明專利第095138481號、第095141664號、第096128743號、第097151913號或第100149594號申請案。上述文獻係全文併入本文中做為參考。
聚醯亞胺前驅物主要係具有以式(A)表示之重覆單元:
其中,G為四價有機基團;P為二價有機基團;n為大於0之整數,較佳是1至1000之整數。
可視需要使用不同基團對上述聚醯亞胺前驅物進行改質。例如,藉由感光性基團進行改質可製備感光型聚醯亞胺前驅物;或藉由調整與式(A)重複單元鍵結之末端基團,可改良聚醯亞胺前驅物之反應性及改良後續製得之聚醯亞胺之性質。
舉例言之,中華民國發明專利第100149594號申請案揭示具有以下式(1)至(4)表示之重覆單元之聚醯亞胺前驅物:
其中,G1獨立為四價有機基團;Rx各自獨立為H或乙烯系不飽和基;R各自獨立為C1-C14烷基、C6-C14芳基、C6-C14芳烷基、酚基或乙烯系不飽和基;D各自獨立為含氮之雜環基團或為OR*基團,其中R*為C1-C20烷基;m為0至100之整數,較佳是5至50之整數,更佳是10至25之整數;及G及P係如本文先前所定義。
上述乙烯系不飽和基,並無特殊限制,其實例包括(但不限於)乙烯基、丙烯基、甲基丙烯基、正丁烯基、異丁烯基、乙烯基苯基、丙烯基苯基、丙烯氧基甲基、丙烯氧基乙基、丙烯氧基丙基、丙烯氧基丁基、丙烯氧基戊基、丙烯氧基己基、甲基丙烯氧基甲基、甲基丙烯氧基乙基、甲基丙烯氧基丙基、甲基丙烯氧基丁基、甲基丙烯氧基戊基、甲基丙烯氧基己基、具下式(5)的基團及具下式(6)的基團:
一般聚醯亞胺雖具有耐熱性及耐化學性佳之優點,但卻有加工性不良之缺點,且能溶解聚醯亞胺之溶劑不多。因此,在應用時多半係使用以聚醯亞胺前驅物進行加工,並在製程後期將其醯亞胺化成聚醯亞胺。可溶性聚醯亞胺則是在聚醯亞胺結構上進行改良,增加聚醯亞胺與溶劑間之溶解度,以改善其加工性。上述溶劑之種類可例如本文以下所述者。
本發明之可溶性聚醯亞胺並無特殊限制,且可為本發明所屬技術領域中具有通常知識者所習知者,如中華民國發明專利第097101740號、第099105794號、第097138725號或第097138792號申請案。上述文獻係全文併入本文中做為參考。
本發明之可溶性聚醯亞胺主要係具有以式(B)表示之重複單元:
其中,C'為四價有機基團;
E'為二價有機基團;t'為大於0之整數,較佳是1至1000之整數。
上述C'四價有機基團之態樣可如本文先前對G基團所定義者。
上述E'二價有機基團之態樣可如本文先前對P基團所定義者。
可視需要使用不同基團對上述可溶性聚醯亞胺進行改質。例如藉由感光性基團進行改質可製備感光型聚醯亞胺;或藉由調整與式(B)重複單元鍵結之末端基團,可改良可溶性聚醯亞胺之性質。
藉由調整與式(B)重複單元鍵結之末端基團之可得經改質可溶性聚醯亞胺,其結構例如(但不限於):
其中,R20'為C2-C20飽和或不飽和之2價有基機團,較佳為-C=C-、
R21'為C2-C20可為雜原子取代之具不飽和基之1價有基機團或-OHC'、E'及t'’係如本文先前所定義。
藉由感光性基團進行改質之可溶性聚醯亞胺較佳(但不限於)係第099105794號、第099105794號、第097138725號或第097138792號申請案所揭示者。
一般而言,聚醯亞胺前驅物及可溶性聚醯亞胺係在極性非質子有機溶劑下製備或調配。
習知技術中為避免乾膜在使用時產生高濃度之揮發性有機物及降低乾膜在儲存時發生塗布膠液流動的流膠(excessive glue)現象,會將完成塗佈之乾膜半成品送入烘箱,使樹脂層乾燥並與支撐體完全貼合。有機溶劑於此步驟幾乎完全揮發,因此,一般而言,傳統乾膜產品之有機溶劑含量小於1wt%。此外,乾膜產品需儲存於低溫環境,以降低水解現象。
不同於以往技術,本發明之乾膜可含有溶劑。溶劑總含量並無特殊限制,可視乾膜之製造程序或者後續加工製程所需進行調整,在本發明中,溶劑總含量以該非感光型聚醯亞胺層總重量計為至少5wt%,可介於5wt%至70wt%之間,例如可為5wt%、10wt%、15wt%、20wt%、25wt%、30wt%、35wt%、40wt%、50wt%、55wt%、60wt%、65wt%及70wt%,較佳係介於25wt%至約65wt%之間,更佳系介於約35wt%至約60wt%之間。本案發明人發現,當溶劑總含量以樹脂層總重量計為至少5wt%,該乾膜具有溶泡效果(bubble-dissolving effect)或具有吸水性。在乾式壓合製程,中,本發明之乾膜能讓基板與乾膜間之空氣溶入乾膜的溶劑中。當應用至濕式壓合製程中,因本發明之聚醯亞胺乾膜可包含親水性溶劑,能與水互溶,因此縱使在水存在下其性質相對穩定,表面不沾黏,轉印能力佳,且由其固化所製得之聚醯亞胺具有良好的物性。因此,不但可增加儲存安定性,且可應用至需使用水或水性溶液的加工製程。因此,本發明之乾膜有效解決習知技術在將覆蓋膜壓合至軟性印刷電路板時所產生的氣泡問題,而不需使用昂貴之真空壓膜設備。
在本發明之一實施態樣中,當溶劑含量過低時(例如低於15wt%,甚至低於5wt%時),乾膜容易發生硬脆,難以壓合至軟板,使
得在壓合過程中溶解氣泡效果差,易產生復泡現象或聚醯亞胺乾膜吸水性不佳,且對軟板之密著性較差;但溶劑含量過多時,尤其是大於70wt%時,將使乾膜之聚醯亞胺層成膜性不佳,故乾膜表面易有沾黏現象,操作性較差,亦無法在壓合過程中達到預期之較佳之移除氣泡效果。
本發明所用之溶劑之種類並無特殊限制。根據本發明之一實施態樣,本發明所用之溶劑包含:二甲基亞碸(DMSO)、二乙基亞碸、苯酚、鄰甲酚、間甲酚、對甲酚、二甲苯酚、鹵代苯酚、鄰苯二酚、四氫呋喃(THF)、二噁烷、二氧戊環、環丙二醇甲醚(PGME)、四乙二醇二甲醚(TGDE)、丁基溶纖劑、γ-丁內酯(γ-butyrolactone;GBL)、二甲苯(xylene)、甲苯(toluene)、六甲基鄰醯胺、丙二醇甲醚
醋酸酯(PGMEA)、 或其混合物,其中:R1"、R9"及R10"各自獨立為C1-C20烷基、C2-C20烯基或C2-C20炔基;R7"為H或C1-C3烷基;R2"為C1-C10烷基;R3"為C4-C20烷基或-C2-C10烷基-O-C2-C10烷基;R4"及R5"各自獨立為C1-C10烷基,或R4"及R5"與其所連接之氧原子一起形成5至6員雜環;
R6"為C1-C15烷基、C2-C20烯基、C4-C8環烷基或
R8"為C2-C10伸烷基;R11"及R12"各自獨立為C1-C10烷基;R13"及R14"各自獨立為C1-C10烷基,或R13"及R14"與其所連接之氮原子一起形成5至6員雜環;R15"為H、C1-C15烷基或C4-C8環烷基;R16"為C1-C4烷基;且R17"為C4-C10烷基。
上述具結構之溶劑之實例,包含但不限於:N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺或N,N-二甲基癸醯胺(N,N-dimethylcapramide,簡稱DMC)。
上述具結構之溶劑之實例,包含但不限於:N-甲基-2-吡咯烷酮(NMP)、N-乙烯基-2-吡咯烷酮、N-乙基-2-吡咯烷酮(NEP)、N-丙基-2-吡咯烷酮或N-辛基-2-吡咯烷酮(N-octyl-2-pyrrolidone,NOP)。
根據本發明之一實施例,所用之溶劑較佳包含:二乙基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二甲基癸醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、環丙二醇甲醚、γ-丁內酯、丙二醇甲
醚醋酸酯、 或其混合物,其中R1"至R15"之定義係如上文所述;更佳包含:N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、
N-乙基-2-吡咯烷酮、γ-丁內酯、 、N,N-二甲基癸醯胺或其混合物。
本發明之聚醯亞胺層可視需要含有本發明所屬技術領域中具有通常知識者習知之任何適當添加劑,例如(但不以此為限):穩定劑(stabilizer)、閉環促進劑、整平劑、消泡劑、偶合劑、催化劑等。上述添加劑之含量亦為本發明所屬技術領域中具有通常知識者可經由例行實驗調整者。
在本發明之一實施態樣中,本發明之聚醯亞胺層可視需要含有選自下列之穩定劑:或其組合,其中:
R25"、R18"、R19"及R20"各自獨立為H、C1-C4烷基或C6-C14芳基,或者R19"及R20"與其連接之氧原子一起形成5至6員雜環,或者R19"及R25"或R20"及R18"與其連接之氧原子及氮原子一起形成5至6員雜環,或者R25"及R18"與其連接的氮原子一起形成5至6員雜環;R21"及R22"各自獨立為C1-C4烷基或C6-C14芳基,或者R21"與R22"與其連接之碳原子一起形成5至6員碳環;且R23"及R24"各自獨立為C1-C4烷基。
根據本發明之一較佳實施例,該穩定劑較佳包含:
或其組合。
添加穩定劑有助於提升乾膜的穩定性及操作性,並進一步提升後續形成之聚醯亞胺的物性。在本發明之一實施態樣中,以非感光型聚醯亞胺層總重量計,穩定劑之總含量係介於約0.01wt%至約5wt%之間,較佳係介於約0.05wt%至約3wt%之間。若含量超過5wt%可能導致形成之聚醯亞胺物性(例如可撓曲性)降低
根據本發明之一實施態様,本發明之聚醯亞胺層可視需要含有金屬密著促進劑。金屬密著促進劑(如銅密著促進劑)可與銅可形成錯合物,從而可提升聚醯亞胺層與銅線路間的接著度。
上述金屬密著促進劑其可為含氮雜環之化合物,例如具有1至3個氮原子的5至6員雜環化合物,例如咪唑系化合物(imidazoles)、吡啶系化合物(pyridines)或三唑系化合物(triazoles);或結構中含有上述含氮雜環的稠合環化合物。上述含氮雜環之化合物可未經取代或經1至3個取代基取代,取代基例如但不限於羥基或具有1至3個氮原子的5
至6員雜環基。在本發明之一實施態樣中,當金屬密著促進劑存在時,以非感光型聚醯亞胺層總重量計,金屬密著促進劑之含量為約0.1wt%至約5wt%之間,較佳為約0.5至約2重量份。
金屬密著促進劑之實例例如但不限於:1,2,3-三唑、1,2,4-三唑、3-胺基-1,2,4-三氮唑(3-Amino-1,2,4-triazole)、3,5-二胺基-1,2,4-三氮唑(3,5-Diamino-1,2,4-triazole)、咪唑(imidazole)、苯並咪唑(benzimidazole)、1,2,3,4-四氫咔唑(1,2,3,4-Tetrahydrocarbazole)、2-羥基苯並咪唑(2-hydroxybenzimidazole)、2-(2-羥基苯基)-1H-苯並咪唑(2-(2-hydroxyphenyl)-1H-benzimidazole)、2-(2-吡啶基)苯並咪唑(2-(2-pyridyl)-benzimidazole)或2-(3-吡啶基)-1H-苯並咪唑(2-(3-pyridyl)-1H-benzimidazole)、或上述之組合。
可用於本發明之偶合劑可選自由以下所組成之群組(但不以此為限):3-胺基丙基三甲氧基矽烷(APrTMOS)、3-三胺基丙基三乙氧基矽烷(APrTEOS)、3-胺基苯基三甲氧基矽烷(APTMOS)、3-胺基苯基三乙氧基矽烷(APTEOS)及其組合。
根據本發明之一實施態様,當本發乾膜之聚醯亞胺層含有聚醯亞胺前驅物時,可視需要聚醯亞胺層中加入閉環促進劑。較佳選用能在加熱,產生鹼性化合物,提供鹼性環境促進醯亞胺化(imidization)反應進行之閉環促進劑。可用於本發明之閉環促進劑包含:
或,其中Yθ為陰離子基團。
本發明之聚醯亞胺乾膜可藉由例如下列步驟製備:(1)準備聚醯亞胺調配物,混合包含聚醯亞胺前驅物或可溶性聚醯亞胺和溶劑;(2)將步驟(1)所得之調配物塗佈於支撐體形成一乾膜半成品;(3)將乾膜半成品送入烘烤爐,加熱乾燥移除部份溶劑,藉此調整聚醯亞胺層中之溶劑含量,形成一聚醯亞胺乾膜;及(4)視需要於該聚醯亞胺乾膜之聚醯亞胺層上施加一保護膜。
上述步驟(3)加熱所需溫度及時間並無特殊限制,其主要目的係以減少在樹脂層中的溶劑含量,例如可使用介於60℃至150℃間中之一適合溫度,歷時30秒至10分鐘進行加熱乾燥。在傳統製備乾膜過程中,為避免使用乾膜時產生高濃度之揮發性有機物,在相對於前述步驟(3)的移除溶劑步驟中,常加熱致使溶劑達幾乎完全揮發程度(含量小於1wt%),然而,與習知步驟相反地,本發明並未在此步驟中將溶劑完全移除,反而保留適量之溶劑於乾膜中。
上述步驟(1)或(3)的溶劑係如前所述,其可為一種或兩種以上溶劑之組合。一般而言,藉由不同溶劑種類的沸點差異,適當地調整加熱溫度及時間,可控制所欲得到之乾膜中溶劑之總含量及比例。
上述步驟(4)的保護膜,其例如但不限於:聚酯樹脂(polyester resin),如聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)或聚萘二甲酸乙二酯(polyethylene naphthalate,PEN);聚甲基丙烯酸酯樹脂(polymethacrylate resin),如聚甲基丙烯酸甲酯(polymethyl methacrylate,PMMA);聚醯亞胺樹脂(polyimide resin);聚苯乙烯樹脂(polystyrene resin);聚環烯烴樹脂(polycycloolefin resin);聚烯烴
樹脂(polycycloolefin resin);聚碳酸酯樹脂(polycarbonate resin);聚胺基甲酸酯樹脂(polyurethane resin);三醋酸纖維素(triacetate cellulose,TAC);或彼等之混合物。較佳為聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚環烯烴樹脂、三醋酸纖維素或其混合物,更佳為聚對苯二甲酸乙二酯。
本發明之乾膜具有溶氣及溶水作用,可在不使用真空壓膜設備的情況下,有效減少存在於乾膜與基板間之氣體。因此,本發明之乾膜可在不使用高壓脫泡機或真空壓膜設備的情況下,利用一般壓合技術(特別是濕式製程之滾輪壓合)與如印刷電路板、晶圓、玻璃、顯示器或觸控面板之基板進行壓合。因此,相較於使用真空壓膜機或其他製程設備之先前技術良率更高,更為符合成本效益。因此可在相較於先前技術簡單之製程步驟下進行操作,所用設備亦較先前技術所使用者更容易取得。
本發明之乾膜適用於印刷電路板,作為供保護印刷電路板上之塗膜用的覆蓋膜,具絕緣性,可保護線路,且具有避免線路氧化及焊接短路之優異效能。此外,本發明之乾膜,可在不使用真空壓膜設備的情況下,有效減少存在於樹脂層與基板間之氣體,藉此可提升產品品質。
先前技術中作為覆蓋膜或鈍化層應用於印刷電路板或晶圓之乾膜,因真空壓膜設備投資成本太高,且製程週期長,生產速度慢,形成商業量產上的瓶頸。本發明之含溶劑之乾膜,可在不使用真空壓膜設備的情況下,即可輕易移除所不欲存在之氣體,因此可以相較於先前技術,更為簡單且符合成本效益之方式應用於印刷電路板或晶圓,甚至是顯示器或觸控面板等領域中。
如前所述,為解決先前技術之問題,本發明提供一種於基板上製備圖案化聚醯亞胺覆蓋膜之新穎方法,其包含下列步驟:(a)提供一聚醯亞胺乾膜,該聚醯亞胺乾膜包含支撐體及位於該支撐體上之非感光型聚醯亞胺層,其中該非感光型聚醯亞胺層包含:(i)聚醯亞胺前驅物或可溶性聚醯亞胺;及(ii)溶劑,其中以該非感光型聚醯亞胺層總重量計,溶劑之含量係至少5wt%;(b)於該聚醯亞胺乾膜上形成一預定圖案;(c)將該已形成預定圖案之聚醯亞胺乾膜以非感光型聚醯亞胺層之面與基板進行壓合;及(d)進行加熱,以形成圖案化聚醯亞胺覆蓋膜。
圖2為根據本發明一實施態樣之於基板上製備圖案化聚醯亞胺覆蓋膜之方法之示意圖。以下茲以圖2為例,進一步說明本發明方法之細節。
如圖2(a)及(b)所示,本發明方法係先提供一包含支撐體21、非感光型聚醯亞胺層22及視需要之保護膜23的聚醯亞胺乾膜20(本發明方法之步驟(a)),並於該聚醯亞胺乾膜上形成一預定圖案(本發明方法之步驟(b))。如圖2(c)所示,在撕除保護膜23後,使已形成預定圖案之聚醯亞胺乾膜對準至基板50的相應位置。隨後如圖2(d)所示,將該已形成預定圖案之聚醯亞胺乾膜以非感光型聚醯亞胺層22之面壓合至基板50(本發明方法之步驟(c)),並移除支撐體21。最後如圖2(e)所示,進行加熱以形成圖案化聚醯亞胺覆蓋膜22'。
本發明之方法(任一步驟或整體)可使用捲對捲(roll-to-roll)方式操作。捲對捲之操作係本發明所屬技術領域中具有通常知識者所熟知者,係指透過自呈捲繞形式之樣品拉出樣品,經處理後再以捲繞方式
將經處理後之樣品收回。以步驟(c)之壓合為例,如圖3所示,呈捲繞形式之基板A於拉出後,在滾輪2及3之間與來自乾膜捲1之乾膜進行壓合(如滾輪壓合),再以捲繞方式收回形成產品B。乾膜捲1之乾膜已在先前之步驟中(即,步驟(b))製備預定圖案。本發明之乾膜可使用連續製程壓合至基板,有利於簡化製程及加快製程速度。
上述步驟(b)可使用機械沖孔(mechanical punch)或雷射鑽孔(laser drill)加工形成該預定圖案形狀,使聚醯亞胺乾膜具有與基板上線路相對應的開口,將此聚醯亞胺乾膜對準基板的相應位置。
上述基板可為印刷電路板、晶圓、顯示器、觸控面板,或其他具圖案化表面之基板。根據本發明之一實施態樣,上述基板係為印刷電路板,尤佳為軟性印刷電路板(Flexible Print Circuit;FPC)。
上述步驟(c)之壓合方式包含滾輪壓合(roller lamination)、熱板壓合(hot press)、真空壓合(vacuum lamination)或真空快壓(vacuum press),上述壓合方式可採乾式製程或濕式製程。
上述乾式製程包含滾輪壓合、熱板壓合,若在不使用真空設備下進行,可能仍有不欲之氣體殘存於圖案化電路板與聚醯亞胺乾膜之間。為了移除不欲之氣體,可視需要在壓合後,進行本發明所屬技術領域中具有通常知識者所熟知之加壓溶泡,促使基板與樹脂層間殘留之空氣迅速溶入樹脂層中。舉例言之,可將上述已施加乾膜之基板,較佳以捲繞方式收回成捲後,整捲進入加壓溶脫泡機進行溶泡,加壓條件較佳為在30至100℃及2至10大氣壓下進行10至60分鐘。
上述濕式製程包含滾輪壓合,係先將液體(通常係水或水性溶液)施加至欲壓合表面上,填滿該表面之凹陷區域,因此可排除聚醯亞胺乾膜與欲壓合表面間存在之空氣。濕式製程可有利於提升乾膜對於圖案化基板之均覆性。
聚醯亞胺及其前驅物(如聚醯胺酸或聚醯胺酸酯等)因易水解,導
致斷鏈發生或過早醯亞胺化,產生不欲之低分子量聚醯亞胺沈澱,影響所得覆蓋膜之性質,故技術領域中認為聚醯亞胺乾膜一般需在低溫或無水環境下儲存或進行加工操作,而亦不適用於濕式壓合製程。然而,本發明之聚醯亞胺乾膜可包含親水性溶劑,能與水互溶,不但具有吸水性,且表面不沾黏,與水或水性溶液相容性佳,縱使在水存在下其性質相對穩定,不會影響所得聚醯亞胺之性質。
在本發明之一較佳實施態樣,係使用濕式製程,在本發明之聚醯亞胺乾膜包含可與液體(水或醇類)互溶的親水性溶劑,可用於本發明之親水性溶劑包含:二甲基亞碸(DMSO)、二乙基亞碸、N,N-二甲基甲醯胺(DMF)、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺(N,N-dimethylacetamide,DMAc)、N,N-二乙基乙醯胺、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、N-乙基-2-吡咯烷酮(N-ethyl-2-pyrrolidone,NEP)、N-丙基-2-吡咯烷酮、N-乙烯基-2-吡咯烷酮、苯酚、鄰甲酚、間甲酚、對甲酚、二甲苯酚、鹵代苯酚、鄰苯二酚、四氫呋喃(THF)、二噁烷、二氧戊環、環丙二醇甲醚(PGME)、四乙二醇二甲醚(TGDE)、丁基溶纖劑、γ-丁內酯(γ-butyrolactone;GBL)、二甲苯(xylene)、甲苯(toluene)、六甲基鄰醯胺、丙二醇甲醚醋酸酯(PGMEA)或其混合物。
根據本發明之一實施例,所用親水性溶劑較佳包含:二乙基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、環丙二醇甲醚、γ-丁內酯、丙二醇甲醚醋酸酯或其混合物。更佳包含:N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯或其混合物。
在本發明之一較佳實施態樣,步驟(c)之壓合方式係使用濕式滾輪壓合製程,可使用捲對捲(roll-to-roll)方式操作,上述壓合溫度及
壓力並無特殊限制,壓合溫度較佳介於50℃至140℃之範圍,壓合壓力較佳介於0.1kg/cm2至15kg/cm2壓力。
本發明乾膜中之聚醯亞胺層係尚未環化或固化之聚醯亞胺前驅物(如聚醯胺酸)或係可溶性聚醯亞胺;因此,相較於習知技術製備覆蓋膜所用之單軸或雙軸拉伸聚醯亞胺成品而言,本發明乾膜中之聚醯亞胺層相對較為柔軟,可在適度加壓下填覆圖案化基板表面之凹處,不需額外藉由黏著層達此目的,壓合時所用之溫度及壓力不但相對較低,且亦無顯著溢膠狀況。此外,在對位錯誤時,可添加溶劑去除聚醯亞胺前驅物及可溶性聚醯亞胺,有利於重工。
上述步驟(d)係藉由加熱形成所欲之圖案化聚醯亞胺覆蓋膜。聚醯亞胺層所含之溶劑及/或與前述溶劑互溶的液體(水或醇類)及/或壓合時溶入聚醯亞胺層之空氣可在此步驟移除;此外,當聚醯亞胺層包含聚醯亞胺前驅物時,亦在此步驟中使該聚醯亞胺前驅物環化、聚合成聚醯亞胺。步驟(d)之加熱溫度及時間並無特殊限制,可視需要調整,只要能達成前述目的即可。根據本發明之一實施態樣中,步驟(d)係以烘箱或紅外線進行加熱,利用紅外線可縮短加熱時間,提高製程效率。
習知技術製備覆蓋膜所用之單軸或雙軸拉伸聚醯亞胺成品具有一定厚度(例如,US2012/0015178(A1)所揭示之10μm至200μm),且為提供足夠之附著力及有效填覆圖案化基板之凹處,所用之黏著劑層亦具有一定厚度(例如,US2012/0015178(A1)所揭示之5μm至50μm),故習知技術製備覆蓋膜厚度約介於15μm至250μm之間。本發明之方法不需使用黏著劑層,且聚醯亞胺層係包含聚醯亞胺前驅物或可溶性聚醯亞胺和溶劑,故當加熱揮發溶劑形成所欲之聚醯亞胺覆蓋膜後,其厚度可視需要輕易調整,因此,可薄型化,製備較薄之覆蓋膜。根據本發明之一實施態樣中,步驟(d)所完成之覆蓋膜之厚度係介於2
μm至30μm之間,例如可為約2、3、5、7、9、10、11、12、13或14μm,較佳係不大於20μm,更佳係不大於15μm。。所以相較於習知製備覆蓋膜之技術而言,以本發明方法製備覆蓋膜,具有容易施工,良率高,易重工等優點;此外,本發明之方法可調整厚度,製備較薄覆蓋膜,即便使用本發明之方法製備與習知覆蓋膜厚度相當之覆蓋膜時,因為本發明之覆蓋膜不含黏著劑,為一單層(one layer)聚醯亞胺結構,所以具有較佳的絕緣性。
本發明之方法不需使用黏著劑,不但可降低翹曲、溢膠問題,所得覆蓋膜具有較佳之耐熱及耐折性,且可有效附著至基板。
以下實施例係用於對本發明作進一步說明,唯非用以限制本發明之範圍。任何熟悉此項技藝之人士可輕易達成之修飾及改變均包括於本案說明書揭示內容及所附申請專利範圍之範圍內。
將15.23克(0.052莫耳)的3,3,4,4-聯苯四甲酸二酐(4,4'-Biphthalic dianhydride,下文簡稱為BPDA)溶於100克的N-甲基-2-吡咯烷酮(下文簡稱為NMP)中,滴入0.959克(0.013莫耳)的正丁醇及0.48克(0.006莫耳)的1-甲基咪唑(1-methylimidazole),於60℃的固定溫度下反應攪拌兩個小時。再將82.88克(0.259莫耳)的間二(三氟甲基)對二胺基聯苯(2,2'-bis(trifluoromethyl)benzidine)及300克的NMP於10℃下加至溶液中,攪拌半小時後再加入60.92克(0.207莫耳)的BPDA及200克的NMP於10℃下攪拌。四小時後,升溫至60℃的固定溫度下反應攪拌八個小時,最後加入0.83克(0.006莫耳)的三氟乙酸乙酯(Ethyl trifluoroacetate)攪拌1個小時,於室溫下加入0.22g的5-氨基四氮唑(5-Aminotetrazole)及24克的NMP攪拌1個小時,可得聚醯亞胺前驅物樹
脂PAA-1,固形份約20wt%。
取PAA-1溶液100重量份,以刮刀均勻塗布在PET(聚對苯二甲酸乙二酯;R310,三菱製)上,於長度為1公尺之烘箱,以溫度為90℃且進料線速為0.45m/min進行烘烤,之後於塗有PAA-1層的一面覆蓋上離型膜(型號:L150L,南亞製),即可得到乾膜。經烘烤後的塗層厚度約30μm,乾膜中的溶劑含量以PAA-1層總重量計為40wt%。
將前述製備例所製得之乾膜取20*20cm,以機械式沖孔機打出1/4"圓孔(即,直徑約6.35mm)後,除去離型膜。
取20*20cm已製作線路的銅箔基板(L/S=30/30μm;L/S為線寬/線距;厚度12.7μm)。於銅箔基板具線路之一面上施覆去離子水,使用熱滾輪,以80℃及5kg/cm2的下壓力將乾膜塗覆有聚醯亞胺前驅物層的一面貼附至銅箔基板具線路之一面上。之後撕除PET膜,再置入氮氣烘箱,以170℃加熱1小時,再以350℃加熱2小時,進行烘烤,製備具有圖案化聚醯亞胺覆蓋膜的電路板FPC-1。
同實施例1之方法,唯在壓合時未在銅箔基板具線路之一面上施覆去離子水。製備具有圖案化聚醯亞胺覆蓋膜的電路板FPC-2。
利用塗布機將環氧樹脂均勻塗布在聚醯亞胺薄膜(KAPTON®,膜厚為12.7μm)上,於80℃加熱3小時,烘烤成15μm的黏著乾膜,覆蓋上離型膜(型號:L150L,南亞製),製備出環氧膠覆蓋膜。
將上述所製得之環氧膠覆蓋膜取20*20cm,以機械式沖孔機打出1/4"圓孔(即,直徑約6.35mm)後,除去離型膜。
取20*20cm已製作線路的銅箔基板(L/S=30/30μm;L/S為線寬/線
距;厚度12.7μm)。將塗覆有環氧樹脂之一面貼附於銅箔基板具線路之一面上,之後以真空快壓機以170℃及100kg/cm2之壓力壓合30分鐘,形成具有圖案化聚醯亞胺覆蓋膜的電路板FPC-3。
取0.01克製備例所製得乾膜之聚醯亞胺前驅物塗層(即不包含PET基板),溶解於二甲基亞碸(DMSO)中,使用安捷倫公司的7890GC氣相層析儀,毛細管(column)型號:DB1701(0.53mm,30mm,1.5μm),實施氣相色層定量分析。
以膜厚機量測各實施例及比較例所製得之電路板之厚度(參圖1之H1及圖2之H2)
以光學顯微鏡[SMZ745T/Nikon](10倍放大)觀測各實施例及比較例所製得之電路板是否有氣泡殘留。無氣泡為Pass,有氣泡為NG。
將各實施例與比較例壓合完成的電路板裁切成15cm×1cm的測試條,將測試條末端處的聚醯亞胺層與銅箔基板些微分開,分別以IPC-TM-650測試方法(Number 2.4.9)進行剝離強度量測。
以耐折檢驗機(Measure Infect Turn(MIT)test machine,金德豪公
司)設備,以彎折角度135度,彎曲半徑R=0.38mm,荷重500g進行耐折測試,記錄電路板至電路性質失效時所承受的之彎曲次數。耐折測試次數越大表示所形成的之聚醯亞胺層物性越好。
各實施例及比較例的測試結果記錄如表1。
本發明之方法係於乾膜上預製開口(預先圖案化)後進行貼合,因此不涉及曝光、顯影等繁複的步驟,故製法簡單且具經濟效益。
由表1可知,本發明之方法利用不含黏著劑層之聚醯亞胺乾膜製備覆蓋膜,不但沒有來自黏著劑或聚醯亞胺本身之溢膠現象,同時可使聚醯亞胺層與銅箔基板間具有優異的密著性。此外,本發明所製得之電路板更加輕薄化並具有較佳耐折性,且無明顯氣泡殘留於聚醯亞胺層與銅箔基板之壓合界面。
20‧‧‧聚醯亞胺乾膜
21‧‧‧保護膜
22‧‧‧非感光型聚醯亞胺層
23‧‧‧支撐體
50‧‧‧軟板/基板
H2‧‧‧厚度
Claims (10)
- 一種於基板上製備圖案化聚醯亞胺覆蓋膜之方法,其包含:(a)提供一聚醯亞胺乾膜,該聚醯亞胺乾膜包含支撐體及位於該支持體上之非感光型聚醯亞胺層,其中該非感光型聚醯亞胺層包含:(i)聚醯亞胺前驅物或可溶性聚醯亞胺;及(ii)溶劑;(b)於該聚醯亞胺乾膜上預製開口,形成一預定圖案;(c)將該已形成預定圖案之聚醯亞胺乾膜以非感光型聚醯亞胺層之面與基板進行壓合;及(d)進行加熱,以形成圖案化聚醯亞胺覆蓋膜;其中以該非感光型聚醯亞胺層總重量計,溶劑之含量係至少5wt%。
- 如請求項1之方法,其中該方法不使用黏著劑。
- 如請求項1之方法,其中該聚醯亞胺覆蓋膜之厚度係介於2μm至30μm之間。
- 如請求項1之方法,其中該基板係為軟性印刷電路板。
- 如請求項1之方法,其中以該非感光型聚醯亞胺層總重量計,溶劑之含量係介於5wt%至70wt%。
- 如請求項1之方法,其中該方法係在捲對捲方式下進行。
- 如請求項1之方法,其中步驟(b)係以機械沖孔或雷射鑽孔形成該預定圖案形狀。
- 如請求項1之方法,其中該步驟(c)之壓合方法可為滾輪壓合、熱板壓合、真空壓合或真空快壓。
- 如請求項1之方法,其中該步驟(c)之壓合方法係濕式製程。
- 如請求項1之方法,其中該溶劑包含:二甲基亞碸、二乙基亞碸、苯酚、鄰甲酚、間甲酚、對甲酚、二甲苯酚、鹵代苯酚、鄰苯二酚、四氫呋喃、二噁烷、二氧戊環、環丙二醇甲醚、四乙二醇二甲醚、丁基溶纖劑、γ-丁內酯、二甲苯、甲苯、六甲基鄰 醯胺、丙二醇甲醚醋酸酯、、、 、、、或其混合物,其中:R1"、R9"及R10"各自獨立為C1-C20烷基、C2-C20烯基或C2-C20炔基;R7"為H或C1-C3烷基;R2"為C1-C10烷基;R3"為C4-C20烷基或-C2-C10烷基-O-C2-C10烷基;R4"及R5"各自獨立為C1-C10烷基,或R4"及R5"與其所連接之氧原子一起形成5至6員雜環; R6"為C1-C15烷基、C2-C20烯基、C4-C8環烷基或;R8"為C2-C10伸烷基;R11"及R12"各自獨立為C1-C10烷基;R13"及R14"各自獨立為C1-C10烷基,或R13"及R14"與其所連接之氮原子一起形成5至6員雜環;R15"為H、C1-C15烷基或C4-C8環烷基;R16"為C1-C4烷基;且R17"為C4-C10烷基。
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TW106111471A TWI617441B (zh) | 2017-03-31 | 2017-03-31 | 於基板上製備圖案化覆蓋膜之方法 |
US15/650,648 US11198792B2 (en) | 2017-03-31 | 2017-07-14 | Method for preparing patterned coverlay on substrate |
JP2017138500A JP6698592B2 (ja) | 2017-03-31 | 2017-07-14 | 基板上にパターン形成されたカバーレイを製造する方法 |
CN201710574795.0A CN107222979B (zh) | 2017-03-31 | 2017-07-14 | 于基板上制备图案化覆盖膜的方法 |
KR1020170089918A KR102008240B1 (ko) | 2017-03-31 | 2017-07-14 | 기판 상에 패턴화된 커버레이를 제조하는 방법 |
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TWI650346B (zh) * | 2016-11-30 | 2019-02-11 | 長興材料工業股份有限公司 | 聚醯亞胺前驅物組合物及其應用 |
CN111279804B (zh) * | 2017-12-20 | 2023-10-24 | 住友电气工业株式会社 | 制造印刷电路板和层压结构的方法 |
CN108449880B (zh) * | 2018-04-08 | 2020-12-25 | 珠海市凯诺微电子有限公司 | 柔性线路板覆盖膜贴合方法 |
CN110835408B (zh) * | 2018-08-16 | 2022-06-03 | 长兴材料工业股份有限公司 | 聚酰亚胺的制备方法 |
TWI729362B (zh) * | 2019-03-13 | 2021-06-01 | 同泰電子科技股份有限公司 | 基板結構及其製作方法 |
TWI696867B (zh) * | 2019-03-22 | 2020-06-21 | 友達光電股份有限公司 | 膠帶結構及使用其之顯示面板和顯示裝置 |
TWI708536B (zh) * | 2019-11-25 | 2020-10-21 | 欣興電子股份有限公司 | 移除局部蓋體的裝置及移除局部蓋體的方法 |
CN111642081A (zh) * | 2020-06-04 | 2020-09-08 | 江西兆信精密电子有限公司 | 一种pcb阻焊生产工艺 |
CN111732910B (zh) * | 2020-06-30 | 2022-05-27 | 晶科绿能(上海)管理有限公司 | 复合封装材料和用其封装的光伏组件 |
CN112670310B (zh) * | 2020-12-22 | 2022-09-20 | 业成科技(成都)有限公司 | 显示器及其制造方法 |
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CN107222979B (zh) | 2021-08-17 |
TW201836846A (zh) | 2018-10-16 |
KR20180111434A (ko) | 2018-10-11 |
KR102008240B1 (ko) | 2019-08-07 |
US20180282577A1 (en) | 2018-10-04 |
US11198792B2 (en) | 2021-12-14 |
CN107222979A (zh) | 2017-09-29 |
JP6698592B2 (ja) | 2020-05-27 |
JP2018174291A (ja) | 2018-11-08 |
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