TWI590948B - 包封膜及使用彼來包封有機電子裝置之方法 - Google Patents
包封膜及使用彼來包封有機電子裝置之方法 Download PDFInfo
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- TWI590948B TWI590948B TW103118019A TW103118019A TWI590948B TW I590948 B TWI590948 B TW I590948B TW 103118019 A TW103118019 A TW 103118019A TW 103118019 A TW103118019 A TW 103118019A TW I590948 B TWI590948 B TW I590948B
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- 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
- B32B27/285—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 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/002—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising natural stone or artificial stone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Description
本申請案有關一種包封膜及一種使用彼者包封有機電子裝置(OED)之方法。
OED為一種包括有機材料層之裝置,該材料層使用電洞及電子生成電荷交換,且此裝置可為例如光伏裝置、整流器、傳送器及有機發光二極體(OLED)。
在OED中,OLED與習用光源比較下尤其消耗較少能量且具有較高響應速度,是完美的薄型顯示裝置或燈具。此外,OLED具有優越之空間利用性,因此預期可應用於各種領域,包括所有類型之可攜型裝置、監視器、筆電及TV。
為擴展OLED之工業相容性及用途,最重要的問題是耐久性。OLED中所包括之有機材料及金屬電極極易因諸如濕氣的外在因素而氧化。是故,包括有OLED之產品對於環境因子極為敏感。為解決前述問題,施用
OED之包封物。然而,薄包封物所用之自動邏輯程序困難,在將包封物附貼於基底基材的過程中因為逐漸變短的頂側拋光面而可能容易發生諸如配向錯誤之缺陷。是故,需要解決該問題的方法。
本申請案旨在提供一種包封膜、一種使用彼者包封OED的產品及一種包封OED的方法。
下文中,參考所附圖式,更詳細的描述本申請案之例示具體實施例。此外,為說明本申請案,略去已知之一般功能或配置的詳細說明。另外,示意的提供附圖以幫助瞭解本申請案,更清楚的說明本申請案,省略與該等描述無關之部分,誇大厚度是用以清楚的表現數個層及區域,本申請案之範圍不受限於圖式中所表現的厚度、尺寸及比例。
本申請案之一態樣是提供一種可用於附貼OED之整體表面之包封膜。該包封膜包括單層或多層包封層,該包封層包括金屬層及包封樹脂。
本發明所使用之語辭"有機電子裝置(OED)"意指一種具有包括有機材料層之結構的產品或裝置,該材料層在一對彼此面對之電極之間使用電洞及電子生成電荷交換,且此產品或裝置可為但不限於例如光伏裝置、整流器、傳送器及有機發光二極體(OLED)。在本申請案之一例示具體實施例中,該OED可為OLED。
根據本申請案之例示具體實施例,該包封膜
包封OED之整體表面,且可包括金屬層、及包括包封樹脂且於室溫之抗拉模數為0.001至500MPa的包封層。
本申請案之包封層不特別限制,只要其滿足
抗拉模數之範圍。本發明所使用之抗拉模數為在25℃溫度下測得之抗拉模數,除非特別另外定義。此外,本文中所使用之抗拉模數可意指在固化之後測量的可固化組份之抗拉模數,除非特別另外定義。於一實例中,該抗拉模數可意指在約100℃固化約120分鐘後測得的抗拉模數、在約1J/cm2或更高輻射劑量下輻射UV射線後測得之抗拉模數或在UV輻射後另外進行熱固化後測得之抗拉模數。
如前文所述,該包封層可具有在室溫為0.001
至500MPa的抗拉模數,例如0.001至490Mpa、0.001至480Mpa、0.001至470Mpa、0.001至460Mpa、0.001至450Mpa、0.001至440Mpa、0.001至430Mpa、0.001至420Mpa、0.001至410Mpa、0.001至400Mpa、0.05至450Mpa、0.1至450Mpa、0.2至450Mpa、0.3至450Mpa或0.5至450Mpa。因為包封層之抗拉模數控制在特定範圍內,故進行在特定溫度執行的製程之包封膜的諸如對準誤差之缺陷的機會可減至最小。
本申請案例示具體實施例的金屬層可為透明
或不透明。用於形成金屬層之材料或方法不特別限制,只要滿足前述熱膨脹係數範圍。例如,金屬層可為薄膜型金屬箔或藉著將金屬沈積於聚合物基底基材上所形成之層。
金屬層可為任一種可具有導熱性及防濕性者。該金屬層可包含金屬氧化物、金屬氮化物、金屬碳化物及金屬氮氧化物、金屬硼氧化物及其混合物中任何一者。例如,該金屬層可包括金屬氧化物,諸如氧化釸、氧化鋁、氧化鈦、氧化銦、氧化錫、氧化銦錫、氧化鉭、氧化鋯、氧化鈮及其混合物中之任一者。該金屬層可藉電解、軋壓、蒸發、電子束蒸發、濺鍍、反應性濺鍍、化學氣相沉積、電漿化學氣相沉積或電子迴旋加速器共振源電漿化學氣相沉積。
該金屬層較好具有50W/mK或更高之熱傳係
數、60W/mK或更高、70W/mK或更高、80W/mK或更高、90W/mK或更高、100W/mK或更高、110W/mK或更高、120W/mK或更高、130W/mK或更高、140W/mK或更高、150W/mK或更高、200W/mK或更高或250W/mK或更高。因為該高值熱傳係數,金屬層接合製程中接合界面所生成之熱可更快的散發。此外,該高熱傳係數快速的將OED操作中累積的熱散發至外部大氣,因而使OED溫度得以保持在低水平,而可減少裂紋及缺陷。
本申請案之一例示具體實施例的金屬層可包
括基底基材。作為聚合物樹脂材料,該基底基材可選自但不限於聚對苯二甲酸伸乙酯、聚四氟乙烯、聚乙烯、聚丙烯、聚丁烯、聚丁二烯、氯乙烯共聚物、聚胺基甲酸酯、乙烯-乙酸乙烯酯、乙烯-丙烯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、聚醯亞胺、尼龍及其組合物。該基底基材可防止在與濕氣接觸時的腐蝕及在製程
中因為摺疊或彎曲而損傷。
本申請案之例示具體實施例中,包封膜之材
料不特別限制,只要包括前述金屬層及包封層,且包封層之結構亦不特別限制。例如,該包封層可形成為單層或具有至少兩層之多層。當包封層係形成為多層結構時,構成包封層之各組份可彼此相同或相異。此情況下,構成包封層之組份可為包封樹脂、吸濕劑、可固化材料或其他添加劑。
於一實例中,包封樹脂可為以苯乙烯為主的
樹脂或彈性體、以聚烯烴為主的樹脂或彈性體、其他彈性體、以聚氧伸烷基為主的樹脂或彈性體、以聚酯為主的樹脂或彈性體、以聚氯乙烯為主的樹脂或彈性體、以聚碳酸酯為主的樹脂或彈性體、以聚苯硫醚為主的樹脂或彈性體、烴類之混合物、以聚醯胺為主的樹脂或彈性體、以丙烯酸酯為主的樹脂或彈性體、以環氧基為主的樹脂或彈性體、以矽為主的樹脂或彈性體、以氟為主的樹脂或彈性體或其混合物。
此情況下,該以苯乙烯為主的樹脂或彈性體
可為例如苯乙烯-乙烯-丁二烯-苯乙烯(SEBS)嵌段共聚物、苯乙烯-異戊二烯-苯乙烯(SIS)嵌段共聚物、丙烯腈-丁二烯-苯乙烯(ABS)嵌段共聚物、丙烯腈-苯乙烯-丙烯酸酯(ASA)嵌段共聚物、苯乙烯-丁二烯-苯乙烯(SBS)嵌段共聚物、以苯乙烯為主的均聚物或其混合物。以烯烴為主的樹脂或彈性體可為例如高密度以聚乙烯
為主的樹脂或彈性體、低密度以聚乙烯為主的樹脂或彈性體、以聚丙烯為主的樹脂或彈性體或其混合物。該彈性體可為例如以酯為主的熱塑性彈性體、以烯烴為主的彈性體、以矽為主的彈性體、以丙烯基為主的彈性體或其混合物。此等者之中,以烯烴為主的熱塑性彈性體可為聚丁二烯樹脂或彈性體或聚異丁烯樹脂或彈性體。該以聚氧伸烷基為主的樹脂或彈性體可為例如以聚氧亞甲基為主的樹脂或彈性體、以聚氧伸乙基為主的樹脂或彈性體或其混合物。該以聚酯為主的樹脂或彈性體可為例如以聚對苯二甲酸伸乙酯為主的樹脂或彈性體、聚對苯二甲酸伸丁酯為主的樹脂或彈性體或其混合物。該以聚氯乙烯為主的樹脂或彈性體可為例如聚偏二氯乙烯。該烴類之混合物可為例如三十六烷(hexatriacotane)或石臘。該以聚醯胺為主的樹脂或彈性體可為例如尼龍。該以丙烯酸酯為主的樹脂或彈性體可為例如聚(甲基)丙烯酸丁酯。該以環氧基為主的樹脂或彈性體可為例如雙酚型諸如雙酚A型、雙酚F型、雙酚S型及其氫化產物;酚醛型諸如酚系酚醛型或甲酚系酚醛型;含氮環型諸如異氰尿酸三縮水甘油酯型或乙內醯脲型;脂環型;脂型;芳香型諸如萘型或聯苯型;縮水甘油型諸如縮水甘油醚型、縮水甘油胺型或縮水甘油酯型;二環型諸如二環戊二烯型;酯型;醚酯型;或其混合物。該以矽為主的樹脂或彈性體可為例如聚二甲基矽氧烷。此外,該以氟為主的樹脂或彈性體可為聚三氟乙烯樹脂或彈性體、聚四氟乙烯樹脂或彈性體、聚氯三氟乙烯樹
脂或彈性體、聚六氟丙烯樹脂或彈性體、聚氟化亞乙烯、聚氟化乙烯、聚氟化乙烯丙烯或其混合物。
所列之樹脂或彈性體可接枝有順丁烯二酐,
與用來製備另一種所列樹脂或彈性體的單體或樹脂或彈性體共聚且藉另一化合物修飾。該化合物可為羧基終端丁二烯-丙烯腈共聚物。
於一例示具體實施例中,作為包封樹脂,可
包括以包括碳-碳雙鍵之烯烴為主的化合物之共聚物,但本申請案無限制。
此外,該包封樹脂可為二烯與包括碳-碳雙鍵
之以烯烴為主的化合物的共聚物。此情況下,以烯烴為主的化合物可包括異丁烯、丙烯或乙烯,該二烯可為可與以烯烴為主的化合物聚合的單體,且可包括例如1-丁烯、2-丁烯、異戊二烯或丁二烯。也就是說,本申請案之包封樹脂可為例如異丁烯單體之均聚物;藉由可與異丁烯單體聚合之單體或其混合物共聚所製備的共聚物。於一實例中,包括碳-碳雙鍵之以烯烴為主的化合物與二烯之共聚物可為丁基橡膠。
該包封樹脂可具有能夠模製成薄膜形式的重
量平均分子量(Mw)。例如,樹脂可具有約100,000至2,000,000、100,000至1,500,000或100,000至1,000,000之重量平均分子量(Mw)。本發明所使用之語辭"重量平均分子量"意指藉凝膠滲透層析(GPC)測量之標準聚苯乙烯的換算數值。然而,該樹脂或彈性體組份可不具有前
述重量平均分子量。例如,當該樹脂或彈性體組份之分子量不足以形成膜時,可在構成包封層之組份中添加另外的黏合劑樹脂。
於而另一具體實施例中,包封樹脂可包括可
固化之樹脂。於一實例中,構成前述包封層之組份不特別限制,只要該包封層滿足該抗拉模數或玻璃轉化溫度,且可包括例如可固化之樹脂。於一實例中,該可固化之樹脂可包括構成第二層包封層之組份,將描述於下文。
可用於本申請案之可固化樹脂的明確種類不
特別限制,例如,可使用技術界已知的各種熱可固化或光可固化樹脂。本文所使用之"熱可固化樹脂"可意指可藉適當之熱施加或陳化製程加以固化的樹脂,且本發明所使用之語辭"光可固化樹脂"意指可藉由輻射電磁波加以固化的樹脂。此外,此情況下,在電磁波範疇中,有微波、IR射線、UV射線、X射線、γ射線及粒子束,諸如α粒子束、質子束、中子束及電子束。在本申請案中,作為光可固化樹脂之實例,可使用陽離子性光可固化樹脂。該陽離子性光可固化樹脂意指可藉由輻射電磁波所引發的陽離子性聚合或陽離子性固化反應加以固化之樹脂。此外,該可固化樹脂可為兼具有熱可固化及光可固化特性的雙重可固化樹脂。
本申請案例示具體實施例可使用的可固化樹
脂的明確種類不特別限制,只要該可固化樹脂具有前述特性。例如,可固化而展現黏著特性之樹脂可包括包括有至
少一種選自縮水甘油基、異氰酸酯基、羥基、羧基或醯胺基的熱可固化官能基或至少一種選自環氧基、環醚基、硫醚基、縮醛基及內酯基之可藉輻射電磁波加以固化的官能基之樹脂。此外,樹脂之明確種類可包括丙烯基樹脂、聚酯樹脂、異氰酸酯樹脂或環氧樹脂,但本申請案不限於此。
作為本申請案中之可固化樹脂,可使用芳族
或脂族或直鏈或支鏈環氧樹脂。在本申請案之一例示具體實施例中,可使用含有至少兩個官能基且環氧基當量為180至1,000g/eq之環氧樹脂。當使用具有前述環氧基當量之環氧樹脂時,可有效的保持固化產物之諸如黏著性能及玻璃轉化溫度的特性。該種環氧樹脂可為甲酚系酚醛環氧樹脂、雙酚A型環氧樹脂、雙酚A型酚醛環氧樹脂、酚系酚醛環氧樹脂、4-官能型環氧樹脂、聯苯型環氧樹脂、三酚甲烷型環氧樹脂、經烷基修飾三酚甲烷型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂及經二環戊二烯修飾之酚型環氧樹脂中之一種或至少兩種之混合物。
本申請案中,可使用分子結構中包括環狀結
構之環氧樹脂,例如,包括芳族基團(例如苯基)之環氧樹脂。當環氧樹脂包括芳族基團時,固化產物可具有優異之熱安定性及化學安定性與低吸濕性,因而增進OED包封結構之可信度。詳言之,可使用於本申請案之含芳族基團之環氧樹脂的實例可為但不限於聯苯型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、經二環戊二烯修飾之
酚型環氧樹脂、以甲酚為主的環氧樹脂、雙酚為主的環氧樹脂、以甲苯酚(xyloc)為主的環氧樹脂、多官能型環氧樹脂、酚系酚醛型環氧樹脂、三酚甲烷型環氧樹脂及經烷基修飾三酚甲烷型環氧樹脂中之一種或至少兩種之混合物。
說明書中,環氧樹脂較佳為經矽烷修飾之環
氧樹脂且更佳為經矽烷修飾之具芳族基的環氧樹脂。相同的,當使用經矽烷修飾以於結構上具有矽烷基的環氧樹脂時,OED對玻璃基材或基材無機材料的黏著性最大化且可增進阻濕性或耐久性及可信度。可使用於本申請案之環氧樹脂的明確種類不特別限制,該樹脂可輕易得自例如製造商Kukdo Chemical,Co.,Ltd.。
如前文所述,該包封層可包括單層或具有至
少兩層之多層。當形成單層的包封層時,該包封層之抗拉模數係如前文所述。此外,當該包封層係由至少兩層形成時,其中至少一層可具有在室溫下0.001至500MPa之抗拉模數。此外,當該包封層包括至少兩層時,該包封層可包括具有在室溫為0.001至500MPa抗拉模數之第一層,及具有在室溫下500至1000MPa之抗拉模數的第二層。
當有機電子二極體以至少兩層包封時,堆疊順序不特別限制,但包括或不包括少量下文將描述之吸濕劑的層可與該有機電子二極體接觸。
在本申請案之一例示具體實施例中,該包封
層可進一步包含吸濕劑。本發明所使用之語辭"吸濕劑"可
意指能夠經由物理或化學反應自外界環境吸附或移除濕氣或蒸氣輸入的任一組份。即,吸濕劑意指反應性或物理性吸附劑或其混合物。
反應性吸濕劑與滲入包封層內之蒸氣、濕氣
或氧化學性反應以吸附濕氣或蒸氣。該物理性吸附劑可延長濕氣或蒸氣滲入包封結構的路徑,以防止滲透,並將防止濕氣及蒸氣穿透包封樹脂之基質結構及與反應性吸濕劑相互作用的能力最大化。
可使用於本申請案之吸濕劑的明確種類可為
但不特別限制於在反應性吸濕劑情況下為諸如氧化鋁、金屬氧化物、金屬鹽或五氧化二磷(P2O5)的一種或至少兩種金屬粉末之混合物,在物理性吸濕劑情況下為二氧化矽、沸石、氧化鈦、氧化鋯或蒙脫土。
此情況下,詳言之,該金屬氧化物可為五氧化二磷(P2O5)、氧化鋰(Li2O)、氧化鈉(Na2O)、氧化鋇(BaO)、氧化鈣(CaO)或氧化鎂(MgO),且金屬鹽可為但不限於硫酸鹽,諸如硫酸鋰(Li2SO4)、硫酸鈉(Na2SO4)硫酸鈣(CaSO4)、硫酸鎂(MgSO4)、硫酸鈷(CoSO4)、硫酸鎵(Ga2(SO4)3)、硫酸鈦(Ti(SO4)2)或硫酸鎳(NiSO4);金屬鹵化物諸如氯化鈣(CaCl2)、氯化鎂(MgCl2)、氯化鍶(SrCl2)、氯化釔(YCl3)、氯化銅(CuCl2)、氟化銫(CsF)、氟化鉭(TaF5)、氟化鈮(NbF5)、溴化鋰(LiBr)、溴化鈣(CaBr2)、溴化銫(CeBr3)、溴化硒(SeBr4)、溴化釩
(VBr3)、溴化鎂(MgBr2)、碘化鋇(BaI2)或碘化鎂(MgI2);或金屬氯酸鹽諸如過氯酸鋇(Ba(ClO4)2)或過氯酸鎂(Mg(ClO4)2)。
於本申請案中,諸如金屬氧化物的吸濕劑可適當的加工且添加於該組成物。例如,視待施加包封膜的OED之種類而定,該包封層可為厚度為30μm或更小的薄膜,此情況下,可能需要碾磨吸濕劑的製程。碾磨吸濕劑時,可使用三輥軋磨、珠磨或球磨。此外,當本申請案包封膜使用於頂部發光型OED時,包封層之滲透性極重要,因此吸濕劑應具有小尺寸。是故,就該用途而言,可能亦需要碾磨製程。
本申請案包封層可包括相對於100重量份包封樹脂為1至100重量份,較佳5至50重量份的吸濕劑。當吸濕劑含量控制於5重量份或更高時,該包封層可展現優異之防濕性及防蒸氣性。此外,當吸濕劑含量控制於50重量份或更低時,該包封層可形成為具有包封結構的薄膜且展現優異之防濕性。然而,含量範圍可根據包封層的位置加以適當的控制,而無特別限制。例如,包封層接近OED之區域中可包括較少量的吸濕劑,例如基於該吸濕劑之總量可包括0至20%。當含量高於20%時,吸濕劑可能因為OED與雜質一起壓製,而可能引發物理性傷害,且因為與濕氣反應後釋出的過量離子性材料,而對負極或無機保護層引發化學性傷害。
說明書中,除非特別另外定義,否則"重量份
"單位是意指組份間之重量比。
本申請案之例示具體實施例中,該包封層可
根據包封樹脂之種類進一步包括膠黏劑。例如,該包封層可在前述包封樹脂以外進一步包括膠黏劑。該膠黏劑可為例如藉由將石油樹脂氫化所得之氫化石油樹脂。該氫化石油樹脂可部分或完全氫化,且可為該等樹脂之混合物。該種膠黏劑與構成包封層之成份可具有高度相容性及優異之防濕性。明確之氫化石油樹脂可為氫化萜為主的樹脂、以氫化酯為主的樹脂或以氫化二環戊二烯為主的樹脂。該膠黏劑可具有約200至5,000之重量平均分子量。該膠黏劑之含量可視需要適當的控制。例如,該膠黏劑可包括於第一層中之量相對於100重量份包封樹脂為5至100重量份。
除前述組份之外,包封層可根據該膜之用途
及製造薄膜之方法包括各種添加劑。例如,在考慮耐久性及加工性之下,包封層可進一步包括可固化之材料。此情況下,該可固化材料可意指在構成包封層之組份之外另外分別包括具有熱可固化官能基及/或活性能量束可固化之官能基的材料。此外,可固化材料包括於包封層中之含量可根據所需之薄膜物性來加以控制。
本申請案之例示具體實施例中,該包封層可
根據包封樹脂之種類進一步包括固化劑。例如,經由與前述包封樹脂反應,可進一步包括可形成交聯結構的固化劑或可起始樹脂之固化反應的起始劑。
該固化劑之適當種類可視包封樹脂之種類或該樹脂中所包括之官能基來選擇及使用。
於一實例中,當該包封樹脂為環氧樹脂時,作為固化劑,可使用例如技術界已知之環氧樹脂固化劑、例如至少一種或兩種之胺固化劑、咪唑固化劑、酚固化劑、磷固化劑及酸酐固化劑,但本申請案不限於此。
於一實例中,該固化劑可為咪唑化合物,其於室溫為固體,且具有80℃或更高之熔點或降解溫度。該化合物可為但不限於2-甲基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑或1-氰基乙基-2-苯基咪唑。
固化劑之含量可根據該組成物之組份加以選擇,例如,包封樹脂之種類或比例。例如,固化劑可包括之量相對於100重量份包封樹脂為1至20重量份、1至10重量份或1至5重量份。然而,該重量比可根據該包封樹脂或該樹脂的官能基的種類及比例或待實現之交聯密度而改變。
當該包封樹脂為可藉輻射活性能量束加以固化的樹脂時,作為起始劑,可使用陽離子性光聚合起始劑。
作為陽離子性光聚合起始劑,可使用鎓鹽或有機金屬鹽系列離子化陽離子性起始劑或有機矽烷系列或潛在磺酸系列起始劑或非離子化陽離子性光聚合起始劑。鎓鹽系列起始劑可為二芳基碘鎓鹽、三芳基硫鎓鹽或芳基
重氮鎓鹽,有機金屬鹽系列起始劑可為鐵芳烴,有機矽烷系列起始劑可為鄰硝基苄基三芳基矽烷基醚、三芳基矽烷基過氧化物或醯基矽烷,且潛在磺酸系列起始劑可為α磺醯氧基酮或α羥基甲基安息香磺酸鹽,但本申請案不受限於此。
於一實例中,作為陽離子性起始劑,可使用離子化陽離子性光聚合起始劑。
此外,當該包封樹脂為可藉輻射活性能量束加以固化的樹脂時,作為起始劑,例如可使用自由基起始劑。
自由基起始劑可為光起始劑或熱起始劑。可考慮固化速度及變黃機率來適當地選擇特定種類之光起始劑。例如,光起始劑可為以安息香-、羥基酮-、胺基酮-或氧化膦-為主之光起始劑,詳言之,為安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香正丁基醚、安息香異丁基醚、乙醯苯、二甲基胺基乙醯苯、2,2-二甲氧基-2-苯基乙醯苯、2,2-二乙氧基-2-苯基乙醯苯、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉-丙烷-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯甲酮、對-苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基硫基氧葱酮、2-乙基硫基氧葱酮、2-氯硫氧葱酮、2,4-二甲基硫基氧葱酮、2,4-二乙基硫基氧葱酮、
苄基二甲基縮酮、乙醯苯二甲基縮酮、對-二甲基胺基苯甲酸酯、寡聚[2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮]或2,4,6-三甲基苯甲醯基-二苯基-氧化膦。
起始劑如固化劑之含量可根據該包封樹脂或
該樹脂的官能基的種類及比例或待實現之交聯密度而改變。例如,起始劑可包括之量相對於100重量份包封樹脂為0.01至10重量份或0.1至3重量份。當起始劑含量太少時,可能無法充分固化,當起始劑含量太大時,固化後之離子性材料的含量增加而破壞黏著劑之持久性,或因為起始劑特性,形成共軛酸,缺點是光學持久性,根據基底基材可能發生腐蝕,因而在考慮該種問題下選擇適當之含量範圍。
包封層可根據該膜之用途及製造薄膜之方法而包括各種材料。例如,當包封層模塑成膜狀或片狀時,在考慮可模塑性之下,該包封層中可包括黏合劑樹脂。
在本申請案之一例示具體實施例中,該包封層可包括填料,較佳為無機填料。該填料可延長濕氣或蒸氣滲入包封結構的路徑,以防止滲透,並經由與包封樹脂及吸濕劑之相互作用將防止濕氣及蒸氣的能力最大化。可使用於本申請案之填料的明確種類可為但不特別限制於例如黏土、滑石及針狀二氧化矽中之一種或至少兩種之混合物。
本申請案中,為增加填料與有機黏合劑之間的黏合效率,作為填料,可使用經有機材料加以表面處理
的產物或可進一步添加偶聯劑。
本申請案包封層可包括相對於100重量份包
封樹脂為1至50重量份,較佳1至20重量份的填料。當填料含量控制於1重量份或更高時,可提供具有優異之阻濕性或阻蒸氣性及優異之機械性質的固化產物。此外,在本申請案中,當填料含量控制於50重量份或更低時,可製造膜型包封層,唯即使形成薄膜型之包封層時,仍可提供展現優異之阻濕特性的包封結構。
本申請案包封膜可具有(但非特別限制)包
括例如基膜或脫離膜(以下可稱為"第一膜")及形成於該基膜或脫離膜上之包封層連同包括金屬層及包封層的結構。
圖1至2為本申請案例示具體實施例的包封膜之剖面圖。
如圖1所示,本申請案包封膜可包括形成於基膜或脫離膜11上之包封層12及金屬層13。此外,在圖2中,該包封層12包括第一層12a及第二層12b。
可使用於本申請案之第一膜的明確種類不特別限制。在本申請案中,作為第一膜,可使用技術界中通用之聚合物膜。在本申請案中,例如,作為基膜及脫離膜,可使用聚對苯二甲酸伸乙酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚胺基甲酸酯膜、乙烯-乙酸乙烯酯膜、乙烯-丙烯共聚物膜、乙烯-丙烯酸乙基共聚物膜、乙烯-丙烯酸甲基共
聚物膜或聚醯胺膜。此外,本申請案之基膜或脫離膜的一或兩表面可施以適當之脫離處理。作為基膜脫離處理之脫離劑實例,可使用以醇酸、以矽、以氟、以不飽和酯、以聚烯烴或蠟為主的脫離劑,此等者之中,就耐熱性而言,較佳係使用以醇酸、以矽或以氟為主的脫離劑,但本申請案不受限於此。
在本申請案中,基膜或脫離膜(第一膜)之
厚度不特別限制,可根據應用來適當的選擇。例如,在本申請案中,該第一膜可具有約10至500μm之厚度,較佳為20至200μm。當厚度小於10μm時,基膜可在製程中輕易的修飾,當厚度大於500μm時,經濟可行性降低。
本申請案包封膜中所包括之包封層的厚度不
特別限制,在考慮膜之應用下,可根據以下條件而適當的選擇。包封層之厚度可為約5至200μm,較佳5至100μm。當包封層厚度小於5μm時,可能無法展現充分之防濕性,當包封層厚度大於200μm時,難以確保加工性,厚度膨脹因濕氣反應性而增加,因而傷害OED之沈積膜,降低經濟可行性。
本申請案之另一態樣提供一種製造包封膜的方法。例示包封膜可藉模塑膜型或片型包封膜而製得。
於一實例中,該方法可包括施加包括構成前述包封層之組份的塗覆溶液於片型或膜型基膜或脫離膜上且將所施加塗覆溶液乾燥而製得。
該塗覆溶液可藉著例如將前述包封層之組份
溶解或分散於適當之溶劑中而製備。於一實例中,該包封層可藉由視需要將吸濕劑或填料溶解或分散於溶劑中、碾磨該吸濕劑或填料並將經碾磨之吸濕劑或填料與包封樹脂混合的方法製得。
製備塗覆溶液所使用之溶劑的種類不特別限
制。然而,當溶劑乾燥時間過長或需要高溫乾燥時,該包封膜之工作性或耐久性可能產生問題,因此可使用揮發溫度為150℃或更低的溶劑。在考慮膜模塑性時,可混合並使用少量揮發溫度在該範圍或更高的溶劑。該溶劑可為但不限於甲基乙基酮(MEK)、丙酮、甲苯、二甲基甲醯胺(DMF)、甲基賽珞蘇(MCS)、四氫呋喃(THF)、二甲苯或N-甲基吡咯啶酮(NMP)中至少一者或兩者。
施加塗覆溶液於基膜或脫離膜之方法可為但
不特別限制於已知塗覆方法,諸如刮刀塗覆、輥塗法、噴塗、凹板塗覆、簾塗法、電暈塗覆(comma coating)或唇塗法。
所施加之塗覆溶液可乾燥,可將溶劑揮發,藉以形成包封層。該乾燥可例如在70至150℃執行1至10分鐘。乾燥條件可在考慮所用溶劑之種類下改變。
乾燥後,可於包封層上形成金屬層。該金屬層可使用技術界已知之技術形成。例如,金屬層可由金屬箔形成或藉著將金屬沈積於聚合物基底基材上所形成。例如,該金屬層可藉電解或軋壓形成。
本申請案之另一態樣提供一種用於包封OED
的產物,其包括基材、形成於該基材上之OED及前述包封OED的包封膜,其中該係附貼於OED整體表面。
在本申請案中,該OED可為OLED。
用於包封OED的產物可進一步包括介於該包封膜與該OED之間的保護膜,以保護該OED。
於一實例中,如圖3所示,用於包封OED之產物可配置成包封膜之包封層12與OED 22及基材21接觸。此外,金屬層13可配置於包封層12上。
本申請案再另一態樣提供一種包封OED的方法,其包括將前述包封膜之包封層施加於上面形成有OED的基材上以附貼於OED之整體表面且固化該包封層。
該包封膜可藉熱輥層積、熱壓或真空壓製該包封膜而施加於OED,但本申請案不特別限制於此。
在本申請案中,根據包封OED之方法,例如,於基材諸如玻璃或聚合物膜上藉真空沈積或濺鍍形成透明電極,在該透明電極上形成有機材料層。該有機材料層可包括電洞注入層、電洞傳輸層、發光層、電子注入層及/或電子傳輸層。之後,進一步於該有機材料層上形成第二電極。接著,將前述包封膜施加於位在基材21上之OED 22頂面上,以覆蓋該OED 22的整個表面。此情況下,施加包封膜之方法可為但不特別限於經由加熱、壓製或高壓將本申請案包封膜施加於形成在基材21上的OED 22頂面之方法。
此外,可執行壓製有OED 22之包封膜的附加
固化製程或附著促進製程,且該製程(主要固化)可在例如加熱艙中執行。主要固化之固化條件可在考慮OED 22之安定性下適當的選擇。
然而,前述形成方法僅為包封OED 22之實例,因此該方法所用之順序或條件可自由改變。此外,在OED 22上形成保護層後,可施加該包封膜,之後固化。
本申請案之包封膜可有效的封阻濕氣或氧氣自外部環境滲入OED內,提供因增加OED使用壽命及耐久性所致之高可信度,去除藉由積合包封材料(encap material)與包封樹脂以將包封樹脂附貼於該包封材料上的製程,使將包封膜附貼於基材上的製程中的對準誤差減至最小。
11‧‧‧基膜或脫離膜
12‧‧‧包封層
12a‧‧‧第一層
12b‧‧‧第二層
13‧‧‧金屬層
21‧‧‧基材
22‧‧‧有機電子裝置
圖1及2為本申請案例示具體實施例的包封膜之剖面圖,且圖3為本申請案例示具體實施例的OED包封產物之剖面視圖。
下文將參考本發明實施例及非本發明之對照例更詳細描述本發明,但本發明範圍不受限於以下實施
例。
100g經矽烷修飾之環氧樹脂(KSR-177,
Kukdo Chemical Co.,Ltd.)、100g經丁二烯橡膠修飾之環氧樹脂(KR-450,Kukdo Chemical Co.,Ltd.)及150g苯氧基樹脂(YP-50,Tohto Kasei Co.,Ltd.)於室溫下添加至反應容器,以甲基乙基酮(MEK)稀釋。將4g作為固化劑之咪唑(Shikoku Chemicals Co.,Ltd.)添加至經均質化之溶液中,高速攪拌1小時,形成供第一層使用之溶液。
吸濕劑溶液係藉由添加100g作為吸濕劑之煅燒白雲石及作為溶劑之固體含量50wt%的MEK而製備。於室溫下將200g經矽烷修飾之環氧樹脂(KSR-177,Kukdo Chemical Co.,Ltd.)及150g苯氧基樹脂(YP-50,Tohto Kasei Co.,Ltd.)添加至反應容器且以MEK稀釋。將4g作為固化劑之咪唑(Shikoku Chemicals Co.,Ltd.)添加至經均質化之溶液中,且將形成之溶液高速攪拌1小時,因而製備供阻濕層使用之溶液。將預先製備之吸濕劑溶液添加至形成之溶液中,使得煅燒白雲石含量相對於
100重量份第二層的包封樹脂為50重量份,因而製備供第二層使用的溶液。
藉由將預先製備之阻濕層用溶液塗覆於脫離PET的脫離表面上且在110℃乾燥該經塗覆表面10分鐘而形成厚度40μm的第二層。藉由層積預先製備之第一及第二層製得多層而製得包封膜,將該多層膜與20μm銅膜層積。
藉如同實施例1所述方法製得包封膜,不同處係在室溫下將100g經矽烷修飾之環氧樹脂(KSR-177,Kukdo Chemical Co.,Ltd.)、100g經丙烯基橡膠修飾之環氧樹脂(KR-692,Kukdo Chemical Co.,Ltd.)及150g苯氧基樹脂(YP-50,Tohto Kasei Co.,Ltd.)添加至反應容器且以MEK稀釋,在經均質化之溶液中添加作為固化劑的4g咪唑(Shikoku Chemicals Co.,Ltd.)且高速攪拌1小時,形成用於第一層的溶液。
藉如同實施例1所述的方法製得包封膜,不同處是於室溫下將50g作為第一層之包封樹脂的聚異丁烯樹脂(重量平均分子量:450,000)及50g作為膠黏劑
之以氫化二環戊二烯為主的樹脂(軟化點:125℃)添加於反應容器中,且以甲苯稀釋10g以DCPD為主的環氧樹脂及1g咪唑(Shikoku Chemicals Co.,Ltd.)以具有固體含量約30wt%。
藉如同實施例1所述的方法製得包封膜,不同處是於室溫下將50g作為阻裂層之包封樹脂的聚異丁烯樹脂(重量平均分子量:450,000)及50g作為膠黏劑之以氫化二環戊二烯為主的樹脂(軟化點:125℃)添加於反應容器中,且以甲苯稀釋20g多官能丙烯基單體(TMPTA)及1g光起始劑以具有約25wt%之固體含量。
吸濕劑溶液之製備係藉由添加100g作為吸濕劑之煅燒白雲石及作為溶劑之甲苯以具有50wt%固體含量。藉如同實施例1所述的方法製得包封膜,不同處是於室溫下將50g作為第一層之包封樹脂的聚異丁烯樹脂(重量平均分子量:450,000)及50g作為膠黏劑之以氫化二環戊二烯為主的樹脂(軟化點:125℃)添加於反應容器中,且以甲苯稀釋及10g多官能丙烯基單體(TMPTA)及1g光起始劑以具有約25wt%之固體含量,且不包括第二層。
將實施例5第一層中所形成的包封層層積於鋁膜上而製得包封膜。
藉如同實施例1所述之方法製造包封膜,不同處為在室溫將200g經矽烷修飾之環氧樹脂(KSR-177,Kukdo Chemical Co.,Ltd.)及150g苯氧基樹脂(YP-50,Tohto Kasei Co.,Ltd.)添加至反應容器,以MEK稀釋,且藉由將4g作為固化劑之咪唑(Shikoku Chemicals Co.,Ltd.)添加至經均質化之溶液中,形成之溶液在高速下攪拌1小時,而製備第一層用之溶液。
藉如同實施例1所述方法製得包封膜,不同處係使用僅由實施例1之第二層形成之包封層。
藉由層積實施例或對照例製得之阻裂層或阻濕層而形成厚度40μm之塗膜。藉著將製造中的塗覆方向設定於長度方向,將所製塗膜裁切成50mm×10mm(長×寬)尺寸,及將試樣之兩邊膠黏至僅具有25mm之長度以製得試樣。之後,膠黏部分於25℃以18mm/min之速
度伸展,及測量抗拉模數。
藉著將實施例及對照例製得之膜層積於覆蓋基材上,將形成之基材層積於玻璃基材之間,且於70℃加壓及熱壓所形成之產物,以製得試樣。之後,試樣在85℃及85%相對濕度下在定溫及定濕槽中保持約300小時。當發生翹曲時,標示為X,而當未發生翹曲時,標示為○。
11‧‧‧基膜或脫離膜
12‧‧‧包封層
13‧‧‧金屬層
Claims (17)
- 一種用來包封有機電子裝置的包封膜,其包含:金屬層;及包封層,其包含包封樹脂,且具有在室溫下為0.001至500MPa之抗拉模數,其中該包封層係附貼於該有機電子裝置的整體表面上。
- 如申請專利範圍第1項之膜,其中該金屬層具有50W/mK或更高之熱傳係數。
- 如申請專利範圍第1項之膜,其中該金屬層係包含金屬氧化物、金屬氮化物、金屬碳化物、金屬氮氧化物、金屬硼氧化物(metal oxyboride)及其混合物中任何一者。
- 如申請專利範圍第3項之膜,其中該金屬層係包含氧化釸、氧化鋁、氧化鈦、氧化銦、氧化錫、氧化銦錫、氧化鉭、氧化鋯、氧化鈮及其混合物中之任一者。
- 如申請專利範圍第1項之膜,其中該金屬層係進一步包含基底基材。
- 如申請專利範圍第5項之膜,其中該基底基材係為聚對苯二甲酸伸乙酯、聚四氟乙烯、聚乙烯、聚丙烯、聚丁烯、聚丁二烯、氯乙烯共聚物、聚胺基甲酸酯、乙烯-乙酸乙烯酯、乙烯-丙烯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、聚醯亞胺、尼龍及其組合物中之任一者。
- 如申請專利範圍第1項之膜,其中該包封層係以單層或至少兩層之形式形成。
- 如申請專利範圍第7項之膜,其中當該包封層係由至少兩層形成時,其中至少一層具有在室溫下0.001至500MPa之抗拉模數。
- 如申請專利範圍第1項之膜,其中該包封樹脂係以苯乙烯為主之樹脂、以聚烯烴為主之樹脂、熱塑性彈性體、以聚氧伸烷基為主之樹脂、以聚酯為主之樹脂、以聚氯乙烯為主之樹脂、以聚碳酸酯為主之樹脂、以聚苯硫醚為主之樹脂、烴之混合物、以聚醯胺為主之樹脂、以丙烯酸酯為主之樹脂、以環氧基為主之樹脂、以矽為主之樹脂、以氟為主之樹脂或其混合物。
- 如申請專利範圍第1項之膜,其中該包封樹脂係包含可固化之樹脂。
- 如申請專利範圍第10項之膜,其中該可固化之樹脂係包含至少一個選自縮水甘油基、異氰酸酯基、羥基、羧基、醯胺基、環氧基、環醚基團、硫醚基、縮醛基及內酯基之可固化官能基。
- 如申請專利範圍第10項之膜,其中該可固化樹脂為在分子結構中包含環狀結構的環氧樹脂。
- 如申請專利範圍第10項之膜,其中該可固化之樹脂係經矽烷修飾之環氧樹脂。
- 如申請專利範圍第1項之膜,其中該包封層係進一步包含吸濕劑。
- 一種用於包封有機電子裝置的產品,其包含:基材;形成於該基材上的有機電子裝置;及如申請專利範圍第1至14項中任一項的包封膜,用以包封該有機電子裝置,其中該包封膜之包封層係附貼於該有機電子裝置的整體表面上。
- 如申請專利範圍第15項之產品,其中該有機電子裝置係有機發光二極體。
- 一種包封有機電子裝置的方法,其包含:將如申請專利範圍第1至14項中任一項的包封膜之包封層施加於表面上有形成有機電子裝置的基材上,以附貼於有機電子裝置的整體表面上;及將包封層固化。
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