TWI647102B - 封裝膜及包含彼之有機電子裝置 - Google Patents
封裝膜及包含彼之有機電子裝置 Download PDFInfo
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- TWI647102B TWI647102B TW104105653A TW104105653A TWI647102B TW I647102 B TWI647102 B TW I647102B TW 104105653 A TW104105653 A TW 104105653A TW 104105653 A TW104105653 A TW 104105653A TW I647102 B TWI647102 B TW I647102B
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 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
- 229910052716 thallium Inorganic materials 0.000 description 1
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- 238000001029 thermal curing Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 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
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
-
- 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
- B32B15/082—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 comprising vinyl resins; comprising acrylic resins
-
- 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
- B32B15/085—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 comprising polyolefins
-
- 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
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Abstract
本發明提供封裝膜、包含彼之有機電子裝置(OED)及該有機電子裝置之製造方法。當使用該封裝膜包封該有機電子裝置時,可實現優良之水氣阻障性,且由於藉由吸收且阻擋內部或外部光而防止光之反射或散射,所以可防止該有機電子裝置之外部缺陷。
Description
本發明關於封裝膜、包含彼之有機電子裝置(OED)及該OED之製造方法。
OED指包括利用電洞和電子產生電荷交換之有機材料層的裝置。該OED之實例可包括光伏打裝置、整流器、和有機發光二極體(OLED)。
於一個示範實施態樣中,OLED具有較低能量消耗及較高反應速度,且更有益於形成比習用光源薄之顯示裝置或光。因為該OLED也具有優良之空間利用率,所以預期該OLED能應用於包括所有類型之可攜式裝置、監視器、筆記型電腦和TV的不同領域。
為了擴充該OLED之商業化及用途,最重要之問題是耐久性。該OLED包括之有機材料和金屬電極非常容易被外部因子如水氣影響而氧化。此外,當顯示器係藉由運用該OLED而實現時,包括互連件沉積於該顯示器之外周部的部分及互連件沒沉積於該顯示器之外周部的部
分。在沒沉積的部分中,外部或內部光可能被反射或散射,且有些從外側見到光亮之部分造成外部缺陷。
本發明致力於提供具有優良水氣阻障性且能藉由吸收並阻擋內部或外部光以預防光之反射或散射而防止OED之外部缺陷的封裝膜、含有彼之OED及OED之製造方法。
後文中,將引用附圖更詳細地描述本發明之示範實施態樣。此外,為了說明本發明,省略了共通功能或構型之相關習知詳細描述。此外,附圖能助於了解本發明,且更清楚地說明本發明,省略與說明無關之部分。為了清楚地表示該圖中之數個層和區域,誇大厚度或尺寸。本發明之範疇不限於圖中所示之厚度、尺寸及比率。
於一態樣中,本發明提供一種有機電子元件之封裝膜。本發明之封裝膜可用以包封或封裝該有機電子元件如OLED之全面積。
該示範封裝膜可包括光吸收區。該光吸收區可意指就該封裝膜之可見光區來看具有15%或更低之透光率的區域。於一實例中,該光吸收區可包括封裝樹脂及光吸收材料。於本發明之又另一個示範實施態樣中,該封裝膜可包括含光吸收區之光吸收層,該光吸收區包含封裝樹脂和光吸收材料且就可見光區來看具有15%或更低之透光率;及水氣阻障層。於另一態樣中,本發明提供一種
OED,其包括基材、存於該基材上之有機電子元件及具有黏附於該有機電子元件全部表面之光吸收區的封裝膜。另一方面,當該封裝膜係以二或更多個層形成時該光吸收區可意指包括依厚度方向之光吸收材料的區域。也就是說,在此案例中,除了該光吸收層之一部分以外,該水氣阻障層之一部分可被定義成該光吸收區。
本文所用之措辭“OED”意指具有包括有機材料層之元件的產品或裝置,該有機材料層利用介於一對面向彼此之電極之間的電洞和電子產生電荷交換,至於實例,可包括光伏打裝置、整流器、發送器和OLED,但是本發明不限於此。於本發明之一實例中,該OED可為OLED。
本文所用之措辭“光吸收層”或“水氣阻障層”可為構成該封裝膜之黏著層、壓敏性黏著層或可固化之壓敏性黏著層。因此,必要時,該封裝膜和該光吸收層及/或該水氣阻障層可以相同意義互相通用。在此,本文所用之措辭“可固化之壓敏性黏著層”意指室溫時保持固態或半固態以黏附黏附體而沒有加熱時產生之流動性引起的氣泡且在凝固之後利用黏著力緊緊地固定住該黏附體之類型的黏著層。於一個示範實施態樣中,該“光吸收層”意指包括該光吸收區之層。此外,於一個示範實施態樣中,該“水氣阻障層”意指水蒸氣穿透率(WVTR)為50g/m2.day或更低,較佳30g/m2.day或更低,更佳20g/m2.day或更低,且又更佳15g/m2.day或更低之層。於本發明中,該
WVTR係等到下述封裝樹脂交聯或固化之後關聯38℃和100%之相對濕度的交聯產物或固化產物之厚度方向測得的速率,且交聯產物或固化產物係形成厚度為80μm之膜形。此外,該WVTR係根據ASTM F1249測量。因為該WVTR係控制於以上範圍,所以可有效地抑制水氣、蒸氣或氧滲入該OED之封裝產物。於本發明中,因為該封裝膜之WVTR位準較低,所以封裝結構顯示優良性能。該WVTR之下限可為,但不特別限於,例如,0、1或3g/m2.day。該水氣阻障層可包括封裝樹脂,且另包括水氣吸收劑。構成該水氣阻障層之組分,例如,該封裝樹脂或該水氣吸收劑,可等於或不同於構成該光吸收層之組分。
本文所用之措辭“封裝組合物”係構成該封裝膜之光吸收層或水氣阻障層的組分。該封裝組合物可包括封裝樹脂、光吸收材料、水氣吸收劑或其他添加物。於該封裝膜之光吸收層和水氣阻障層中,該封裝組合物之組分的類型和含量,除了該光吸收材料,例如,該封裝樹脂以外,該水氣吸收劑、其他添加物或填料皆可能彼此相同或不同。除非特地另行例舉,否則對下述封裝組合物之描述相當於該封裝膜之光吸收層和水氣阻障層全部。
於一實例中,該封裝膜之結構沒有特別限制。該封裝膜具有單層結構或包括至少兩層之多層結構。於一實例中,當該封裝膜具有單層結構時,可把上述光吸收層包括在內,且當該封裝膜具有至少兩層之多層結構時,可把上述光吸收層和該水氣阻障層包括在內。
第1圖係根據本發明之封裝膜的斷面示意圖。示範封裝膜1可包括光吸收層2。此外,如第2至4圖所示,該封裝膜1可具有含至少兩層之多層結構,且在此案例中,該封裝膜1可包括至少一個光吸收層2。於一實例中,當該封裝膜1具有如第1圖所示之單層結構時,可把該光吸收層2包括在內。明確地說,當該封裝膜1包括單層結構時,如第1(a)圖所示,該光吸收層可包括光吸收材料3,或如第1(b)圖所示,該光吸收層可包括光吸收材料3和水氣吸收劑5。此外,如第2圖所示,當該封裝膜1具有雙層結構時,可把光吸收層2和水氣阻障層4包括在內。當該封裝膜具有多層結構時,光吸收層和水氣阻障層之堆疊順序沒有特別限制。此外,當該封裝膜具有包括至少三層之多層結構時,該水氣阻障層可具有多層結構。當該水氣阻障層具有多層結構時,可把該光吸收層佈置於該至少兩個水氣阻障層之間,或可把該光吸收層形成於堆疊至少兩個水氣阻障層之結構的一或兩個表面上。第3圖顯示該光吸收層2係佈置於兩個水氣阻障層4和6之間,且該二水氣阻障層中之一者(水氣阻障層6)不包括水氣吸收劑5或考慮到包封時與有機電子元件接觸而包括小量之水氣吸收劑5。第4圖顯示該光吸收層2係形成於堆疊該二水氣阻障層4和6之結構之一表面上,且該二水氣阻障層4和6中之一者(水氣阻障層6)不包括水氣吸收劑5或考慮到包封時與有機電子元件接觸而包括小量之水氣吸收劑5。此外,該封裝膜可包括至少兩個光
吸收層。在此案例中,兩個光吸收層可連續地堆疊,且該二光吸收層之間可包括該水氣阻障層。
於本發明之一示範實施態樣中,該封裝膜可包括光吸收區,該光吸收區包含封裝樹脂和光吸收材料,且就可見光區來看具有15%或更低之透光率。於該封裝膜中,除了包括小量光吸收材料或不包括光吸收材料以外,非光吸收區,不是該光吸收區,可由與構成該光吸收區之組分相同的組分組成。該非光吸收區可就可見光區來看具有15%或更低之透光率。該形成光吸收區之封裝膜部分沒有特別限制,但是例如,該光吸收區可能形成於該封裝膜之至少一個外周部。本文所用之措辭“外周部”意指周圍邊緣。也就是說,該膜之外周部可意指該膜之周圍邊緣。於另一個示範實施態樣中,該光吸收區可形成於該封裝膜之全面積。也就是說,當該封裝膜係以平面視圖觀察時,該封裝膜全面積可具有15%或更低之透光率,或僅該封裝膜至少一個外周部可具有15%或更低之透光率。於本發明中,當膜具有單層結構時,該透光率可為相對於可見光區之透光率,其係依照該光吸收區之厚度方向測量。此外,當該膜係形成多層結構時,該透光率可為以該包括至少一個光吸收層及/或至少一個水氣阻障層之多層堆疊結構測量的透光率。例如,當根據本發明之封裝膜係以平面示意圖觀察時,上述光吸收區可為依照該具有堆疊結構之膜的厚度方向具有15%或更低之透光率的區域。於一實例中,於根據本發明之可見光區域中的透光率下限可為,但是不
特別限於,0%。該透光率可為,例如,0.2至15%、0.5%至15%、1%至15%、1%至14%、1%至13%、2%至12%、3%至11%、或3%至10%。特別是,當該顯示器係利用OLED實現時,把互連件沉積於側表面上之顯示器部分和互連件沒沉積之顯示器部分包括在內。因此,於該沒沉積之部分中,外部光可能被反射或散射,且在此,該封裝膜用以吸收且阻擋反射光或散射光。於一實例中,該透光率可於550nm利用UV-Vis光譜儀測量。
第5至8圖係本發明之封裝膜的平面視圖。
如上所述,於該封裝膜中,如第5圖所示,光吸收區可形成於該封裝膜之全面積,但是本發明不限於此。也就是說,當該封裝膜係以平面視圖觀察時,如第6至8圖所示,該光吸收區可形成於至少一個外周部。也就是說,當將於可見光區之透光率為15%或更低的封裝膜1的區域稱作光吸收區或第一區10,且於可見光區之透光率為大於15%的區域可被稱作非光吸收區或第二區11時,該封裝膜之全面積可為該第一區10。或者,僅該封裝膜1之一外周部可為該第一區10。也就是說,如第6圖所示,四個外周部之一係該第一區10,且其餘者可為第二區11。或者,如第8圖所示,全部四個外周部可皆為第一區10。在此,各外周部厚度可根據普通熟悉此技藝者應用該封裝膜之領域和用途適度地調整。此外,本文所用之措辭“第一區10”可以與上述光吸收區相同之意義使用。
於本發明中,構成該光吸收層或水氣阻障層之封裝組合物可由已知材料形成。例如,如上所述,該構成光吸收層之封裝組合物可包括該封裝樹脂和該光吸收材料。此外,該光吸收材料可由普通熟悉此技藝者適當調整該材料之種類或含量使該封裝膜之光吸收區具有以上範圍之透光率。
於本發明之一示範實施態樣中,該構成封裝組合物之封裝樹脂沒有特別限制。該光吸收層和該水氣阻障層皆可包括本文所述之封裝樹脂。
於一實例中,該封裝樹脂可於室溫為固態或半固態,較佳為固態。在此,當該樹脂於室溫為固態或半固態時,該樹脂可能於室溫沒有流動性。例如,本文使用之“於室溫為固態或半固態”可意指於室溫之標的物黏度大約為106泊或更高或大約107泊或更高。在此,該黏度係於5%應變和1Hz頻率使用Advanced Rheometric Expansion System(ARES)測量。
當該封裝樹脂於室溫為固態或半固態時,其能以未固化狀態保持於膜或片形。因此,在使用該封裝膜包封或封裝該有機電子元件時,可防止加諸於該元件之物理或化學損壞,且可平順地進行該程序。此外,可防止在包封或封裝該有機電子元件時加入氣泡或該元件之使用期限縮減。該封裝樹脂之黏度上限沒有特別限制,且例如,可考慮加工性而控制於大約109泊或更低之範圍。
例如,該封裝樹脂可為丙烯酸樹脂、環氧樹
脂、矽氧烷樹脂、氟樹脂、苯乙烯樹脂、聚烯烴樹脂、熱塑性彈性體、聚氧伸烷基樹脂、聚酯樹脂、聚氯乙烯樹脂、聚碳酸酯樹脂、聚苯硫醚樹脂、聚醯胺樹脂或其混合物。
在此,該苯乙烯樹脂可為,例如,苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、丙烯腈-丁二烯-苯乙烯嵌段共聚物(ABS)、丙烯腈-苯乙烯-丙烯酸酯嵌段共聚物(ASA)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯系均聚物或其混合物。該烯烴樹脂可為,例如,高密度聚乙烯系樹脂、低密度聚乙烯系樹脂、聚丙烯系樹脂或其混合物。該熱塑性彈性體可為,例如,酯系熱塑性彈性體、烯烴系熱塑性彈性體或其混合物。在此,至於該烯烴系熱塑性彈性體,可使用聚丁二烯樹脂或聚異丁烯樹脂。至於該聚氧伸烷基樹脂,可使用,例如,聚氧伸甲基系樹脂、聚氧伸乙基系樹脂或其混合物。至於該聚酯樹脂,可使用,例如,聚對苯二甲酸乙二酯系樹脂、聚對苯二甲酸丁二酯系樹脂或其混合物。至於該聚氯乙烯樹脂,可使用,例如,聚偏氯乙烯。此外,可使用烴樹脂,例如,三十六烷或烷烴之混合物。至於該聚醯胺樹脂,可使用,例如,耐龍。至於該丙烯酸酯樹脂,可使用,例如,聚(甲基)丙烯酸丁酯。至於該矽氧樹脂,可使用,例如,聚二甲基矽氧烷。此外,至於該氟樹脂,可使用聚三氟乙烯樹脂、聚四氟乙烯樹脂、聚氯三氟乙烯樹脂、聚六
氟丙烯樹脂、聚偏氟乙烯、聚氟乙烯、聚氟化乙烯丙烯或其混合物。
以上列示之樹脂可接枝於,例如,與列示之樹脂中的另一者或供製備樹脂用之單體聚合,或由不同化合物改質的順丁烯二酸酐。至於該不同化合物之實例,可使用末端為羧基之丁二烯-丙烯腈共聚物。
於一實例中,該封裝組合物之封裝樹脂可包括聚異丁烯系樹脂。該聚異丁烯系樹脂可基於疏水性而具有低WVTR和低表面能。明確地說,至於該聚異丁烯系樹脂,可使用,例如,異丁烯單體之均聚物;或藉由將另一種與異丁烯單體聚合之單體共聚合製備而成的共聚物。在此,該另一種與異丁烯單體聚合之單體可為,例如,1-丁烯、2-丁烯、異戊二烯或丁二烯。於一實例中,該共聚物可為丁基橡膠。
至於該封裝樹脂之組分,可使用具有能模塑成膜形之重量平均分子量(Mw)的基底樹脂。於一實例中,該能模塑成膜形之重量平均分子量的範圍可為大約100,000至2,000,000、100,000至1,500,000或100,000至1,000,000。本文所用之措辭“重量平均分子量”意指藉由凝膠滲透層析儀(GPC)測得之相對於標準聚苯乙烯的換算值。
此外,至於該封裝樹脂之組分,可使用以上組分中之一者或至少二者。當使用至少兩種組分時,可使用至少二不同類型之樹脂、至少兩種具有不同重量平均分
子量之樹脂或至少二不同類型之重量平均分子量不同的樹脂。
於又另一個示範實施態樣中,根據本發明之封裝樹脂可為可固化之樹脂。可用於本發明之特定類型的可固化之樹脂沒有特別限制,且可使用例如,此技藝中已知之不同可熱固化或可光固化之樹脂。本文所用之措辭“可熱固化之樹脂”意指能透過適當加熱之程序或老化程序固化的樹脂,且本文所用之措辭“可光固化之樹脂”意指能藉由放射電磁波而固化之樹脂。此外,該可固化之樹脂可為包括所有熱固化和光固化特性之兩用可固化之樹脂。於一實例中,由於該封裝組合物係由下述含有光吸收材料之可固化之樹脂構成,所以本發明之可固化之樹脂可為可熱固化之樹脂,不是可光固化之樹脂,但是本發明不限於此。
本發明之特定類型的可固化之樹脂可為具有上述特性之任何類型而沒有特別限制。例如,該可固化之樹脂可藉由固化而具有黏著特性,且可為包括至少一個可熱固化之官能基如縮水甘油基、異氰酸酯基、羥基、羧基或醯胺基的樹脂,或包括至少一個能藉由放射電磁波而固化之官能基如環氧基、環醚基、硫醚基、縮醛基或內酯基的樹脂。此外,特定類型之上述樹脂可為丙烯酸樹脂、聚酯樹脂、異氰酸酯樹脂或環氧樹脂,但是本發明不限於此。
於本發明中,至於該可固化之樹脂,可使用
芳族或脂族或線性或分支環氧樹脂。於本發明之一示範實施態樣中,包括至少兩個官能基且具有180至1,000g/eq之環氧當量的環氧樹脂皆可使用。由於使用該具有以上範圍之環氧當量之環氧樹脂,因而可有效地保持該固化產物之性質如黏著性能和玻璃轉化溫度。此環氧樹脂可為甲酚-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-酚醛環氧樹脂、四官能性環氧樹脂、聯苯型環氧樹脂、三酚甲烷型環氧樹脂、經烷基改質之三酚甲烷環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂及經二環戊二烯改質之酚型環氧樹脂中之一者或至少二者的混合物。
於本發明中,至於該可固化之樹脂,可使用分子結構中包括環狀結構的環氧樹脂,或可使用包括芳族基(例如,苯基)的環氧樹脂。當該環氧樹脂包括芳族基時,固化產物可具有優良之熱和化學安定性,且顯示低水氣吸收量,且因此可增進該OED之封裝結構的可靠度。至於該能用於本發明之包含芳族的環氧樹脂,聯苯型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、經二環戊二烯改質之酚型環氧樹脂、甲酚系環氧樹脂、雙酚系環氧樹脂、二甲苯系環氧樹脂、多官能性環氧樹脂、酚-酚醛環氧樹脂、三酚甲烷型環氧樹脂及經烷基改質之三酚甲烷環氧樹脂中之一者或至少二者的混合物皆可使用,但是本發明不限於此。
於本發明中,至於該環氧樹脂,可使用經矽
烷改質之環氧樹脂或具有芳族基之經矽烷改質之環氧樹脂。同樣地,當使用具有結構上經矽烷改質之甲矽烷基的環氧樹脂時,可將對玻璃基材或該OLED基材之無機材料的黏著性最大化,且可增進水氣阻障性或耐久性及可靠度。能用於本發明之特定類型的該環氧樹脂沒有特別限制,且這樣之樹脂可自製造商如Kukdo Chemical有限公司輕易地購得。
於本發明之一示範實施態樣中,該封裝膜之光吸收區可包括光吸收材料,且該光吸收材料之類型和含量可由普通熟悉此技藝者適當地加以控制以滿足上述膜透光率之範圍。
本文所用之措辭“光吸收材料”可為能吸收可見光之材料,例如,顏料或染料。
於一實例中,該光吸收材料可為非傳導性材料。當該包括光吸收材料之封裝組合物係製成能應用於包封該OED之膜形時,若該膜具有導電度,將引發驅動該OED時之運作失常。因此,於本發明之一示範實施態樣中,該光吸收材料可為非傳導性材料。
該光吸收材料沒有特別限制,但是可為,例如,顏料或染料。於一實例中,該光吸收材料可為能吸收全範圍波長或特定波長範圍之光的任何材料,且可為,但是不特別限於,例如,碳黑、碳奈米管、茀(C6)、酞花青衍生物、卟啉衍生物、三苯基胺衍生物或其混合物。於一實例中,該光吸收材料可佔相對於100重量份之封裝樹
脂0.6重量份或更高、0.6至50重量份、0.6至35重量份、0.7至30重量份、0.8至25重量份、0.9至20重量份或0.9至18重量份。因為該光吸收材料係於以上範圍內調整,當該封裝組合物係施用於OED時,內部或外部光可被有效吸收且阻擋以防止該光之反射或散射。
於又另一個示範實施態樣中,該光吸收材料可視需要調整以吸收特定波長範圍之光源。
本發明之封裝膜的光吸收層或水氣阻障層可視需要包括水氣吸收劑。本文所用之措辭“水氣吸收劑”可包括所有能吸附或移除自外在環境透過物理或化學反應滲入的水氣或蒸氣之組分。也就是說,該水氣吸收劑可為水氣反應性吸收劑、物理吸收劑或其混合物。
該水氣反應性吸收劑藉由與滲入該封裝膜之蒸氣、水氣或氧之化學反應吸附水氣或蒸氣。滲入該物理吸收劑之作用可藉由延長水氣或蒸氣滲入該封裝結構之移動途徑而抑制,且該物理吸收劑可透過與該封裝樹脂之基體結構和該水氣反應性吸收劑之交互作用將對水氣和蒸氣之阻擋性質最大化。
能用於本發明之特定類型的水氣吸收劑並沒有特別限制,且例如,該水氣反應性吸收劑可為金屬粉末如氧化鋁、金屬氧化物、金屬鹽和五氧化磷(P2O5)中之一者或至少二者的混合物,且該物理吸收劑可為氧化矽、沸石、氧化鈦、氧化鋯或蒙脫石。
在此,明確地說,該金屬氧化物可為氧化鋰
(Li2O)、氧化鈉(Na2O)、氧化鋇(BaO)、氧化鈣(CaO)或氧化鎂(MgO),且該金屬鹽可為,但是不限於,硫酸鹽如硫酸鋰(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);金屬鹵化物如氯化鈣(CaCl2)、氯化鎂(MgCl2)、氯化鋇(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)、溴化鈰(CeBr3)、溴化硒(SeBr4)、溴化釩(VBr3)、溴化鎂(MgBr2)、碘化鋇(BaI2)或碘化鎂(MgI2);或金屬氯酸鹽如高氟酸鋇(Ba(ClO4)2)或高氯酸鎂(Mg(ClO4)2),但是本發明不限於此。
於本發明中,該水氣吸收劑如金屬氧化物可經適度地處理,且混於該組合物。例如,依據該封裝膜施用之OED類型,該封裝組合物可形成為厚度為30μm或更小之薄膜的形態,且在此案例中,可能需要該水氣吸收劑之磨細程序。為了將該水氣吸收劑磨細,可使用三輥式研磨機、珠磨機或球磨機。
本發明之封裝膜的光吸收層或水氣阻障層可包括相對於100重量份之封裝樹脂0至100、1至90、5至80或10至60重量份之水氣吸收劑。該水氣吸收劑係任選之組分,且因此可不被包括在內。然而,因為該水氣吸收劑之含量係控制於5重量份或更高,所以固化產物可
顯示優良之水氣和蒸氣阻擋性。此外,因為該水氣吸收劑之含量係控制於100重量份或更低,所以可形成薄膜型封裝結構,且可顯示優良之水氣阻障性。
在此說明書中,除非特地另行定義,否則該單位“重量份”意指組分之間的重量比。
在本發明之一示範實施態樣中,該水氣吸收劑可根據用於包封有機電子元件之結構適當地控制。例如,於與該有機電子元件接觸之層中,該水氣吸收劑可以該封裝膜之水氣吸收劑總重量為基準計為0至20%包括在內。例如,如第3和4圖所示,當該元件與該二水氣阻障層4和6中之一者(水氣阻障層6)接觸時,在該有機電子元件包封時該水氣阻障層6係佈置於另一個水氣阻障層4下面,下方水氣阻障層6可包括以該水氣吸收劑之總重量為基準計為0至20%的水氣吸收劑,且沒與該有機電子元件接觸之上方水氣阻障層4可包括以該水氣吸收劑之總重量為基準計為80至100%的水氣吸收劑。
本發明之封裝膜的光吸收層或水氣阻障層可包括填料,且較佳地,必要時無機填料。該填料可延長水氣或蒸氣滲入該封裝結構之移動途徑而抑制滲透,且透過與該封裝樹脂之基體結構和該水氣吸收劑之交互作用將對水氣和蒸氣之阻擋性最大化。能用於本發明之特定類型的填料可為,但是不特別限於,例如,黏土、滑石和氧化矽中之一者或至少二者的混合物。
此外,在本發明中,為了提高對該填料和有
機黏合劑之黏合效率,至於填料,可使用以有機材料處理過表面之產物,或可同時使用偶合劑。
本發明之封裝膜的光吸收層或水氣阻障層可包括相對於100重量份之封裝樹脂0至50、1至40或1至20重量份之填料。在本發明中,該填料係任選組分,且可不被包括於該封裝膜中。然而,該填料之含量係控制於1重量份或更高,且因此可提供具有優良之水氣或蒸氣阻擋性和物性的封裝結構。此外,在本發明中,當該填料之含量係控制於50重量份或更低時,該封裝膜可製造成膜形,且甚至當該封裝膜係製造成薄膜時,可提供顯示優良之水氣阻障性的固化產物。
本文所用之措辭“封裝結構”可為具有單層或多層結構之上述封裝膜,且可為用於包封包括封裝膜之OED的產物,該封裝膜包封該OED之全部表面和有機電子元件。
此外,於一實例中,該封裝膜可另包括分散劑使該光吸收材料或該水氣吸收劑可被均勻地分散。至於能用於本文之分散劑,可使用,例如,對該光吸收材料之表面具有親和力且與該封裝樹脂具有相容性的非離子型表面活性劑。
在本發明之一示範實施態樣中,該封裝膜之光吸收層或水氣阻障層可根據該封裝樹脂之類型另包括固化劑。例如,能藉由與上述封裝樹脂之反應形成交聯結構的固化劑或能開始該樹脂之固化反應的起始劑可另包括在
內。
該固化劑之適當類型可根據該封裝樹脂或該樹脂包括之官能基的類型挑選且使用。
於一實例中,當該封裝樹脂係環氧樹脂時,可使用,例如,胺固化劑、咪唑固化劑、酚固化劑、磷固化劑和酸酐固化劑中之一者或至少二者作為此技藝已知之環氧樹脂的固化劑,但是本發明不限於此。
於一實例中,可使用於室溫為固體且熔點或降解溫度為80℃或更高之咪唑化合物作為該固化劑。此化合物可為,但是不限於,例如,2-甲基咪唑、2-十七基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑或1-氰乙基-2-苯基咪唑。
該固化劑之含量可根據,例如,該封裝樹脂之類型或比率挑選。例如,該固化劑可佔相對於100重量份之封裝樹脂1至20、1至10或1至5重量份。然而,該重量比可根據該封裝樹脂或該樹脂之官能基之類型或比率或待實行之交聯密度而變更。
當該封裝樹脂係可藉由活性能量射線之放射而固化的樹脂時,可使用,例如,陽離子型光聚合起始劑作為起始劑。
至於該陽離子型光聚合起始劑,鎓鹽-或有機金屬鹽-系離子化陽離子型起始劑或有機矽烷-或潛在性磺酸(latent sulfonic acid)-系離子化陽離子型光聚合起始劑或未離子化陽離子型光聚合起始劑皆可使用。該鎓鹽系
起始劑可為二芳基錪鹽、三芳基銃鹽或芳基偶氮鎓鹽,該有機金屬鹽-系起始劑可為芳基鐵(iron arene),該有機矽烷系起始劑可為鄰-硝基苯甲基三芳基矽烷基醚、過氧化三芳基矽烷基或醯基矽烷,且該潛在性磺酸-系起始劑可為α-磺醯氧基酮或α-羥甲基苯偶姻磺酸酯,但是本發明不限於此。
於一實例中,可使用離子化陽離子型光聚合起始劑作為該陽離子型起始劑。
此外,當該封裝樹脂係能藉由活性能量射線之放射而固化的樹脂時,可使用,例如,自由基起始劑作為起始劑。
該自由基起始劑可為光起始劑或熱起始劑。特定類型之光起始劑可考量固化速度和黃化可能性而適當地挑選。例如,該光起始劑可為苯偶姻-、羥基酮-、胺基酮-或氧化膦為底質之光起始劑,且明確地說,苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、苯乙酮、二甲基胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、苯甲酮、對-苯基苯甲酮、4,4'-二乙基胺基苯甲酮、二氯苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮,2,4-二甲基噻
噸酮、2,4-二乙基噻噸酮、苯甲基二甲基縮酮、苯乙酮二甲基縮酮、對-二甲基胺基苯甲酸酯、寡聚合[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-二苯基-氧化膦。
該起始劑之含量,像該固化劑,可根據該封裝樹脂或該樹脂之官能基之類型或比率或待實行之交聯密度而變更。例如,該起始劑可佔相對於100重量份之封裝樹脂0.01至10重量份或0.1至3重量份。
本發明之封裝膜的光吸收層或水氣阻障層可另包括高分子量樹脂。當本發明之封裝組合物係模塑成膜或片形時,該高分子量樹脂可能適於改善模塑性。此外,當熱熔程序係進行時,該高分子量樹脂可當高溫黏度控制劑用於控制流動性。
能用於本文之高分子量樹脂的類型沒有特別限制,只要該樹脂與該封裝樹脂之另一種組分具有相容性即可。能用於本文之高分子量樹脂的特定實例係重量平均分子量為20,000或更高之樹脂,例如,苯氧基樹脂、丙烯酸酯樹脂、高分子量環氧樹脂、超高分子量環氧樹脂、含高極性官能基之橡膠及含高極性官能基之反應性橡膠中之一者或至少二者的混合物,但是本發明不限於此。
當本發明之封裝組合物包括該高分子量樹脂時,該樹脂之含量係根據期望之物性調整,且沒有特別限制。例如,在本發明中,該高分子量樹脂可佔相對於100重量份之封裝樹脂,大約200重量份或更低,較佳150重
量份或更低,且更佳大約100重量份或更低。因為本發明之高分子量樹脂的含量係控制於200重量份或更低,所以與該樹脂組合物之各組分的相容性可以有效地保持,且因此該樹脂可當黏著劑使用。
在根據本發明之構成光吸收層或水氣阻障層之封裝組合物中,除了上述組分以外,可根據用途、該封裝樹脂之類型和封裝膜之製程而包括不同黏著劑,其將在下文中描述而不會影響本發明之效果。例如,該封裝組合物可根據期望物性包括適當範圍之含量的偶合劑、交聯劑、可固化材料、增黏劑、UV安定劑或抗氧化劑。在此,該可固化材料可意指具有分開包括在內之可熱固化之官能基及/或活性能量射線可固化之官能基的材料,而非上述構成光吸收層之組分。例如,該可固化材料可意指包括下述官能基中之至少二者的化合物:能藉由活性能量射線之放射參與聚合的官能基(例如,包括乙烯基不飽和雙鍵之官能基如丙烯醯基或甲基丙烯醯基)及某官能基(如環氧基或氧雜環丁烷基(oxetane group))。
在本發明之一示範實施態樣中,除了該光吸收層或該水氣阻障層以外,該封裝膜可另包括金屬層。根據本發明之一示範實施態樣的金屬層可能是透明性或半透明性。該金屬層可為薄膜型金屬箔層或藉由將金屬沉積於聚合物基底膜上而形成之層。該金屬層可由能具有導熱率和水氣阻障性之任何材料形成而沒有限制。該金屬層可包括金屬、金屬氧化物、金屬氮化物、金屬碳化物、金屬氧
氮化物、金屬氧硼化物、和其混合物中之任一者。例如,該金屬層可包括藉由將至少一種金屬元素或非金屬元素加於一種金屬而製備的合金,例如,鐵-鎳合金或不銹鋼(SUS)。此外,於一實例中,該金屬層可包括銅、鋁、鎳、氧化矽、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。該金屬層可藉由電解法、輥軋法、汽化法、電子束汽化法、濺射法、反應性濺射法、化學氣相沉積法、電漿化學氣相沉積法或電子迴旋共振源電漿化學氣相沉積法沉積。在本發明之一示範實施態樣中,該金屬層可藉由反應性濺射法沉積。在本發明之一示範實施態樣中,該包括金屬層之封裝膜可藉由該金屬層利用該光吸收區防止該OED之互連件未沉積部分的外部光反射或散射。
於一實例中,在包括鏡面反射(SCI)測量時該金屬層可具有15至90、18至88或20至86%之反射率。此外,在排除鏡面反射(SCE)測量時該金屬層可具有15至80、18至75、20至70或20至65%之反射率。在此,該SCI表示全反射,且該SCE表示散射引起之不規則反射。該反射率可藉由此技藝中已知之方法利用,例如,Konika Minolta製造之CM2006d測量(測量條件:來自M/I+E、M/SCI、M/SCE、S/I+E、S/SCI和S/SCE之任一個預定值、來自UV 0至100%之任一個預定值、來自D65、D50、C、A、F2、F6、F7、F8、F10、F11和F12之任一種光源及10°或2°之觀察視角)。當本發明之封裝
膜包括金屬層時,由於該OED之金屬互連件與該金屬層之間的反射率差異,在自外在環境觀察該OED時,觀察到該互連件。特別是,當該光吸收層包括水氣吸收劑或填料時,或當該水氣阻障層包括水氣吸收劑或填料時,該光吸收層或該水氣阻障層當作光散射之中間層使用。因此,使得形成於該OED之一表面上的偏光鏡反射率降低之效果降低,且因此使不含該金屬互連件之部分看起來模糊不清。因此,如上所述,該包括金屬層之封裝膜可藉由該金屬層利用光吸收區防止該OED之互連件未沉積部分的外部光反射或散射。
該金屬層可具有以下導熱率:50W/mK或更高、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。因為該金屬層具有上述高導熱率,所以在接觸該金屬層之過程中接觸界面處產生之熱可更輕易地排出。此外,由於該高導熱率,使該OED運轉時累積之熱迅速排至外在環境,且因此該OED之溫度可保持較低,且龜裂和缺陷之產生減少了。
本文所用之措辭“導熱率”係材料透過傳導傳送熱之能力的程度,且單位可為W/mK。該單位顯示於相同溫度和距離之材料傳送熱之程度,且係關於距離單位(米)和溫度單位(凱氏)之熱單位(瓦)。
本發明之封裝膜的結構可為,但是不特別限於,例如,包括基底膜或離型膜(後文中,也稱作“第一膜”);及該形成於基底膜或離型膜上之光吸收層或水氣阻障層的結構。
本發明之封裝膜可另包括形成於光吸收層或水氣阻障層上之基底膜或離型膜(後文中,也稱作“第二膜”)。
能用於本發明之特定類型的第一膜沒有特別限制。在本發明中,可使用,例如,此技藝中通常使用之聚合物作為該第一膜。在本發明中,可使用,例如,聚對苯二甲酸乙二酯膜、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-丙烯酸乙酯共聚物膜、乙烯-丙烯酸甲酯共聚物膜或聚醯亞胺膜作為該基底或離型膜。此外,本發明之基底膜或離型膜的一或二表面可以適當離型處理。至於該基底膜之離型處理時使用的離型劑實例,可使用以醇酸-、矽酮-、氟-、不飽和酯-、聚烯烴-或石蠟-為底質之離型劑,且從耐熱性之觀點來看,較佳為使用以醇酸-、矽酮-或氟-為底質之離型劑,但是本發明不限於此。
此外,能用於本發明之第二膜類型(後文中,稱作“覆蓋膜”)也沒有特別限制。例如,在本發明中,與該第一膜相比,可使用與以上列示之第一膜種類相同或不同類型的膜作為該第二膜。此外,在本發明中,該
第二膜也可以適當離型處理法處理。
在本發明中,上述基底膜或離型膜(第一膜)之厚度可,但是不特別限於,根據用途而適當地挑選。例如,本發明之第一膜的厚度可為大約10至500μm,且較佳20至200μm。當該厚度小於10μm時,該基底膜可以製造程序輕易地變形,且當該厚度大於500μm時,使經濟可行性降低。
在本發明中,該第二膜之厚度也沒有特別限制。在本發明中,例如,該第二膜之厚度可調設成與該第一膜相同。在本發明中,在考量加工性時,該第二膜之厚度可調設成較小於該第一膜。
本發明之封裝膜中包括的光吸收層或水氣阻障層之厚度沒有特別限制,且可考量該膜應用之用途而根據以下條件適當地挑選。本發明之封裝膜中包括的光吸收層或水氣阻障層之厚度可為大約5至200μm,且較佳10至150μm。
在本發明中,該封裝膜之製造方法沒有特別限制。例如,該封裝膜可藉由包括以下步驟之方法製造:以包括上述封裝組合物之塗佈液塗佈基底膜或離型膜的第一操作步驟;及將該第一操作步驟塗佈之塗佈液乾燥的第二操作步驟。
光吸收層或水氣阻障層之堆疊方法沒有特別限制。例如,該形成於單獨離型膜上之光吸收層或水氣阻障層可以層疊,藉以形成具有多層結構之封裝膜,且水氣
阻障層可直接形成於該光吸收層上,或反之亦然。
在本發明之封裝膜的製造方法中,可另包括附帶地將基底膜或離型膜壓於已在該第二操作步驟中乾燥之塗佈液上的第三操作步驟。
本發明之第一操作步驟在於藉由將上述封裝組合物溶於或分散於適當溶劑中而製備塗佈液。在此操作步驟中,該塗佈液包括之封裝樹脂含量可根據期望之水氣阻障性和膜模塑性適當地控制。
在製備本發明之塗佈液時使用的溶劑類型沒有特別限制。然而,當該溶劑之乾燥時間過長,或必需於高溫乾燥時,可能發生該封裝膜之可加工性或耐久性的問題,且因此較佳地使用汽化溫度為100℃或更低之溶劑。在本發明中,在考量膜模塑性時,可混合小量汽化溫度於以上範圍或更高之溶劑。能用於本發明之溶劑實例可使用甲基乙基酮(MEK)、丙酮、甲苯、二甲基甲醯胺(DMF)、甲基溶纖劑(MCS)、四氫呋喃(THF)或N-甲基吡咯烷酮(NMP)中之一者或至少二者的混合物,但是本發明不限於此。
在本發明之第一操作步驟中,以該塗佈液塗佈基底膜或離型膜之方法可為,但是不特別限於,例如,已知方法如刮刀塗法、輥塗法、噴塗法、凹版塗佈法、帘塗法、缺角輪塗法或唇模塗法(lip coating)。
本發明之第二操作步驟在於藉由將該第一操作步驟時塗佈之塗佈液乾燥而形成光吸收層或水氣阻障
層。也就是說,在本發明之第二操作步驟中,該光吸收層或該水氣阻障層可藉由加熱塗於該膜上之塗佈液將該溶劑乾燥且移除而形成。在此,乾燥條件沒有特別限制,且例如,該乾燥步驟可於70至200℃進行經過1至10分鐘。
在本發明之封裝膜的製法中,經過該第二操作步驟之後,可進一步進行將另一個基底膜或離型膜壓在該形成於該膜上之光吸收層或水氣阻障層上的第三操作步驟。
本發明之第三操作步驟可藉由將另一個離型膜或基底膜(覆蓋膜或第二膜)壓在以該塗佈液塗佈該膜而形成之光吸收層或水氣阻障層上且透過熱輥層疊或加壓將該塗層乾燥而進行。
此外,如第9圖所示,本發明關於一種OED,其包括基材21;有機電子元件23,其包括存於該基材上之透明電極層、存於該透明電極層上且包括至少一個發射層之有機層及存於該有機層上之反射電極層;及該封裝膜1,其包封該有機電子元件23之整個表面,且具有就可見光區來看透光率為15%或更低之光吸收區。
該有機層可形成不同結構,只要有包括發射層,該不同結構可另包括此技藝已知之不同功能層。該有機層能包括在內之層可為電子注入層、電洞阻擋層、電子轉移層、電洞轉移層及電洞注入層。
此技藝中已知之形成彼的不同材料和方法可用以形成電洞或電子注入電極層和有機層,例如,發射
層、電子注入或轉移層或電洞注入或轉移層,但是本發明不限於此。
本發明之有機電子元件23可為OLED。
於一實例中,根據本發明之OED可為底部發射OED。
該OED可另包括於該封裝膜與該有機電子元件之間保護該有機電子元件的保護膜。
此外,該OED可包括封裝膜,該封裝膜另包括金屬層,且在此案例中,可省略將在下文中描述之覆蓋基材。
於本發明之又另一實施態樣中,OED之製造方法包括形成包括將有機電子元件形成於基材上,該有機電子元件包括透明電極層、存於該透明電極層上且包括至少一個發射層之有機層及存於該有機層上之反射電極層;及將上述封裝膜施用於其上形成有機電子元件之基材上以包封該有機電子元件之整個表面。
將該封裝膜施用於該OED之操作可藉由該封裝膜之熱輥層壓、熱壓或真空壓製進行,但是本發明並不特別限於此。
將該封裝膜施用於該OED之操作可於50至90℃進行,且接著固化可藉由於70至110℃之溫度範圍加熱或放射UV射線而於其上進行。
第9圖係根據本發明之一示範實施態樣的OED之截面圖。
根據本發明之OED製造方法,例如,藉由真空沉積或濺射將透明電極形成於該基材21如玻璃或膜上,且將有機材料層形成於該透明電極上。該有機材料層可包括電洞注入層、電洞轉移層、發射層、電子注入層及/或電子轉移層。其後,再將第二電極形成於該有機材料層上。之後,將上述封裝膜1施用於於該基材21上之OED 23的上方部分以將該OED 23完全覆蓋。在此,該封裝膜1之施用方法沒有特別限制,且可為加熱、壓製或在壓熱器中處理本發明之封裝膜1已經事先轉移,例如,至形成於該基材21上之OED 23上,的覆蓋基材22(例如,玻璃或聚合物膜)。在此操作步驟中,例如,當該封裝膜1轉移至該覆蓋基材22時,等到形成於該膜上之基底或離型膜可以脫層之後,該封裝膜1可透過真空壓製機或真空層合機轉移至該覆蓋基材22同時加熱。在此操作步驟中,當該封裝膜1之固化係於預定範圍或更大進行時,該封裝膜1之內聚強度或黏著強度可能會降低,且因此程序溫度可控制於大約100℃或更低,且程序時間可控制於5分鐘內。同樣地,連在透過熱壓將該經轉移封裝膜1之覆蓋基材22施用於該OED 23時,也可使用真空壓製機或真空層合機。此操作步驟之溫度條件可按上述調設,且程序時間可調設於10分鐘內。
此外,在本發明中,可對該壓製OED之封裝膜進行另一個固化程序,且此固化程序(主要固化)可,例如,於加熱艙或UV艙,且較佳加熱艙中進行。該主要
固化之條件可考量該OED之安定性適當地挑選。
然而,上述製造程序僅為包封本發明之OED的實例,且程序順序或程序條件可加以改變而沒有限制。例如,在本發明中,該轉移和壓製程序之順序可改為將本發明之封裝膜1轉移至該基材21上之OED 23,且壓緊該覆蓋基材22。此外,可將保護層形成於該OED 23上,可將該封裝膜施用於該保護層,且接著可在其上進行固化而不含該覆蓋基材22。
當OED係利用根據本發明之示範實施態樣的封裝膜包封時,能實現優良之水氣阻障性,且因為光之反射或散射係藉由吸收且阻擋內部或外部光而防止,所以能防止該OED之外部缺陷。
1‧‧‧封裝膜
2‧‧‧光吸收層
3‧‧‧光吸收材料
4、6‧‧‧水氣阻障層
5‧‧‧水氣吸收劑
10‧‧‧第一區(光吸收區)
11‧‧‧第二區(非光吸收區)
21‧‧‧基材
22‧‧‧覆蓋基材
23‧‧‧有機電子元件
第1至4圖係根據本發明之一示範實施態樣的封裝膜之截面圖;第5至8圖係根據本發明之一示範實施態樣的封裝膜之平面圖;且第9圖係根據本發明之一示範實施態樣的OED之截面圖。
後文中,本發明之示範實施態樣將引用根據本發明之實施例和非根據本發明之比較例詳細描述。然而,本發明之範疇並不限於將揭露於下文之實施態樣。
藉由將一次粒徑為大約20nm或更小之碳黑(#2600 Mitsubishi Carbon black)當成光吸收材料且將甲基乙基酮(MEK)當成溶劑以10重量%之固體濃度添加而製備碳黑分散溶液。另一方面,藉由將100g之煅燒白雲石當成水氣吸收劑且將MEK當成溶劑以50重量%之固體濃度添加而製備水氣吸收劑溶液。
於室溫將200g之經矽烷改質之環氧樹脂(KSR-177,Kukdo Chemical有限公司)和150g之苯氧基樹脂(YP-50,Tohto Kasei有限公司)加於反應器,且以MEK稀釋。藉由將4g之咪唑(Shikoku Chemicals股份有限公司)當作固化劑加於該均質化溶液,且於高速攪拌所產生之溶液1小時而製備供光吸收層用之溶液。該供光吸收層用之溶液係藉由下述方式製備:將預先準備之水氣吸收劑溶液加於該溶液以具有相對於100重量份之光吸收層封裝樹脂30重量份之煅燒白雲石含量,添加該碳黑分散溶液以具有相對於100重量份之光吸收層封裝樹脂10重量份之碳黑含量,並將溶液混合。
封裝膜係藉由以該光吸收層溶液塗佈離型PET膜之離型面形成厚度為20μm之光吸收層且於130℃
將該塗佈液乾燥3分鐘製造而成。
藉由將一次粒徑為大約20nm或更小之碳黑(#2600 Mitsubishi Carbon black)當成光吸收材料且將MEK當成溶劑以10重量%之固體濃度添加而製備碳黑分散溶液。
於室溫將200g之經矽烷改質之環氧樹脂(KSR-177,Kukdo Chemical有限公司)和150g之苯氧基樹脂(YP-50,Tohto Kasei有限公司)加於反應器,且以MEK稀釋。藉由將4g之咪唑(Shikoku Chemicals股份有限公司)當作固化劑加於該均質化溶液,且於高速攪拌所產生之溶液1小時而製備供光吸收層用之溶液。該供光吸收層用之溶液係藉由下述方式製備:將預先準備之碳黑分散溶液添加於所產生之溶液並混合以具有相對於100重量份之光吸收層封裝樹脂10重量份之碳黑含量。
另一方面,藉由將100g之煅燒白雲石當成水氣吸收劑且將MEK當成溶劑以50重量%之固含量添加而製備水氣吸收劑溶液。
於室溫將200g之經矽烷改質之環氧樹脂(KSR-177,Kukdo Chemical有限公司)和150g之苯氧基樹脂(YP-50,Tohto Kasei有限公司)加於反應器,且以MEK稀釋。藉由將4g之咪唑(Shikoku Chemicals股份有限公司)當作固化劑加於該均質化溶液,且於高速攪拌所
產生之溶液1小時而製備水氣阻障層溶液。將該事先製備之水氣吸收劑溶液加於該溶液以具有相對於100重量份之水氣阻障層封裝樹脂30重量份之煅燒白雲石含量。
厚度為20μm之水氣阻障層係藉由以該水氣阻障層溶液塗佈離型PET膜之離型面且於130℃將所產生之表面乾燥3分鐘而形成。根據上述相同方法,厚度為10μm之光吸收層係藉由以該光吸收層溶液塗佈離型PET膜之離型面且於130℃將所產生之表面乾燥3分鐘而形成。將該水氣阻障層和該光吸收層層疊,藉以製造具有包括該水氣阻障層和該光吸收層之雙層結構的封裝膜。
厚度為20μm之水氣阻障層係藉由以實施例2製備之水氣阻障層溶液塗佈離型PET膜之離型面且於130℃將所產生之表面乾燥3分鐘而形成。根據上述相同方法,厚度為5μm之光吸收層係藉由以實施例2製備之光吸收層溶液塗佈離型PET膜之離型面且於130℃將所產生之表面乾燥3分鐘而形成。
將該水氣阻障層和該光吸收層層疊以具有包括該光吸收層/水氣阻障層/光吸收層之三層結構,藉以製造封裝膜。
除了將碳黑分散溶液添加以具有相對於100
重量份之光吸收層封裝樹脂1重量份之碳黑含量以外,封裝膜係藉由實施例1所述之相同方法製造。
除了將水氣吸收劑添加以具有相對於100重量份之封裝樹脂10重量份之含量以外,封裝膜係藉由實施例2所述之相同方法製造。
除了將碳黑分散溶液添加以具有相對於100重量份之光吸收層封裝樹脂0.5重量份之碳黑含量以外,封裝膜係藉由實施例1所述之相同方法製造。
以上製造之膜的光吸收區之透光率係利用UV-Vis光譜儀於550nm測量。當該膜係以單層結構形成時,透光率係依照厚度方向在光吸收層之光吸收區測量,且當該膜係以多層結構形成時,透光率係在多數層堆疊之情況依照厚度方向在光吸收區測量。
OED係藉由將實施例或比較例製造之封裝膜施加於形成在玻璃上之有機電子元件的全部表面,且將金屬互連件連於該OED製造而成。明確地說,藉由真空沉積將
透明電極形成於玻璃上,且將有機材料層形成於該透明電極上。該有機材料層包括電洞注入層、電洞轉移層、發射層、電子注入層和電子轉移層。其後,將反射電極進一步形成於該有機材料層上。之後,將實施例或比較例製造之封裝膜施加於該玻璃上之有機電子元件的上方部分以覆蓋全部有機電子元件(透明電極、反射電極和有機材料層)(移除離型PET)。另一方面,該封裝膜係藉由將厚度為20μm之銅膜層疊於該光吸收層及/或該水氣阻障層之一表面上製造而成的封裝膜(在包括鏡面反射SCI測量時該銅膜之一表面(光澤面)的反射率為58.32%且另一個表面(粗糙面)的反射率為20.7%)。此外,在排除鏡面反射SCE測量時該銅膜之一表面(光澤面)的反射率為45.59%且另一個表面(粗糙面)的反射率為20.02%)。
當將該OED置於白色背景上,且離大約1m觀看(亮度150 lux或更高)時,以肉眼觀察是否偵測或偵測不到互連件。當以肉眼偵測到互連件時,將其表示成O,且當以肉眼偵測不到互連件時,將其表示成X。
Claims (20)
- 一種有機電子元件之封裝膜,其包含:光吸收區,其包含封裝樹脂及相對於100重量份之封裝樹脂佔0.6重量份或更多之光吸收材料,且就可見光區來看具有15%或更低之透光率;及金屬層,其中該金屬層於包括鏡面反射SCI測量時具有15至90%之反射率,或於排除鏡面反射SCE測量時具有15至80%之反射率。
- 如申請專利範圍第1項之膜,其中該光吸收區係形成於該封裝膜之至少一個外周部。
- 如申請專利範圍第1項之膜,其中該光吸收區係形成於該封裝膜之全面積。
- 如申請專利範圍第1項之膜,該封裝樹脂包含丙烯酸樹脂、環氧樹脂、矽氧烷樹脂、氟樹脂、苯乙烯樹脂、聚烯烴樹脂、熱塑性彈性體、聚氧伸烷基樹脂、聚酯樹脂、聚氯乙烯樹脂、聚碳酸酯樹脂、聚伸苯硫醚樹脂、聚醯胺樹脂或其混合物。
- 如申請專利範圍第1項之膜,其中該封裝樹脂包含可固化樹脂。
- 如申請專利範圍第5項之膜,其中該可固化樹脂係熱可固化樹脂。
- 如申請專利範圍第5項之膜,其中該可固化樹脂包含選自縮水甘油基、異氰酸酯基、羥基、羧基、醯胺基、環氧基、環醚基、硫醚基、縮醛基及內酯基中之至少一個可固化官能基。
- 如申請專利範圍第5項之膜,其中該可固化樹脂係分子結構中包含環狀結構之環氧樹脂。
- 如申請專利範圍第5項之膜,其中該可固化樹脂係經矽烷改質之環氧樹脂。
- 如申請專利範圍第1項之膜,其中該光吸收材料係非傳導性材料。
- 如申請專利範圍第1項之膜,其中該光吸收材料係選自由碳黑、奈米碳管、茀、酞花青衍生物、卟啉衍生物及三苯基胺衍生物所組成之群組中的至少一者。
- 如申請專利範圍第1項之膜,其另包含水氣吸收劑。
- 如申請專利範圍第12項之膜,其中該水氣吸收劑係選自由P2O5、Li2O、Na2O、BaO、CaO、MgO、Li2SO4、Na2SO4、CaSO4、MgSO4、CoSO4、Ga2(SO4)3、Ti(SO4)2、NiSO4、CaCl2、MgCl2、SrCl2、YCl3、CuCl2、CsF、TaF5、NbF5、LiBr、CaBr2、CeBr3、SeBr4、VBr3、MgBr2、BaI2、MgI2、Ba(ClO4)2及Mg(ClO4)2所組成之群組中的至少一者。
- 如申請專利範圍第1項之膜,其包含:包含該光吸收區之光吸收層;及水氣阻障層。
- 如申請專利範圍第14項之膜,其中該水氣阻障層具有50g/m2.day或更小之水蒸氣穿透率(WVTR)。
- 如申請專利範圍第1項之膜,其中該金屬層具有50W/mK或更高之導熱率。
- 一種有機電子裝置,其包含:基材;有機電子元件,其包含存於該基材上之透明電極層、存於該透明電極層上且包含至少一個發射層之有機層及存於該有機層上之反射電極層;及封裝膜,其包封該有機電子元件之整個表面,且包含就可見光區來看具有15%或更低之透光率的光吸收區;及金屬層,其中該金屬層於包括鏡面反射SCI測量時具有15至90%之反射率,或於排除鏡面反射SCE測量時具有15至80%之反射率。
- 如申請專利範圍第17項之有機電子裝置,其中該光吸收區係形成於該封裝膜之至少一個外周部。
- 如申請專利範圍第17項之有機電子裝置,其中該光吸收區係形成於該封裝膜之全面積。
- 一種有機電子裝置之製造方法,其包含:將有機電子元件形成於基材上,該有機電子元件包含透明電極層、存於該透明電極層上且包含至少一個發射層之有機層及存於該有機層上之反射電極層;及將申請專利範圍第1項之封裝膜施用於其上形成有機電子元件之基材上以包封該有機電子元件之整個表面。
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