TWI527697B - 積層體及包含利用其所製造之基板之裝置 - Google Patents
積層體及包含利用其所製造之基板之裝置 Download PDFInfo
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- TWI527697B TWI527697B TW103113108A TW103113108A TWI527697B TW I527697 B TWI527697 B TW I527697B TW 103113108 A TW103113108 A TW 103113108A TW 103113108 A TW103113108 A TW 103113108A TW I527697 B TWI527697 B TW I527697B
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- polyimide
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Description
本發明係關於一種包含一可撓性基板及一載體基板之積層體,其中該可撓性基板容易自載體基板分離,無需進一步之程序(如雷射或光照射),從而有助於製備一具有該可撓性基板之裝置(例如,一可撓式顯示裝置)。本發明亦有關於一包含一使用該積層體製造之基板之裝置。
基於平面顯示器(flat panel displays,FPDs)易於製造大面積且可減少其厚度及重量,顯示裝置市場正在快速變化。此類平面顯示器包括液晶顯示器(liquid crystal displays,LCDs)、有機發光顯示器(organic light emitting displays,OLEDs)、及電泳裝置(electrophoresis devices)。
於近期更致力擴展平面顯示器之應用及用途中,應用可撓性基板於平面顯示器之所謂的可撓式顯示裝置特別受到矚目。基於如智慧型手機之可攜裝置,此類可撓式顯示裝置之應用特別受到重視且其應用領域也逐漸延伸。
在製造可撓式顯示裝置中,用於形成及處理顯
示裝置結構之程序相當重要,如塑膠基板(TOP)上之薄膜電晶體(TFTs)。然而,由於包含於可撓式顯示裝置之可撓性基板之可撓性,當可撓性基板直接用來取代現有玻璃基板以形成裝置結構時,在製程方面仍然有許多問題。
具體而言,當施加一衝擊時,包含於一可撓性基板之薄膜玻璃往往是易碎的。由於這樣的傾向,用於製造一顯示基板之製程係以薄膜玻璃設置於載體玻璃上的狀態進行。圖1例示一根據習知技術用於製造具有可撓性基板之裝置(例如,可撓式顯示裝置)之製程。
參考圖1,由適當材料(如矽)組成之犧牲層2係形成於一載體基板1(例如玻璃基板)上,且一可撓性基板3形成於其上。之後,根據於一玻璃基板上製造一裝置之習知製程,如薄膜電晶體之裝置結構係形成於由該載體基板1支撐之可撓性基板3上。然後,對該載體基板照射雷射或光,以破壞該犧牲層2並分離其上形成有該裝置結構之可撓性基板3,完成一具有該可撓性基板3之裝置(例如,一可撓式顯示裝置)之製備。
根據習知之方法,然而,雷射或光照射影響該裝置結構,增加缺陷之風險。再者,需要用於雷射或光照射之系統以及額外製程,不利地使整個裝置製程複雜化且顯著增加製造成本。
雖然於圖1中沒有例示,由於該犧牲層及該可撓性基板間之黏著性不足,其常常需要於由a-Si組成之該犧牲層2及該可撓性基板3之間形成一額外的黏著層。這
樣使得整個製程更為複雜且雷射及光照射之條件更為嚴苛,增加裝置可靠性可能受到不利影響的風險。
(專利文件1)PCT國際公開號第WO 2000-066507號(2000年11月9日公開)
本發明之一目的係提供一積層體以及製造該積層體之方法,該積層體包括一可撓性基板及一容易自該可撓性基板分離之載體基板,無需進一步程序,例如雷射或光照射,從而適合用在製備一具有該可撓性基板之裝置(例如,一可撓式顯示裝置)。
本發明之另一目的係提供一使用該積層體製造之裝置基板以及用以製造該裝置基板之方法。
本發明之又一目的係提供一包含使用該積層體製造之基板之裝置。
本發明之一態樣係提供一種積層體,包括:一載體基板;一第一聚醯亞胺樹脂層,其設置於該載體基板之至少一表面上;以及一第二聚醯亞胺樹脂層,其設置於該第一聚醯亞胺樹脂層上;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(coefficient of thermal expansion,CTE)等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且當一不會導致該第一聚醯亞胺樹脂層中發生化
學變化之物理刺激施加至該積層體時,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度係降低。
在100至200℃之溫度下,該第一聚醯亞胺樹脂層及該第二聚醯亞胺樹脂層之熱膨脹係數差可為60ppm/℃以下。
可施加該物理刺激以使該積層體之橫截面外露。
於施加該物理刺激之前,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層可具有至少1N/cm之黏著強度,且於施加該物理刺激之後,該第一聚醯亞胺樹脂層具有不大於0.3N/cm之從該第二聚醯亞胺樹脂層剝離之剝離強度。
該第一聚醯亞胺樹脂層可包括一第一聚醯亞胺樹脂,其具有不大於0.5之如方程式1所計算之相似性分數:[方程式1]相似性分數=αFIT(k1×Ls二酐,i+k2×Ls二胺,j)k 0
其中,Ls二酐,i=Exp[-k3×Coeffi]×Vi y 0,Ls二胺,j=Exp[-k4×Coeffj]×Vj y 0,k0=2.00,y0=-1.00,k1=206.67,k2=124.78,
k3=3.20,k4=5.90,Coeffi及Coeffj係分別為使用ADRIANA.Code(電腦化學,Molecular Networks GmbH)計算由二酐i及二胺j作為該聚醯亞胺之單體之結構之分子非球面性(molecular asphericities),Vi及Vj係分別為使用ADRIANA.Code(電腦化學,Molecular Networks GmbH)計算由二酐i及二胺j作為該單體之結構之麥克恩體積(McGowan volumes),以及若exp(-4.0×|Coeff i -Coeff j |)+0.08<0.90,αFIT為1.0,且若exp(-4.0×|Coeff i -Coeff j |)+0.080.90,αFIT為0.1至0.95之常數。
當一醯亞胺化度定義為:塗佈一包含一聚醯胺酸樹脂之組成物並於200℃以上之溫度醯亞胺化後,於紅外線(IR)光譜之1350至1400cm-1或1550至1650cm-1所觀察之CN鍵之累積強度(integrated intensity)相對於該組成物於500℃以上之溫度醯亞胺化後,於相同波長範圍所觀察之CN鍵之累積強度(100%)之百分比時,該第一聚醯亞胺樹脂可具有60%至99%之醯亞胺化度。
該第一聚醯亞胺樹脂可具有200℃以上之玻璃轉移溫度以及400℃以上之熱裂解溫度。
該第一聚醯亞胺樹脂層可藉由:於一載體基板上塗佈一包含一聚醯亞胺樹脂或其前驅物之組成物,並於等於該第二聚醯亞胺樹脂層之固化溫度或低於該第二聚醯亞胺樹脂層之固化溫度0至200℃之溫度下固化而形成。
該第一聚醯亞胺樹脂層包括一第一聚醯亞胺樹脂,其藉由反應一如化學式1之芳香族四羧酸二酐(aromatic tetracarboxylic dianhydride)與一具有直鏈結構之芳香族二胺化合物,以製備一聚醯胺酸,並於200℃以上之溫度固化該聚醯胺酸製備而得,
其中,A為如化學式2a或2b之四價芳香族有機基團,
其中,R11為一C1-C4烷基或C1-C4鹵烷基,a為0至3之整數,且b為0至2之整數,
其中,R12至R14各自獨立為C1-C4烷基或C1-C4鹵烷基,c及e各自獨立為0至3之整數,d為0至4之整數,且f為0至3之整數。
該芳香族二胺化合物可如化學式4a或4b所
示,
其中,R21為C1-C10烷基或C1-C10鹵烷基,且l為0至4之整數,
其中,R22及R23各自獨立為C1-C10烷基或C1-C10鹵烷基,X為一選自由-O-、-CR24R25-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO-、-SO2-、-O[CH2CH2O]q-、C6-C18單環及多環伸環烷基、C6-C18單環及多環亞芳基、及其組合所組成之群組,R24及R25各自獨立選自由氫原子、C1-C10烷基、及C1-C10鹵烷基所組成之群組,q為1或2之整數,m及n各自獨立為0至4之整數,且p為0或1之整數。
該第一聚醯亞胺樹脂層於100至200℃溫度下可具有不大於30ppm/℃之熱膨脹係數以及於450℃以上之1%熱裂解溫度(1% thermal decomposition temperature,Td1%)。
該第一聚醯亞胺樹脂層可具有0.05至5μm之厚度。
該第二聚醯亞胺樹脂層可包括一具有50至99%醯亞胺化度及200℃以上玻璃轉移溫度之第二聚醯亞
胺樹脂。
本發明之另一態樣係提供一種製造積層體之方法,包括:於一載體基板之至少一表面上形成一包含一第一聚醯亞胺樹脂之第一聚醯亞胺樹脂層;以及藉由塗佈一包含一第二聚醯亞胺樹脂或其之前驅物之組成物並固化該組成物,以於該第一聚醯亞胺樹脂層上形成一第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數。
該第一聚醯亞胺樹脂層可藉由於該載體基板之至少一表面上塗佈一包含一第一聚醯亞胺樹脂或其前驅物之組成物並固化該組成物而形成。
該第一聚醯亞胺樹脂層之固化製程可於200℃以上之溫度下進行,以及該第二聚醯亞胺樹脂層之固化製程可於等於該第一聚醯亞胺樹脂層之固化溫度或高於該第一聚醯亞胺樹脂層之固化溫度0至200℃之溫度下進行。
該製造積層體之方法可更包括一步驟:於形成該第一或第二聚醯亞胺樹脂層之步驟後,在300℃以上之溫度下熱處理該第一或第二聚醯亞胺樹脂層1至30分鐘。
本發明之又一態樣係提供一種製造裝置基板之方法,包括:於一載體基板之至少一表面上形成一包含一第一聚醯亞胺樹脂之第一聚醯亞胺樹脂層;於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或其之前驅物之組成物並固化該組成物,以製備一具有第二聚醯亞
胺樹脂層之一積層體;施加一物理刺激至該積層體而不導致該第一聚醯亞胺樹脂層中發生化學變化;以及由形成於該載體基板上之該第一聚醯亞胺樹脂層上分離該第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)可等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數。
施加該物理刺激以使該積層體之橫截面外露。
本發明之再一態樣係提供一種藉由一方法製造之裝置,該方法包括:於一載體基板之至少一表面上製造一積層體,其包括一第一聚醯亞胺樹脂層;於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或其之前驅物之組成物並固化該組成物以製備一積層體;於該積層體之該第二聚醯亞胺樹脂層上形成一裝置結構;施加一物理刺激至其上形成有該裝置結構之該積層體而不導致該第一聚醯亞胺樹脂層中發生化學變化,並由該積層體之該第一聚醯亞胺樹脂層上分離其上形成該裝置結構之第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且藉由一物理刺激降低該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度。
該裝置可選自由太陽能電池、有機發光二極體裝置、半導體裝置、及顯示裝置所組成之群組。
該顯示裝置可為可撓式有機電致發光裝置。
根據本發明之各種態樣之其他實施態樣之細節係包含於以下說明書中。
於本發明之積層體中,藉由一相對小之物理刺激(如切割)之施加,不需雷射或光照射,即可輕易自該載體基板分離包含一聚醯亞胺樹脂層之可撓式基板。因此,使用該基層有助於製備一包含該可撓性基板之裝置(例如,一可撓式顯示裝置)。
根據本發明,由於不需要額外的程序,例如雷射或光照射,可簡化該裝置之製造程序且可大幅降低製造成本。此外,該裝置可避免可靠性劣化及雷射或光照射導致之缺陷發生,確保該裝置之優異特性。
10‧‧‧載體基板
20‧‧‧第一聚醯亞胺樹脂層
30‧‧‧第二聚醯亞胺樹脂層
40‧‧‧裝置結構
100‧‧‧積層體
圖1例示一用以製造一包含可撓性基板之裝置之習知製程之示意圖。
圖2例示根據本發明實施態樣之積層體之結構之剖視圖。
圖3a及3b係分別為例示根據本發明另一實施態樣之一裝置基板之製程及使用一積層體製造顯示裝置之製程示意圖。
圖4係測試例1之隨溫度變化之包含不同第一聚醯亞胺樹脂層之積層體之維度變化之結果圖。
圖5係測試例3之隨可撓性基板厚度變化之剝離層之剝
離強度變化之結果圖。
圖6係測試例5之固化剝離層後隨接續熱處理之次數增加之剝離層之剝離強度變化之結果圖。
如本發明允許各種變化及諸多實施態樣,具體實施態樣將例示於圖式並詳細描述於說明書中。然而,此並不旨在限制本發明實際之具體模式,並且應當理解的是,不悖離本發明之精神及技術範疇之變化、等同物及替代物都包含於本發明中。於本發明說明書中,當相關技術之細節描述被認為可能不必要地模糊本發明之本質時,將省略其之。
應當理解的是,當一元件,如層、膜、薄膜或基板被稱為在另一元件「上」或「之上」,其可直接於該另一元件上或也可存在一個以上之介入元件。應當理解的是,當一元件,如層、膜、薄膜或基板被稱為在另一元件「下」或「之下」時,其可直接於該另一元件下或也可存在一個以上之介入元件。
除非另有所述,使用於此之術語「物理刺激」旨在包含不導致化學變化之機械性刺激,如剝離、切割、摩擦、拉伸及壓縮,且其係指一種不管其使用之方法或模式可使一積層體之橫截面外露之刺激。在某些情況下,該物理刺激可具有每單位面積0至0.1N之強度。亦即,該物理刺激之施加意指不論使用何種方法而使一積層體之橫截面外露。較佳地,以這樣的方式施加物理刺激,以使形成
於一可撓性基板末端之一積層體以一預定間距外露兩個以上橫截面。
該物理刺激係施加以使該積層體之橫截面外露並且其可具有不大於0.1N之強度。施加物理刺激以外露該積層體之橫截面之方法之具體實例包括但不限於:切割、雷射切割、及鑽石切割(diamond scribing)。
本發明之一實施態樣提供一積層體,包括:一載體基板;一第一聚醯亞胺樹脂層,其設置於該載體基板之至少一表面上;以及一第二聚醯亞胺樹脂層,其設置於該第一聚醯亞胺樹脂層上;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且當一不會導致該第一聚醯亞胺樹脂層中發生化學變化之物理刺激施加至該積層體時,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度係降低。
使用於此之術語「黏著強度」係指於施加該物理刺激前之該第一聚醯亞胺樹脂對該第二聚醯亞胺樹脂層之黏著強度,而術語「剝離強度(peel strength)」係指於施加該物理刺激後之該第一聚醯亞胺樹脂對該第二聚醯亞胺樹脂層之黏著強度。術語「黏著強度」可與術語「剝離強度」交換使用。
本發明亦提供一製造積層體之方法,其步驟包括:藉由於一載體基板之至少一表面上塗佈一包含第一聚醯亞胺樹脂或其前驅物之組成物,以形成一第一聚醯亞胺
樹脂層,以及藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或其前驅物之組成物並固化該組成物,以形成一第二聚醯亞胺樹脂層。
本發明亦提供一種製造裝置基板之方法,其步驟包括:藉由於一載體基板之至少一表面上塗佈一包含第一聚醯亞胺樹脂或其前驅物之組成物並固化之,以形成一第一聚醯亞胺樹脂層;於第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或其前驅物之組成物並固化該組成物以製造一積層體;以及藉由施加一物理刺激至該積層體而不導致該第一聚醯亞胺樹脂層中發生化學變化,以從該積層體之該第一聚醯亞胺樹脂層分離該第二聚醯亞胺樹脂層。
本發明亦提供一種藉由前述方法製造之裝置基板。
本發明亦提供一種包括藉由前述方法製造之裝置基板之裝置。
根據本發明之實施例,將詳細描述一積層體、一製造該積層體之方法、一使用該積層體製造之裝置基板、一製造該裝置基板之方法、一包括該裝置基板之裝置、及一製造該裝置之方法。
本發明之一實施態樣提供一種積層體,包括:一載體基板;一第一聚醯亞胺樹脂層,其設置於該載體基板之至少一表面上;以及一第二聚醯亞胺樹脂層,其設置於該第一聚醯亞胺樹脂層上;其中,在100至200℃之溫度
下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)不大於該第二聚醯亞胺樹脂層之熱膨脹係數,且當一不會導致該第一聚醯亞胺樹脂層中發生化學變化之物理刺激施加至該積層體時,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度係降低。
如本案發明人所進行之實驗之結果,其發現:當包含一具有特定特性之聚醯亞胺樹脂之第一聚醯亞胺樹脂層設置於該載體基板及該第二聚醯亞胺樹脂層之間作為一可撓性基板(一裝置(例如可撓式顯示裝置)之基板)時,施加一簡單物理刺激使得該可撓性基板容易自該剝離層分開而不需照射雷射或光,適於製造具有可撓性基板之裝置。這樣的功能及功效被認為是將稍後描述之第一聚醯亞胺樹脂層之特性所貢獻的。
圖2係為例示根據本發明之一實施例之積層體之結構之橫截面圖。圖2之結構僅為例示目的,本發明並非以此為限。
參照圖2,本發明之積層體100包括一載體基板10、一包含一第一聚醯亞胺樹脂並設置於該載體基板之至少一表面上之第一聚醯亞胺樹脂層20、以及一包含第二聚醯亞胺樹脂並設置於該第一聚醯亞胺樹脂層上之第二聚醯亞胺樹脂層30。
該載體基板10可為任何用以支撐該第二聚醯亞胺樹脂層30之基板,從而於該積層體100上可易於製造一裝置。適合的載體基板之具體例包括玻璃基板、金屬基
板(如不鏽鋼基板)、及其多層結構。較佳為最容易應用於製造一裝置之玻璃基板。
可透過蝕刻(如:臭氧氣氛下之電暈處理(corona treatment)、火焰處理、濺鍍、UV照射或電子束照射)預處理該載體基板10。此預處理可增強該載體基板對該第一聚醯亞胺樹脂層之黏著性。
該載體基板10之厚度及尺寸可根據應用該載體基板之裝置種類而適當地選擇。考量基板透光性,該載體基板10之厚度較佳為0.1至50mm。在此範圍中,該載體基板之機械強度是足夠高的,以支撐該第二聚醯亞胺樹脂層30。
該第一聚醯亞胺樹脂層20設置於該載體基板10之至少一表面上。
該第一聚醯亞胺樹脂層20具有高於一預定程度之黏著強度,從而適合在隨後的製程中固定及支撐該第二聚醯亞胺樹脂層30,以製造一包含形成於該第二聚醯亞胺樹脂層30上之裝置結構之裝置。然而,於完成該裝置製程後,藉由一簡單的物理刺激(如無雷射或光之照射之切割)可減少該第一聚醯亞胺樹脂層20對該第二聚醯亞胺樹脂層30之黏著強度,因此,該第一聚醯亞胺樹脂層20可容易與該第二聚醯亞胺樹脂層30分離。
更具體地,於施加該物理刺激前,該第一聚醯亞胺樹脂層20對該第二聚醯亞胺樹脂層30具有至少約1N/cm、至少約2N/cm、或約3至5N/cm之黏著強度,但於
施加該物理刺激後,可具有約0.3N/cm以下,例如約0.2N/cm以下、約0.1N/cm以下、或約0.001至0.05N/cm之剝離強度。
可於表1所示之條件下測量該第一聚醯亞胺樹脂層20之剝離強度。
具體而言,可透過下列程序決定該剝離強度。首先,該第一聚醯亞胺樹脂層及該第二聚醯亞胺樹脂層係依序形成於一玻璃基板上以製造一積層體樣本。施加一物理刺激將該積層體樣本切割為一具有10mm寬之矩形。使用該測試儀於表1所示的條件下測量由該第一聚醯亞胺樹脂層剝離該第二聚醯亞胺樹脂層之末端所需之力量。用於測量該力量之測試儀及條件可與表1所示用於剝離強度測離者相同。
藉由控制各種因子,例如聚醯亞胺樹脂之單體之種類及含量、聚醯亞胺樹脂之醯亞胺化度及熱膨脹係數(CTE)等,可達到所需之該第一聚醯亞胺樹脂層之黏著強度及剝離強度。
具體而言,可藉由塗佈一包含一聚醯亞胺樹脂
或一作為其之前驅物之聚醯胺酸之組成物,並固化該組成物而形成該第一聚醯亞胺樹脂層,並且,於本發明中,控制該第一聚醯亞胺樹脂層於100至200℃之溫度下之熱膨脹係數(CTE),使其等於或低於該第二聚醯亞胺樹脂層之熱膨脹係數。
該第一及第二聚醯亞胺樹脂層於100至200℃之溫度下之熱膨脹係數之差異可不高於60ppm/℃、不高於50ppm/℃、不高於40ppm/℃、不高於30ppm/℃、或不高於25ppm/℃。於此,於100至200℃之溫度下之熱膨脹係數(CTE)可意指於上述溫度範圍內之熱膨脹係數之平均值。
透過滿足上述熱膨脹係數之關係,可降低該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之剝離強度,使得其易於藉由一簡單物理刺激而自該第二聚醯亞胺樹脂層分離。
如本案發明人進行之實驗之結果,其可確認用於製備該聚醯亞胺樹脂之固化溫度條件、該聚醯亞胺樹脂之醯亞胺化度、及該聚醯亞胺樹脂層之剝離強度可滿足表2所示之關係。
如表2所示,當藉由於該載體基板塗佈一包含一作為該第一聚醯亞胺樹脂之前驅物之聚醯胺酸樹脂之組成物,並於約200℃以上或250℃至500℃固化該組成物,
包含於該第一聚醯亞胺樹脂層之聚醯亞胺樹脂具有約60%至99%、約70%至98%、或約75%至96%之醯亞胺化度,且該第一聚醯亞胺樹脂層具有不大於約0.3N/cm之剝離強度。如上所述,使用根據此實施態樣之積層體,顯著地簡化一用於製造一包含該可撓性基板之裝置(如一可撓式顯示裝置)之製程。在此,該聚醯亞胺樹脂之醯亞胺化度可定義為:塗佈一包含一聚醯亞胺前驅物(例如一聚醯胺酸樹脂)之組成物並於200℃以上之溫度醯亞胺化後,於紅外線(IR)光譜之1350至1400cm-1或1550至1650cm-1所觀察之CN鍵之累積強度(integrated intensity)相對於該組成物於500℃以上之溫度醯亞胺化後,於相同波長範圍所觀察之CN鍵之累積強度(100%)之百分比。
於固化溫度控制下製備之該聚醯亞胺樹脂可具有至少約200℃、至少約300℃、或至少約350℃至500℃之玻璃轉移溫度以及至少400℃或400℃至600℃之裂解溫度(decomposition temperature)。由於該第一聚醯亞胺樹脂之良好耐熱性,在裝置之製造之製程過程中,該第一聚醯亞胺樹脂層在高溫下具有高耐受性,且可防止在製造裝置的過程中於該積層體上之翹曲。此外,該第一聚醯亞胺樹脂層可防止裝置可靠性之劣化。是以,使用該第一聚醯亞胺樹脂層有助於製造具有提升特性及高可靠性之一裝置。
具體而言,根據此實施態樣之該積層體之該第一聚醯亞胺在100至200℃之溫度下可具有不高於約30
ppm/℃、不高於約25ppm/℃、或約1至17ppm/℃之熱膨脹係數(CTE)以及450℃以上之1%熱裂解溫度(1% thermal decomposition temperature,Td1%)。
符合結構及物理性質方面需求之該第一聚醯亞胺樹脂層20可自該第二聚醯亞胺樹脂層30完全剝離,從而不影響一裝置基板之透光率及光學性質。
本案發明人發現該剝離層之黏著強度隨著用以組成該剝離層之聚醯亞胺之二酐及二胺之種類而變化。基於此發現,本案發明人提供一用以定量評估該剝離層之黏著強度之方法。具體而言,本案發明人發展一基於相似性分數(similarity score)之單體組合。一較高之相似性分數表示一具有對一圓球有較高結構相似性之非直鏈/非平面結構。於此,一較低之相似性分數表示一具有對一圓球有較低結構相似性之直鏈/平面結構。於本發明中,該相似性分數較佳為不大於0.5。
該相似性係如方程式1所計算。
[方程式1]相似性分數=αFIT(k1×Ls二酐,i+k2×Ls二胺,j)k 0
其中,Ls二酐,i=Exp[-k3×Coeffi]×Vi y 0,Ls二胺,j=Exp[-k4×Coeffj]×Vj y 0,k0=2.00,y0=-1.00,k1=206.67,
k2=124.78,k3=3.20,k4=5.90,Coeffi及Coeffj分別為使用ADRIANA.Code(電腦化學,Molecular Networks GmbH)計算由二酐i及二胺j作為該聚醯亞胺之單體之之結構之分子非球面性(molecular asphericities),Vi及Vj分別為使用ADRIANA.Code(電腦化學,Molecular Networks GmbH)計算由二酐i及二胺j作為該單體之結構之麥克恩體積(McGowan volumes),以及若exp(-4.0×|Coeff i -Coeff j |)+0.08<0.90,αFIT為1.0,且若exp(-4.0×|Coeff i -Coeff j |)+0.080.90,αFIT為0.1至0.95之常數。
於方程式1,若exp(-4.0×|Coeff i -Coeff j |)+0.080.90,αFIT為0.1至0.95之常數,較佳為0.2至0.5,最佳為0.33。
ADRIANA.Code為由德國Molecular Networks GmbH發展之軟體,主要用以計算分子之本質物理、化學及電性質。當分子之結構資訊輸入該軟體時,可計算該分子之非球面性及麥克恩體積。
可藉由聚合作為單體之四羧酸二酐化合物及二胺化合物以製備作為該第一聚醯亞胺樹脂前驅物之聚醯胺酸。
適合作為單體之四羧酸二酐之具體例包括均苯四甲酸二酐(pyromellitic dianhydride,PMDA)、3,3',4,4'-聯苯四羧酸二酐(3,3’,4,4’-biphenyltetracarboxylic
dianhydride,BPDA)、內消旋-丁烷-1,2,3,4-四羧酸二酐(meso-buthane-1,2,3,4-tetracarboxylic dianhydride)、3,3',4,4'-二苯甲酮四羧酸二酐(3,3’,4,4’-benzophenone tetracarboxylic dianhydride,BTDA)、2,3,3',4'-二苯醚四羧酸二酐(2,3,3’,4’-dipheny1ether tetracarboxylic dianhydride,ODPA)、3,3',4,4'-二苯基碸四羧酸二酐(3,3’,4,4’-diphenylsulfone tetracarboxylic dianhydride,DSDA)、4,4'-(六氟異丙烯)二酞酸酐(4,4’-(hexafluoroisopropylidene)diphthalic anhydride)、3,3',4,4'-聯苯四羧酸二酐(3,3’,4,4’-biphenyltetracarboxylic dianhydride,S-BPDA)、1,2,3,4-環丁烷四羧酸二酐(1,2,3,4-cyclobutane tetracarboxylic dianhydride)、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐(1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride)、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐(1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride)、1,2,3,4-環戊烷四羧酸二酐(1,2,3,4-cyclopentane tetracarboxylic dianhydride)、1,2,4,5-環己烷四甲酸二酐(1,2,4,5-cyclohexane tetracarboxylic dianhydride)、3,4-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride)、5-(2,5-二氧代四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸二酐(5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dica rboxylic dianhydride)、2,3,5-三羧基-2-環戊烷乙酸二酐(2,3,5-tricarboxy-2-cyclopentane acetic dianhydride)、二環
[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐(bicyclo[2.2.2]octo-7-en-2,3,5,6-tetracarboxylic dianhydride)、2,3,4,5-四氫呋喃四羧酸二酐(2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride)、3,5,6-三羧基-2-降冰片烷乙酸二酐(3,5,6-tricarboxy-2-norbornane acetic dianhydride)、及其衍生物。應當了解的是,也可使用其他各種四羧酸二酐。
適合做為單體之二胺化合物之具體例包括:芳香二胺,例如對苯二胺(p-phenylenediamine,PDA)、間苯二胺(m-phenylenediamine,m-PDA)、2,4,6-三甲基-1,3-苯二胺(2,4,6-trimethyl-1,3-phenylenediamine)、2,3,5,6-四甲基-1,4-苯二胺(2,3,5,6-tetramethyl-1,4-phenylenediamine)、4,4'-二氨基二苯基醚(4,4’-diaminodiphenyl ether)、3,4'-二氨基二苯基醚(3,4’-diaminodiphenyl ether)、3,3'-二氨基二苯基醚(3,3’-diaminodiphenyl ether)、4,4'-二氨基二苯硫醚(4,4’-diaminodiphenyl sulfide)、4,4'-二氨基二苯甲烷(4,4’-diaminodiphenylmethane)、3,4'-二氨基二苯甲烷(3,4’-diaminodiphenylmethane)、3,3'-二氨基二苯甲烷(3,3’-diaminodiphenylmethane)、4,4'-亞甲基-雙(2-甲基苯胺)(4,4’-methylene-bis(2-methylaniline))、4,4'-亞甲基-雙(2,6-二甲基苯胺)(4,4’-methylene-bis(2,6-dimethylaniline))、4,4'-亞甲基-雙(2,6-二乙基苯胺)(4,4’-methylene-bis(2,6-diethylaniline))、4,4'-亞甲基-雙(2-異丙基-6-甲基苯胺)(4,4’-methylene-bis(2-isopropyl-6-methylaniline))、4,4'-
亞甲基-雙(2,6-二異丙基苯胺)(4,4’-methylene-bis(2,6-diisopropylaniline))、4,4'-二氨基二苯碸(4,4’-diaminodiphenylsulfone)、3,3'-二氨基二苯砜(3,3’-diaminodiphenylsulfone)、聯苯胺(benzidine)、鄰聯甲苯胺(o-tolidine)、間聯甲苯胺(m-tolidine)、3,3',5,5'-四甲基聯苯胺(3,3’,5,5’-tetramethylbenzidine)、2,2'-雙(三氟甲基)聯苯胺(2,2’-bis(trifluoromethyl)benzidine)、1,4-雙(4-氨基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene)、1,3-雙(4-氨基苯氧基)苯(1,3-bis(4-aminophenoxy)benzene)、1,3-雙(3-氨基苯氧基)苯(1,3-bis(3-aminophenoxy)benzene)、雙[4-(4-氨基苯氧基)苯基]碸(bis[4-(4-aminophenoxy)phenyl]sulfone)、雙[4-(3-氨基苯氧基)苯基]碸(bis[4-(3-aminophenoxy)phenyl]sulfone)、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷(2,2-bis[4-(4-aminophenoxy)phenyl]propane)、2,2-雙[4-(3-氨基苯氧基)苯基]丙烷(2,2-bis[4-(3-aminophenoxy)phenyl]propane)、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷(2,2-bis[4-(4-aminophenoxy)phenyl]propane,6HMDA)、2,2'-雙(三氟甲基)聯苯胺(2,2’-bis(trifluoromethyl)benzidine,TFMB)、3,3'-雙(三氟甲基)-4,4'-二氨基聯苯(3,3’-bis(trifluoromethyl)-4,4’-diaminobiphenyl,3,3’-TFDB)、4,4'-雙(3-氨基苯氧基)二苯碸(4,4’-bis(3-aminophenoxy)diphenylsulfone,DBSDA)、雙(3-氨基苯基)碸(bis(3-aminophenyl)sulfone,3DDS)、雙(4-氨基
苯基)碸(bis(4-aminophenyl)sulfone,4DDS)、1,3-雙(3-氨基苯氧基)苯(1,3-bis(3-aminophenoxy)benzene,APB-133)、1,4-雙(4-氨基苯氧基)苯(1,4-bis(4-aminophenoxy)benzene,APB-134)、2,2'-雙[3(3-氨基苯氧基)苯基]六氟丙烷(2,2’-bis[3(3-aminophenoxy)phenyl]hexafluoropropane,3-BDAF)、(2,2'-雙[4(4-氨基苯氧基)苯基]六氟丙烷(2,2’-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,4-BDAF)、2,2'-雙(3-氨基苯基)六氟丙烷(2,2’-bis(3-aminophenyl)hexafluoropropane,3,3’-6F)、2,2'-雙(4-氨基苯基)六氟丙烷(2,2’-bis(4-aminophenyl)hexafluoropropane,4,4’-6F)、及4,4'-氧聯二苯胺(4,4’-oxydianiline,ODA);及脂肪族二胺(aliphatic diamines),例如1,6-己二胺(1,6-hexanediamine)、1,4-環己二胺(1,4-cyclohexanediamine)、1,3-環己二胺(1,3-cyclohexanediamine)、1,4-雙(氨基甲基)環己烷(1,4-bis(aminomethyl)cyclohexane)、1,3-雙(氨基甲基)環己烷(1,3-bis(aminomethyl)cyclohexane)、4,4'-二氨基二環己基甲烷(4,4’-diaminodicyclohexylmethane)、4,4'-二氨基-3,3'-二甲基二環己基甲烷(4,4’-diamino-3,3’-dimethyldicyclohexylmethane)、4,4'-二氨基-3,3'-二甲基二環己基甲烷(4,4’-diamino-3,3’-dimethyldicyclohexylmethane)、1,2-雙-(2-氨基乙氧基)乙烷(1,2-bis-(2-aminoethoxy)ethane)、雙(3-氨基丙基)醚(bis(3-aminopropyl)ether)、1,4-雙(3-氨基丙基)
哌嗪(1,4-bis(3-aminopropyl)piperazine)、3,9-雙(3-氨基丙基)-2,4,8,10-四氧雜螺[5.5]十一烷(3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane)、及1,3-雙(3-氨基丙基)四甲基二矽氧烷(1,3-bis(3-aminopropyl)tetramethyldisiloxane)。
四羧酸二酐化合物及二胺化合物之種類並無特別限制,然而重要的是該酸二酐在芳香環間不具有連結結構,以更適當地符合該第一聚醯亞胺樹脂層在物性方面(例如,前述之低CTE範圍及剝離強度)之需求。
該四羧酸二酐化合物較佳為一如化學式1所示之芳香族四羧酸二酐:
其中,A為一由酸二酐衍生之四價芳香族有機基團,具體為如化學式2a或2b之四價芳香族有機基團:
其中,R11為一C1-C4烷基(例如甲基、乙基或丙基)或C1-C4鹵烷基(例如氟甲基(fluoromethyl)、溴甲基(bromomethyl)、氯甲基(chloromethyl)或三氟甲基
(trifluoromethyl)),a為0至3之整數,且b為0至2之整數,
其中,R12至R14各自獨立為C1-C4烷基(例如甲基、乙基或丙基)或C1-C4鹵烷基(例如氟甲基(fluoromethyl)、溴甲基(bromomethyl)、氯甲基(chloromethyl)或三氟甲基(trifluoromethyl)),c及e各自獨立為0至3之整數,較佳為0,d為0至4之整數,較佳為0,且f為0至3之整數。
具體而言,該四羧酸二酐較佳為化學式3a之均苯四甲酸二酐(pyromellitic dianhydride,PMDA)或化學式3b之3,3',4,4'-聯苯四羧酸二酐(3,3’,4,4’-biphenyltetracarboxylic dianhydride,BPDA):
於化學式3b之化合物中,該結構為直鏈狀且兩個苯環係直接連結而無連結結構。
當該第一聚醯亞胺樹脂層20之填充密度(packing density)增加,分子間空間減少,因而分子難以互相滲透,導致低鍵結強度。結果,該第一聚醯亞胺樹脂層20對覆於其上之第二聚醯亞胺樹脂層30之黏著強度係減少。該填充密度可透過CTE表示。填充密度越高,CTE值越低,反之亦然。據此,為了製備符合物性方面需求之第一聚醯亞胺樹脂層,該二胺化合物較佳為一具有直鏈結構之芳香族二胺化合物,具體而言,為如化學式4a或4b之芳香族二胺化合物:
其中,R21為一C1-C10烷基(例如,甲基、乙基或丙基)或C1-C4鹵烷基(例如,氟甲基、溴甲基、氯甲基、三氟甲基),且1為0至4之整數,較佳為0,
其中,R22及R23各自獨立為一C1-C10烷基(例如,甲基、乙基或丙基)或or C1-C4鹵烷基(例如,氟甲基、溴甲基、氯甲基、三氟甲基),X為選自由-O-、-CR24R25-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-S-、-SO-、-SO2-、-O[CH2CH2O]q-、C6-C18單環及多環亞環烷基cycloalkylene(例如,亞環己基(cyclohexylene)和降冰片烯(norbornene))、C6-C18單環及多環
亞芳基(例如,亞苯基(phenylene)及萘基(naphthalene))、及其組合所組成之群組,R24及R25各自獨立選自由氫原子、C1-C10烷基(例如,甲基、乙基或丙基)、及C1-C10鹵烷基(例如,氟甲基、溴甲基、氯甲基、三氟甲基),q為1或2之整數,m及n各自獨立為0至4之整數,較佳為0,且p為0或1之整數,較佳為0。
芳香族二胺化合物之例子較佳包括對苯二胺(p-phenylenediamine,PDA)、聯苯胺(benzidine,BZD)、間聯甲苯二胺(m-tolidine)、或2,2'-雙(三氟甲基)聯苯胺(2,2’-bis(trifluoromethyl)benzidine,TFMB)。
於一極性有機溶劑中聚合該些單體以製備所需之第一聚醯酸樹脂。於上述固化溫度下,可在一醯亞胺化催化劑(如胺催化劑)存在或不存在下,將該聚醯胺酸樹脂醯亞胺化以製備該第一聚醯亞胺樹脂。藉由本領域技術人員習知之適當方法可控制除了固化溫度外之其他用於製備該第一聚醯亞胺樹脂之條件,因而將省略其之進一步說明。
該第一聚醯亞胺層20可具有0.05至5μm、0.05至4μm、0.05至3μm、0.05至2μm、或0.05至1μm之厚度。
當該第一聚醯亞胺樹脂層之厚度減少,其對該載體基板之黏著強度增加。然而,該第一聚醯亞胺樹脂層之過薄厚度導致該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度增加,導致該第一聚醯亞胺樹脂層自該
第二聚醯亞胺樹脂層之剝離性變差。於上述定義之厚度範圍內,係確保該第一聚醯亞胺樹脂層對該載體基板之高黏著強度及該第一聚醯亞胺樹脂層自該第二聚醯亞胺樹脂層之良好剝離性。
於該積層體中,該第二聚醯亞胺樹脂層30設置於該第一聚醯亞胺樹脂層20上。
該第二聚醯亞胺樹脂層包括一第二聚醯亞胺樹脂,其在等於或高於該第一聚醯亞胺樹脂層之固化溫度0至200℃之溫度下固化。該第二聚醯亞胺樹脂可具有50至99%或70至95%之醯亞胺化度。
該第二聚醯亞胺樹脂可具有至少約200℃、至少約300℃、或約350℃至500℃之玻璃轉移溫度(Tg)以及至少400℃或400℃至600℃之裂解溫度(Td)。該聚醯亞胺樹脂之良好耐熱性消除該聚合物層可能在隨後製造該積層體或裝置基板之加熱過程中變形之風險,並使該基板及裝置之耐熱性提升。
該第二聚醯亞胺樹脂層30於100至200℃之溫度下可具有約60ppm/℃以下、約50ppm/℃以下、約40ppm/℃以下、或約1至30ppm/℃之熱膨脹係數(CTE)以及450℃以上或470℃以上之1%熱裂解溫度(Td1%)。
較佳地,在100至200℃之溫度下,該第二聚醯亞胺樹脂層之熱膨脹係數(CTE)等於或低於該第一聚醯亞胺樹脂層之熱膨脹係數。在100至200℃之溫度下,該第一及該第二聚醯亞胺樹脂層之熱膨脹係數間之差異可為
不高於60ppm/℃、不高於50ppm/℃、不高於40ppm/℃、不高於30ppm/℃、或不高於25ppm/℃。在此所指在100至200℃之溫度下之熱膨脹係數(CTE)可意指於上述溫度範圍中之熱膨脹係數之平均值。
藉由滿足前數CTE關係,可減少該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之剝離強度,從而其可易於藉由一簡單物理刺激而自該第二聚醯亞胺樹脂層分離。
該第二聚醯亞胺樹脂層所需物理性質可藉由控制各種因子(例如單體之種類及含量、聚醯亞胺樹脂之製程及反應條件、以及固化條件)以達成。
舉例而言,可藉由將作為單體之四羧酸二酐及二胺化合物進行聚合,製備一聚醯胺酸樹脂,並固化該聚醯胺酸樹脂以製備該第二聚醯亞胺樹脂。該第二聚醯亞胺樹脂層也可藉由乾燥一含有聚醯亞胺樹脂之溶液形式之組成物所形成。該四羧酸二酐及該二胺化合物係與該第一聚醯亞胺樹脂製備中所述相同。然而,該第二聚醯亞胺樹脂層所需物理性質可藉由控制該四羧酸二酐及該二胺間之反應比例而達成。具體而言,所需用量為每莫耳四羧酸二酐使用0.8至1.2莫耳或0.9至1.1莫耳之二胺。
具有上述物理性質之該第二聚醯亞胺樹脂層30可具有0.5至50μm、1至50μm、2至50μm、3至50μm、或3至30μm之厚度。具體而言,較佳地,相對於該第一聚醯亞胺樹脂層,該第二聚醯亞胺樹脂層30具有
一適當的厚度。舉例而言,該第二聚醯亞胺樹脂層30之厚度大於該第一聚醯亞胺層厚度之10至500倍、20至400倍、30至300倍、或50至200倍。
具有上述結構之該積層體100可根據包含下列步驟之方法製備:藉由於一載體積板10之至少一表面上塗佈一含有一第一聚醯亞胺樹脂或其之前驅物之組成物,接著固化該組成物以形成一第一聚醯亞胺樹脂層20(步驟1);以及藉由於該第一聚醯亞胺樹脂層上塗佈一含有一第二聚醯亞胺樹脂或其之前驅物之組成物,接著固化該組成物以形成一第二聚醯亞胺樹脂層30(步驟2)。
以下,將詳細描述個別步驟。於步驟1,該第一聚醯亞胺樹脂層20係形成於該載體基板10上。
該載體基板10與前述相同。於形成該第一聚醯亞胺樹脂層20前,該載體基板可透過蝕刻(例如臭氧氣氛下之電暈處理(corona treatment under an ozone atmosphere)、火焰處理(flame treatment)、濺鍍(sputtering)、紫外線照射(UV irradiation)或電子束照射(e-beam irradiation))預處理。此預處理增加該載體基板對該第一聚醯亞胺樹脂層20之黏著性。
用於該積層體之該第一聚醯亞胺樹脂可藉由:於該載體基板之至少一表面上塗佈一包含一第一聚醯亞胺樹脂或其之前驅物之組成物並固化該組成物而形成。當製備該第一聚醯亞胺樹脂層20中使用一聚醯胺酸樹脂,於固化過程中可能需進行該聚醯胺酸樹脂之醯亞胺化。
可透過本領域任何適當的習知技術塗佈該組成物。用於塗佈該組成物之適當技術之具體例包括旋鍍(spin coating)、浸塗(dip coating)、及棒塗(bar coating)。可適當地使用澆鑄(Casting)、輥塗(rolling)或噴灑塗佈(spray coating)進行一連續製程。
於固化之前,可進一步執行乾燥以去除存在於用以形成該第一聚醯亞胺樹脂層之組成物中的有機溶劑。該組成物可透過本領域任何適當的習知技術乾燥。特別是,該組成物可於140℃以下之溫度下乾燥。
該固化製程可於與該第二聚醯亞胺樹脂層之固化溫度相同或低於該第二聚醯亞胺樹脂層之固化溫度0至200℃之溫度下進行。具體而言,可藉由加熱至200℃以上或250至500℃之溫度進行該固化製程。此加熱處理也可於上述定義之溫度範圍內,以多階段各種溫度下進行。
該固化時間並不特別受限且可為,例如,3至30分鐘之範圍內。
於固化之後,更可選擇性進行熱處理。隨後之熱處理較佳於至少300℃之溫度下進行1至30分鐘。該熱處理可僅進行一次。反之,該熱處理可於多階段中進行兩次以上。舉例而言,該熱處理可於三階段中進行:在200至250℃之第一熱處理、在300至350℃之第二熱處理、及在400至450℃之第三熱處理。
於步驟2,該第二聚醯亞胺樹脂層30係形成於該第一聚醯亞胺樹脂層20上,以製備該積層體。
可藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或一做為其之前驅物之第二聚醯胺酸樹脂之組成物,並固化該組成物,以形成該第二聚醯亞胺樹脂層30。該第二聚醯亞胺樹脂及其前驅物可與前述相同。
用於形成該第二聚醯亞胺樹脂層之組成物可更包括至少一選自由:常見用於聚醯亞胺樹脂層之黏結劑(binders)、溶劑(solvents)、交聯劑(cross-linkers)、起始劑(initiators)、分散劑(dispersants)、塑化劑(plasticizers)、黏性改質劑(viscosity modifiers)、UV吸收劑(UV absorbers)、光敏單體(photosensitive monomers)、及敏化劑(sensitizers)之添加劑。
用以形成該第二聚醯亞胺樹脂層之固化製程可透過加熱至200℃以上之溫度進行。較佳地,該製程可於等於或高於該第一聚醯亞胺樹脂層之固化溫度0至200℃之溫度下進行。該熱處理也可於上述定義之溫度範圍內,以多階段各種溫度下進行。
於所製得之積層體中,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層呈現適當的黏著強度,從而於隨後裝置之製備程序中適當固定並支撐該第二聚醯亞胺樹脂層。據此,根據本發明之實施態樣之積層體之用途適於製造一包含該第二聚醯亞胺樹脂層之裝置(例如,可撓式顯示裝置)之基板。此外,可於該積層體上適當地進行製造裝置之製程,甚至不需要以雷射或光照射分離該第二聚醯亞胺
樹脂層,可製造具有優異特性之裝置。是以,可簡化具有該第二聚醯亞胺樹脂層之裝置之製程並且也可減少製造成本。
本發明之又一實施態樣係提供一使用該積層體製造之裝置基板及用於製造該裝置基板之方法。
可藉由包含下列步驟之方法製造該裝置基板:藉由於一載體基板之至少一表面上塗佈一包含一聚醯亞胺樹脂或其之前驅物之組成物,接著固化該組成物以形成一第一聚醯亞胺樹脂層;藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂或其前驅物之組成物,接著固化該組成物以形成一第二聚醯亞胺樹脂層;以及施加一物理刺激至該第二聚醯亞胺樹脂層,以由形成於該載體基板上之該第一聚醯亞胺樹脂層上分離該第二聚醯亞胺樹脂層;其中,可在等於或低於該第二聚醯亞胺樹脂層之固化溫度0至200℃之溫度下進行該第一聚醯亞胺樹脂層之固化。
圖3a為一例示用於根據本發明之一實施態樣之裝置基板之製程之示意圖。圖3a僅為例示且本發明不以此為限。
參考圖3a,本發明之裝置基板可藉由包含下列步驟之方法製造:(S1)於一載體基板10之至少一表面上形成一第一聚醯亞胺樹脂層20;(S2)於該第一聚醯亞胺樹脂層20上形成一第二聚醯亞胺樹脂層30以製造一積層體;以及(S3及S4)施加一物理刺激p至該積層體而不於該第一聚醯
亞胺樹脂層中導致化學變化,並且自形成於該載體基板10上之該第一聚醯亞胺樹脂層20分離該第二聚醯亞胺樹脂層30。於等於或低於該第二聚醯亞胺樹脂固化溫度0至200℃之溫度下進行該第一聚醯亞胺樹脂層之固化製程。可藉由本領域使用之一般方法分離該第二聚醯亞胺樹脂層。舉例而言,可使用吸引法(suction)分離該可撓性基板,但本發明並不以此為限。任何方法皆可選擇,其需要較一般方法更小的力以減少製造過程中對顯示裝置之損害。
於製造該裝置基板之方法中,分離該第二聚醯亞胺樹脂層30之步驟之前的步驟可與用以製造該積層體之方法相同。
該第二聚醯亞胺樹脂層30可藉由施加一合適的物理刺激(例如,切割、雷射切割或鑽石切割)而分離。具體說明,可施加不大於0.1N之物理刺激以分離該第二聚醯亞胺樹脂。
藉由該方法製造之裝置基板包括藉由施加一相對小之物理刺激(例如切割)而不需進一步處理(例如雷射或光照射),而自該載體基板分離第二聚醯亞胺樹脂層。據此,使用該裝置基板可防止一裝置因雷射或光照射導致之可靠性劣化或發生缺陷。此確保了裝置之改善特性。
本發明之又一實施態樣係提供一包含該裝置基板之裝置。
具體而言,該裝置可為一可撓式顯示裝置,例如具有該第二聚醯亞胺樹脂層之太陽能電池(例如,可撓式
太陽能電池)、一有機發光二極體(organic light emitting diode,OLED)照明裝置(例如可撓式OLED照明裝置)、一具有該第二聚醯亞胺樹脂層之半導體裝置、一有機電致發光裝置、一電泳裝置、或一LCD裝置。尤其較佳為一有機電致發光裝置。
如圖3b所示,該裝置可藉由包含下列步驟之方法製造:於一載體基板10之至少一表面上依序形成一第一聚醯亞胺樹脂層20及一第二聚醯亞胺樹脂層30以獲得一積層體;於該積層體之第二聚醯亞胺樹脂層上形成一裝置結構40(如一裝置之製造步驟);以及施加一無雷射或光照射之物理刺激p以分離其上形成有該裝置結構40之該第二聚醯亞胺樹脂層30。
該裝置結構可隨著將製造於該第二聚醯亞胺樹脂層上之裝置之種類而變化。該裝置結構可為一通常者,例如,一包含閘電極(gate electrode)之半導體裝置結構、一包含薄膜電晶體陣列之顯示裝置結構、一具有P/N結(P/N junction)之二極體裝置結構、一包含有機發光層之OLED結構、或一太陽能電池結構。舉例而言,該裝置結構可為一有機電致發光裝置結構,包括:一透明電極,其設置於該第二聚醯亞胺樹脂層之背側且包含例如氧化銦錫(indium tin oxide,ITO);一發光部,其設置於該透明電極之背側且包括例如一有機化合物;以及一金屬電極,其設置於該發光部之背側且包括例如一金屬。
如上所述,本發明之裝置包括:藉由一物理刺
激之施加而無需進一步製程(如雷射或光照射)而自該載體基板上分離之第二聚醯亞胺樹脂層,係做為一基板。使用該第二聚醯亞胺樹脂層作為一可撓性基板可確保該裝置之特性提升且可使該裝置可靠性高。
本發明可以許多不同形式實施且不應解釋為限於本文所闡述之實施態樣。
實施例1:基層體之製備
聚合1mol之BPDA及0.99mol之PDA以製備一聚醯胺酸。將一包含3wt%之該聚醯胺酸樹脂及97wt%作為溶劑之DMAc之組成物塗佈於作為載體基板之無鹼玻璃之一表面,從而於乾燥後之厚度為0.1μm。所得塗佈物接連於120℃之溫度下乾燥並於250℃之溫度下固化(30分鐘),以形成該包含一聚醯亞胺樹脂(以下,稱為第一聚醯亞胺樹脂)之第一聚醯亞胺樹脂層。
接著,聚合1mol之BPDA及0.99mol之TFMB以製備一聚醯胺酸。將一包含12wt%之該聚醯胺酸樹脂及88wt%作為溶劑之DMAc之組成物塗佈於作為載體基板之無鹼玻璃之一表面,從而於乾燥後之厚度為15μm。所得塗佈物接連於100℃之溫度下乾燥並於350℃之溫度下固化(60分鐘)以形成一包含一聚醯亞胺樹脂(以下,稱為第二聚醯亞胺樹脂)之剝離層。所得積層體(測試積層體1-1)具有一結構,其中,係依序設置該載體基板、包含BPDA-PDA聚醯亞胺樹脂之第一聚醯亞胺樹脂層、及作為一可撓性基板之包含BPDA-TFMB聚醯亞胺樹脂之第二聚醯亞胺樹脂
層。
測試積層體之製備
除了該第一聚醯亞胺樹脂及可撓性基板之該第二聚醯亞胺樹脂之種類如表3所示變化,測試積層體係以與實施例1相同之方法製備。
於表3中,BPDA表示聯苯四羧酸二酐(biphenyl-tetracarboxylic dianhydride),PDA表示對苯二胺(p-phenylenediamine),TFMB表示2,2'-雙(三氟甲基)聯苯胺(2,2’-bis(trifluoromethyl)benzidine),mPDA表示間苯二胺,PMDA表示均苯四甲酸二酐,且ODA表示4,4’-二氨基二苯醚(4,4’-oxydianiline)。
測試例1:第一聚醯亞胺樹脂層之物理性質之評估
測試積層體之第一聚醯亞胺樹脂層之密度、熱膨脹係數(CTE)、玻璃轉移溫度(Tg)、黏著強度、及剝離強度。
具體而言,係藉由使用一膠帶且無施加物理刺激(無切割)測量自每個積層體之該第一聚醯亞胺樹脂層剝
離第二聚醯亞胺樹脂層所需之力量以決定該黏著強度。藉由將每一積層體切割為一寬10mm且長100mm之矩形,並藉由使用質構儀(texture analyzer,TA.XT plus,Stable micro systems)測量當以50mm/min之速率剝離該第二聚醯亞胺樹脂層之末端時所需力量。結果如表4所示。
於表中,「-」意指無測量。
由表4結果所示,測試積層體1-1至1-4之剝離強度遠低於測試積層體1-5,測試積層體1-1至1-4之每一者係包括該含有使用化學式1之四羧酸二酐及具有直鏈結構之二胺化合物製備之聚醯亞胺之第一聚醯亞胺樹脂層,測試積層體1-5包含使用透過一連結基團連接芳香環之四羧酸二酐製備之聚醯亞胺。
另一方面,雖然於芳香環之間無交聯結構,測試積層體1-3及1-4呈現較測試積層體1-1及1-2高之剝離強度。測試積層體1-3及1-4之剝離強度較高之原因是因為三氟甲基基團降低了該第一聚醯亞胺樹脂層之填充密度(packing density),導致該第一聚醯亞胺樹脂層與該第二聚醯亞胺樹脂層之間之較高黏著強度。然而,測試積層體1-3及1-4相較於使用包含於芳香環間之交聯結構之二胺之測試積層體1-5,呈現較低之剝離強度。
可觀察到測試積層體1-1及1-5隨著溫度在尺寸上的變化,且結果如圖4所示。如圖4所示,不同於測試積層體1-1,測試積層體1-5在約350℃經歷一急遽的尺寸變化。
測試例2:依據固化溫度之黏著強度及剝離強度之評估。
除了在如表5所示各種溫度進行固化以形成該第一聚醯亞胺樹脂層外,積層體係以與實施例1相同之方法製造。
藉由如測試例1所述之相同方法,測量根據用以形成該些積層體之第一聚醯亞胺樹脂層之固化溫度下該第二聚醯亞胺樹脂層之黏著強度及剝離強度。
於25℃/RH 55%儲存該些積層體1天後,觀察於施加物理刺激前之黏著強度之變化以及觀察進行一物理刺激-切割後之剝離強度之變化。結果如表5所示。
[表5]
如上表所示,物理刺激之施加導致在剝離強度之顯著降低。此降低顯著超過預定之固化溫度(250℃)。
觀察於製造後與儲存在25℃/RH 55%下7天後立即固化之實施例1之積層體之黏著強度及剝離強度。結果如表6所示。
如上表所示,該物理刺激之施加導致剝離強度降低。黏著強度隨時間增加。剝離強度隨時間降低,但其降低並不顯著。
測試例3:依據第二聚醯亞胺樹脂厚度之剝離強度之評估
除了第一及第二聚醯亞胺樹脂種類和第二聚醯亞胺樹脂層之厚度如表7所示變化之外,測試積層體係以如實施例1之相同方法製造。
透過如測試例1所述之相同方法於測試積層體上測量剝離強度。結果如表8及圖5所示。
於表8中,用於作為該可撓性基板之第二聚醯亞胺樹脂之BPDA-TFMB為一透明聚醯亞胺樹脂,且用於該可撓性基板之作為第二聚醯亞胺樹脂之BPDA-PDA為一有色聚醯亞胺樹脂。
如測試結果所示,當第二聚醯亞胺樹脂層之厚度減少,剝離強度係增加。相較於包含透明BPDA-TFMB作為第二聚醯亞胺樹脂之測試積層體,包含有色BPDA-PDA作為該第二聚醯亞胺樹脂之測試積層體依據該第二聚醯亞胺樹脂之厚度在剝離強度上有顯著變化。
測試例4:依據固化條件之第一聚醯亞胺樹脂層之剝離強度之評估
除了用以形成該第一聚醯亞胺樹脂層之固化溫度及時間如表9所示變化,測試積層體係以如實施例1之相同方法製造。
係透過如測試例1所述之相同方法測量測試積層體4-1至4-10之剝離強度。測試結果如表9所示。
如測試結果所示,經歷短時間的相對低溫固化之積層體呈現比不使用第一聚醯亞胺樹脂之積層體高的剝離強度,但在相同溫度下固化較長時間之積層體呈現比不使用第一聚醯亞胺樹脂之積層體低的剝離強度。
在相對高溫下固化之積層體在剝離強度上依據固化時間並未呈現實質差異。在相對高溫下經過短時間
固化之積層體呈現低剝離強度。
測試例5:依據第一聚醯亞胺樹脂種類之剝離強度之評估
除了用於形成該剝離層之第一聚醯亞胺樹脂之種類及用於形成該可撓性基板之第二聚醯亞胺樹脂之種類如表10所示變化,測試積層體係以如實施例1之相同方法製造。
於上表中,BZD及mTOL分別表示聯苯胺(benzidine)及間聯甲苯胺(m-tolidine)。
透過如測試例1所述之相同方法測量測量該些測試積層體。測試結果如表11所示。
測試積層體5-4具有比其他測試積層體高很多的剝離強度的理由,認為是因為用於該剝離層之第一聚醯亞胺樹脂之二胺於芳香環之間包含交聯結構。該交聯結構的存在導致低填充密度及分子間空間的增加。因此,利於分子的滲透而導致高結合強度。
當使用BPDA-TFMB作為用於該可撓性基板之第二聚醯亞胺樹脂所測量獲得之剝離強度係與透過方程式1計算之相似性分數比較。結果如表12所示。
A:接受;NA:不接受
如表12結果所示,當相似性分數不大於0.5時,係獲得較佳的剝離強度。
除了於固化該剝離層後在一加熱板上以300℃進行熱處理30分鐘之外,測試積層體係以如實施例1之相同方法製造。固化及熱處理條件如表13所示。於測試積層體5-5、5-6及5-7中,熱處理係分別重複1、3及5次。
依據該第一聚醯亞胺樹脂層固化後之熱處理次數,於測試積層體上觀察剝離強度之變化。透過如測試例1所述之相同方法測量該剝離強度。結果如表14及圖6所示。
如上表所示,雖該第一聚醯亞胺樹脂層形成後之熱處理次數增加,在剝離強度上並無顯著變化。
測試例6:聚醯亞胺樹脂之物理性質之評估
評估可用以形成本發明之剝離層及可撓性基板之聚合物層之聚醯亞胺樹脂之物理性質。
製備如表15所示四羧酸二酐及二胺化合物。聚合1mol四羧酸二酐及0.99mol之一種二胺化合物以製備一聚醯胺酸樹脂。將一含有12wt%之聚醯胺酸樹脂及88wt%之作為溶劑之DMAc之組成物塗佈於作為一載體基板之無鹼玻璃之一表面上,從而乾燥後之厚度為10-15μm。所得塗佈物接著於120℃之溫度下乾燥並於250℃之溫度
下固化以形成一聚醯亞胺樹脂層。
測量該聚醯亞胺樹脂層之聚醯亞胺樹脂之醯亞胺化度及玻璃轉移溫度(Tg)。測量包含該聚醯亞胺樹脂之聚醯亞胺樹脂層之熱膨脹係數(CTE)及1%熱裂解溫度(Td1%)。
具體而言,藉由以下程序測量該醯亞胺化度。首先,塗佈含有該聚醯胺酸樹脂之組成物,藉由聚合如表15所示之單體而製得該聚醯胺酸樹脂。然後,該組成物於200℃以上及500℃以上之溫度進行醯亞胺化。該醯亞胺化度定義為於200℃以上之溫度醯亞胺化該組成物後,其於紅外線光譜之1350至1400cm-1或1550至1650cm-1所觀察之CN鍵之累積強度(integrated intensity)相對於該組成物於500℃以上之溫度醯亞胺化後,於相同波長範圍所觀察之CN鍵之累積強度(100%)之百分比。
使用示差熱卡掃描計(DSC 2010,TA instrument)以10℃/min之加熱速率測量玻璃轉移溫度。
藉由使用一熱重分析儀(thermogravimetric analyzer,TG-DTA2000),於氮氣氣氛下,以10℃/min之加熱速率測量該聚醯亞胺膜,於初始重量減少1%之溫度判定1%熱裂解溫度(Td1%)。作為測試片之聚醯亞胺膜置於5g負載/15μm膜厚並於100-200℃之溫度範圍內以5℃/min之速率下測得之線性熱膨脹係數之平均值定義為該熱膨脹係數。使用熱機械分析儀(thermomechanical analyzer,TMA4000)測量該線性熱膨脹係數。結果如表15所示。
測試例7:依據固化溫度之剝離強度之變化
除了使用PMDA-PDA用於作為剝離層之第一聚醯亞胺樹脂,使用BPDA-PDA用於作為可撓性基板之第二聚醯亞胺樹脂,且固化溫度如表16所示變化之外,係以如實施例1之相同方法製備測試積層體。測量該測試積層體之黏著強度及剝離強度。結果如表16所示。
測試例8:依據製備形成剝離層之聚醯亞胺之共聚合莫耳比之剝離強度之評估
除了使用不同莫耳比之BPDA及PMDA作為酸二酐以形成剝離層之外,係以如實施例1之相同方法製備測試積層體。使用作為酸二酐之環己烷四羧酸二酐(cyclohexane tetracarboxylic dianhydride,BPDA_H)及作為二胺化合物之4-氨基-N-(4-氨基苯基)苯甲醯胺(4-amino-N-(4-aminophenyl)benzamide,DABA)與4,4'-二氨基二苯基醚(4,4’-diaminodiphenyl ether,ODA)以9:1之莫耳比
製備用於形成可撓性基板之第二聚醯亞胺。測量該些測試積層體之黏著強度及剝離強度。結果如表17所示。
測試例9:依據可撓性基板種類之剝離強度之評估
係如測試例8之相同方法形成兩個剝離層。藉由反應作為酸二酐之環己烷四羧酸二酐(tetracarboxylic dianhydride,BPDA_H)與作為二胺化合物之莫耳比為9:1之4-氨基-N-(4-氨基苯基)苯甲醯胺(4-amino-N-(4-aminophenyl)benzamide,DABA)及間苯二胺(m-phenylenediamine,mPDA)以製備用於形成一可撓性基板之聚醯亞胺。使用一種剝離層及可撓性基板製造一積層體9-1。藉由反應作為酸二酐之莫耳比為1:1之4,4'-(六氟異丙烯)二酞酸二酐(4,4’-(hexafluoroisopropylidene)diphthalic dianhydride,6FDA)及均苯四甲酸二酐(pyromellitic dianhydride,PMDA)與對苯二胺(para-phenylenediamine,PDA)以製備用以形成一可撓性機板之聚醯亞胺。另一剝離層及
該可撓性基板係用以製造一積層體9-2。測量該些積層體之黏著強度及剝離強度。結果如表18所示。
測試例10:依據剝離層之BPDA含量之剝離強度之評估
製備具有如表19所示組成物之該些測試積層體。評估該些剝離層之黏著強度及剝離強度。其可確認隨著PMDA含量增加,該些剝離層呈現較低之剝離強度。
雖已詳細描述本發明之具體實施例,本領域技術人員應當理解的是該些詳細描述僅為較佳實施態樣且本發明之範疇並不以此為限。因此,本發明之真實範疇應如隨附之申請專利範圍及等同物所定義。
10‧‧‧載體基板
20‧‧‧第一聚醯亞胺樹脂層
30‧‧‧第二聚醯亞胺樹脂層
100‧‧‧積層體
Claims (24)
- 一種積層體,包括:一載體基板;一第一聚醯亞胺樹脂層,係設置於該載體基板之至少一表面上;以及一第二聚醯亞胺樹脂層,係設置於該第一聚醯亞胺樹脂層上;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)係等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且當一不會導致該第一聚醯亞胺樹脂層中發生化學變化之物理刺激施加至該積層體時,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度係降低。
- 如申請專利範圍第1項所述之積層體,其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層及該第二聚醯亞胺樹脂層之熱膨脹係數差係為60ppm/℃以下。
- 如申請專利範圍第1項所述之積層體,其中,施加該物理刺激以使該積層體之橫截面外露。
- 如申請專利範圍第1項所述之積層體,其中,於施加該物理刺激之前,該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層具有至少1N/cm之黏著強度,且於施加該物理刺激之後,該第一聚醯亞胺樹脂層具有不大於0.3N/cm之從該第二聚醯亞胺樹脂層剝離之剝離強度。
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂具有不大於0.5之如方程式1所計算之相似性分數,[方程式1]相似性分數=αFIT(k1×Ls二酐,i+k2×Ls二胺,j)k0其中,Ls二酐,i=Exp[-k3×Coeffi]×Vi y0,Ls二胺,j=Exp[-k4×Coeffj]×Vj y0,k0=2.00,y0=-1.00,k1=206.67,k2=124.78,k3=3.20,k4=5.90,Coeffi及Coeffj係分別為使用ADRIANA.Code(Molecular Networks GmbH)計算由二酐i及二胺j作為該聚醯亞胺之單體之結構之分子非球面性(molecular asphericities),Vi及Vj係分別為使用ADRIANA.Code(Molecular Networks GmbH)計算由二酐i及二胺j作為該單體之結構之麥克恩體積(McGowan volumes),以及若exp(-4.0×|Coeffi-Coeffj|)+0.08<0.90,αFIT為1.0,且若exp(-4.0×|Coeffi-Coeffj|)+0.08≧0.90,αFIT為0.1至0.95之常數。
- 如申請專利範圍第1項所述之積層體,其中,當一醯亞 胺化度定義為:塗佈一包含一聚醯胺酸樹脂之組成物並於200℃以上之溫度醯亞胺化後,於紅外線(IR)光譜之1350至1400cm-1或1550至1650cm-1所觀察之CN鍵之累積強度(integrated intensity)相對於該組成物於500℃以上之溫度醯亞胺化後,於相同波長範圍所觀察之CN鍵之累積強度(100%)之百分比時,該第一聚醯亞胺樹脂具有60%至99%之醯亞胺化度。
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂之玻璃轉移溫度係為200℃以上。
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂層係藉由:於該載體基板上塗佈一包含一聚醯亞胺樹脂或其前驅物之組成物,並於等於該第二聚醯亞胺樹脂層之固化溫度或低於該第二聚醯亞胺樹脂層之固化溫度0至200℃之溫度下固化而形成。
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂層包括一第一聚醯亞胺樹脂,其藉由反應一如化學式1之芳香族四羧酸二酐(aromatic tetracarboxylic dianhydride)與一具有直鏈結構之芳香族二胺化合物,以製備一聚醯胺酸,並於200℃以上之溫度固化該聚醯胺酸製備而得,
- 如申請專利範圍第9項所述之積層體,其中,該芳香族二胺化合物係如化學式4a或4b所示,
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂層於100至200℃溫度下具有不大於30ppm/℃之熱膨脹係數以及於450℃以上之1%熱裂解溫度(Td1%)。
- 如申請專利範圍第1項所述之積層體,其中,該第一聚醯亞胺樹脂層具有0.05至5μm之厚度。
- 如申請專利範圍第1項所述之積層體,其中,該第二聚醯亞胺樹脂層包括一具有50至99%醯亞胺化度及200℃以上玻璃轉移溫度之第二聚醯亞胺樹脂。
- 一種製造積層體之方法,包括:於一載體基板之至少一表面上形成一包含一第一聚醯亞胺樹脂之第一聚醯亞胺樹脂層;以及藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞 胺樹脂之前驅物之組成物並固化該組成物,以形成一第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)係等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且藉由一物理刺激降低該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度。
- 如申請專利範圍第14項所述之方法,其中,該第一聚醯亞胺樹脂層係藉由:於該載體基板之至少一表面上塗佈一包含一第一聚醯亞胺樹脂或其前驅物之組成物並固化該組成物而形成。
- 如申請專利範圍第15項所述之方法,其中,該第一聚醯亞胺樹脂層之固化製程係於200℃以上之溫度下進行,以及該第二聚醯亞胺樹脂層之固化製程係於等於該第一聚醯亞胺樹脂層之固化溫度或高於該第一聚醯亞胺樹脂層之固化溫度0至200℃之溫度下進行。
- 如申請專利範圍第15項所述之方法,更包括一步驟:於形成該第一聚醯亞胺樹脂層或該第二聚醯亞胺樹脂層之步驟後,在300℃以上之溫度下熱處理該第一聚醯亞胺樹脂層或該第二聚醯亞胺樹脂層1至30分鐘。
- 一種製造裝置基板之方法,包括:於一載體基板之至少一表面上形成一包含一第一聚醯亞胺樹脂之第一聚醯亞胺樹脂層; 藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂之前驅物之組成物並固化該組成物,以形成一第二聚醯亞胺樹脂層而製造一積層體;施加一物理刺激至該積層體而不導致該第一聚醯亞胺樹脂層中發生化學變化;以及由形成於該載體基板上之該第一聚醯亞胺樹脂層上分離該第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)係等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且藉由一物理刺激降低該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度。
- 如申請專利範圍第18項所述之方法,其中,施加該物理刺激以使該積層體之橫截面外露。
- 一種使用如申請專利範圍第18項所述之方法所製造之裝置基板。
- 一種製造裝置之方法,包括:於一載體基板之至少一表面上形成一包含一第一聚醯亞胺樹脂之第一聚醯亞胺樹脂層;藉由於該第一聚醯亞胺樹脂層上塗佈一包含一第二聚醯亞胺樹脂之前驅物之組成物並固化該組成物而製造一積層體,以形成一第二聚醯亞胺樹脂層;於該積層體之可撓性基板上形成一裝置結構; 施加一物理刺激至其上形成有該裝置結構之該積層體,而不導致該第一聚醯亞胺樹脂層中發生化學變化;以及由形成於該載體基板上之該第一聚醯亞胺樹脂層上分離該第二聚醯亞胺樹脂層;其中,在100至200℃之溫度下,該第一聚醯亞胺樹脂層之熱膨脹係數(CTE)係等於或小於該第二聚醯亞胺樹脂層之熱膨脹係數,且藉由一物理刺激降低該第一聚醯亞胺樹脂層對該第二聚醯亞胺樹脂層之黏著強度。
- 一種使用如申請專利範圍第21項所述之方法所製造之裝置。
- 如申請專利範圍第22項所述之裝置,其中,該裝置係選自由太陽能電池、有機發光二極體裝置、半導體裝置、及顯示裝置所組成之群組。
- 如申請專利範圍第23項所述之裝置,其中,該顯示裝置係為可撓式有機電致發光裝置。
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