TW201831562A - 感光性樹脂組成物、使用其的黑色像素界定層及顯示裝置 - Google Patents
感光性樹脂組成物、使用其的黑色像素界定層及顯示裝置 Download PDFInfo
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- TW201831562A TW201831562A TW106132704A TW106132704A TW201831562A TW 201831562 A TW201831562 A TW 201831562A TW 106132704 A TW106132704 A TW 106132704A TW 106132704 A TW106132704 A TW 106132704A TW 201831562 A TW201831562 A TW 201831562A
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- resin composition
- photosensitive resin
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- 239000000126 substance Substances 0.000 claims abstract description 206
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本發明提供包含以下的感光性樹脂組成物:(A)包含由化學式1表示的結構單元的黏合劑樹脂;(B)黑色著色劑;(C)光可聚合單體;(D)光聚合引發劑;以及(E)溶劑,使用感光性樹脂組成物製造的黑色像素界定層,以及包含黑色像素界定層的顯示裝置。
Description
本發明是有關於一種感光性樹脂組成物、使用其的黑色像素界定層以及顯示裝置。
[相關申請的交叉引用]
本申請要求2017年2月16日在韓國知識産權局提交的韓國專利申請第10-2017-0021056號的優先權和權益,其全部內容以引用的方式並入本文中。
在製造濾色器、液晶顯示材料、顯示裝置(如有機發光二極體)、顯示裝置面板材料等必須使用到感光性樹脂組成物。舉例來說,在著色層(如紅色、綠色、藍色等)之間的邊緣上需要如黑色像素界定層(black pixel defining layer)的感光性樹脂膜以增强彩色液晶顯示器或有機發光二極體等的對比或發色團效應(chromophore effect)。
此感光性樹脂膜主要可由黑色感光性樹脂組成物形成。確切地說,用作顯示裝置面板的材料的感光性樹脂層(如像素界定層等)應具有小錐角(taper angle)以確保可加工性和裝置可靠性。另外,應使用吸收可見光區中的光的著色劑(如顔料、染料等)以確保擋光特性。
常規地,聚醯亞胺、聚苯並惡唑或其前驅體已用作感光性樹脂組成物的黏合劑樹脂以便獲得耐熱性、敏感性或低脫氣(out-gas)特徵,但對比率和敏感性可能降低且在曝光之後的圖案形成期間錐角可能增加。
因此,已進行開發能够解决所述缺點的用於黑色像素界定層的感光性樹脂組成物的研究。
本發明一實施例提供具有低錐度和極佳耐熱性的感光性樹脂組成物。
本發明一實施例提供包含以下的感光性樹脂組成物:(A)包含由化學式1表示的結構單元的黏合劑樹脂;(B)黑色著色劑;(C)光可聚合單體;(D)光聚合引發劑;以及(E)溶劑。 [化學式1]在化學式1中, L1
、L3
以及L4
獨立地爲*-C(=O)-*、經取代或未經取代的C1到C20伸烷基或經取代或未經取代的C6到C20伸芳基, L2
爲由化學式2表示的鍵聯基團,且 R5
和R6
獨立地爲氫原子或羧基, [化學式2]其中,在化學式2中, R1
到R4
獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基,且 n爲1到10的整數。
所述L1
和L3
可獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基,L4
可爲經三氟甲基取代的C1到C20伸烷基,且R5
和R6
可獨立地爲氫原子。
所述L1
和L3
可獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基,L4
可爲*-C(=O)-*,且R5
和R6
可獨立地爲羧基。
所述黏合劑樹脂可更包含由化學式3到化學式5表示的結構單元中的一個。 [化學式3][化學式4][化學式5]在化學式3到化學式5中, L5
到L7
獨立地由化學式2、化學式6或化學式7表示,且 L8
爲*-C(=O)-*或經取代或未經取代的C1到C20伸烷基, [化學式2][化學式6][化學式7]在化學式2、化學式6以及化學式7中, R1
到R4
獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基, n爲1到10的整數, L9
爲*-S(=O)2
-*或*-C(CF3
)2
-*,且 R7
到R9
獨立地爲羥基或羧基。
所述黏合劑樹脂可包含由化學式8-1到化學式8-4表示的官能團中的任一個。 [化學式8-1][化學式8-2][化學式8-3][化學式8-4]在化學式8-1到化學式8-4中, L10
和L11
獨立地爲經取代或未經取代的C1到C10伸烷基,且 R10
爲氫原子或經取代或未經取代的C1到C10烷基。
所述黏合劑樹脂可包括由化學式9到化學式12表示的結構單元中的一個。 [化學式9][化學式10][化學式11][化學式12]在化學式9到化學式12中, n爲1到10的整數。
所述黏合劑樹脂可具有5,000克/莫耳到20,000克/莫耳的重量平均分子量。
所述感光性樹脂組成物可以更包含卡哆類(cardo-based)黏合劑樹脂。
所述黑色著色劑可包括無機黑色顔料、有機黑色顔料或其組合。
所述光可聚合單體可包含化合物,所述化合物包含至少兩個由化學式13表示的官能團。 [化學式13]在化學式13中, R0
爲氫原子或經取代或未經取代的C1到C10烷基,且 L12
爲單鍵或經取代或未經取代的C1到C10伸烷基。
所述包含至少兩個由化學式13表示的官能團的化合物可爲由化學式13-1或化學式13-2表示的化合物。 [化學式13-1][化學式13-2]在化學式13-1和化學式13-2中, p、q、r和s獨立地爲1到10的整數。
按所述感光性樹脂組成物的總量計,所述感光性樹脂組成物可包含1重量%到30重量%的(A)黏合劑樹脂;1重量%到25重量%的(B)黑色著色劑;0.5重量%到20重量%的(C)光可聚合單體;0.1重量%到5重量%的(D)光聚合引發劑;以及餘量的(E)溶劑。
所述感光性樹脂組成物可更包含丙二酸、3-氨基-1,2-丙二醇、矽烷類偶合劑、表面活性劑、自由基聚合引發劑或其組合的添加劑。
本發明另一實施例提供一種使用所述感光性樹脂組成物製造的黑色像素界定層。
本發明另一實施例提供一種包含黑色像素界定層的顯示裝置。
所述顯示裝置可爲有機發光二極體(OLED)。
本發明的其它實施例包含在以下具體實施方式中。
因此,根據一實施例的感光性樹脂組成物可具有快速顯影起始時間和極佳耐熱性以及維持低錐角,且因此具有極佳可加工性,且因而可以使得有可能形成精確像素。又一實施例提供一種包括所述感光性樹脂層的彩色濾光片。
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。
在下文中詳細地描述本發明的實施例。然而,這些實施例是示例性,本發明不限於此,並且本發明的範圍是由申請專利範圍所界定。
如本文所用,當不另外提供特定定義時,術語“烷基”指的是C1到C20烷基,術語“烯基”指的是C2到C20烯基,術語“環烯基”指的是C3到C20環烯基,術語“雜環烯基”指的是C3到C20雜環烯基,術語“芳基”指的是C6到C20芳基,術語“芳烷基”指的是C6到C20芳烷基,術語“伸烷基”指的是C1到C20伸烷基,術語“伸芳基”指的是C6到C20伸芳基,術語“烷基伸芳基”指的是C6到C20烷基伸芳基,術語“伸雜芳基”指的是C3到C20伸雜芳基,且術語“伸烷氧基”指的是C1到C20伸烷氧基。
如本文所用,當不另外提供特定定義時,“經取代”指的是至少一個氫原子經鹵素原子(F、Cl、Br或I)、羥基、C1到C20烷氧基、硝基、氰基、胺基、伸氨基、叠氮基、甲脒基(amidino group)、肼基(hydrazino group)、伸肼基(hydrazono group)、羰基(carbonyl group)、氨甲醯基(carbamyl group)、硫醇基、酯基、醚基、羧基或其鹽、磺酸基或其鹽、磷酸或其鹽、C1到C20烷基、C2到C20烯基、C2到C20炔基、C6到C20芳基、C3到C20環烷基、C3到C20環烯基、C3到C20環炔基、C2到C20雜環烷基、C2到C20雜環烯基、C2到C20雜環炔基、C3到C20雜芳基或其組合的取代基置換。
如本文所用,當不另外提供特定定義時,“雜”是指在化學式中包含至少一個N、O、S和P的雜原子。
如本文中所用,當不另外提供特定定義時,“(甲基)丙烯酸酯”是指“丙烯酸酯”和“甲基丙烯酸酯”兩者,並且“(甲基)丙烯酸”是指“丙烯酸”和“甲基丙烯酸”。
如本文所用,當不另外提供定義時,術語“組合”是指混合或共聚合。此外,“共聚合”是指嵌段共聚合到無規共聚合,並且“共聚物”是指嵌段共聚物到無規共聚物。
在本說明書的化學式中,除非另外提供具體定義,否則當沒有在應給出的位置處繪製化學鍵時,氫在所述位置處鍵結。
如本文所用,卡哆類樹脂指的是在主鏈中包含至少一個選自化學式14-1到化學式14-11的官能團的樹脂。
如本文中所用,當不另外提供特定定義時,“*”指示其中連接相同或不同原子或化學式的點。
根據一實施例的感光性樹脂組成物包含(A)包含由化學式1表示的結構單元的黏合劑樹脂;(B)黑色著色劑;(C)光可聚合單體;(D)光聚合引發劑;以及(E)溶劑。 [化學式1]在化學式1中, L1
、L3
以及L4
獨立地爲*-C(=O)-*、經取代或未經取代的C1到C20伸烷基或經取代或未經取代的C6到C20伸芳基, L2
爲由化學式2表示的鍵聯基團,且 R5
和R6
獨立地爲氫原子或羧基, [化學式2]其中,在化學式2中, R1
到R4
獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基,且 n爲1到10的整數。
一般來說,單獨用作感光性樹脂組成物的黏合劑樹脂的聚醯亞胺(或其前驅體)樹脂分類成曝光區通過顯影溶解的正型和曝光區經固化且保留的負型,但當感光性樹脂組成物包含黑色著色劑時,由於紫外線(UV)的透射率减少,在實現精細圖案上,正型樹脂可能會有問題。另外,負型的聚醯亞胺(或其前驅體)樹脂對於鹼性水溶液具有高可溶性且因此在單獨使用黏合劑樹脂中具有限制。
但是,根據一實施例的感光性樹脂組成物使用包含由化學式1表示的結構單元的黏合劑樹脂且因此對於有機溶劑具有可溶性、對於鹼性水溶液具有極佳溶解性和高耐熱性。
確切地說,負型感光性樹脂能够通過控制黏合劑樹脂結構中施加醯亞胺化結構的比率來調節以鹼性水溶液作爲顯影液的可溶性,且同時通過光聚合引發劑在主結構的末端引入可交聯官能團以通過黏合劑樹脂自身的曝光施加交聯特性而獲得極佳精細圖案。以此方式,感光性樹脂組成物可通過調節可溶醯亞胺結構與聚醯亞胺(或其前驅體(醯胺酸))結構之間的共聚比率而對於鹼性水溶液具有適當的可溶性,且藉由在聚合物(黏合劑樹脂)的末端引入可交聯官能團,以通過UV照射使曝光區交聯、通過顯影將非曝光區形成爲精細圖案以及在大於或等於約350℃下對所述圖案進行熱固化而具有極佳耐熱性(通過TGA分析的大於或等於約350℃的1重量%損失溫度)。
在下文中,具體地描述每種組分。
(A)黏合劑樹脂
舉例來說,在化學式1中,L1
和L3
可獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基,L4
可爲經三氟甲基取代的C1到C20伸烷基,且R5
和R6
可獨立地爲氫原子。
舉例來說,在化學式1中,L1
和L3
可獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基,L4
可爲*-C(=O)-*,且R5
和R6
可獨立地爲羧基。
除了由化學式1表示的結構單元以外,黏合劑樹脂可更包含由化學式3到化學式5表示的結構單元中的一個,其可進一步改進顯影性和耐熱性。 [化學式3][化學式4][化學式5]在化學式3到化學式5中, L5
到L7
獨立地由化學式2、化學式6或化學式7表示,且 L8
爲*-C(=O)-*或經取代或未經取代的C1到C20伸烷基, [化學式2][化學式6][化學式7]在化學式2、化學式6以及化學式7中, R1
到R4
獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基, n爲1到10的整數, L9
爲*-S(=O)2
-*或*-C(CF3
)2
-*,且 R7
到R9
獨立地爲羥基或羧基。
黏合劑樹脂可在末端處包含可交聯官能團。舉例來說,可交聯官能團可由化學式8-1到化學式8-4表示,但不限於此。 [化學式8-1][化學式8-2][化學式8-3][化學式8-4]在化學式8-1到化學式8-4中, L10
和L11
獨立地爲經取代或未經取代的C1到C10伸烷基,且 R10
爲氫原子或經取代或未經取代的C1到C10烷基。
舉例來說,黏合劑樹脂可包含由化學式9到化學式12表示的結構單元中的一個,但不限於此。 [化學式9][化學式10][化學式11][化學式12]在化學式9到化學式12中, n爲1到10的整數。
所述包含由化學式1表示的結構單元的黏合劑樹脂可具有5,000克/莫耳到20,000克/莫耳的重量平均分子量。當黏合劑樹脂具有所述範圍內的重量平均分子量時,可獲得極佳圖案形成能力,並且可提供可具有極佳機械熱特性的薄膜。
根據一實施例的感光性樹脂組成物可以更包含卡哆類黏合劑樹脂作爲黏合劑樹脂。
卡哆類黏合劑樹脂可包含由化學式14表示的結構單元。 [化學式14]在化學式14中, R11
和R12
獨立地爲氫原子或經取代或未經取代的(甲基)丙烯醯氧基烷基, R13
和R14
獨立地爲氫原子、鹵素原子或經取代或未經取代的C1到C20烷基,且 Z1
爲單鍵、O、CO、SO2
、CR17
R18
、SiR19
R20
(其中R17
到R20
獨立地爲氫原子或經取代或未經取代的C1到C20烷基)或由化學式14-1到化學式14-11表示的鍵聯基團中的一個, [化學式14-1][化學式14-2][化學式14-3][化學式14-4][化學式14-5]在化學式14-5中, Ra
爲氫原子、乙基、C2
H4
Cl、C2
H4
OH、CH2
CH=CH2
或苯基。 [化學式14-6][化學式14-7][化學式14-8][化學式14-9][化學式14-10][化學式14-11]Z2
爲酸酐殘基,且 t1和t2獨立地爲0到4的整數。
卡哆類黏合劑樹脂的重量平均分子量可爲500克/莫耳到50,000克/莫耳,例如1,000克/莫耳到30,000克/莫耳。當卡哆類黏合劑樹脂所述範圍內的重量平均分子量時,可在製造感光有機膜期間無殘餘物的情况下和在顯影期間無膜厚度損失的情况下很好地形成圖案。
卡哆類黏合劑樹脂可在兩個末端中的至少一個處包含由化學式15表示的官能團。 [化學式15]在化學式15中, Z3
由化學式15-1到化學式15-7表示。 [化學式15-1]其中在化學式15-1中,Rb
和Rc
獨立地爲氫原子、經取代或未經取代的C1到C20烷基、酯基或醚基。 [化學式15-2][化學式15-3][化學式15-4][化學式15-5]在化學式15-5中,Rd
爲O、S、NH、經取代或未經取代的C1到C20伸烷基、C1到C20烷基胺基或C2到C20烯基胺基。 [化學式15-6][化學式15-7]
卡哆類樹脂可例如通過混合以下中的至少兩個來製備:含芴化合物,如9,9-雙(4-環氧乙烷基甲氧基苯基)芴(9,9-bis (4-oxiranylmethoxyphenyl)fluorene)等;酐化合物,如苯四甲酸二酐(benzenetetracarboxylic acid dianhydride)、萘四甲酸二酐、聯苯四甲酸二酐、二苯甲酮四甲酸二酐(benzophenonetetracarboxylic acid dianhydride)、苯均四酸二酐(pyromellitic dianhydride)、環丁烷四甲酸二酐(cyclobutanetetracarboxylic acid dianhydride)、苝四甲酸二酐(perylenetetracarboxylic acid dianhydride)、四氫呋喃四甲酸二酐(tetrahydrofurantetracarboxylic acid dianhydride)、四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)等;二醇化合物,如乙二醇、丙二醇、聚乙二醇等;醇化合物,如甲醇、乙醇、丙醇、正丁醇、環己醇、苯甲醇等;溶劑類化合物,如丙二醇甲基乙基乙酸酯、N-甲基吡咯烷酮等;磷化合物,如三苯膦等;以及胺或銨鹽化合物,如氯化四甲銨、溴化四乙銨、苯甲基二乙胺、三乙胺、三丁胺、氯化苯甲基三乙銨等。
當除了包含由化學式1表示的結構單元的黏合劑樹脂以外,根據一實施例的感光性樹脂組成物還包含卡哆類黏合劑樹脂時,由於光固化期間的良好敏感性而可改進顯影性且可進一步改進形成精細圖案的能力。
按感光性樹脂組成物的總量計,黏合劑樹脂可以1重量%到30重量%,例如10重量%到20重量%的量包含在內。當包含所述範圍內的黏合劑樹脂時,可改進敏感性、顯影性、解析度(resolution)和圖案線性度。
(B)黑色著色劑
根據一實施例的感光性樹脂組成物中的黑色著色劑可包含無機黑色顔料、有機黑色顔料或其組合,以改進擋光特性且容易地實現黑色。通過顔色混合RGB黑等的黑色顔料可單獨或以混合物形式使用。舉例來說,黑色著色劑可包含苯胺黑、苝黑、鈦黑、花青黑、木質素黑、內醯胺類有機黑、RGB黑、碳黑或其組合。RGB黑指的是通過混合紅色顔料、綠色顔料、藍色顔料、紫羅蘭色顔料、黃色顔料、紫色顔料等的至少兩種顔色(非黑色)顔料而顯示黑色的顔料。有機黑色顔料可爲由化學式A表示的內醯胺類有機黑。 [化學式A]
當黑色著色劑爲有機黑色顔料或有機黑色顔料與碳黑(其爲無機黑色顔料)的混合物時,分散劑可與其一起使用以分散顔料。確切地說,顔料可用分散劑在表面上預處理或可在製備組成物期間與顔料一起添加分散劑。
分散劑可以是非離子分散劑、陰離子分散劑、陽離子分散劑等。分散劑的特定實例可爲聚烷二醇和其酯、聚氧化烯、多元醇酯環氧烷(polyhydric alcohol ester alkylene oxide)加成産物、醇環氧烷(alcohol alkylene oxide)加成産物、磺酸酯、磺酸鹽、羧酸酯、羧酸鹽、烷基醯胺環氧烷(alkyl amide alkylene oxide)加成産物、烷基胺(alkyl amide)等,並且這些可單獨使用或以兩種或多於兩種的混合物形式使用。
可商購的分散劑的實例可包含德國畢克有限公司(BYK Co., Ltd.)製造的迪斯畢克(DISPERBYK)-101、迪斯畢克-130、迪斯畢克-140、迪斯畢克-160、迪斯畢克-161、迪斯畢克-162、迪斯畢克-163、迪斯畢克-164、迪斯畢克-165、迪斯畢克-166、迪斯畢克-170、迪斯畢克-171、迪斯畢克-182、迪斯畢克-2000、迪斯畢克-2001;埃夫卡化學品公司(EFKA Chemicals Co.)製造的埃夫卡-47、埃夫卡-47EA、埃夫卡-48、埃夫卡-49、埃夫卡-100、埃夫卡-400、埃夫卡-450;澤內卡公司(Zeneka Co.)製造的索斯波斯(Solsperse) 5000、索斯波斯12000、索斯波斯13240、索斯波斯13940、索斯波斯17000、索斯波斯20000、索斯波斯24000GR、索斯波斯27000、索斯波斯28000等;或味之素株式會社(Ajinomoto Inc)製造的PB711、PB821等。
按感光性樹脂組成物的總量計,分散劑可以0.1重量%到15重量%的量包含在內。當包含所述範圍內的分散劑時,在製造黑色界定層材料期間,歸因於改進的分散特性,組成物具有極佳穩定性、顯影性以及圖案形成能力。
顔料可使用水溶性無機鹽和潤濕劑預處理。當顔料經預處理時,顔料的平均粒徑可變得更精細。
可通過將顔料與水溶性無機鹽以及潤濕劑捏合,接著過濾並且洗滌所述捏合的顔料來進行預處理。
捏合可以在約40℃到約100℃的溫度下進行,且可以通過在用水等洗去無機鹽之後過濾顔料來進行過濾和洗滌。
水溶性無機鹽的實例可爲氯化鈉、氯化鉀等,但不限於此。潤濕劑可使顔料與水溶性無機鹽均勻混合以及均勻粉碎。潤濕劑的實例包含烷二醇單烷基醚,如乙二醇單乙醚、丙二醇單甲醚、二乙二醇單甲醚等;和醇,如乙醇、異丙醇、丁醇、己醇、環己醇、乙二醇、二乙二醇、聚乙二醇、丙三醇聚乙二醇等。這些可以單獨使用或以兩種或大於兩種的混合物形式使用。
捏合之後的顔料可具有5奈米到200奈米,例如5奈米到150奈米範圍內的平均粒徑。當顔料具有所述範圍內的平均粒徑時,可以改進顔料分散液的穩定性且像素解析度可能不會劣化。
確切地說,顔料可以包含隨後將描述的分散劑和溶劑的顔料分散液形式使用,且所述顔料分散液可包含固體顔料、分散劑以及溶劑。按顔料分散液的總量計,固體顔料可以5重量%到40重量%,例如8重量%到30重量%的量包含在內。
黑色著色劑可以按感光性樹脂組成物的總量計的1重量%到25重量%,例如2重量%到10重量%的固體含量包含在內。舉例來說,黑色著色劑可以按感光性樹脂組成物的總量計的5重量%到70重量%(參考顔料分散液)的量包含在內。當包含所述範圍內的黑色著色劑時,可改進著色效應和顯影性能。
(C)光可聚合單體
根據一實施例的感光性樹脂組成物中的光可聚合單體可爲單一化合物或兩種或大於兩種不同種類的化合物的混合物。
當光可聚合單體爲兩種或大於兩種化合物的混合物時,兩種化合物中的一種可爲包含至少兩個由化學式13表示的官能團的化合物。 [化學式13]在化學式13中, R0
爲氫原子或經取代或未經取代的C1到C10烷基,且 L12
爲單鍵或經取代或未經取代的C1到C10伸烷基。
舉例來說,包含至少兩個由化學式13表示的官能團的化合物可包含2到6個由化學式13表示的官能團。在此狀况下,在圖案形成過程的曝光期間,出現足够聚合且可形成具有改進的耐熱性、耐光性以及耐化學性的圖案。
舉例來說,包含至少兩個由化學式13表示的官能團的化合物可爲由化學式13-1或化學式13-2表示的化合物。 [化學式13-1][化學式13-2]在化學式13-1和化學式13-2中, p、q、r以及s獨立地爲1到10的整數。
當光可聚合單體爲兩種或大於兩種化合物的混合物時,兩種化合物中的另一化合物可爲具有至少一個烯系不飽和雙鍵的(甲基)丙烯酸的單官能或多官能性酯化合物。
具有至少一個烯系不飽和雙鍵的(甲基)丙烯酸的單官能或多官能性酯化合物可例如爲乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯(bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate)、季戊四醇二(甲基)丙烯酸酯(pentaerythritoltri(meth)acrylate, pentaerythritoltetra(meth)acrylate)、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇六(甲基)丙烯酸酯、二季戊四醇二(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、雙酚A環氧(甲基)丙烯酸酯(bisphenol A epoxy(meth)acrylate)、乙二醇單甲醚(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯(trimethylolpropanetri(meth)acrylate)、三(甲基)丙烯醯氧基磷酸乙酯(tris(meth)acryloyloxyethyl phosphate)、酚醛清漆環氧(甲基)丙烯酸酯(novolac epoxy (meth)acrylate)或其組合。
可商購的具有至少一個烯系不飽和雙鍵的(甲基)丙烯酸的單官能或多官能性酯化合物的實例如下。單官能性(甲基)丙烯酸酯的實例可包含阿尼克斯(Aronix)M-101®
、M-111®
、M-114®
(東亞合成化工株式會社(Toagosei Chemistry Industry Co., Ltd.));卡亞拉德(KAYARAD)TC-110S®
、TC-120S®
(日本化藥株式會社(Nippon Kayaku Co., Ltd.));V-158®
、V-2311® (
大阪有機化工株式會社(Osaka Organic Chemical Ind., Ltd.))等。雙官能性(甲基)丙烯酸酯的實例可包含阿尼克斯M-210®
、M-240®
、M-6200®
(東亞合成化工株式會社)、卡亞拉德和大(HDDA)®
、HX-220®
、R-604®
(日本化藥株式會社)、V-260®
、V-312®
、V-335 HP®
(大阪有機化學株式會社)等。三官能性(甲基)丙烯酸酯的實例可包含阿尼克斯M-309®
、M-400®
、M-405®
、M-450®
、M-7100®
、M-8030®
、M-8060®
(東亞合成化工株式會社)、卡亞拉德騰塔(TMPTA)®
、DPCA-20®
、DPCA-30®
、DPCA-60®
、DPCA-120®
(日本化藥株式會社)、V-295®
、V-300®
、V-360®
、V-GPT®
、V-3PA®
、V-400®
(大阪由岐化工株式會社(Osaka Yuki Kayaku Kogyo Co. Ltd.))等。産物可單獨使用或以兩種或大於兩種的混合物形式使用。
光可聚合單體可用酸酐處理以改進顯影性。
光可聚合單體可以按感光性樹脂組成物的總量計的0.5重量%到20重量%,例如1重量%到10重量%的量包含在內。當包含所述範圍內的光可聚合單體時,反應性不飽和化合物在圖案形成過程中的曝光期間充分固化且具有極佳可靠性,且因此可形成具有改進的耐熱性、耐光性以及耐化學性,並且還具有極佳解析度和緊密接觸特性的圖案。
(D)光聚合引發劑
根據一實施例的感光性樹脂組成物包含光聚合引發劑。光聚合引發劑可包含苯乙酮類化合物(acetophenone-based compound)、二苯甲酮類化合物(benzophenone-based compound)、噻噸酮類化合物(thioxanthone-based compound)、安息香類化合物(benzoin-based compound)、三嗪類化合物(triazine-based compound)、肟類化合物(oxime-based compound)等。
苯乙酮類化合物的實例可以是2,2'-二乙氧基苯乙酮、2,2'-二丁氧基苯乙酮、2-羥基-2-甲基苯丙酮、對叔丁基三氯苯乙酮、對叔丁基二氯苯乙酮、4-氯苯乙酮、2,2'-二氯-4-苯氧基苯乙酮、2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉基丙-1-酮、2-苯甲基-2-二甲氨基-1-(4-嗎啉基苯基)-丁-1-酮等。
二苯甲酮類化合物的實例可爲二苯甲酮、苯甲酸苯甲醯酯、苯甲酸苯甲醯基甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4,4'-雙(二甲氨基)二苯甲酮、4,4'-雙(二乙氨基)二苯甲酮、4,4'-二甲氨基二苯甲酮、4,4'-二氯二苯甲酮、3,3'-二甲基-2-甲氧基二苯甲酮等。
噻噸酮類化合物的實例可爲噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮等。
安息香類化合物的實例可爲安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、苯甲基二甲基縮酮等。
三嗪類化合物的實例可爲2,4,6-三氯-s-三嗪、2-苯基4,6-雙(三氯甲基)-s-三嗪、2-(3',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4'-甲氧基萘基)-4,6-雙(三氯甲基)-s-三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)-s-三嗪、2-聯苯4,6-雙(三氯甲基)-s-三嗪、雙(三氯甲基)-6-苯乙烯基-s-三嗪、2-(萘並-1-基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基萘酚-基)-4,6-雙(三氯甲基)-s-三嗪、2-4-雙(三氯甲基)-6-向日葵基-s-三嗪、2-4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-s-三嗪等。
肟類化合物的實例可包含O-醯肟類化合物2-(O-苯甲醯基肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、1-(O-乙醯肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-哢唑-3-基]乙酮、O-乙氧基羰基-α-羥氨基-1-苯基丙-1-酮等。O-醯肟類化合物的實例可包含1,2-辛二酮、2-二甲氨基-2-(4-甲苯甲基)-1-(4-嗎啉-4-基-苯基)-丁-1-酮、1-(4-苯硫基苯基)-丁烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯硫基苯基)-辛烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-苯硫基苯基)-辛-1-酮肟-O-乙酸酯、1-(4-苯硫基苯基)-丁-1-酮肟-O-乙酸酯等。
除所述化合物以外,光聚合引發劑可更包含哢唑類化合物、二酮類化合物、硼酸鋶類化合物(sulfonium borate-based compound)、重氮類化合物(diazo-based compound)、咪唑類化合物(imidazole-based compound)、聯咪唑類化合物(biimidazole-based compound)、芴類化合物(fluorene-based compound)等。
光聚合引發劑可以按感光性樹脂組成物的總量計的0.1重量%到5重量%,例如1重量%到3重量%的量包含在內。當包含所述範圍內的光聚合引發劑時,組成物可在用於製備黑色像素界定層的圖案形成過程期間在曝光時充分光聚合,實現極佳敏感性且改進透射率。
(E)溶劑
溶劑爲與黏合劑樹脂、包含黑色著色劑的顔料分散液、光可聚合單體以及光聚合引發劑具有相容性的材料,但不與其反應。
溶劑的實例可包含醇,如甲醇、乙醇等;醚,如二氯乙醚、正丁基醚、二季戊基醚、甲基苯基醚、四氫呋喃等;二醇醚,如乙烯二醇單甲醚、乙烯二醇單乙醚、乙烯二醇二甲醚等;乙二醇乙醚乙酸酯,如乙二醇乙醚乙酸甲酯、乙二醇乙醚乙酸乙酯、乙二醇乙醚乙酸二乙酯等;卡必醇,如甲基乙基卡必醇、二乙基卡必醇、二亞乙基二醇單甲醚、二亞乙基二醇單乙醚、二亞乙基二醇二甲醚、二亞乙基二醇乙基甲醚、二亞乙基二醇二乙醚等;丙二醇烷基醚乙酸酯,如丙二醇甲醚乙酸酯、丙二醇丙醚乙酸酯等;芳族烴,如甲苯、二甲苯等;酮,如甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、甲基-正丙酮、甲基-正丁酮、甲基-正戊酮、2-庚酮等;飽和脂族單羧酸烷基酯,如乙酸乙酯、乙酸正丁酯、乙酸異丁酯等;乳酸酯,如乳酸甲酯、乳酸乙酯等;氧基乙酸烷基酯,如氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯等;烷氧基乙酸烷基酯,如甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等;3-氧基丙酸烷基酯,如3-氧基丙酸甲酯、3-氧基丙酸乙酯等;3-烷氧基丙酸烷基酯,如3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯等;2-氧基丙酸烷基酯,如2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等;2-烷氧基丙酸烷基酯,如2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸甲酯等;2-氧基-2-甲基丙酸酯,如2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯等;2-烷氧基-2-甲基丙酸烷基的單氧基單羧酸烷基酯,如2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等;酯,如丙酸2-羥乙酯、丙酸2-羥基-2-甲基乙酯、乙酸羥乙酯、丁酸2-羥基-3-甲基甲酯等;以及酮酸酯,如丙酮酸乙酯等,且另外包含高沸點溶劑,如N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲亞碸、苯甲基乙醚、二己醚、乙醯丙酮、異佛酮、己酸、辛酸、1-辛醇、1-壬醇、苯甲醇、乙酸苯甲酯、苯甲酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、γ-丁內酯、碳酸亞乙酯、碳酸亞丙酯、乙二醇乙醚乙酸苯酯(phenyl cellosolve acetate)等。
考慮混溶性(miscibility)和反應性,可優選地使用二醇醚,如乙二醇單乙醚、乙二醇二甲醚、乙二醇二乙醚(ethylene glycol diethylether)、二乙二醇乙基甲醚等;乙二醇烷基醚乙酸酯(ethylene glycol alkyl ether acetates),如乙二醇乙醚乙酸乙酯(ethyl cellosolve acetate)等;酯,如丙酸2-羥乙酯(2-hydroxyethyl propionate)等;卡必醇(carbitols),如二乙二醇單甲醚(diethylene glycolmonomethylether)等;丙二醇烷基醚乙酸酯(propylene glycol alkyl ether acetates),如丙二醇單甲醚乙酸酯(propylene glycolmonomethyl ether acetate)、丙二醇丙醚乙酸酯(propylene glycolpropyletheracetate)等。
溶劑以餘量使用,例如按感光性樹脂組成物的總量計的30重量%到80重量%。當包含所述範圍內的溶劑時,感光性樹脂組成物可具有適當黏度,從而致使黑色像素界定層的塗佈特性改進。
(F)其它添加劑
另一方面,感光性樹脂組成物可更包含丙二酸、3-氨基-1,2-丙二醇、矽烷類偶合劑、表面活性劑、自由基聚合引發劑或其組合的添加劑。
矽烷類偶合劑可具有反應性取代基的乙烯基、羧基、甲基丙烯醯氧基(methacryloxy group)、異氰酸酯基(isocyanate group)、環氧基等,以改進與襯底的緊密接觸特性。
矽烷類偶合劑的實例可包含三甲氧基矽烷基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸酯基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷等。這些可以單獨使用或以兩種或大於兩種的混合物形式使用。
矽烷類偶合劑可以按100重量份感光性樹脂組成物計的0.01重量份到10重量份的量包含在內。當包含所述範圍內的矽烷類偶合劑時,可改進緊密接觸特性、儲存特性等。
必要時,感光性樹脂組成物可更包含表面活性劑,例如氟類表面活性劑和/或矽酮類表面活性劑以改進塗佈特性和預防缺陷。
氟類表面活性劑的實例可爲商業氟類表面活性劑,如BM-1000®
,和BM-1100®
(BM化學公司(BM Chemie Inc.));麥格菲斯(MEGAFACE)F 142D®
、F 172®
、F 173®
、F 183®
以及F 554®
(大日本油墨化工有限公司(Dainippon Ink Kagaku Kogyo Co., Ltd.));福勒拉德(FULORAD)FC-135®
、福勒拉德FC-170C®
、福勒拉德FC-430®
以及福勒拉德FC-431®
(住友3M有限公司(Sumitomo 3M Co., Ltd.));索龍(SURFLON)S-112®
、索龍S-113®
、索龍S-131®
、索龍S-141®
以及索龍S-145®
(朝日玻璃有限公司(Asahi Glass Co., Ltd.));以及SH-28PA®
、SH-190®
、SH-193®
、SZ-6032®
以及SF-8428®
等(東麗矽酮有限公司(Toray Silicone Co., Ltd.))。
矽酮類表面活性劑可爲畢克(BYK)-307、畢克-333、畢克-361N、畢克-051、畢克-052、畢克-053、畢克-067A、畢克-077、畢克-301、畢克-322、畢克-325等,其由畢克化學(BYK Chem)制得且爲可商購的。
表面活性劑可以按100重量份感光性樹脂組成物計的0.001重量份到5重量份的量使用。當包含所述範圍內的表面活性劑時,可確保極佳的IZO襯底或玻璃襯底上的潤濕以及塗佈均一性,可能不産生色斑(stain)。
此外,除非添加劑使感光性樹脂組成物的特性劣化,否則感光性樹脂組成物可包含預定量的其它添加劑,如抗氧化劑、穩定劑等。
根據一實施例的感光性樹脂組成物可爲正型或負型,但應爲負型以完全去除區域中的殘餘物,在所述區域中,圖案在曝光和顯影具有擋光特性的組成物之後被暴露。
另一實施例提供通過曝光、顯影以及固化感光性樹脂組成物製造的黑色像素界定層。
製造黑色像素界定層的方法如下。
(1)塗佈和膜形成
在經歷預定預處理的襯底(如玻璃襯底或ITO襯底)上,使用旋塗或狹縫塗佈(spin or slit coating)、滾塗方法、絲網印刷方法、塗覆器(applicator)方法等,塗佈感光性樹脂組成物以具有所需厚度,且在約70℃到約110℃下加熱約1分鐘到10分鐘以去除溶劑,形成感光性樹脂層。
(2)曝光
通過安置罩幕且接著輻射約200奈米到約500奈米範圍內的光化射線(actinic ray),使感光性樹脂層圖案化。通過使用例如具有低壓、高壓或超高壓的汞燈、金屬鹵化物燈、氬氣激光器等光源進行輻射。還可以使用X射線、電子束等。
當使用高壓汞燈時,曝光工藝使用例如約500毫焦/平方厘米或小於500毫焦/平方厘米的光劑量(使用365奈米傳感器)。然而,光劑量可視各種組分的種類、其組合比率以及乾膜厚度而變化。
(3)顯影
曝光工藝後,使用鹼性水溶液來溶解和去除曝光部分之外的不必要部分使曝光膜顯影,形成圖案。
(4)後處理
顯影的圖像圖案可經後加熱,從而實現就耐熱性、耐光性、緊密接觸特性、耐破裂性、耐化學性、高强度、儲存穩定性等來說的極好質量。舉例來說,顯影後,可在氮氣氛圍下在約250℃的對流烘箱中進行熱處理約1小時。
另一實施例提供一種包含黑色像素界定層的顯示裝置。
顯示裝置可爲有機發光二極體(OLED)。
在下文中,參考實例更詳述說明本發明。然而,這些實例在任何意義上都不解釋爲限制本發明的範圍。
(實例)
(合成黏合劑樹脂)
合成實例
1
將12.3克6-FDA(4,4`-(六氟亞異丙基)雙苯二甲酸酐)(6-FDA 4,4`-(hexafluoroisopropylidene)diphthalic anhydride)添加至61.5克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加10.2克SiDA([雙(3-氨基丙基)]聚二甲基矽氧烷)[KF-8010,信越化學有限公司(Shin-Etsu Chemical Co., Ltd.)],且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加7.51克吡啶(pyridine)和4.85克乙酸酐(Ac2
O),且攪拌獲得的混合物3小時。在將溫度降低至室溫後,向其中添加0.51克甲基丙烯酸2-羥乙酯(HEMA),且攪拌獲得的混合物6小時。隨後,將水添加至反應混合物,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以製備包含由化學式9表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法(Gel Permeation Chromatography))以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲10,800克/莫耳,且黏合劑樹脂的多分散性(polydispersity)爲3.28。 [化學式9]在化學式9中, n爲8的整數。
合成實例
2
將12.3克6-FDA(4,4`-(六氟亞異丙基)雙苯二甲酸酐)添加至61.5克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加5.1克SiDA([雙(3-氨基丙基)]聚二甲基矽氧烷)[KF-8010,信越化學有限公司(Shin-Etsu Chemical Co., Ltd.)],且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加3.75克吡啶和2.42克乙酸酐(Ac2
O),且攪拌獲得的混合物3小時。在將溫度降低至室溫後,向其中添加0.51克甲基丙烯酸2-羥乙酯(HEMA),且攪拌獲得的混合物6小時。隨後,向其中添加2.95克3-DAS(3-氨基苯基碸),且使獲得的混合物反應6小時,完成反應。將反應混合物添加至水,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以獲得包含由化學式10表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法)以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲9,200克/莫耳,且黏合劑樹脂的多分散性爲1.86。 [化學式10]在化學式10中, n爲8的整數。
合成實例
3
將12.3克6-FDA(4,4`-(六氟亞異丙基)雙苯二甲酸酐)添加至61.5克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加3.27克SiDA([雙(3-氨基丙基)]聚二甲基矽氧烷)[PAM-E,信越化學有限公司(Shin-Etsu Chemical Co., Ltd.)],且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加7.96克吡啶和5.14克乙酸酐(Ac2
O),且攪拌獲得的混合物3小時。在將溫度降低至室溫後,向其中添加0.33克甲基丙烯酸2-羥乙酯(HEMA),且攪拌獲得的混合物6小時。將反應混合物添加至水,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以獲得包含由化學式9表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法)以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲13,800克/莫耳,且黏合劑樹脂的多分散性爲1.86。 [化學式9]在化學式9中, n爲1的整數。
合成實例
4
將6.04克PMDA(苯均四酸二酐)添加至61.5克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加5.29克SiDA([雙(3-氨基丙基)]聚二甲基矽氧烷)[PAM-E,信越化學有限公司(Shin-Etsu Chemical Co., Ltd.)],且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加3.89克吡啶和2.51克乙酸酐(Ac2
O),且攪拌獲得的混合物3小時。在將溫度降低至室溫後,向其中添加0.40克甲基丙烯酸2-羥乙酯(HEMA),且攪拌獲得的混合物6小時。隨後,向其中添加4.51 g APAF(2,2-雙(3-氨基-4-羥基苯基)六氟丙烷(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane)),且使獲得的混合物反應6小時,完成反應。將反應混合物添加至水,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以獲得包含由化學式11表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法)以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲11,800克/莫耳,且黏合劑樹脂的多分散性爲2.80。 [化學式11]在化學式11中, n爲1的整數。
合成實例
5
將12.3克6-FDA(4,4`-(六氟亞異丙基)雙苯二甲酸酐)添加至61.5克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加1.20克甲基丙烯酸2-羥乙酯(HEMA)和10.22克吡啶,且攪拌獲得的混合物2小時。接著,向其中添加1.40克DAB(3,5-二氨基苯甲酸),且在室溫下攪拌獲得的混合物1小時,向其中添加3.47克SiDA([雙(3-氨基丙基)]聚二甲基矽氧烷)[PAM-E,信越化學有限公司],且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加6.12克乙酸酐(Ac2
O),且使獲得的混合物反應6小時,完成反應。將反應混合物添加至水,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以獲得包含由化學式12表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法)以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲5,800克/莫耳,且黏合劑樹脂的多分散性爲2.29。 [化學式12]在化學式12中, n爲1的整數。
合成比較例
1
將12.3克6-FDA(4,4`-(六氟亞異丙基)雙苯二甲酸酐)添加至86.6克N-甲基-2-吡咯烷酮(NMP)且接著在氮氣通過裝備有攪拌器、恆溫器、氮氣注射器以及冷凝器的四頸燒瓶時,將其溶解於所述燒瓶中。當固體完全溶解時,向其中添加3.25克3-氨基苯基碸(3-DAS),並且在室溫下攪拌獲得的混合物2小時。在將溫度增加至90℃之後,向其中添加5.6克吡啶和2.05克乙酸酐(Ac2
O),且攪拌獲得的混合物3小時。在將溫度降低至室溫後,向其中添加1.6克甲基丙烯酸2-羥乙酯(HEMA),且攪拌獲得的混合物6小時。隨後,向其中添加3.25克3-氨基苯基碸(3-DAS),且使獲得的混合物反應6小時,完成反應。將反應混合物添加至水,且過濾其中産生的沉澱,用水充分地洗滌,且在50℃下和在减壓下,乾燥大於或等於24小時,以製備包含由化學式X表示的結構單元的黏合劑樹脂。當通過GPC(凝膠滲透色譜法)以標準聚苯乙烯進行測量時,黏合劑樹脂的重量平均分子量爲7,800克/莫耳,且黏合劑樹脂的多分散性爲1.8。 [化學式X]
(感光性樹脂組成物的製備)
實例
1
到實例
9
以及比較例
1
和比較例
2
將光聚合引發劑溶解於溶劑中以具有表1中示出的組成,且在室溫下攪拌溶液2小時。此處,向其中添加黏合劑樹脂和光可聚合單體,且在室溫下攪拌混合物1小時。接著,向其中添加表面活性劑(其它添加劑)和黑色著色劑,且在室溫下攪拌獲得的混合物1小時,且完全攪拌自其獲得的溶液2小時。溶液經三次過濾去除雜質以製備每一感光性樹脂組成物。
[表1] (單位:克) ( A )黏合劑樹脂
(A-1)合成實例1的黏合劑樹脂 (A-2)合成實例2的黏合劑樹脂 (A-3)合成實例3的黏合劑樹脂 (A-4)合成實例4的黏合劑樹脂 (A-5)合成實例5的黏合劑樹脂 (A-6)合成比較例1的黏合劑樹脂 (A-7)卡哆類黏合劑樹脂(V259ME,新日鐵公司(Nippon Steel Corporation))( B ) 黑色著色劑
內醯胺類(lactam-based)有機黑色顔料分散液(CI-IM-126,阪田公司(SAKATA Corp.);有機黑色顔料的固體含量:15重量%)( C )光可聚合單體
二季戊四醇六(甲基)丙烯酸酯(dipentaerythritol hexa(meth)acrylate)(DPHA,日本化藥株式會社)( D ) 光聚合引發劑
肟類(Oxime-based)引發劑(NCI-831,艾迪科公司(ADEKA Corp.))( E ) 溶劑
丙二醇單甲醚乙酸酯(PGMEA,西格瑪-奧德裏奇公司(Sigma-Aldrich Corporation))( F ) 其它添加劑
氟類表面活性劑(F-554,大日本油墨化工株式會社(DIC Co., Ltd.))
評估
用森美斯(SEMES)製造的K-SPINNER分別將根據實例1到實例9以及比較例1和比較例2的感光性樹脂組成物以300轉/分旋塗於玻璃襯底上以形成每一樹脂塗層。隨後,將經塗佈襯底在100℃熱板上乾燥(預烘烤)100秒以具有1.5微米的厚度。接著,樹脂塗層經由罩幕(間隙:100微米)通過100毫焦/平方厘米的能量强度內的光化能量射線(如紫外(UV)射線等)而被曝光。曝光層(也就是經曝光的樹脂塗層)在顯影液(0.048% KOH水溶液,23℃,120秒)中顯影以形成固化的圖案化層。接著,將圖案化層置於380℃對流烘箱中且經後烘烤1小時。
(1)分別在玻璃襯底上塗佈-預烘烤-曝光感光性樹脂組成物之後,通過用肉眼判定感光性樹脂組成物分別在何時開始顯影和圖案化而獲得顯影起始時間,且結果顯示於表2中。
(2)在曝光期間使用i線曝光器(i10c)以獲得5微米隔離線圖案。隨後,圖案化層在380℃對流烘箱中後烘烤1小時,且接著通過使用掃描電子顯微鏡(S-4300 FE-SEM設備,日立有限公司(Hitachi Ltd.))測量其錐角,且結果顯示於表2中。
(3)進行關於感光性樹脂組成物的TGA分析以獲得1重量%損失溫度,且結果顯示於表2中。
[表2]
參看表2,根據一實施例的感光性樹脂組成物包含黏合劑樹脂,所述的黏合劑樹脂包含由化學式1表示的結構單元,其相比於包含不包含所述結構單元的黏合劑樹脂的感光性樹脂組成物顯示極佳耐熱性以及快速顯影起始時間和明顯改進且較大的圖案形狀界面上的線性。
雖然已經結合目前視爲實用示例性實施例的內容來描述本發明,但應理解本發明不限於所公開的實施例,而是相反,本發明旨在涵蓋包括在所附申請專利範圍的精神和範圍內的各種修改和等效配置。因此,上述實施例應理解爲示例性的但不以任何方式限制本發明。以下,詳細闡述本發明的實施例。然而,這些實施例爲示例性的,本發明並非僅限於此且本發明是由申請專利範圍的範圍所界定。
無。
無。
Claims (16)
- 一種感光性樹脂組成物,包括: (A)包含由化學式1表示的結構單元的黏合劑樹脂; (B)黑色著色劑; (C)光可聚合單體; (D)光聚合引發劑;以及 (E)溶劑, [化學式1]其中,在化學式1中, L1 、L3 以及L4 獨立地爲*-C(=O)-*、經取代或未經取代的C1到C20伸烷基或經取代或未經取代的C6到C20伸芳基, L2 爲由化學式2表示的鍵聯基團,且 R5 和R6 獨立地爲氫原子或羧基, [化學式2]其中,在化學式2中, R1 到R4 獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基,且 n爲1到10的整數。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中L1 和L3 獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基, L4 爲經三氟甲基取代的C1到C20伸烷基,以及 R5 和R6 獨立地爲氫原子。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中L1 和L3 獨立地爲未經取代的C1到C20伸烷基或未經取代的C6到C20伸芳基, L4 爲*-C(=O)-*,且 R5 和R6 獨立地爲羧基。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述黏合劑樹脂更包含由化學式3到化學式5表示的結構單元中的一個: [化學式3][化學式4][化學式5]其中,在化學式3到化學式5中, L5 到L7 獨立地由化學式2、化學式6或化學式7表示,且 L8 爲*-C(=O)-*或經取代或未經取代的C1到C20伸烷基, [化學式2][化學式6][化學式7]其中,在化學式2、化學式6以及化學式7中, R1 到R4 獨立地爲經取代或未經取代的C1到C20烷基或經取代或未經取代的C6到C20芳基, n爲1到10的整數, L9 爲*-S(=O)2 -*或*-C(CF3 )2 -*,且 R7 到R9 獨立地爲羥基或羧基。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述黏合劑樹脂包含由化學式8-1到化學式8-4表示的官能團中的任一個: [化學式8-1][化學式8-2][化學式8-3][化學式8-4]其中,在化學式8-1到化學式8-4中, L10 和L11 獨立地爲經取代或未經取代的C1到C10伸烷基,且 R10 爲氫原子或經取代或未經取代的C1到C10烷基。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述黏合劑樹脂包含由化學式9到化學式12表示的結構單元中的一個: [化學式9][化學式10][化學式11][化學式12]其中,在化學式9到化學式12中, n爲1到10的整數。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述黏合劑樹脂具有5,000克/莫耳到20,000克/莫耳的重量平均分子量。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述感光性樹脂組成物更包含卡哆類黏合劑樹脂。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述黑色著色劑包含無機黑色顔料、有機黑色顔料或其組合。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述光可聚合單體包含化合物,所述化合物包含至少兩個由化學式13表示的官能團: [化學式13]其中,在化學式13中, R0 爲氫原子或經取代或未經取代的C1到C10烷基,且 L12 爲單鍵或經取代或未經取代的C1到C10伸烷基。
- 如申請專利範圍第10項所述的感光性樹脂組成物,其中包含至少兩個由化學式13表示的官能團的所述化合物爲由化學式13-1或化學式13-2表示的化合物: [化學式13-1][化學式13-2]其中在化學式13-1和化學式13-2中, p、q、r以及s獨立地爲1到10的整數。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中按所述感光性樹脂組成物的總量計,所述感光性樹脂組成物包含: 1重量%到30重量%的(A)所述黏合劑樹脂; 1重量%到25重量%的(B)所述黑色著色劑; 0.5重量%到20重量%的(C)所述光可聚合單體; 0.1重量%到5重量%的(D)所述光聚合引發劑;以及 餘量的(E)所述溶劑。
- 如申請專利範圍第1項所述的感光性樹脂組成物,其中所述感光性樹脂組成物更包含丙二酸、3-氨基-1,2-丙二醇、矽烷類偶合劑、表面活性劑、自由基聚合引發劑或其組合的添加劑。
- 一種黑色像素界定層,其使用如申請專利範圍第1項所述的感光性樹脂組成物製造。
- 一種顯示裝置,包括如申請專利範圍第14項所述的黑色像素界定層。
- 如申請專利範圍第15項所述的顯示裝置,其中所述顯示裝置爲有機發光二極體。
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-
2017
- 2017-02-16 KR KR1020170021056A patent/KR102064297B1/ko active Active
- 2017-09-22 US US15/712,663 patent/US10676570B2/en active Active
- 2017-09-25 TW TW106132704A patent/TWI657100B/zh active
- 2017-10-13 CN CN201710968197.1A patent/CN108445713B/zh active Active
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| KR102064297B1 (ko) | 2020-01-09 |
| CN108445713A (zh) | 2018-08-24 |
| US10676570B2 (en) | 2020-06-09 |
| TWI657100B (zh) | 2019-04-21 |
| KR20180094651A (ko) | 2018-08-24 |
| US20180230269A1 (en) | 2018-08-16 |
| CN108445713B (zh) | 2021-10-15 |
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