TW202406972A - High molecular weight compound and organic electroluminescent element using the same wherein the high molecular weight compound includes a triarylamine structural unit with a fluorine ring; and a triarylamine structural unit with a dibenzofuran ring, dibenzothiophene ring or carbazole ring on its main chain - Google Patents

High molecular weight compound and organic electroluminescent element using the same wherein the high molecular weight compound includes a triarylamine structural unit with a fluorine ring; and a triarylamine structural unit with a dibenzofuran ring, dibenzothiophene ring or carbazole ring on its main chain Download PDF

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TW202406972A
TW202406972A TW112120620A TW112120620A TW202406972A TW 202406972 A TW202406972 A TW 202406972A TW 112120620 A TW112120620 A TW 112120620A TW 112120620 A TW112120620 A TW 112120620A TW 202406972 A TW202406972 A TW 202406972A
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molecular weight
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high molecular
weight compound
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富樫和法
篠田美香
吉澤由香
北原秀良
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日商保土谷化學工業股份有限公司
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Abstract

The object of the present invention is to provide a polymer material that is excellent in hole injections and transport performance, has electron blocking ability, and has a high stability in a thin film state. Furthermore, an object of the present invention is to provide an organic EL element that has an organic layer (thin film) formed of the above-mentioned polymer material and has high luminous efficiency and a long usage cycle. The present invention is a high molecular weight compound, wherein its main chain includes: a triarylamine structural unit with a fluorine ring; and a triarylamine structural unit with a dibenzofuran ring, dibenzothiophene ring or carbazole ring. The high molecular weight compound preferably contains a thermally cross-linkable structural unit in the molecular main chain.

Description

高分子量化合物及使用其等之有機電致發光元件High molecular weight compounds and organic electroluminescent devices using the same

本發明係關於一種適用於適合各種顯示裝置之自發光元件即有機電致發光元件(有機EL元件)的高分子量化合物、及使用該等高分子量化合物之有機EL(Electroluminescence，電致發光)元件。The present invention relates to a high molecular weight compound suitable for use in an organic electroluminescent element (organic EL element), which is a self-luminous element suitable for various display devices, and an organic EL (Electroluminescence) element using the high molecular weight compound.

有機EL元件由於為自發光性元件，故而與液晶元件相比係較明亮且視認性優異，並且能夠進行清晰之顯示，因此業界進行了積極之研究。Since organic EL elements are self-luminous elements, they are brighter and have excellent visibility compared to liquid crystal elements, and can provide clear displays, so the industry has been actively researching them.

有機EL元件具有於陽極與陰極之間夾持有機化合物薄膜(有機層)之構成。作為薄膜之形成方法，大致分為真空蒸鍍法與塗佈法。真空蒸鍍法為主要使用低分子化合物，於真空中在基板上形成薄膜之方法，係已經實用化之技術。另一方面，塗佈法為主要使用高分子化合物，藉由噴墨或印刷等，使用溶液於基板上形成薄膜之方法，其材料之使用效率較高，適於大面積化、高清化，係今後之大面積有機EL顯示器不可缺少之技術。The organic EL element has a structure in which an organic compound thin film (organic layer) is sandwiched between an anode and a cathode. Thin film formation methods are roughly divided into vacuum evaporation methods and coating methods. Vacuum evaporation is a method that mainly uses low-molecular compounds to form thin films on substrates in a vacuum. It is a technology that has been put into practical use. On the other hand, the coating method mainly uses polymer compounds to form a thin film on a substrate using a solution through inkjet or printing. Its material usage efficiency is high and it is suitable for large-area and high-definition systems. An indispensable technology for future large-area organic EL displays.

關於使用低分子材料之真空蒸鍍法，材料之使用效率極低，若大型化，則陰影遮罩之撓曲變大，難以對大型基板進行均勻之蒸鍍。又，亦存在製作成本亦增高等問題。Regarding the vacuum evaporation method using low-molecular materials, the efficiency of material use is extremely low. If the size is increased, the deflection of the shadow mask becomes larger, making it difficult to evaporate uniformly on large substrates. In addition, there are also problems such as increased production costs.

另一方面，藉由塗佈使高分子材料溶解於有機溶劑而成之溶液，於大型基板上亦能夠形成均勻之膜，由此可使用以噴墨法或印刷法為代表之塗佈法。因此，能夠提高材料之使用效率，並能夠大幅削減元件製作所需之製作成本。On the other hand, a uniform film can be formed on a large substrate by coating a solution in which a polymer material is dissolved in an organic solvent. Therefore, a coating method such as an inkjet method or a printing method can be used. Therefore, the efficiency of material use can be improved, and the manufacturing cost required for component manufacturing can be significantly reduced.

迄今為止，對使用高分子材料之有機EL元件進行了各種研究，但存在發光效率或壽命等元件特性未必充分之問題(例如參照專利文獻1～專利文獻5)。Various studies have been conducted on organic EL devices using polymer materials, but there is a problem that device characteristics such as luminous efficiency and lifetime are not necessarily sufficient (see, for example, Patent Documents 1 to 5).

又，迄今為止，作為使用高分子材料之有機EL元件中之代表性之電洞傳輸材料，已知有稱為TFB(1,2,4,5-Tetrakis(trifluoromethyl)benzene，1,2,4,5-四(三氟甲基)苯)之茀聚合物(參照專利文獻6～專利文獻7)。然而，TFB之電洞傳輸性不充分，且電子阻擋性亦不充分，因此存在一部分電子穿過發光層，從而無法期待發光效率提昇之問題。又，與相鄰層之膜密接性低，因此存在亦無法期待元件之長壽化之問題。 [先前技術文獻] [專利文獻] Furthermore, as a representative hole transport material in organic EL devices using polymer materials, TFB (1,2,4,5-Tetrakis(trifluoromethyl)benzene, 1,2,4) has been known so far. , 5-tetrakis(trifluoromethyl)benzene) fluorine polymer (see Patent Documents 6 to 7). However, TFB has insufficient hole transport properties and insufficient electron blocking properties. Therefore, there is a problem that some electrons pass through the light-emitting layer, and thus the luminous efficiency cannot be expected to be improved. In addition, there is a problem in that the film adhesion to the adjacent layer is low, and therefore the longevity of the device cannot be expected. [Prior technical literature] [Patent Document]

[專利文獻1]日本專利特開2005-272834號公報 [專利文獻2]日本專利特開2007-119763號公報 [專利文獻3]日本專利特開2007-162009號公報 [專利文獻4]日本專利特開2007-177225號公報 [專利文獻5]國際公開第2005/049546號 [專利文獻6]日本專利第4375820號公報 [專利文獻7]國際公開第2005/059951號 [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-272834 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-119763 [Patent Document 3] Japanese Patent Application Publication No. 2007-162009 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-177225 [Patent Document 5] International Publication No. 2005/049546 [Patent Document 6] Japanese Patent No. 4375820 [Patent Document 7] International Publication No. 2005/059951

(發明所欲解決之問題)(The problem that the invention wants to solve)

本發明之目的在於提供一種高分子材料，該高分子材料於電洞之注入、傳輸性能方面優異，具有電子阻擋能力，且於薄膜狀態下之穩定性較高。進而，本發明之目的在於提供一種有機EL元件，該有機EL元件具有由上述高分子材料所形成之有機層(薄膜)，且發光效率高，壽命較長。 (解決問題之技術手段) The object of the present invention is to provide a polymer material that is excellent in hole injection and transport properties, has electron blocking ability, and has high stability in a thin film state. Furthermore, an object of the present invention is to provide an organic EL element that has an organic layer (thin film) formed of the above-mentioned polymer material and has high luminous efficiency and long life. (Technical means to solve problems)

本發明人等注意到於分子主鏈包含具有茀環之三芳基胺構造單位之高分子量化合物具有較高之電洞注入、傳輸能力，進而亦可期待寬能隙化這一情況，而合成了包含各種三芳基胺構造單位之高分子量化合物並進行了研究，結果完成了本發明。The present inventors noticed that a high molecular weight compound containing a triarylamine structural unit with a fluorine ring in the main chain of the molecule has high hole injection and transport capabilities, and can also expect wide energy gaps, and synthesized High molecular weight compounds containing various triarylamine structural units were studied, and as a result, the present invention was completed.

即，本發明如下所述。That is, the present invention is as follows.

[1]一種高分子量化合物，其包含下述通式(1)所表示之重複單位A、及下述通式(2)所表示之重複單位B，並且以聚苯乙烯換算，具有10,000以上且未滿1,000,000之重量平均分子量。[1] A high molecular weight compound containing a repeating unit A represented by the following general formula (1) and a repeating unit B represented by the following general formula (2), and having a polystyrene equivalent of 10,000 or more and The weight average molecular weight is less than 1,000,000.

[化1] [Chemical 1]

[化2] 式中， R 1及R 3分別獨立地表示氫原子、氘原子、氰基、硝基、鹵素原子、或碳數40以下之烷基、烷氧基、環烷基、環烷氧基、烯基、或芳氧基。 a、b及c為以下之整數。 a＝0、1、2或3 b＝0、1、2、3或4 c＝0或1 R 2分別獨立地表示碳數3～40之烷基、烷氧基、或環烷基。 L表示伸苯基，n表示0～3之整數。 X分別獨立地表示氫原子、胺基、一價芳基、或一價雜芳基。 Y為氧原子(O)、硫原子(S)、或下述式(3)所示之基。 [Chemicalization 2] In the formula, R 1 and R 3 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, or an alkyl group with less than 40 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, or an alkene group. group, or aryloxy group. a, b and c are the following integers. a=0, 1, 2 or 3 b=0, 1, 2, 3 or 4 c=0 or 1 R 2 each independently represents an alkyl group, alkoxy group or cycloalkyl group having 3 to 40 carbon atoms. L represents a phenylene group, and n represents an integer of 0 to 3. X each independently represents a hydrogen atom, an amine group, a monovalent aryl group, or a monovalent heteroaryl group. Y is an oxygen atom (O), a sulfur atom (S), or a group represented by the following formula (3).

[化3] 式中之R 4表示經取代或未經取代之芳基、或者經取代或未經取代之烷基。 [Chemical 3] R 4 in the formula represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.

[2]如[1]之高分子量化合物，其中，於上述通式(1)及(2)中，R 1及R 3為氫原子。 [2] The high molecular weight compound of [1], wherein in the above general formulas (1) and (2), R 1 and R 3 are hydrogen atoms.

[3]如[1]或[2]所記載之高分子量化合物，其中，於上述通式(1)中，R 2為碳數3～40之烷基。 [3] The high molecular weight compound according to [1] or [2], wherein in the general formula (1), R 2 is an alkyl group having 3 to 40 carbon atoms.

[4]如[1]或[2]所記載之高分子量化合物，其中，於上述通式(1)及(2)中，X為二苯基胺基、苯基、萘基、二苯并呋喃基、二苯并噻吩基、菲基、茀基、咔唑基、茚并咔唑基、或吖啶基。[4] The high molecular weight compound as described in [1] or [2], wherein in the above general formulas (1) and (2), X is diphenylamino group, phenyl group, naphthyl group, dibenzo Furyl, dibenzothienyl, phenanthrenyl, fenyl, carbazolyl, indenocarbazolyl, or acridinyl.

[5]如[1]或[2]所記載之高分子量化合物，其包含下述通式(4)所表示之具有熱交聯性構造單位Q之重複單位。[5] The high molecular weight compound according to [1] or [2], which contains a repeating unit having a thermally crosslinkable structural unit Q represented by the following general formula (4).

[化4] 式中， R 3、X及a均與通式(1)中所示者定義相同。 [Chemical 4] In the formula, R 3 , X and a have the same definitions as those shown in the general formula (1).

[6]如[5]所記載之高分子量化合物，其中，於上述通式(4)中，熱交聯性構造單位Q為下述通式(5a)～(5af)所示之構造。[6] The high molecular weight compound according to [5], wherein in the general formula (4), the thermally crosslinkable structural unit Q has a structure represented by the following general formulas (5a) to (5af).

[化5] [Chemistry 5]

[化6] [Chemical 6]

上述通式(5a)～(5af)中之R 1、R 2、a及b均與通式(1)中所示者定義相同。 R 1 , R 2 , a and b in the above general formulas (5a) to (5af) are all defined the same as those shown in the general formula (1).

[7]一種有機電致發光元件，其具有一對電極及夾持於其間之有機層，其中，上述有機層使用[1]或[2]所記載之高分子量化合物作為構成材料。[7] An organic electroluminescent element having a pair of electrodes and an organic layer sandwiched therebetween, wherein the organic layer uses the high molecular weight compound described in [1] or [2] as a constituent material.

[8]如[7]所記載之有機電致發光元件，其中，上述有機層為電洞傳輸層。[8] The organic electroluminescent device according to [7], wherein the organic layer is a hole transport layer.

[9]如[7]所記載之有機電致發光元件，其中，上述有機層為電子阻擋層。[9] The organic electroluminescent device according to [7], wherein the organic layer is an electron blocking layer.

[10]如[7]所記載之有機電致發光元件，其中，上述有機層為電洞注入層。[10] The organic electroluminescent device according to [7], wherein the organic layer is a hole injection layer.

[11]如[7]所記載之有機電致發光元件，其中，上述有機層為發光層。 (對照先前技術之功效) [11] The organic electroluminescent element according to [7], wherein the organic layer is a light-emitting layer. (Compare the effectiveness of previous technologies)

上述之本發明之高分子量化合物具有如下特性： (1)電洞之注入特性良好， (2)電洞之移動度較大， (3)寬能隙，於電子阻擋能力方面優異。 The above-mentioned high molecular weight compound of the present invention has the following characteristics: (1) The hole injection characteristics are good, (2) The mobility of electric holes is large, (3) Wide energy gap, excellent in electron blocking ability.

由此種高分子量化合物所形成之有機層適合用作電洞傳輸層、電子阻擋層、電洞注入層或發光層，使用上述有機層之有機EL元件具有如下優點： (1)發光效率及電效率較高， (2)實用驅動電壓較低， (3)壽命較長。 The organic layer formed from such a high molecular weight compound is suitable for use as a hole transport layer, an electron blocking layer, a hole injection layer or a light emitting layer. Organic EL devices using the above organic layer have the following advantages: (1) The luminous efficiency and electrical efficiency are high, (2) The practical driving voltage is low, (3) Longer life.

即，本發明之高分子量化合物由於電洞傳輸能力高、電子阻擋能力優異，故作為塗佈型有機EL元件用化合物較優異。藉由使用該化合物製作塗佈型有機EL元件，可獲得較高之發光效率及電效率，並且可改善耐久性。That is, the high molecular weight compound of the present invention has high hole transporting ability and excellent electron blocking ability, and therefore is excellent as a compound for coating-type organic EL elements. By using this compound to produce coating-type organic EL elements, higher luminous efficiency and electrical efficiency can be obtained, and durability can be improved.

＜重複單位A及重複單位B＞ 本發明之高分子量化合物包含下述通式(1)所表示之重複單位A、及下述通式(2)所表示之重複單位B。 ＜Repeating unit A and repeating unit B＞ The high molecular weight compound of the present invention contains repeating unit A represented by the following general formula (1) and repeating unit B represented by the following general formula (2).

[化7] [Chemical 7]

[化8] 式中， R 1及R 3分別獨立地表示氫原子、氘原子、氰基、硝基、鹵素原子、或碳數40以下之烷基、烷氧基、環烷基、環烷氧基、烯基、或芳氧基。 a、b及c為以下之整數。 a＝0、1、2或3 b＝0、1、2、3或4 c＝0或1 R 2分別獨立地表示碳數3～40之烷基、烷氧基、或環烷基。 L表示伸苯基，n表示0～3之整數。 X分別獨立地表示氫原子、胺基、一價芳基、或一價雜芳基。 Y為氧原子(O)、硫原子(S)、或下述式(3)所示之基。 [Chemical 8] In the formula, R 1 and R 3 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, or an alkyl group with less than 40 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, or an alkene group. group, or aryloxy group. a, b and c are the following integers. a=0, 1, 2 or 3 b=0, 1, 2, 3 or 4 c=0 or 1 R 2 each independently represents an alkyl group, alkoxy group or cycloalkyl group having 3 to 40 carbon atoms. L represents a phenylene group, and n represents an integer of 0 to 3. X each independently represents a hydrogen atom, an amine group, a monovalent aryl group, or a monovalent heteroaryl group. Y is an oxygen atom (O), a sulfur atom (S), or a group represented by the following formula (3).

[化9] 式中之R 4表示經取代或未經取代之芳基、或者經取代或未經取代之烷基。 [Chemical 9] R 4 in the formula represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.

作為上述通式(1)及(2)中之R 1及R 3所表示之鹵素原子，可例舉氟原子、氯原子、溴原子及碘原子等。 作為上述R 1及R 3所表示之碳數40以下之烷基、烷氧基、環烷基、環烷氧基、烯基、及芳氧基，分別較佳為碳數1～8之烷基、碳數1～8之烷氧基、碳數5～10之環烷基、碳數5～10之環烷氧基、碳數2～6之烯基、及碳數6～10之芳氧基。 Examples of the halogen atom represented by R 1 and R 3 in the general formulas (1) and (2) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. As the alkyl group having 40 or less carbon atoms, alkoxy group, cycloalkyl group, cycloalkoxy group, alkenyl group, and aryloxy group represented by R 1 and R 3 , each is preferably an alkyl group having 1 to 8 carbon atoms. group, alkoxy group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, cycloalkoxy group having 5 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and aromatic group having 6 to 10 carbon atoms. Oxygen group.

作為上述烷基、烷氧基、環烷基、環烷氧基、烯基、及芳氧基，可例示以下之基。 烷基(碳數1～8)：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、正己基、異己基、新己基、正庚基、異庚基、新庚基、正辛基、異辛基、新辛基等。 烷氧基(碳數1～8)：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基等。 環烷基(碳數5～10)：環戊基、環己基、1-金剛烷基、2-金剛烷基等。 環烷氧基(碳數5～10)：環戊氧基、環己氧基、環庚氧基、環辛氧基、1-金剛烷氧基、2-金剛烷氧基等。 烯基(碳數2～6)：乙烯基、烯丙基、異丙烯基、2-丁烯基等。 芳氧基(碳數6～10)：苯氧基、甲苯氧基等。 Examples of the alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, alkenyl group, and aryloxy group include the following groups. Alkyl group (carbon number 1 to 8): methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl Base, isohexyl, neohexyl, n-heptyl, isoheptyl, neoheptyl, n-octyl, isooctyl, neooctyl, etc. Alkoxy (carbon number 1 to 8): methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n- Heptyloxy, n-octyloxy, etc. Cycloalkyl group (carbon number 5 to 10): cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, etc. Cycloalkoxy group (carbon number 5 to 10): cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, etc. Alkenyl group (carbon number 2 to 6): vinyl, allyl, isopropenyl, 2-butenyl, etc. Aryloxy group (carbon number 6 to 10): phenoxy group, tolyloxy group, etc.

關於本發明之高分子量化合物，為便於合成，上述通式(1)中之R 3與上述通式(2)中之R 3較佳為相同之基。 又，上述通式(1)及(2)中之R 1及R 3較佳為全部為氫原子。 Regarding the high molecular weight compound of the present invention, in order to facilitate synthesis, R 3 in the above general formula (1) and R 3 in the above general formula (2) are preferably the same group. Moreover, it is preferable that R 1 and R 3 in the above general formulas (1) and (2) are all hydrogen atoms.

作為上述通式(1)中之R 2所表示之碳數3～40之烷基、烷氧基、及環烷基之例，可例舉與上述基相同之基。 Examples of the alkyl group, alkoxy group and cycloalkyl group having 3 to 40 carbon atoms represented by R 2 in the general formula (1) include the same groups as the above groups.

關於本發明之高分子量化合物，為提高溶解性，R 2較佳為碳數3～40之烷基，更佳為碳數3～10之烷基，最佳為正己基或正辛基。 Regarding the high molecular weight compound of the present invention, in order to improve solubility, R 2 is preferably an alkyl group with 3 to 40 carbon atoms, more preferably an alkyl group with 3 to 10 carbon atoms, and most preferably is n-hexyl or n-octyl.

作為上述通式(1)及(2)中之X所表示之一價芳基、及一價雜芳基，可例示以下之基。 芳基：苯基、萘基、蒽基、菲基、茀基、茚基、芘基、苝基、丙二烯合茀基等。 雜芳基：吡啶基、嘧啶基、三嗪基、呋喃基、吡咯基、噻吩基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、茚并咔唑基、苯并 唑基、苯并噻唑基、喹 啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、 啶基、啡啉基、吖啶基、咔啉基等。 Examples of the monovalent aryl group and the monovalent heteroaryl group represented by X in the general formulas (1) and (2) include the following groups. Aryl group: phenyl, naphthyl, anthracenyl, phenanthrenyl, benzoyl, indenyl, pyrenyl, perylene, allenyl, etc. Heteroaryl: pyridyl, pyrimidinyl, triazinyl, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, Indenocarbazolyl, benzo Azolyl, benzothiazolyl, quinine Phenyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, Aldinyl, phenanthrolinyl, acridinyl, carbolinyl, etc.

又，上述胺基、芳基及雜芳基可具有取代基。作為取代基，除氘原子、氰基、硝基等以外，還可例舉以下之基。 鹵素原子，例如氟原子、氯原子、溴原子、碘原子； 烷基，尤其是碳數1～8者，例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、正己基、異己基、新己基、正庚基、異庚基、新庚基、正辛基、異辛基、新辛基； 烷氧基，尤其是碳數1～8者，例如甲氧基、乙氧基、丙氧基； 烯基，例如乙烯基、烯丙基； 芳氧基，例如苯氧基、甲苯氧基； 芳基，例如苯基、聯苯基、聯三苯基、萘基、蒽基、菲基、茀基、茚基、芘基、苝基、丙二烯合茀基、聯伸三苯基(triphenylenyl)； 雜芳基，例如吡啶基、嘧啶基、三嗪基、噻吩基、呋喃基、吡咯基、喹啉基、異喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、茚并咔唑基、苯并 唑基、苯并噻唑基、喹 啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、咔啉基； 芳基乙烯基，例如苯乙烯基、萘乙烯基； 醯基，例如乙醯基、苯甲醯基。 Moreover, the above-mentioned amino group, aryl group and heteroaryl group may have a substituent. As a substituent, in addition to a deuterium atom, a cyano group, a nitro group, etc., the following groups can also be mentioned. Halogen atoms, such as fluorine atom, chlorine atom, bromine atom, iodine atom; Alkyl group, especially those with 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, neoheptyl, n-octyl, isooctyl, neooctyl ; Alkoxy group, especially those with 1 to 8 carbon atoms, such as methoxy, ethoxy, propoxy; Alkenyl, such as vinyl, allyl; Aryloxy, such as phenoxy, tolyloxy ; Aryl groups, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, benzyl, indenyl, pyrenyl, perylene, allenyl, biphenyl, triphenyl ( triphenylenyl); heteroaryl, such as pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, indenocarbazolyl, benzo Azolyl, benzothiazolyl, quinine Phylyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carbolinyl; Arylvinyl, such as styryl, naphthylvinyl; Cylyl, such as acetyl, Benzoyl.

又，該等取代基可進一步具有上述所例示之取代基。 進而，該等取代基較佳為分別獨立存在，但該等取代基彼此亦可經由單鍵、可具有取代基之亞甲基、氧原子或硫原子相互鍵結而形成環。 Moreover, these substituents may further have the substituents illustrated above. Furthermore, these substituents preferably exist independently, but these substituents may be bonded to each other through a single bond, an optionally substituted methylene group, an oxygen atom or a sulfur atom to form a ring.

例如，上述芳基或雜芳基可具有苯基作為取代基，該苯基可進一步具有苯基作為取代基。即，以芳基為例，該芳基可為聯苯基、聯三苯基、聯伸三苯基。For example, the above-mentioned aryl group or heteroaryl group may have a phenyl group as a substituent, and the phenyl group may further have a phenyl group as a substituent. That is, taking an aryl group as an example, the aryl group may be a biphenyl group, a biphenyl group, or a biphenyl group.

關於本發明之高分子量化合物，為便於合成，較佳為上述通式(1)中之X與上述通式(2)中之X為相同之基，更佳為X全部為氫原子。Regarding the high molecular weight compound of the present invention, in order to facilitate synthesis, it is preferable that X in the above general formula (1) and X in the above general formula (2) be the same group, and more preferably all X are hydrogen atoms.

上述通式(1)中之L所表示之伸苯基可具有取代基。作為取代基，可例舉與上述X可具有之取代基相同之基，該等取代基可進一步具有取代基。The phenylene group represented by L in the above general formula (1) may have a substituent. Examples of the substituent include the same substituents as the substituents that the above-mentioned X may have, and these substituents may further have substituents.

上述通式(1)中之n表示L之數量。關於本發明之高分子量化合物，就電洞之注入、傳輸性能、電子阻擋能力及薄膜穩定性之方面而言，較佳為n為0或1。n in the above general formula (1) represents the number of L. Regarding the high molecular weight compound of the present invention, in terms of hole injection, transport performance, electron blocking ability and film stability, n is preferably 0 or 1.

於上述通式(2)中，Y為氧原子(O)、硫原子(S)、或下述式(3)所示之基。In the above general formula (2), Y is an oxygen atom (O), a sulfur atom (S), or a group represented by the following formula (3).

[化10] 式中之R 4表示經取代或未經取代之芳基、或者經取代或未經取代之烷基。 [Chemical 10] R 4 in the formula represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.

作為上述R 4所表示之烷基之例，可例舉與上述基相同之基。又，作為芳基之例，可例舉與上述基相同之基。 Examples of the alkyl group represented by the above-mentioned R 4 include the same groups as the above-mentioned groups. Examples of the aryl group include the same groups as the above-mentioned groups.

關於本發明之高分子量化合物，就電洞之注入、傳輸性能、電子阻擋能力及薄膜穩定性之方面而言，Y較佳為氧原子(O)。Regarding the high molecular weight compound of the present invention, Y is preferably an oxygen atom (O) in terms of hole injection, transport performance, electron blocking ability and film stability.

於本發明中，將上述通式(1)所表示之重複單位A之具體例於圖1至圖5中示為重複單位1-1～1-28。又，將上述通式(2)所表示之重複單位B之具體例於圖6至圖17中示為重複單位2-1～2-68。再者，於圖1至圖17所示之化學構造中，虛線表示與相鄰之重複單位之鍵結鍵，自環延伸之末端為自由之實線表示其自由末端為甲基。作為重複單位，表示較佳之具體例，但本發明中使用之重複單位並不限於該等示例。In the present invention, specific examples of the repeating unit A represented by the general formula (1) are shown in Figures 1 to 5 as repeating units 1-1 to 1-28. In addition, specific examples of the repeating unit B represented by the above general formula (2) are shown as repeating units 2-1 to 2-68 in FIGS. 6 to 17 . Furthermore, in the chemical structures shown in Figures 1 to 17, the dotted lines represent the bonds with adjacent repeating units, and the free solid lines extending from the ring end represent the free end of the methyl group. As the repeating unit, preferred specific examples are shown, but the repeating unit used in the present invention is not limited to these examples.

又，於本發明中，將上述之通式(1)、通式(2)及通式(4)中之X之具體例於圖18及圖19中示為取代基1～48。再者，於圖18及圖19所示之化學式中，波浪線表示鍵結部位。作為取代基，表示較佳之具體例，但本發明中所使用之X並不限於該等示例。Furthermore, in the present invention, specific examples of X in the above-mentioned general formula (1), general formula (2) and general formula (4) are shown as substituents 1 to 48 in FIGS. 18 and 19 . Furthermore, in the chemical formulas shown in Figures 18 and 19, wavy lines represent bonding sites. As the substituent, preferred specific examples are shown, but X used in the present invention is not limited to these examples.

＜高分子量化合物＞ 關於包含上述通式(1)及通式(2)所表示之重複單位之本發明之高分子量化合物，就進一步提高電洞之注入特性、電洞之移動度、電子阻擋能力、薄膜穩定性、耐熱性等特性，且確保成膜性之觀點而言，藉由GPC(Gel Permeation Chromatography，凝膠滲透層析法)測得之以聚苯乙烯換算之重量平均分子量較佳為10,000以上且未滿1,000,000，更佳為10,000以上且未滿500,000，進而較佳為在10,000以上且未滿300,000之範圍。 ＜High molecular weight compounds＞ The high molecular weight compound of the present invention containing the repeating unit represented by the above general formula (1) and general formula (2) further improves hole injection characteristics, hole mobility, electron blocking ability, film stability, From the viewpoint of ensuring properties such as heat resistance and film-forming properties, the weight average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography) is preferably 10,000 or more and less than 10,000. 1,000,000, more preferably 10,000 or more and less than 500,000, further preferably 10,000 or more and less than 300,000.

為提高熱交聯性，本發明之高分子量化合物較佳為包含下述通式(4)所表示之具有熱交聯性構造單位Q之重複單位。In order to improve the thermal crosslinkability, the high molecular weight compound of the present invention preferably contains a repeating unit having a thermally crosslinkable structural unit Q represented by the following general formula (4).

[化11] 式中， R 3、X及a均與通式(1)中所示者定義相同。 [Chemical 11] In the formula, R 3 , X and a have the same definitions as those shown in the general formula (1).

關於本發明之高分子量化合物，為便於合成，上述通式(4)中之R 3較佳為與上述通式(1)及(2)中之R 3相同之基，又，上述通式(4)中之X較佳為與上述通式(1)及(2)中之X相同之基。 Regarding the high molecular weight compound of the present invention, in order to facilitate synthesis, R 3 in the above general formula (4) is preferably the same group as R 3 in the above general formulas (1) and (2), and the above general formula ( X in 4) is preferably the same group as X in the above general formulas (1) and (2).

作為熱交聯性構造單位Q之具體例，可例舉下述通式(5a)～(5af)所示之構造。Specific examples of the thermally crosslinkable structural unit Q include structures represented by the following general formulas (5a) to (5af).

[化12] [Chemical 12]

[化13] [Chemical 13]

上述通式(5a)～(5af)中之R 1、R 2、a及b均與通式(1)中所示者定義相同。 R 1 , R 2 , a and b in the above general formulas (5a) to (5af) are all defined the same as those shown in the general formula (1).

再者，於上述式(5a)～(5af)中，虛線表示與相鄰之構造單位之鍵結鍵，自環延伸之末端為自由之實線表示其末端為甲基。In addition, in the above-mentioned formulas (5a) to (5af), the dotted line represents the bond with the adjacent structural unit, and the free solid line extending from the end of the ring represents the end of the methyl group.

本發明之高分子量化合物較佳為包含1莫耳%以上、尤其是30莫耳%以上之重複單位A，於以此種量包含重複單位A之條件下，以1莫耳%以上、尤其是10～60莫耳%之量包含重複單位B，進而，以Q表示通式(4)所表示之重複單位時，較佳為以1莫耳%以上、尤其是10～20莫耳%之量包含重複單位Q，以滿足上述條件之方式包含重複單位A、B及Q對於形成有機EL元件之有機層而言最佳。The high molecular weight compound of the present invention preferably contains 1 mol% or more, especially 30 mol% or more of the repeating unit A. Under the condition that the repeating unit A is included in this amount, it is preferably 1 mol% or more, especially 30 mol% or more. The amount of 10 to 60 mol% includes the repeating unit B. Furthermore, when Q represents the repeating unit represented by the general formula (4), the amount is preferably 1 mol% or more, especially 10 to 20 mol%. Including the repeating unit Q, including the repeating units A, B and Q in a manner that satisfies the above conditions is optimal for forming the organic layer of the organic EL device.

本發明之高分子量化合物係藉由利用鈴木聚合反應或哈特維希-布赫瓦爾德(HARTWIG-BUCHWALD)聚合反應分別形成C-C鍵或C-N鍵而使各構造單位形成連鎖從而合成。即，準備具有各構造單位之單位化合物，將該單位化合物適當硼酸酯化或鹵化，並使用適當之觸媒進行縮聚反應，藉此可合成本發明之高分子量化合物。The high molecular weight compound of the present invention is synthesized by forming C-C bonds or C-N bonds respectively using Suzuki polymerization or HARTWIG-BUCHWALD polymerization to link each structural unit. That is, the high molecular weight compound of the present invention can be synthesized by preparing a unit compound having each structural unit, suitably borating or halogenating the unit compound, and performing a polycondensation reaction using an appropriate catalyst.

例如，包含60莫耳%之重複單位A、30莫耳%之重複單位B、10莫耳%之重複單位Q之高分子量化合物為下述通式(5)所表示者。For example, a high molecular weight compound containing 60 mol% of repeating unit A, 30 mol% of repeating unit B, and 10 mol% of repeating unit Q is represented by the following general formula (5).

[化14] [Chemical 14]

將本發明之高分子量化合物溶解於苯、甲苯、二甲苯、大茴香醚等芳香族系有機溶劑中而製備塗佈液，將該塗佈液塗佈於指定之基材上並加熱乾燥，藉此能夠形成於電洞注入性、電洞傳輸性、電子阻擋性等特性方面優異之薄膜。所得之薄膜之耐熱性亦良好，進而與其他層之密接性亦良好。The high molecular weight compound of the present invention is dissolved in an aromatic organic solvent such as benzene, toluene, xylene, and anisole to prepare a coating liquid. The coating liquid is coated on a designated substrate and heated and dried. This can form a thin film with excellent characteristics such as hole injection properties, hole transport properties, and electron blocking properties. The resulting film also has good heat resistance and good adhesion to other layers.

本發明之高分子量化合物可用作有機EL元件之電洞注入層及/或電洞傳輸層之構成材料。由本發明之高分子量化合物所形成之電洞注入層及電洞傳輸層與由習知之材料所形成者相比，電洞之注入性較高，移動度較大，電子阻擋性較高，可將發光層內生成之激子封閉，進而能夠提昇電洞與電子再結合之概率，從而獲得高發光效率，並且能夠實現驅動電壓下降、有機EL元件之耐久性提昇之優點。The high molecular weight compound of the present invention can be used as a constituent material of the hole injection layer and/or the hole transport layer of the organic EL device. Compared with those formed of conventional materials, the hole injection layer and the hole transport layer formed by the high molecular weight compound of the present invention have higher hole injection properties, greater mobility, and higher electron blocking properties, and can The excitons generated in the light-emitting layer are sealed, thereby increasing the probability of recombination of holes and electrons, thereby obtaining high luminous efficiency, and achieving the advantages of reduced driving voltage and improved durability of organic EL elements.

又，與習知之材料相比，具有如上所述之電特性之本發明之高分子量化合物為寬能隙，可有效封閉激子，因此當然亦可適合用於電子阻擋層或發光層。In addition, compared with conventional materials, the high molecular weight compound of the present invention has the above-mentioned electrical characteristics and has a wide energy gap, which can effectively block excitons. Therefore, it is of course also suitable for use in an electron blocking layer or a light-emitting layer.

＜有機EL元件＞ 具備使用上述本發明之高分子量化合物而形成之有機層的有機EL元件例如具有圖20所示之構造。即，於玻璃基板1(可為透明樹脂基板等其他透明基板)上設置有透明陽極2、電洞注入層3、電洞傳輸層4、電子阻擋層5、發光層6、電子傳輸層7及陰極8。 ＜Organic EL element＞ An organic EL element having an organic layer formed using the high molecular weight compound of the present invention has, for example, a structure shown in FIG. 20 . That is, a transparent anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, an electron transport layer 7 and Cathode 8.

當然，應用本發明之高分子量化合物之有機EL元件並不限於上述之層構造，可於發光層6與電子傳輸層7之間設置電洞阻擋層，進而，亦可於陰極8與電子傳輸層7之間設置電子注入層。進而，亦可省略若干層。例如，亦可設為於基板1上設置有陽極2、電洞傳輸層4、發光層6、電子傳輸層7及陰極8之簡易之層構造。又，亦可設為將具有相同功能之層重疊而成之2層構造。Of course, the organic EL device using the high molecular weight compound of the present invention is not limited to the above-mentioned layer structure. A hole blocking layer can be provided between the light-emitting layer 6 and the electron transport layer 7. Furthermore, a hole blocking layer can also be provided between the cathode 8 and the electron transport layer. An electron injection layer is set between 7. Furthermore, some layers may be omitted. For example, a simple layer structure in which the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 7 and the cathode 8 are provided on the substrate 1 can also be used. Furthermore, it may be a two-layer structure in which layers having the same functions are overlapped.

本發明之高分子量化合物充分利用其電洞注入性或電洞傳輸性等特性，而適宜用作上述設置於陽極2與陰極8之間之有機層(例如電洞注入層3、電洞傳輸層4、電子阻擋層5或發光層6)之形成材料。The high molecular weight compound of the present invention makes full use of its hole injection or hole transport properties, and is suitable for use as the above-mentioned organic layer (such as the hole injection layer 3, the hole transport layer) disposed between the anode 2 and the cathode 8 4. Materials for forming the electron blocking layer 5 or the light-emitting layer 6).

於上述有機EL元件中，透明陽極2可由本身公知之電極材料形成，藉由於基板1(玻璃基板等透明基板)上蒸鍍如ITO(Indium Tin Oxides，氧化銦錫)或金之類之工作函數較大之電極材料而形成。In the above-mentioned organic EL element, the transparent anode 2 can be formed of a well-known electrode material, by evaporating a working function such as ITO (Indium Tin Oxides, indium tin oxide) or gold on the substrate 1 (a transparent substrate such as a glass substrate). formed from larger electrode materials.

又，設置於透明陽極2上之電洞注入層3可使用將本發明之高分子量化合物溶解於例如甲苯、二甲苯、大茴香醚等芳香族系有機溶劑而成之塗佈液而形成。即，將該塗佈液藉由旋轉塗佈、噴墨等塗佈於透明陽極2上，藉此可形成電洞注入層3。In addition, the hole injection layer 3 provided on the transparent anode 2 can be formed using a coating liquid in which the high molecular weight compound of the present invention is dissolved in an aromatic organic solvent such as toluene, xylene, and anisole. That is, the coating liquid is applied on the transparent anode 2 by spin coating, inkjet, or the like, thereby forming the hole injection layer 3 .

又，於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，上述電洞注入層3亦可不使用本發明之高分子量化合物，而使用習知公知之材料、例如以下材料來形成。 以酞菁銅為代表之卟啉化合物； 星射型三苯胺衍生物； 具有以單鍵或不含雜原子之二價基連結而成之構造之芳胺(例如三苯胺三聚體及四聚體)； 如六氰基氮雜聯三伸苯之類之受體性雜環化合物； 塗佈型高分子材料，例如聚(3,4-乙二氧基噻吩)(PEDOT，poly(3,4-ethylene dioxythiophene))、聚(苯乙烯磺酸鹽)(PSS，poly(styrene sulfonate))等。 Furthermore, in an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, the hole injection layer 3 may not use the high molecular weight compound of the present invention, but may use conventionally known materials, such as the following materials. form. Porphyrin compounds represented by copper phthalocyanine; Star-rayed triphenylamine derivatives; Aromatic amines with a structure linked by single bonds or divalent groups without heteroatoms (such as triphenylamine trimers and tetramers); Receptive heterocyclic compounds such as hexacyanoazabiterphenylene; Coated polymer materials, such as poly(3,4-ethylenedioxythiophene) (PEDOT, poly(3,4-ethylene dioxythiophene)), poly(styrene sulfonate) (PSS, poly(styrene sulfonate) )wait.

使用此種材料之層(薄膜)之形成可藉由利用蒸鍍法、旋轉塗佈法或噴墨法等之塗佈而成膜。對於其他層亦同樣，根據成膜材料之種類，可利用蒸鍍法或塗佈法進行成膜。A layer (thin film) using such a material can be formed by coating using a vapor deposition method, a spin coating method, an inkjet method, or the like. The same applies to other layers. Depending on the type of film-forming material, the film can be formed by evaporation or coating.

設置於上述電洞注入層3上之電洞傳輸層4亦與電洞注入層3同樣，可使用本發明之高分子量化合物並藉由利用旋轉塗佈或噴墨等之塗佈來形成。The hole transport layer 4 provided on the above-mentioned hole injection layer 3 can also be formed by spin coating or inkjet coating using the high molecular weight compound of the present invention, similarly to the hole injection layer 3 .

又，於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，亦可使用習知公知之電洞傳輸材料來形成電洞傳輸層4。作為此種電洞傳輸材料，具有代表性者如下。 聯苯胺衍生物，例如：N,N'-二苯基-N,N'-二(間甲苯基)聯苯胺(以下簡稱為TPD)；N,N'-二苯基-N,N'-二(α-萘基)聯苯胺(以下簡稱為NPD)；N,N,N',N'-四聯苯基聯苯胺。 胺系衍生物，例如1,1-雙[4-(二-4-甲苯胺基)苯基]環己烷(以下簡稱為TAPC)。 各種三苯胺三聚體及四聚體。 可用於電洞注入層之塗佈型高分子材料。 In addition, in an organic EL element having an organic layer formed using the high molecular weight compound of the present invention, a conventionally known hole transport material can also be used to form the hole transport layer 4 . Representative examples of such hole transport materials are as follows. Benzidine derivatives, such as: N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (hereinafter referred to as TPD); N,N'-diphenyl-N,N'- Bis(α-naphthyl)benzidine (hereinafter referred to as NPD); N,N,N',N'-tetradiphenylbenzidine. Amine derivatives, such as 1,1-bis[4-(di-4-toluidino)phenyl]cyclohexane (hereinafter referred to as TAPC). Various triphenylamine trimers and tetramers. Coated polymer material that can be used in the hole injection layer.

上述之電洞傳輸層之化合物，包含本發明之高分子量化合物在內，可分別單獨成膜，亦可混合2種以上而成膜。又，亦可使用上述化合物中之1種或數種來形成數個層，將積層有此種層之多層膜作為電洞傳輸層。The above-mentioned compounds of the hole transport layer, including the high molecular weight compound of the present invention, can be formed into a film individually, or two or more types can be mixed to form a film. Alternatively, one or more of the above compounds may be used to form a plurality of layers, and a multilayer film in which such layers are laminated may be used as a hole transport layer.

又，於圖20所示之具備使用本發明之高分子量化合物而形成之有機層的有機EL元件中，亦可設為兼具電洞注入層3與電洞傳輸層4之層，此種電洞注入、傳輸層可使用PEDOT等高分子材料並藉由塗佈而形成。Furthermore, in the organic EL device shown in FIG. 20 that has an organic layer formed using the high molecular weight compound of the present invention, a layer having both the hole injection layer 3 and the hole transport layer 4 can also be used. Hole injection and transmission layers can be formed by coating using polymer materials such as PEDOT.

再者，於電洞傳輸層4(電洞注入層3亦同樣)中，可使用於該層所通常使用之材料中P摻雜有三溴苯基胺六氯銻或軸烯衍生物(例如參照WO2014/009310)等者。又，可使用具有TPD基本骨架之高分子化合物等來形成電洞傳輸層4(或電洞注入層3)。Furthermore, in the hole transport layer 4 (the same applies to the hole injection layer 3), the material commonly used in this layer may be P-doped with tribromophenylamine hexachloroantimony or an axene derivative (for example, refer to WO2014/009310) and others. In addition, the hole transport layer 4 (or the hole injection layer 3) can be formed using a polymer compound having a TPD basic skeleton.

進而，如圖20所示，可於電洞傳輸層與發光層之間設置電子阻擋層，例如，可使用本發明之高分子量化合物並藉由利用旋轉塗佈或噴墨等之塗佈來形成。Furthermore, as shown in FIG. 20 , an electron blocking layer can be provided between the hole transport layer and the light-emitting layer. For example, the high molecular weight compound of the present invention can be used and formed by coating using spin coating or inkjet. .

又，於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，亦可使用具有電子阻擋作用之公知之電子阻擋性化合物、例如咔唑衍生物、或具有三苯基矽烷基且具有三芳基胺構造之化合物等來形成電子阻擋層。具有代表性者如下。 咔唑衍生物，例如：4,4',4''-三(N-咔唑基)三苯胺(以下簡稱為TCTA)；9,9-雙[4-(咔唑-9-基)苯基]茀；1,3-雙(咔唑-9-基)苯(以下簡稱為mCP)；2,2-雙(4-咔唑-9-苯基)金剛烷(以下簡稱為Ad-Cz)。 具有三芳基胺構造之化合物，例如9-[4-(咔唑-9-基)苯基]-9-[4-(三苯基矽烷基)苯基]-9H-茀。 In addition, in an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, a known electron blocking compound having an electron blocking effect, such as a carbazole derivative or a compound having a triphenylsilyl group, can also be used. And compounds with a triarylamine structure are used to form an electron blocking layer. The representative ones are as follows. Carbazole derivatives, such as: 4,4',4''-tris(N-carbazolyl)triphenylamine (hereinafter referred to as TCTA); 9,9-bis[4-(carbazol-9-yl)benzene 1,3-bis(carbazol-9-yl)benzene (hereinafter referred to as mCP); 2,2-bis(4-carbazol-9-phenyl)adamantane (hereinafter referred to as Ad-Cz ). Compounds with a triarylamine structure, such as 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluoride.

電子阻擋層亦係，包含本發明之高分子量化合物在內，可分別單獨成膜，亦可混合2種以上而成膜。又，亦可使用上述化合物中之1種或數種來形成數個層，將積層有此種層之多層膜作為電子阻擋層。The electron blocking layer can also be formed into a film including the high molecular weight compound of the present invention individually, or two or more types thereof can be mixed to form a film. Alternatively, one or more of the above compounds may be used to form a plurality of layers, and a multilayer film in which such layers are laminated may be used as an electron blocking layer.

於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，發光層6除可使用以Alq 3為代表之羥喹啉衍生物之金屬錯合物以外，還可使用鋅或鈹、鋁等各種金屬錯合物、蒽衍生物、雙苯乙烯基苯衍生物、芘衍生物、 唑衍生物、聚對苯乙炔衍生物等發光材料來形成。 In an organic EL element having an organic layer formed using the high molecular weight compound of the present invention, the light-emitting layer 6 may use zinc or beryllium in addition to a metal complex of a hydroxyquinoline derivative represented by Alq 3 . , various metal complexes such as aluminum, anthracene derivatives, bistyrylbenzene derivatives, pyrene derivatives, It is formed from luminescent materials such as azole derivatives and poly(p-phenylene vinylene) derivatives.

又，亦可由主體材料及摻雜劑材料構成發光層6。作為此時之主體材料，除上述發光材料以外，還可使用噻唑衍生物、苯并咪唑衍生物、聚二烷基茀衍生物等，進而，亦可使用上述之本發明之高分子量化合物。作為摻雜劑材料，可使用喹吖酮、香豆素、紅螢烯、苝及該等之衍生物、苯并吡喃衍生物、玫瑰紅衍生物、胺基苯乙烯衍生物等。In addition, the light-emitting layer 6 may be composed of a host material and a dopant material. As the host material in this case, in addition to the above-mentioned light-emitting materials, thiazole derivatives, benzimidazole derivatives, polydialkyl fluoride derivatives, etc. can also be used. Furthermore, the above-mentioned high molecular weight compound of the present invention can also be used. As dopant materials, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rose bengal derivatives, aminostyrene derivatives, etc. can be used.

此種發光層6亦可設為使用各發光材料中之1種或2種以上之單層構成，亦可設為積層有數個層之多層構造。The light-emitting layer 6 may have a single-layer structure using one or two or more kinds of each light-emitting material, or may have a multi-layer structure in which several layers are laminated.

進而，亦可使用磷光發光材料作為發光材料來形成發光層6。作為磷光發光材料，可使用銥或鉑等之金屬錯合物之磷光發光體。例如可使用Ir(ppy) 3等綠色之磷光發光體、FIrpic、FIr6等藍色之磷光發光體、Btp 2Ir(acac)等紅色之磷光發光體等，該等磷光發光材料可摻雜至電洞注入、傳輸性之主體材料或電子傳輸性之主體材料中使用。 Furthermore, a phosphorescent light-emitting material may be used as the light-emitting material to form the light-emitting layer 6 . As the phosphorescent light-emitting material, a phosphorescent light-emitting body of a metal complex such as iridium or platinum can be used. For example, green phosphorescent emitters such as Ir(ppy) 3 , blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp 2 Ir(acac), etc. can be used. These phosphorescent luminescent materials can be doped into the electrolyte. Used in hole injection, transmission host materials or electron transport host materials.

再者，關於將磷光性發光材料摻雜至主體材料，為避免濃度淬滅，較佳為以相對於發光層整體為1～30重量百分比之範圍藉由共蒸鍍進行摻雜。Furthermore, regarding doping the phosphorescent light-emitting material into the host material, in order to avoid concentration quenching, doping is preferably performed by co-evaporation in a range of 1 to 30 weight percent relative to the entire light-emitting layer.

又，亦可使用PIC-TRZ、CC2TA、PXZ-TRZ、4CzIPN等CDCB(Carbazolyl Dicyanobenzene，咔唑基二氰基苯)衍生物等放射延遲螢光之材料作為發光材料(參照Appl. Phys. Let.,98,083302(2011)、Chem. Comumm., 48, 11392(2012)、Nature, 492, 234(2012))。In addition, materials that emit delayed fluorescence, such as CDCB (Carbazolyl Dicyanobenzene) derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, can also be used as the luminescent material (see Appl. Phys. Let. ,98,083302(2011), Chem. Comum., 48, 11392(2012), Nature, 492, 234(2012)).

藉由使本發明之高分子量化合物擔載被稱為摻雜劑之螢光發光體、磷光發光體或放射延遲螢光之材料來形成發光層6，可實現驅動電壓下降、發光效率得到改善之有機EL元件。By supporting the high molecular weight compound of the present invention with a fluorescent emitter, a phosphorescent emitter, or a material that radiates delayed fluorescence called a dopant to form the luminescent layer 6, the driving voltage can be reduced and the luminous efficiency can be improved. Organic EL element.

於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，可使用本發明之高分子量化合物作為電洞注入、傳輸性之主體材料。除此以外，亦可使用4,4'-二(N-咔唑基)聯苯(以下簡稱為CBP)、TCTA、mCP等咔唑衍生物等。In an organic EL element having an organic layer formed using the high molecular weight compound of the present invention, the high molecular weight compound of the present invention can be used as a host material with hole injection and transport properties. In addition, carbazole derivatives such as 4,4'-bis(N-carbazolyl)biphenyl (hereinafter referred to as CBP), TCTA, and mCP can also be used.

又，於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，可使用對雙(三苯基矽烷基)苯(以下簡稱為UGH2)、及2,2',2''-(1,3,5-伸苯基)-三(1-苯基-1H-苯并咪唑)(以下簡稱為TPBI)等作為電子傳輸性之主體材料。Furthermore, in an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, p-bis(triphenylsilyl)benzene (hereinafter referred to as UGH2) and 2,2',2'' can be used -(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (hereinafter referred to as TPBI) and the like are used as the host material for electron transport.

於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，設置於發光層6與電子傳輸層7之間之電洞阻擋層(圖20中未表示)可使用本身公知之具有電洞阻擋作用之化合物來形成。作為此種具有電洞阻擋作用之公知化合物之例，可例舉以下者。 2,9-二甲基-4,7-聯苯-1,10-啡啉(以下簡稱為BCP)等啡啉衍生物； 雙(2-甲基-8-喹啉)-4-苯基酚鋁(III)(以下簡稱為BAlq)等羥喹啉衍生物之金屬錯合物； 各種稀土類錯合物； ***衍生物； 三 衍生物； 二唑衍生物。 In an organic EL element having an organic layer formed using the high molecular weight compound of the present invention, the hole blocking layer (not shown in FIG. 20 ) disposed between the light-emitting layer 6 and the electron transport layer 7 can be made using a well-known method. Compounds that block holes are formed. Examples of such known compounds having a hole blocking effect include the following. 2,9-Dimethyl-4,7-biphenyl-1,10-phenanthroline (hereinafter referred to as BCP) and other phenanthroline derivatives; Bis(2-methyl-8-quinoline)-4-phenyl Metal complexes of hydroxyquinoline derivatives such as aluminum phenolate (III) (hereinafter referred to as BAlq); various rare earth complexes; triazole derivatives; III derivative; Oxidazole derivatives.

該等材料亦可用於形成以下所述之電子傳輸層7，進而，亦可用作電洞阻擋層兼電子傳輸層7。These materials can also be used to form the electron transport layer 7 described below, and further, can also be used as the hole blocking layer and electron transport layer 7 .

此種電洞阻擋層亦可設為單層或多層之積層構造，各層可使用上述之具有電洞阻擋作用之化合物中之1種或2種以上而成膜。This type of hole blocking layer may also be a single layer or a multi-layer laminated structure, and each layer may be formed using one or more of the above-mentioned compounds having hole blocking effects.

於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，電子傳輸層7除使用本身公知之電子傳輸性之化合物、例如以Alq 3、BAlq為代表之羥喹啉衍生物之金屬錯合物而形成以外，還可使用各種金屬錯合物、吡啶衍生物、嘧啶衍生物、***衍生物、三 衍生物、 二唑衍生物、噻二唑衍生物、碳二醯亞胺衍生物、喹 啉衍生物、啡啉衍生物、噻咯衍生物、苯并咪唑衍生物等而形成。 In an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, the electron transport layer 7 uses well-known electron transport compounds, such as hydroxyquinoline derivatives represented by Alq 3 and BAlq. In addition to metal complexes, various metal complexes, pyridine derivatives, pyrimidine derivatives, triazole derivatives, and triazole derivatives can also be used. derivative, Oxidazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinine It is formed from pholine derivatives, phenanthroline derivatives, silole derivatives, benzimidazole derivatives, etc.

該電子傳輸層7亦可設為單層或多層之積層構造，各層可使用上述之電子傳輸性化合物中之1種或2種以上而成膜。The electron transport layer 7 may also have a single layer or a multi-layer laminated structure, and each layer may be formed using one or more of the above-mentioned electron transport compounds.

進而，於具備使用本發明之高分子量化合物而形成之有機層之有機EL元件中，視需要而設置之電子注入層(圖20中未表示)亦可使用本身公知者、例如氟化鋰、氟化銫等鹼金屬鹽、氟化鎂等鹼土類金屬鹽、氧化鋁等金屬氧化物、喹啉鋰等有機金屬錯合物等而形成。Furthermore, in an organic EL element having an organic layer formed using the high molecular weight compound of the present invention, the electron injection layer (not shown in FIG. 20 ) provided as necessary can also use one known per se, such as lithium fluoride, fluoride, etc. It is formed from alkali metal salts such as cesium chloride, alkaline earth metal salts such as magnesium fluoride, metal oxides such as aluminum oxide, and organic metal complexes such as lithium quinolate.

作為具備使用本發明之高分子量化合物而形成之有機層之有機EL元件的陰極8，可使用如鋁之類之工作函數較低之電極材料、及如鎂銀合金、鎂銦合金、鋁鎂合金之類之工作函數更低之合金作為電極材料。As the cathode 8 of the organic EL element having an organic layer formed using the high molecular weight compound of the present invention, an electrode material with a low work function such as aluminum, magnesium silver alloy, magnesium indium alloy, aluminum magnesium alloy can be used. Alloys with lower work functions are used as electrode materials.

如上所述，藉由使用本發明之高分子量化合物來形成電洞注入層、電洞傳輸層、電子阻擋層、及發光層中之至少任一層，可獲得發光效率及電效率較高、實用驅動電壓較低、發光開始電壓亦較低、且具有極其優異之耐久性之有機EL元件。尤其是，該有機EL元件具有較高之發光效率，並且驅動電壓下降，電流耐性得到改善，最大發光亮度得到提昇。 [實施例] As mentioned above, by using the high molecular weight compound of the present invention to form at least any one of the hole injection layer, the hole transport layer, the electron blocking layer, and the light-emitting layer, higher luminous efficiency and electrical efficiency, and practical driving can be obtained An organic EL element with low voltage, low emission start voltage, and extremely excellent durability. In particular, the organic EL element has high luminous efficiency, the driving voltage is reduced, the current tolerance is improved, and the maximum luminous brightness is increased. [Example]

以下，藉由下述實施例來對本發明進行說明。 再者，於以下說明中，將本發明之高分子量化合物所具有之通式(1)所表示之重複單位表示為「重複單位A」，將通式(2)所表示之重複單位表示為「重複單位B」，將具有熱交聯性構造單位Q之通式(4)所表示之重複單位表示為「重複單位Q」。 Hereinafter, the present invention will be described through the following examples. In addition, in the following description, the repeating unit represented by the general formula (1) of the high molecular weight compound of the present invention is represented by "repeating unit A", and the repeating unit represented by the general formula (2) is represented by " "Repeating unit B" represents the repeating unit represented by the general formula (4) having the thermally crosslinkable structural unit Q as "repeating unit Q".

又，所合成之化合物之純化係藉由利用管柱層析儀之純化、利用溶劑之晶析法來進行。化合物之鑑定係藉由NMR分析來進行。In addition, the purification of the synthesized compound is performed by purification using a column chromatograph and crystallization using a solvent. Identification of compounds is carried out by NMR analysis.

合成以下之中間物1～3以製作本發明之高分子量化合物。The following intermediates 1 to 3 are synthesized to prepare high molecular weight compounds of the present invention.

＜中間物1之合成＞＜Synthesis of Intermediate 1＞

[化15] [Chemical 15]

中間物1用於導入圖1所示之重複單位1-1之部分構造。Intermediate 1 is used to introduce part of the structure of the repeating unit 1-1 shown in Figure 1 .

將下述成分添加至進行了氮氣置換之反應容器中，並通入氮氣30分鐘。 N,N-雙(4-溴苯基)-9,9-二-正辛基-9H-茀-2-胺：16.7 g 雙(聯頻那醇)硼酸酯：11.9 g 乙酸鉀：5.7 g 1,4-二 烷：170 ml 繼而，加入{1,1'-雙(二苯基膦)二茂鐵}鈀(II)二氯化物之二氯甲烷加成物0.19 g並加熱，於100℃下攪拌7小時。冷卻至室溫後，加入水及甲苯，並進行分液操作，藉此採取有機層。用無水硫酸鎂對該有機層進行脫水後，於減壓下進行濃縮，藉此獲得粗製物。用管柱層析儀(乙酸乙酯/正己烷＝1/20)對粗製物進行純化，藉此獲得中間物1之白色粉體7.6 g(產率40%)。 The following components were added to a nitrogen-substituted reaction vessel, and nitrogen was introduced for 30 minutes. N,N-Bis(4-bromophenyl)-9,9-di-n-octyl-9H-quin-2-amine: 16.7 g Bis(bipinacol)borate: 11.9 g Potassium acetate: 5.7 g 1,4-two Alkane: 170 ml. Then, 0.19 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphine)ferrocene}palladium(II) dichloride was added, heated, and stirred at 100°C for 7 hours. . After cooling to room temperature, water and toluene were added, and liquid separation was performed to collect the organic layer. The organic layer was dehydrated over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified using column chromatography (ethyl acetate/n-hexane=1/20), thereby obtaining 7.6 g of white powder of Intermediate 1 (yield 40%).

＜中間物2之合成＞＜Synthesis of Intermediate 2＞

[化16] [Chemical 16]

中間物2用於導入作為熱交聯性構造單位Q之通式(5e)所示之構造單位。Intermediate 2 is used to introduce the structural unit represented by the general formula (5e) as the thermally cross-linkable structural unit Q.

將下述成分添加至進行了氮氣置換之反應容器中，並通入氮氣30分鐘。 N,N-雙(4-溴苯基)-N-(苯并環丁烯-4-基)-胺：8.0 g 雙(聯頻那醇)硼酸酯：9.9 g 乙酸鉀：4.6 g 1,4-二 烷：80 ml 繼而，加入{1,1'-雙(二苯基膦)二茂鐵}鈀(II)二氯化物之二氯甲烷加成物0.3 g並加熱，於90℃下攪拌11小時。冷卻至室溫後，加入自來水及甲苯，並進行分液操作，藉此採取有機層。用無水硫酸鎂對該有機層進行脫水後，於減壓下進行濃縮，藉此獲得粗製物。用甲苯/甲醇＝1/2使粗製物再結晶，藉此獲得中間物2之白色粉體3.4 g(產率35%)。 The following components were added to a nitrogen-substituted reaction vessel, and nitrogen was introduced for 30 minutes. N,N-bis(4-bromophenyl)-N-(benzocyclobuten-4-yl)-amine: 8.0 g Bis(bipinacol)borate: 9.9 g Potassium acetate: 4.6 g 1 ,4-two Alkane: 80 ml. Then, 0.3 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphine)ferrocene}palladium(II) dichloride was added and heated, and stirred at 90°C for 11 hours. . After cooling to room temperature, tap water and toluene were added, and liquid separation was performed to collect the organic layer. The organic layer was dehydrated over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized using toluene/methanol = 1/2, thereby obtaining 3.4 g of white powder of intermediate 2 (yield 35%).

＜中間物3之合成＞＜Synthesis of Intermediate 3＞

[化17] [Chemical 17]

中間物3用於導入圖6所示之重複單位2-1之部分構造。Intermediate 3 is used to introduce part of the structure of the repeating unit 2-1 shown in Figure 6 .

將下述成分添加至進行了氮氣置換之反應容器中，並通入氮氣30分鐘。 雙(對溴苯基)-2-二苯并呋喃胺：32.0 g 雙(聯頻那醇)硼酸酯：34.6 g 乙酸鉀：19.1 g 1,4-二 烷：150 ml 繼而，加入{1,1'-雙(二苯基膦)二茂鐵}鈀(II)二氯化物之二氯甲烷加成物0.5 g並加熱，於100℃下攪拌13小時。冷卻至室溫後，加入自來水及氯仿，並進行分液操作，藉此採取有機層。用無水硫酸鈉對該有機層進行脫水後，於減壓下進行濃縮，藉此獲得粗製物。用甲苯/甲醇＝1/1使粗製物再結晶，藉此獲得中間物3之類白色粉體18.6 g(產率48%)。 The following components were added to a nitrogen-substituted reaction vessel, and nitrogen was introduced for 30 minutes. Bis(p-bromophenyl)-2-dibenzofuranamine: 32.0 g Bis(bipinacol)borate: 34.6 g Potassium acetate: 19.1 g 1,4-bis Alkane: 150 ml. Then, 0.5 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphine)ferrocene}palladium(II) dichloride was added and heated, and stirred at 100°C for 13 hours. . After cooling to room temperature, tap water and chloroform were added, and liquid separation was performed to collect the organic layer. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized using toluene/methanol = 1/1, thereby obtaining 18.6 g of white powder such as intermediate 3 (yield 48%).

＜實施例1＞ 高分子量化合物I之合成； 將下述成分添加至進行了氮氣置換之反應容器中，並通入氮氣30分鐘。 中間物1：3.6 g 中間物2：0.4 g 中間物3：1.3 g 1,3-二溴苯：1.7 g 磷酸三鉀：7.4 g 甲苯：9 ml 水：5 ml 1,4-二 烷：27 ml <Example 1> Synthesis of High Molecular Weight Compound I; The following components were added to a nitrogen-substituted reaction vessel, and nitrogen was introduced for 30 minutes. Intermediate 1: 3.6 g Intermediate 2: 0.4 g Intermediate 3: 1.3 g 1,3-dibromobenzene: 1.7 g Tripotassium phosphate: 7.4 g Toluene: 9 ml Water: 5 ml 1,4-dibromobenzene Alkane: 27 ml

繼而，加入乙酸鈀(II)1.5 mg、及三鄰甲苯基膦12.3 mg並加熱，於88℃下攪拌8小時。其後，加入苯基硼酸19 mg並攪拌1小時，繼而，加入溴苯261 mg並攪拌1小時。加入甲苯50 ml、5 wt%之N,N-二乙基二硫代胺基甲酸鈉水溶液50 ml並加熱，於回流下攪拌2小時。冷卻至室溫後，進行分液操作，藉此採取有機層，利用飽和食鹽水洗淨3次。用無水硫酸鈉對有機層進行脫水後，於減壓下進行濃縮，藉此獲得粗聚合物。將粗聚合物溶解於甲苯中，加入矽膠進行吸附純化，進行過濾以去除矽膠。於減壓下對所得之濾液進行濃縮，向乾燥硬化物中加入甲苯100 ml以使其溶解，並滴加至300 ml正己烷中，過濾取出所獲得之沈澱物。重複該操作4次並進行乾燥，藉此獲得3.2 g(產率76%)高分子量化合物I。Then, 1.5 mg of palladium (II) acetate and 12.3 mg of tri-o-tolylphosphine were added, heated, and stirred at 88° C. for 8 hours. Thereafter, 19 mg of phenylboronic acid was added and stirred for 1 hour, and then 261 mg of bromobenzene was added and stirred for 1 hour. Add 50 ml of toluene and 50 ml of 5 wt% sodium N,N-diethyldithiocarbamate aqueous solution, heat, and stir under reflux for 2 hours. After cooling to room temperature, liquid separation was performed to collect the organic layer and wash it three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude polymer. Dissolve the crude polymer in toluene, add silica gel for adsorption purification, and filter to remove the silica gel. The obtained filtrate was concentrated under reduced pressure, 100 ml of toluene was added to the dry hardened material to dissolve it, and added dropwise to 300 ml of n-hexane, and the obtained precipitate was filtered out. This operation was repeated 4 times and dried, thereby obtaining 3.2 g (yield 76%) of high molecular weight compound I.

高分子量化合物I之用GPC測得之平均分子量、分散度如下。 數量平均分子量Mn(以聚苯乙烯換算)：64,000 重量平均分子量Mw(以聚苯乙烯換算)：141,000 分散度(Mw/Mn)：2.2 The average molecular weight and dispersion of high molecular weight compound I measured by GPC are as follows. Number average molecular weight Mn (converted to polystyrene): 64,000 Weight average molecular weight Mw (converted to polystyrene): 141,000 Dispersion (Mw/Mn): 2.2

又，對高分子量化合物I進行NMR測定。根據圖21所示之 1H-NMR測定結果，高分子量化合物I之化學組成式如下。 In addition, NMR measurement was performed on the high molecular weight compound I. According to the 1 H-NMR measurement results shown in Figure 21, the chemical composition formula of the high molecular weight compound I is as follows.

[化18] (高分子量化合物I) [Chemical 18] (High molecular weight compound I)

根據上述化學組成可知，高分子化合物I包含60莫耳%之重複單位A，包含30莫耳%之重複單位B，以10莫耳%之量含有重複單位Q。再者，各構造單位之莫耳比係根據 1H-NMR測定結果所得之推算值。 According to the above chemical composition, it can be seen that the polymer compound I contains 60 mol% of the repeating unit A, 30 mol% of the repeating unit B, and 10 mol% of the repeating unit Q. In addition, the molar ratio of each structural unit is an estimated value based on 1 H-NMR measurement results.

＜實施例2＞ 使用實施例1中合成之高分子量化合物I，於ITO基板上製作膜厚80 nm之塗佈膜，用離子化電位測定裝置(住友重機械工業股份有限公司製造，PYS-202型)測定工作函數。高分子量化合物I之工作函數為5.62 eV。 <Example 2> Using the high molecular weight compound I synthesized in Example 1, a coating film with a film thickness of 80 nm was produced on an ITO substrate, and the work function was measured using an ionization potential measuring device (model PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.) . The work function of high molecular weight compound I is 5.62 eV.

相較於NPD、TPD等通常之電洞傳輸材料所具有之工作函數5.4 eV，高分子量化合物I顯示出適宜之能階，可知具有良好之電洞傳輸能力及電洞注入性。Compared with the work function of 5.4 eV of common hole transport materials such as NPD and TPD, high molecular weight compound I shows a suitable energy level, which shows that it has good hole transport ability and hole injection property.

＜實施例3＞ 使用實施例1中合成之高分子量化合物I，於石英基板上製作膜厚50 nm之蒸鍍膜，用市售之分光光度計測定紫外可見吸收光譜，根據長波長側之吸收端之波長算出帶隙。又，根據工作函數及帶隙之值算出電子親和力。高分子量化合物I之帶隙為3.14 eV，所算出之電子親和力為2.48 eV。 再者，作為通常之電洞傳輸材料之NPD之帶隙為3.00 eV，電子親和力為2.40 eV。 <Example 3> Use the high molecular weight compound I synthesized in Example 1 to prepare an evaporated film with a thickness of 50 nm on a quartz substrate. Use a commercially available spectrophotometer to measure the UV-visible absorption spectrum. Calculate the band gap based on the wavelength of the absorption end on the long wavelength side. . Furthermore, the electron affinity is calculated based on the work function and band gap values. The band gap of high molecular weight compound I is 3.14 eV, and the calculated electron affinity is 2.48 eV. Furthermore, as a common hole transport material, NPD has a band gap of 3.00 eV and an electron affinity of 2.40 eV.

相較於NPD，高分子量化合物I為寬能隙，即便對電子親和力進行比較亦顯示出適宜之能階，可知具有良好之電子阻擋能力。Compared with NPD, the high molecular weight compound I has a wide energy gap and shows a suitable energy level even when comparing the electron affinities, indicating that it has good electron blocking ability.

＜實施例4＞ 藉由以下方法製作圖20所示之層構造之有機EL元件。 <Example 4> An organic EL element with the layer structure shown in Fig. 20 was produced by the following method.

具體而言，用有機溶劑將成膜有膜厚50 nm之ITO之玻璃基板1洗淨後，藉由UV(Ultraviolet，紫外線)/臭氧處理洗淨ITO表面。以覆蓋設置於該玻璃基板1上之透明陽極2(ITO)之方式，藉由旋轉塗佈法使PEDOT/PSS(Ossila製造)以50 nm之厚度成膜，於加熱板上以200℃乾燥10分鐘而形成電洞注入層3。Specifically, the glass substrate 1 on which the ITO film with a film thickness of 50 nm is formed is washed with an organic solvent, and then the ITO surface is washed by UV (Ultraviolet, ultraviolet)/ozone treatment. To cover the transparent anode 2 (ITO) provided on the glass substrate 1, PEDOT/PSS (manufactured by Ossila) was formed into a film with a thickness of 50 nm by the spin coating method, and dried on a hot plate at 200°C for 10 minutes to form the hole injection layer 3.

將下述構造式之高分子量化合物(HTM-1)以0.4 wt%溶解於甲苯中而製備塗佈液。將以上述方式形成有電洞注入層3之基板移至用乾燥氮氣進行置換後之手套式操作箱內，於加熱板上以230℃乾燥10分鐘後，使用上述塗佈液並藉由旋轉塗佈法於電洞注入層3上形成15 nm厚度之塗佈層，進而，於加熱板上以220℃乾燥30分鐘而形成電洞傳輸層4。A high molecular weight compound (HTM-1) of the following structural formula was dissolved in toluene at 0.4 wt% to prepare a coating liquid. Move the substrate with the hole injection layer 3 formed in the above manner to a glove box that has been replaced with dry nitrogen. After drying on a hot plate at 230°C for 10 minutes, use the above coating liquid and spin coating. A coating layer with a thickness of 15 nm was formed on the hole injection layer 3 by the cloth method, and then dried on a hot plate at 220° C. for 30 minutes to form the hole transport layer 4 .

[化19] [Chemical 19]

將實施例1中獲得之高分子量化合物I以0.4 wt%溶解於甲苯中而製備塗佈液。使用上述塗佈液並藉由旋轉塗佈法於以上述方式形成之電洞傳輸層4上形成15 nm厚度之塗佈層，進而，於加熱板上以220℃乾燥30分鐘而形成電子阻擋層5。The high molecular weight compound I obtained in Example 1 was dissolved in toluene at 0.4 wt% to prepare a coating liquid. Using the above coating liquid, a coating layer with a thickness of 15 nm was formed on the hole transport layer 4 formed in the above manner by spin coating, and then dried on a hot plate at 220° C. for 30 minutes to form an electron blocking layer. 5.

將以上述方式形成有電子阻擋層5之基板安裝於真空蒸鍍機內並減壓至0.001 Pa以下。藉由藍色發光材料(EMD-1)與主體材料(EMH-1)之共蒸鍍，於電子阻擋層5上形成膜厚34 nm之發光層6。再者，於共蒸鍍中，將蒸鍍速度比設為EMD-1：EMH-1＝4：96。The substrate with the electron blocking layer 5 formed in the above manner is installed in a vacuum evaporation machine and the pressure is reduced to less than 0.001 Pa. By co-evaporating the blue luminescent material (EMD-1) and the host material (EMH-1), a luminescent layer 6 with a film thickness of 34 nm is formed on the electron blocking layer 5 . In addition, in co-evaporation, the evaporation speed ratio was set to EMD-1:EMH-1=4:96.

[化20] [Chemistry 20]

藉由使用電子傳輸材料(ETM-1)及(ETM-2)之共蒸鍍，於上述所形成之發光層6上形成膜厚20 nm之電子傳輸層7。再者，於共蒸鍍中，將蒸鍍速度比設為ETM-1：ETM-2＝50：50。By co-evaporation using electron transport materials (ETM-1) and (ETM-2), an electron transport layer 7 with a film thickness of 20 nm was formed on the light-emitting layer 6 formed above. In addition, in co-evaporation, the vapor deposition speed ratio was set to ETM-1:ETM-2=50:50.

[化21] [Chemistry 21]

最後，以膜厚成為100 nm之方式蒸鍍鋁而形成陰極8。 將以此種方式形成有透明陽極2、電洞注入層3、電洞傳輸層4、電子阻擋層5、發光層6、電子傳輸層7及陰極8之玻璃基板移動至用乾燥氮氣進行置換後之手套式操作箱內，使用UV硬化樹脂來貼合密封用之其他玻璃基板，從而製成有機EL元件。對於所製作之有機EL元件，於大氣中、常溫下進行特性測定。又，測定了對所製作之有機EL元件施加直流電壓時之發光特性。上述測定結果示於表1中。 Finally, aluminum was evaporated to form a cathode 8 such that the film thickness became 100 nm. The glass substrate with the transparent anode 2, the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the light emitting layer 6, the electron transport layer 7 and the cathode 8 formed in this way is moved to be replaced with dry nitrogen. In a glove-type operation box, UV curing resin is used to bond other glass substrates for sealing to make organic EL elements. The characteristics of the produced organic EL element were measured in the atmosphere and at normal temperature. Furthermore, the luminescence characteristics when a DC voltage was applied to the produced organic EL element were measured. The above measurement results are shown in Table 1.

＜比較例1＞ 代替高分子量化合物I，將TFB(電洞傳輸性聚合物)以0.4 wt%溶解於甲苯中而製備塗佈液，使用該塗佈液來形成電子阻擋層5，除此以外，以與實施例4完全相同之方式製作有機EL元件。 ＜Comparative example 1＞ In place of the high molecular weight compound I, TFB (hole transporting polymer) was dissolved in toluene at 0.4 wt% to prepare a coating liquid, and the electron blocking layer 5 was formed using this coating liquid. 4 Make organic EL devices in exactly the same way.

[化22] [Chemistry 22]

TFB(電洞傳輸性聚合物)為聚[(9,9-二辛基茀基-2,7-二基)-共聚-(4,4'-(N-(4-第二丁基苯基))二苯基胺](American Dye Source公司製造，Hole Transport Polymer ADS259BE)。對於該比較例1之有機EL元件，與實施例4同樣地評估各種特性，將其結果示於表1中。TFB (hole transporting polymer) is poly[(9,9-dioctylbenzyl-2,7-diyl)-copolymer-(4,4'-(N-(4-dibutylbenzene) base)) diphenylamine] (Hole Transport Polymer ADS259BE manufactured by American Dye Source Co., Ltd.). Regarding the organic EL element of Comparative Example 1, various characteristics were evaluated in the same manner as in Example 4, and the results are shown in Table 1.

於各種特性之評估中，電壓、亮度、發光效率及電效率為流通電流密度10 mA/cm 2之電流時之值。又，元件壽命係以時間形式進行測定，該時間係將發光開始時之發光亮度(初始亮度)設為700 cd/m 2而進行定電流驅動時，發光亮度衰減至560 cd/m 2(將初始亮度設為100%時，相當於80%：80%衰減)為止之時間。 In the evaluation of various characteristics, voltage, brightness, luminous efficiency, and electrical efficiency are values when a current with a current density of 10 mA/ cm2 is flowing. In addition, the device life is measured in the form of time, which is the time when the luminous brightness at the beginning of light emission (initial luminance) is set to 700 cd/m 2 and constant current driving is performed, the luminous brightness decays to 560 cd/m 2 (set When the initial brightness is set to 100%, it is equivalent to the time until 80%: 80% attenuation).

[表1]    電子阻擋層 電壓 [V] 亮度 [cd/m 2] 發光效率 [cd/A] 電效率 [lm/W] 元件壽命80%衰減 實施例4 高分子量化合物I 4.02 752 7.52 5.89 136小時 比較例1 TFB 4.02 550 5.50 4.29 11小時 [Table 1] electron blocking layer Voltage[V] Brightness [cd/m 2 ] Luminous efficiency [cd/A] Electrical efficiency [lm/W] 80% reduction in component life Example 4 High molecular weight compound I 4.02 752 7.52 5.89 136 hours Comparative example 1 TFB 4.02 550 5.50 4.29 11 hours

如表1所示，關於流通電流密度10 mA/cm 2之電流時之發光效率，相對於比較例1之有機EL元件之5.50 cd/A，實施例4之有機EL元件為7.52 cd/A，效率較高。又，關於元件壽命(80%衰減)，相對於比較例1之有機EL元件之11小時，實施例4之有機EL元件為136小時，壽命較長。 (產業上之可利用性) As shown in Table 1, the luminous efficiency of the organic EL element of Example 4 was 7.52 cd/A compared to 5.50 cd/A of the organic EL element of Comparative Example 1 when a current density of 10 mA/cm 2 was passed. Higher efficiency. Furthermore, regarding the element life (80% attenuation), compared to 11 hours of the organic EL element of Comparative Example 1, the organic EL element of Example 4 has a longer life of 136 hours. (industrial availability)

本發明之高分子量化合物由於電洞傳輸能力較強、電子阻擋能力優異，故作為塗佈型有機EL元件用化合物較優異。藉由使用該化合物製作塗佈型有機EL元件，可獲得較高之發光效率及電效率，並且可改善耐久性。例如，可拓展至家電製品或照明用途中。The high molecular weight compound of the present invention has strong hole transport ability and excellent electron blocking ability, so it is excellent as a compound for coating-type organic EL devices. By using this compound to produce coating-type organic EL elements, higher luminous efficiency and electrical efficiency can be obtained, and durability can be improved. For example, it can be expanded to home appliances or lighting applications.

1:玻璃基板 2:透明陽極 3:電洞注入層 4:電洞傳輸層 5:電子阻擋層 6:發光層 7:電子傳輸層 8:陰極 1:Glass substrate 2: Transparent anode 3: Hole injection layer 4: Hole transport layer 5:Electron blocking layer 6: Luminous layer 7:Electron transport layer 8:Cathode

圖1係適合作為本發明之通式(1)所表示之重複單位A的重複單位1-1～1-6之化學構造。 圖2係適合作為本發明之通式(1)所表示之重複單位A的重複單位1-7～1-12之化學構造。 圖3係適合作為本發明之通式(1)所表示之重複單位A的重複單位1-13～1-18之化學構造。 圖4係適合作為本發明之通式(1)所表示之重複單位A的重複單位1-19～1-24之化學構造。 圖5係適合作為本發明之通式(1)所表示之重複單位A的重複單位1-25～1-28之化學構造。 圖6係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-1～2-6之化學構造。 圖7係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-7～2-12之化學構造。 圖8係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-13～2-18之化學構造。 圖9係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-19～2-24之化學構造。 圖10係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-25～2-30之化學構造。 圖11係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-31～2-36之化學構造。 圖12係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-37～2-42之化學構造。 圖13係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-43～2-48之化學構造。 圖14係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-49～2-54之化學構造。 圖15係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-55～2-60之化學構造。 圖16係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-61～2-66之化學構造。 圖17係適合作為本發明之通式(2)所表示之重複單位B的重複單位2-67～2-68之化學構造。 圖18係本發明中適合作為通式(1)、通式(2)及通式(4)中之X的取代基1～24之化學構造。 圖19係本發明中適合作為通式(1)、通式(2)及通式(4)中之X的取代基25～48之化學構造。 圖20係本發明之有機EL元件之層構成之例。 圖21係實施例1之高分子量化合物I之 1H-NMR(Hydrogen-Nuclear Magnetic Resonance，氫-核磁共振)圖表。 Figure 1 shows the chemical structure of repeating units 1-1 to 1-6 suitable as repeating unit A represented by the general formula (1) of the present invention. Figure 2 shows the chemical structure of repeating units 1-7 to 1-12 suitable as repeating unit A represented by the general formula (1) of the present invention. Figure 3 shows the chemical structure of repeating units 1-13 to 1-18 suitable as repeating unit A represented by the general formula (1) of the present invention. Figure 4 shows the chemical structure of repeating units 1-19 to 1-24 suitable as repeating unit A represented by the general formula (1) of the present invention. Figure 5 shows the chemical structure of repeating units 1-25 to 1-28 suitable as repeating unit A represented by the general formula (1) of the present invention. Figure 6 shows the chemical structures of repeating units 2-1 to 2-6 suitable as the repeating unit B represented by the general formula (2) of the present invention. Figure 7 shows the chemical structure of repeating units 2-7 to 2-12 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 8 shows the chemical structure of repeating units 2-13 to 2-18 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 9 shows the chemical structures of repeating units 2-19 to 2-24 suitable as repeating units B represented by the general formula (2) of the present invention. Figure 10 shows the chemical structure of repeating units 2-25 to 2-30 suitable as the repeating unit B represented by the general formula (2) of the present invention. Figure 11 shows the chemical structure of repeating units 2-31 to 2-36 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 12 shows the chemical structure of repeating units 2-37 to 2-42 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 13 shows the chemical structure of repeating units 2-43 to 2-48 suitable as repeating unit B represented by general formula (2) of the present invention. Figure 14 shows the chemical structure of repeating units 2-49 to 2-54 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 15 shows the chemical structure of repeating units 2-55 to 2-60 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 16 shows the chemical structure of repeating units 2-61 to 2-66 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 17 shows the chemical structure of repeating units 2-67 to 2-68 suitable as repeating unit B represented by the general formula (2) of the present invention. Figure 18 shows chemical structures suitable as substituents 1 to 24 of X in general formula (1), general formula (2) and general formula (4) in the present invention. Figure 19 shows chemical structures suitable as substituents 25 to 48 of X in general formula (1), general formula (2) and general formula (4) in the present invention. Figure 20 is an example of the layer structure of the organic EL element of the present invention. Figure 21 is a 1 H-NMR (Hydrogen-Nuclear Magnetic Resonance, hydrogen-nuclear magnetic resonance) chart of the high molecular weight compound I in Example 1.

Claims (11)

一種高分子量化合物，其包含下述通式(1)所表示之重複單位A、及下述通式(2)所表示之重複單位B，並且以聚苯乙烯換算，具有10,000以上且未滿1,000,000之重量平均分子量； [化1] [化2] 式中， R 1及R 3分別獨立地表示氫原子、氘原子、氰基、硝基、鹵素原子、或碳數40以下之烷基、烷氧基、環烷基、環烷氧基、烯基、或芳氧基， a、b及c為以下之整數， a＝0、1、2或3 b＝0、1、2、3或4 c＝0或1 R 2分別獨立地表示碳數3～40之烷基、烷氧基、或環烷基， L表示伸苯基，n表示0～3之整數， X分別獨立地表示氫原子、胺基、一價芳基、或一價雜芳基， Y為氧原子(O)、硫原子(S)、或下述式(3)所示之基， [化3] 式中之R 4表示經取代或未經取代之芳基、或者經取代或未經取代之烷基。 A high molecular weight compound containing a repeating unit A represented by the following general formula (1) and a repeating unit B represented by the following general formula (2), and having a polystyrene equivalent of 10,000 or more and less than 1,000,000 The weight average molecular weight; [Chemistry 1] [Chemicalization 2] In the formula, R 1 and R 3 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, or an alkyl group with less than 40 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, or an alkene group. group, or aryloxy group, a, b and c are the following integers, a=0, 1, 2 or 3 b=0, 1, 2, 3 or 4 c=0 or 1 R 2 independently represents the carbon number 3 to 40 alkyl groups, alkoxy groups, or cycloalkyl groups, L represents a phenylene group, n represents an integer from 0 to 3, and X independently represents a hydrogen atom, an amino group, a monovalent aryl group, or a monovalent hetero group. Aryl group, Y is an oxygen atom (O), a sulfur atom (S), or a group represented by the following formula (3), [Chemical 3] R 4 in the formula represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group. 如請求項1之高分子量化合物，其中，於上述通式(1)及(2)中，R 1及R 3為氫原子。 The high molecular weight compound of claim 1, wherein in the above general formulas (1) and (2), R 1 and R 3 are hydrogen atoms. 如請求項1或2之高分子量化合物，其中，於上述通式(1)中，R 2為碳數3～40之烷基。 The high molecular weight compound of claim 1 or 2, wherein in the above general formula (1), R 2 is an alkyl group having 3 to 40 carbon atoms. 如請求項1或2之高分子量化合物，其中，於上述通式(1)及(2)中，X為二苯基胺基、苯基、萘基、二苯并呋喃基、二苯并噻吩基、菲基、茀基、咔唑基、茚并咔唑基、或吖啶基。The high molecular weight compound of claim 1 or 2, wherein in the above general formulas (1) and (2), X is diphenylamino, phenyl, naphthyl, dibenzofuranyl, dibenzothiophene base, phenanthrenyl, fluorenyl, carbazolyl, indenocarbazolyl, or acridinyl. 如請求項1或2之高分子量化合物，其包含下述通式(4)所表示之具有熱交聯性構造單位Q之重複單位； [化4] 式中， R 3、X及a均與通式(1)中所示者定義相同。 The high molecular weight compound of claim 1 or 2, which contains a repeating unit having a thermally crosslinkable structural unit Q represented by the following general formula (4); [Chemical 4] In the formula, R 3 , X and a have the same definitions as those shown in the general formula (1). 如請求項5之高分子量化合物，其中，於上述通式(4)中，熱交聯性構造單位Q為下述通式(5a)～(5af)所示之構造； [化5] [化6] 式中， R 1、R 2、a及b均與通式(1)中所示者定義相同。 The high molecular weight compound of claim 5, wherein in the above general formula (4), the thermally crosslinkable structural unit Q is a structure represented by the following general formulas (5a) to (5af); [Chemical 5] [Chemical 6] In the formula, R 1 , R 2 , a and b have the same definitions as those shown in the general formula (1). 一種有機電致發光元件，其具有一對電極及夾持於其間之有機層，其中，上述有機層使用請求項1或2之高分子量化合物作為構成材料。An organic electroluminescent element having a pair of electrodes and an organic layer sandwiched therebetween, wherein the organic layer uses the high molecular weight compound of claim 1 or 2 as a constituent material. 如請求項7之有機電致發光元件，其中，上述有機層為電洞傳輸層。The organic electroluminescent device of claim 7, wherein the organic layer is a hole transport layer. 如請求項7之有機電致發光元件，其中，上述有機層為電子阻擋層。The organic electroluminescent device of claim 7, wherein the organic layer is an electron blocking layer. 如請求項7之有機電致發光元件，其中，上述有機層為電洞注入層。The organic electroluminescent device of claim 7, wherein the organic layer is a hole injection layer. 如請求項7之有機電致發光元件，其中，上述有機層為發光層。The organic electroluminescent element of claim 7, wherein the organic layer is a light-emitting layer.
TW112120620A 2022-07-07 2023-06-02 High molecular weight compound and organic electroluminescent element using the same wherein the high molecular weight compound includes a triarylamine structural unit with a fluorine ring; and a triarylamine structural unit with a dibenzofuran ring, dibenzothiophene ring or carbazole ring on its main chain TW202406972A (en)

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