TW202017970A - Polymer and use of same - Google Patents

Abstract

According to the present invention, a polymer which contains, for example, a repeating unit represented by formula AA has both excellent charge transport properties and excellent solubility in organic solvents; and excellent characteristics are able to be achieved in cases where this polymer is dissolved in an organic solvent by itself or together with a dopant substance, and then applied to electronic elements including an organic EL element.

Description

聚合物及其利用Polymers and their use

本發明係有關於一種聚合物及其利用。The present invention relates to a polymer and its use.

具有電荷輸送性之低分子化合物或高分子化合物係於有機電致發光(EL)元件或有機太陽電池等各種的電子元件中使用。 其中，重複單元具有有助於高電荷輸送性之如三苯基胺之三芳基胺的聚合物(下稱三芳基胺聚合物)，由於其電荷輸送性高，而有諸多相關之報導例(例如專利文獻1～3)。Low-molecular compounds or polymer compounds having charge transport properties are used in various electronic devices such as organic electroluminescence (EL) devices and organic solar cells. Among them, the repeating unit has a triarylamine polymer such as triphenylamine which contributes to high charge transportability (hereinafter referred to as triarylamine polymer). Due to its high charge transportability, there are many related reported examples ( For example, Patent Documents 1 to 3).

另一方面，在顯示器等領域業已實用化之有機EL元件係包含電洞注入層、電洞輸送層等有機機能層，而此有機機能層，為了實現降低元件的驅動電壓或延長壽命等高性能化係擔負重要的作用。 有機EL元件之有機機能層的形成方法可大致分類為以蒸鍍法為代表的乾式製程，及以旋轉塗佈法為代表的濕式製程；隨著近來顯示器的大面積化，而愈來愈需要形成更大面積的有機機能層。在此情況下，便有人著手開發以濕式製程形成有機機能層的有機EL元件(例如專利文獻4～6)。On the other hand, organic EL devices that have been put into practical use in the field of displays include organic functional layers such as a hole injection layer and a hole transport layer. This organic functional layer is designed to achieve high performance such as reducing the driving voltage of the device or extending the life. The chemical system plays an important role. The formation method of the organic functional layer of the organic EL device can be roughly classified into a dry process represented by the vapor deposition method and a wet process represented by the spin coating method; with the recent increase in the area of the display, it is getting more and more It is necessary to form an organic functional layer with a larger area. Under such circumstances, some people have started to develop organic EL devices in which organic functional layers are formed by a wet process (for example, Patent Documents 4 to 6).

基於此種背景，有人積極著手開發供形成電洞注入層、電洞輸送層等有機機能層的濕式製程用材料，而為了實現更高性能的有機EL顯示器，常要求更高機能的新型材料。 而且，使用可望獲得能有助於高機能之高電荷輸送性的三芳基胺聚合物的新穎濕式製程用材料雖為有前景的候選材料之一，惟重複單元僅具有三苯基胺的聚合物，隨溶劑的種類而定有些溶解性低，而有可使用於使用該聚合物之組成物的調製之溶劑的選擇範圍較小的問題。 [先前技術文獻] [專利文獻]Based on this background, some people are actively working on the development of materials for the wet process of forming organic functional layers such as hole injection layers and hole transport layers, and in order to achieve higher performance organic EL displays, new materials with higher functions are often required . Moreover, the use of novel wet process materials that can be expected to obtain triarylamine polymers that can contribute to high performance and high charge transportability is one of the promising candidate materials, but the repeating unit has only triphenylamine The polymer may have a low solubility depending on the type of solvent, and there is a problem that the choice of the solvent that can be used for the preparation of the composition using the polymer is small. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特開2011-105790號公報 [專利文獻2]日本特開2012-102286號公報 [專利文獻3]日本特開2014-001399號公報 [專利文獻4]國際公開第2015/050253號 [專利文獻5]國際公開第2017/047644號 [專利文獻6]國際公開第2018/110535號[Patent Document 1] Japanese Patent Laid-Open No. 2011-105790 [Patent Document 2] Japanese Unexamined Patent Publication No. 2012-102286 [Patent Document 3] Japanese Patent Laid-Open No. 2014-001399 [Patent Literature 4] International Publication No. 2015/050253 [Patent Literature 5] International Publication No. 2017/047644 [Patent Literature 6] International Publication No. 2018/110535

[發明所欲解決之課題][Problems to be solved by the invention]

本發明係有鑑於上述實情而完成者，茲以提供一種對有機溶劑之溶解性良好的聚合物及其製造方法，以及包含由該聚合物所構成之電荷輸送性物質的電荷輸送性組成物、由該電荷輸送性組成物而得到之電荷輸送性薄膜及具有該電荷輸送性薄膜的有機EL元件為目的。 [解決課題之手段]The present invention has been completed in view of the above facts, and hereby provides a polymer having good solubility in organic solvents, a method for manufacturing the same, and a charge-transporting composition including a charge-transporting substance composed of the polymer, The purpose of the charge-transporting thin film obtained from the charge-transporting composition and the organic EL device having the charge-transporting thin film. [Means to solve the problem]

本案發明人等為達成上述目的而致力累積多次研究的結果發現，重複單元中與既定的三苯基胺結構共同包含-NH-結構的聚合物其對有機溶劑之溶解性良好，而完成本發明。The inventors of this case have worked hard to accumulate the results of multiple studies to find that the polymer containing the -NH- structure in the repeating unit together with the predetermined triphenylamine structure has good solubility in organic solvents. invention.

亦即，本發明係提供： 1.一種聚合物，其係包含式(P1)所示之重複單元；

[式中，Ph表示1,4-伸苯基，G表示式(A01)～(A18)之任一者所示之一價基團：

(式中，L⁰¹ 表示-S-、-O-、-CO-、-CH₂ -、-(CH₂ )₂ -、 -C(CH₃ )₂ -、-CF₂ -、-(CF₂ )₂ -、-C(CF₃ )₂ -或茀-9,9-二基， L⁰² 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基， L⁰³ 及L⁰⁴ 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基， Z⁰¹ ～Z¹⁸ 表示取代為芳香環之取代基，彼此獨立表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或碳數2～20之炔基， R表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或可經氟原子取代之碳數2～20之炔基， Ar表示式(S1)～(S6)之任一者所示之基，

a⁰¹¹ ～a¹⁸³ 彼此獨立為表示取代為芳香環之取代基數的整數， a⁰⁷¹ 、a⁰⁸¹ 、a⁰⁹¹ 、a¹⁰¹ 及a¹¹¹ 為0～3， a⁰⁵¹ 、a⁰⁶¹ 、a⁰⁷² 、a⁰⁸² 、a⁰⁹² 、a¹⁰² 、a¹¹² 、a¹¹³ 、a¹¹⁴ 、a¹²¹ 、a¹³¹ 、a¹⁴¹ 、a¹⁵¹ 、a¹⁶¹ 、a¹⁷¹ 、a¹⁸¹ 、a¹⁸² 及a¹⁸³ 為0～4， a⁰¹¹ 、a⁰⁵² 、a⁰⁶² 、a¹²² 、a¹²³ 及a¹³² 為0～5， a⁰²¹ 、a¹³³ 、a¹⁴² 、a¹⁴³ 、a¹⁵² 、a¹⁵³ 、a¹⁶² 及a¹⁶³ 為0～7， a⁰³¹ 及a⁰⁴¹ 為0～9)]； 2.如1之聚合物，其中前述G為式(A01-1)～(A01-3)之任一者所示之基：

(式中，Z⁰¹ 表示與前述相同意義)； 3.一種聚合物，其係包含式(E1)所示之重複單元；

； 4.一種電荷輸送性組成物，其係包含由如1～3之任一種聚合物所構成的電荷輸送性物質及有機溶劑； 5.如4之電荷輸送性組成物，其係進一步包含電荷接受性物質或電荷接受性物質前驅物； 6.一種電荷輸送性薄膜，其係由如4或5之電荷輸送性組成物而得到； 7.一種有機電致發光元件，其係具有如6之電荷輸送性薄膜； 8.一種如1之聚合物的製造方法，其特徵為使式(A1)所示之三苯基胺衍生物與式(H1)所示之三苯基胺衍生物反應；

(式中，X彼此獨立表示氯原子、溴原子、碘原子或假鹵素基，Ph及G表示與前述相同意義)。 [發明之效果]That is, the present invention provides: 1. A polymer comprising a repeating unit represented by formula (P1);

[In the formula, Ph represents 1,4-phenylene, G represents a monovalent group represented by any one of formulas (A01) to (A18):

(In the formula, L ⁰¹ represents -S-, -O-, -CO-, -CH ₂ -, -(CH ₂ ) ₂ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -(CF ₂ ) ₂ -, -C(CF ₃ ) ₂ -or Fu-9-9,9-diyl, L ⁰² independently of each other represents a hydrogen atom, a C 1-20 alkyl group which may be substituted by a fluorine atom, and may be substituted by a fluorine atom Alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms which may be substituted with fluorine atoms or aryl having 6 to 20 carbon atoms which may be substituted with R, L ⁰³ and L ⁰⁴ independently represent a hydrogen atom, C 1-20 alkyl group which may be substituted with a fluorine atom, C 2-20 alkenyl group which may be substituted with a fluorine atom, C 2-20 alkynyl group which may be substituted with a fluorine atom or R may be substituted Aryl groups having 6 to 20 carbon atoms, Z ⁰¹ to Z ¹⁸ represent substituents substituted with aromatic rings, and independently represent alkyl groups having 1 to 20 carbon atoms which may be substituted by fluorine atoms, and 2 carbon atoms which may be substituted by fluorine atoms -20 alkenyl group or C 2-20 alkynyl group, R represents a C 1-20 alkyl group which may be substituted by a fluorine atom, a C 2-20 alkenyl group which may be substituted by a fluorine atom or fluorine An atom-substituted alkynyl group having 2 to 20 carbon atoms, Ar represents a group represented by any one of formulas (S1) to (S6),

a ⁰¹¹ to a ¹⁸³ are independently integers representing the number of substituents substituted into aromatic rings, a ⁰⁷¹ , a ⁰⁸¹ , a ⁰⁹¹ , a ¹⁰¹ and a ¹¹¹ are 0 to 3, a ⁰⁵¹ , a ⁰⁶¹ , a ⁰⁷² , a ⁰⁸² , a ⁰⁹² , a ¹⁰² , a ¹¹² , a ¹¹³ , a ¹¹⁴ , a ¹²¹ , a ¹³¹ , a ¹⁴¹ , a ¹⁵¹ , a ¹⁶¹ , a ¹⁷¹ , a ¹⁸¹ , a ¹⁸² and a ¹⁸³ are 0-4, a ⁰¹¹ , a ⁰⁵² , a ⁰⁶² , a ¹²² , a ¹²³ and a ¹³² are 0 to 5, a ⁰²¹ , a ¹³³ , a ¹⁴² , a ¹⁴³ , a ¹⁵² , a ¹⁵³ , a ¹⁶² and a ¹⁶³ are 0 to 7, a ⁰³¹ and a ⁰⁴¹ is 0-9)]; 2. A polymer as in 1, wherein the aforementioned G is a group represented by any one of formulas (A01-1) to (A01-3):

(In the formula, Z ⁰¹ represents the same meaning as described above); 3. A polymer comprising the repeating unit represented by formula (E1);

4. A charge-transporting composition comprising a charge-transporting substance composed of any polymer such as 1 to 3 and an organic solvent; 5. A charge-transporting composition such as 4 further comprising a charge Receptive substance or charge-receiving substance precursor; 6. A charge-transporting thin film obtained from a charge-transporting composition such as 4 or 5; 7. An organic electroluminescent element having a composition such as 6 Charge-transporting film; 8. A method for producing a polymer as described in 1, characterized by reacting a triphenylamine derivative represented by formula (A1) with a triphenylamine derivative represented by formula (H1);

(In the formula, X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G have the same meanings as described above). [Effect of invention]

本發明之聚合物由於其重複單元中與既定的三苯基胺結構共同包含-NH-結構，而兼備優良之電荷輸送性與對有機溶劑之優良的溶解性，藉由使該聚合物單獨或與摻雜物質或摻雜物質前驅物共同溶解於有機溶劑，可容易地調製能提供在適用於以有機EL元件為首的電子元件時可實現優良之特性的電荷輸送性薄膜之電荷輸送性組成物。 尤其是藉由將本發明之電荷輸送性薄膜作為有機EL元件的電洞注入層使用，可獲得特性優良的有機EL元件。The polymer of the present invention contains -NH- structure in the repeating unit together with the predetermined triphenylamine structure, and has both excellent charge transportability and excellent solubility in organic solvents. It is easily dissolved in an organic solvent together with a dopant substance or a dopant substance precursor, and can be easily prepared as a charge-transporting composition that can provide a charge-transporting thin film that can achieve excellent characteristics when applied to electronic devices including organic EL devices . In particular, by using the charge-transporting thin film of the present invention as a hole injection layer of an organic EL element, an organic EL element having excellent characteristics can be obtained.

[實施發明之形態][Forms for carrying out the invention]

以下，就本發明更詳細地加以說明。 本發明之聚合物係包含式(P1)所示之重複單元。Hereinafter, the present invention will be described in more detail. The polymer of the present invention contains a repeating unit represented by formula (P1).

Ph表示1,4-伸苯基，G表示式(A01)～(A18)之任一者所示之一價基團。Ph represents 1,4-phenylene, and G represents a monovalent group represented by any one of formulas (A01) to (A18).

L⁰¹ 表示-S-、-O-、-CO-、-CH₂ -、-(CH₂ )₂ -、-C(CH₃ )₂ -、-CF₂ -、-(CF₂ )₂ -、-C(CF₃ )₂ -或茀-9,9-二基。L ⁰¹ represents -S-, -O-, -CO-, -CH ₂ -, -(CH ₂ ) ₂ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -(CF ₂ ) ₂ -, -C(CF ₃ ) ₂ -or Fu-9,9-diyl.

L⁰² 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基。L ⁰² independently represents a hydrogen atom, a C 1-20 alkyl group which may be substituted with a fluorine atom, an C 2-20 alkenyl group which may be substituted with a fluorine atom, and a C 2-20 carbon atom which may be substituted with a fluorine atom An alkynyl group or an aryl group having 6 to 20 carbon atoms which may be substituted by R.

碳數1～20之烷基可為直鏈狀、分支狀、環狀任一種，作為其具體例係可舉出甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、n-戊基、n-戊-2-基、n-戊-3-基、n-己基、n-己-2-基、n-己-3-基、n-庚基、n-庚-2-基、n-庚-3-基、n-庚-4-基、n-辛基、n-辛-2-基、n-辛-3-基、n-辛-4-基、n-壬基、n-癸基等碳數1~20之直鏈狀或分支狀烷基；環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基等碳數3~20之環狀烷基。The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, s-butyl, t-butyl, n-pentyl, n-pent-2-yl, n-pent-3-yl, n-hexyl, n-hex-2-yl, n-hex -3-yl, n-heptyl, n-hept-2-yl, n-hept-3-yl, n-hept-4-yl, n-octyl, n-oct-2-yl, n-octyl Straight-chain or branched alkyl groups with 1 to 20 carbon atoms, such as -3-yl, n-oct-4-yl, n-nonyl, n-decyl, etc.; cyclopropyl, cyclobutyl, cyclopentyl, Cyclic alkyl groups with 3 to 20 carbon atoms, such as cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

碳數2～20之烯基可為直鏈狀、分支狀、環狀任一種，作為其具體例係可舉出乙烯基、n-1-丙烯基、n-2-丙烯基、1-甲基乙烯基、n-1-丁烯基、n-2-丁烯基、n-3-丁烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、1-乙基乙烯基、1-甲基-1-丙烯基、1-甲基-2-丙烯基、n-1-戊烯基、n-1-癸烯基等。The alkenyl group having 2 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include vinyl, n-1-propenyl, n-2-propenyl, and 1-methyl. Vinyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1- Ethyl vinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl and the like.

碳數2～20之炔基可為直鏈狀、分支狀、環狀任一種，作為其具體例係可舉出乙炔基、n-1-丙炔基、n-2-丙炔基、n-1-丁炔基、n-2-丁炔基、n-3-丁炔基、1-甲基-2-丙炔基、n-1-戊炔基、n-2-戊炔基、n-3-戊炔基、n-4-戊炔基、1-甲基-n-丁炔基、2-甲基-n-丁炔基、3-甲基-n-丁炔基、1,1-二甲基-n-丙炔基、n-1-己炔基、n-1-癸炔基等。The alkynyl group having 2 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include ethynyl, n-1-propynyl, n-2-propynyl, and n. -1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1 , 1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl and the like.

作為碳數6～20之芳基的具體例，可舉出苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, and 2 -Phenanthrene, 3-phenanthrene, 4-phenanthrene, 9-phenanthrene, etc.

L⁰³ 及L⁰⁴ 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基。L ⁰³ and L ⁰⁴ independently represent a hydrogen atom, a C 1-20 alkyl group which may be substituted with a fluorine atom, an C 2-20 alkenyl group which may be substituted with a fluorine atom, and a C 2 number which may be substituted with a fluorine atom ~20 alkynyl or C 6-20 aryl which may be substituted by R.

Z⁰¹ ～Z¹⁸ 表示取代為芳香環之取代基，彼此獨立表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或可經氟原子取代之碳數2～20之炔基。Z ⁰¹ to Z ¹⁸ represent substituents substituted with aromatic rings, and independently represent C 1-20 alkyl groups which may be substituted by fluorine atoms, C 2-20 alkenyl groups which may be substituted by fluorine atoms, or fluorine groups C2-20 alkynyl substituted by atoms.

R表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或可經氟原子取代之碳數2～20之炔基。R represents a C 1-20 alkyl group which may be substituted with a fluorine atom, an C 2-20 alkenyl group which may be substituted with a fluorine atom, or a C 2-20 alkynyl group which may be substituted with a fluorine atom.

L⁰³ 及L⁰⁴ 、Z⁰¹ ～Z¹⁸ 及R中的碳數1～20之烷基、碳數2～20之烯基及碳數2～20之炔基以及L⁰³ 及L⁰⁴ 中的碳數6～20之芳基之具體例可舉出與前述相同者。L ⁰³ and L ⁰⁴ , Z ⁰¹ to Z ¹⁸ and R, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl and L ⁰³ and L ⁰⁴ carbon Specific examples of the aryl groups of 6 to 20 include the same as described above.

作為式(A01)所示之基的較佳實例，可舉出以下者，但不限定於此等。

(式中，Z⁰¹ 表示與前述相同意義)。As preferred examples of the base represented by the formula (A01), the following can be mentioned, but it is not limited thereto.

(In the formula, Z ⁰¹ represents the same meaning as described above).

式(A01-1)～(A01-3)中，基於所得聚合物的溶解性與電荷輸送性觀點，Z⁰¹ 較佳為可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基，更佳為可經氟原子取代之碳數1～20之烷基，再更佳為可經氟原子取代之碳數1～10之烷基，再更佳為可經氟原子取代之碳數1～8之烷基。 又，當式(A01-1)～(A01-3)中的取代基Z⁰¹ 為可經氟原子取代之碳數1～20之烷基時，該烷基鍵結於芳香環的鍵結處較佳位於該烷基之二級或三級碳原子上，更佳位於二級碳原子上。 具體而言，式(A01-1)～(A01-3)中，Z⁰¹ 較佳為異丙基、異丁基、s-丁基、t-丁基、n-戊-2-基、n-戊-3-基、n-己-2-基、n-己-3-基、n-庚-2-基、n-庚-3-基、n-庚-4-基、n-辛-2-基、n-辛-3-基、n-辛-4-基等，但不限定於此等。In formulas (A01-1) to (A01-3), from the viewpoint of the solubility and charge transportability of the obtained polymer, Z ^{01 is} preferably a C 1-20 alkyl group which may be substituted with a fluorine atom, and may be subjected to fluorine The C2-C20 alkenyl group substituted by atoms and the C2-C20 alkynyl group substituted by fluorine atoms are more preferably C1-C20 alkyl groups substituted by fluorine atoms, and even more preferably The C 1-10 alkyl group substituted with a fluorine atom is even more preferably a C 1-8 alkyl group substituted with a fluorine atom. In addition, when the substituent Z ⁰¹ in the formulas (A01-1) to (A01-3) is a C 1-20 alkyl group which may be substituted with a fluorine atom, the alkyl group is bonded to the bonding point of the aromatic ring It is preferably on the secondary or tertiary carbon atom of the alkyl group, more preferably on the secondary carbon atom. Specifically, in formulas (A01-1) to (A01-3), Z ^{01 is} preferably isopropyl, isobutyl, s-butyl, t-butyl, n-pent-2-yl, n -Pent-3-yl, n-hex-2-yl, n-hex-3-yl, n-hept-2-yl, n-hept-3-yl, n-hept-4-yl, n-octyl -2-yl, n-oct-3-yl, n-oct-4-yl, etc., but not limited to these.

本發明中，式(P1)中之烷基、烯基及炔基的碳數，基於對有機溶劑之溶解性觀點，較佳為15以下，更佳為10以下，再更佳為8以下，再更佳為5以下；芳基的碳數較佳為15以下，更佳為10以下。In the present invention, the carbon number of the alkyl group, alkenyl group, and alkynyl group in formula (P1) is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less, from the viewpoint of solubility in organic solvents. Even more preferably, it is 5 or less; the carbon number of the aryl group is preferably 15 or less, and more preferably 10 or less.

Ar表示式(S1)～(S6)之任一者所示之基。

Ar represents a base represented by any one of formulas (S1) to (S6).

a⁰¹¹ ～a¹⁸³ 彼此獨立為表示取代為芳香環之取代基數的整數。 a⁰⁷¹ 、a⁰⁸¹ 、a⁰⁹¹ 、a¹⁰¹ 及a¹¹¹ 為0～3。 a⁰⁵¹ 、a⁰⁶¹ 、a⁰⁷² 、a⁰⁸² 、a⁰⁹² 、a¹⁰² 、a¹¹² 、a¹¹³ 、a¹¹⁴ 、a¹²¹ 、a¹³¹ 、a¹⁴¹ 、a¹⁵¹ 、a¹⁶¹ 、a¹⁷¹ 、a¹⁸¹ 、a¹⁸² 及a¹⁸³ 為0～4。 a⁰¹¹ 、a⁰⁵² 、a⁰⁶² 、a¹²² 、a¹²³ 及a¹³² 為0～5。 a⁰²¹ 、a¹³³ 、a¹⁴² 、a¹⁴³ 、a¹⁵² 、a¹⁵³ 、a¹⁶² 及a¹⁶³ 為0～7。 a⁰³¹ 及a⁰⁴¹ 為0～9。a ⁰¹¹ to a ¹⁸³ are independent of each other and represent an integer indicating the number of substituents substituted with an aromatic ring. a ⁰⁷¹ , a ⁰⁸¹ , a ⁰⁹¹ , a ¹⁰¹ and a ^{111 are} from 0 to 3. a ⁰⁵¹ , a ⁰⁶¹ , a ⁰⁷² , a ⁰⁸² , a ⁰⁹² , a ¹⁰² , a ¹¹² , a ¹¹³ , a ¹¹⁴ , a ¹²¹ , a ¹³¹ , a ¹⁴¹ , a ¹⁵¹ , a ¹⁶¹ , a ¹⁷¹ , a ¹⁸¹ , a ¹⁸² And a ¹⁸³ is 0-4. a ⁰¹¹ , a ⁰⁵² , a ⁰⁶² , a ¹²² , a ¹²³ and a ¹³² are 0-5. a ⁰²¹ , a ¹³³ , a ¹⁴² , a ¹⁴³ , a ¹⁵² , a ¹⁵³ , a ¹⁶² and a ^{163 are 0-7} . a ⁰³¹ and a ⁰⁴¹ are 0-9.

如考量原料化合物之取得性或合成容易性、所得聚合物之溶解性、所得電荷輸送性薄膜之電荷輸送性等的平衡，a⁰¹¹ 較佳為0～3，更佳為1或2；a⁰²¹ ～a¹⁸³ 較佳為0或1，更佳為0。Considering the balance of ^availability or ease of synthesis of raw material compounds, solubility of the obtained polymer, charge transportability of the obtained charge transporting film, etc., a ^{011 is} preferably 0 to 3, more preferably 1 or 2; a ⁰²¹ ~a ^{183 is} preferably 0 or 1, more preferably 0.

本發明之聚合物未必有全部的重複單元具有同一結構之必要，亦可包含式(P1)所包含之不同結構的重複單元。又，各單元可隨機地鍵結，亦能以嵌段聚合物形式鍵結。The polymer of the present invention may not necessarily have all the repeating units to have the same structure, and may also include repeating units of different structures included in formula (P1). In addition, each unit can be randomly bonded, and can also be bonded in the form of a block polymer.

本發明之聚合物中的式(P1)所示之重複單元的含量，基於獲得電荷輸送性與溶解性優良的聚合物之觀點，在聚合物所含之總重複單元中，較佳為50莫耳%以上，更佳為70莫耳%以上，再更佳為90莫耳%以上，再更佳為95莫耳%以上，最佳為100莫耳%。The content of the repeating unit represented by the formula (P1) in the polymer of the present invention is preferably 50% of the total repeating units contained in the polymer from the viewpoint of obtaining a polymer excellent in charge transportability and solubility Ear% or more, more preferably 70 mole% or more, even more preferably 90 mole% or more, even more preferably 95 mole% or more, and most preferably 100 mole %.

本發明之聚合物的重量平均分子量通常為1,000～100,000，而基於對有機溶劑之溶解性之觀點，較佳為20,000以下，更佳為10,000以下；基於電荷輸送性之觀點，較佳為3,000以上，更佳為5,000以上。此外，本發明中的重量平均分子量係根據凝膠滲透層析(下稱GPC)分析之以標準聚苯乙烯換算所得的平均分子量。The weight average molecular weight of the polymer of the present invention is usually 1,000 to 100,000, and from the viewpoint of solubility in organic solvents, it is preferably 20,000 or less, more preferably 10,000 or less; from the viewpoint of charge transportability, it is preferably 3,000 or more , More preferably 5,000 or more. In addition, the weight-average molecular weight in the present invention is the average molecular weight obtained by standard polystyrene conversion based on gel permeation chromatography (hereinafter referred to as GPC) analysis.

本發明之聚合物可使式(A1)所示之三苯基胺衍生物與式(H1)所示之三苯基胺衍生物反應來製造。The polymer of the present invention can be produced by reacting the triphenylamine derivative represented by formula (A1) with the triphenylamine derivative represented by formula (H1).

(式中，X彼此獨立表示氯原子、溴原子、碘原子或假鹵素基，Ph及G表示與前述相同意義)。

(In the formula, X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G have the same meanings as described above).

作為假鹵素基，可舉出甲磺醯氧基、三氟甲磺醯氧基、九氟丁磺醯氧基等(氟)烷基磺醯氧基；苯磺醯氧基、甲苯磺醯氧基等芳香族磺醯氧基等。Examples of the pseudo-halogen group include (fluoro)alkylsulfonyloxy groups such as mesyloxy, trifluoromethanesulfonyloxy, nonafluorobutanesulfonyloxy; benzenesulfonyloxy, tosylate Aromatic sulfonyloxy and other groups.

式(A1)所示之三苯基胺衍生物與式(H1)所示之三苯基胺衍生物的饋入比，相對於式(H1)所示之三苯基胺衍生物，可將式(A1)所示之三苯基胺衍生物取1當量以上，宜為1～1.5當量左右。The feed ratio of the triphenylamine derivative represented by the formula (A1) to the triphenylamine derivative represented by the formula (H1), relative to the triphenylamine derivative represented by the formula (H1), the The triphenylamine derivative represented by formula (A1) should be 1 equivalent or more, preferably about 1 to 1.5 equivalents.

作為用於上述反應之觸媒，可舉出例如氯化銅、溴化銅、碘化銅等的銅觸媒；Pd(PPh₃ )₄ (肆(三苯基膦)鈀)、Pd(PPh₃ )₂ Cl₂ (雙(三苯基膦)二氯鈀)、Pd(dba)₂ (雙(二苄叉丙酮)鈀)、Pd₂ (dba)₃ (參(二苄叉丙酮)二鈀)、Pd(P-t-Bu₃ )₂ (雙(三(t-丁基膦))鈀)、Pd(OAc)₂ (乙酸鈀)等的鈀觸媒等。此等觸媒可單獨使用，亦可組合2種以上使用。又，此等觸媒亦可與周知之合宜的配位子共同使用。 作為此種配位基，可舉出三苯基膦、三-o-甲苯基膦、二苯基甲基膦、苯基二甲基膦、三甲基膦、三乙基膦、三丁基膦、三-t-丁基膦、二-t-丁基(苯基)膦、二-t-丁基(4-二甲胺基苯基)膦、1,2-雙(二苯基膦)乙烷、1,3-雙(二苯基膦)丙烷、1,4-雙(二苯基膦)丁烷、1,1’-雙(二苯基膦)二茂鐵等三級膦、亞磷酸三甲酯、亞磷酸三乙酯、亞磷酸三苯酯等三級亞磷酸酯等。Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; Pd(PPh ₃ ) ₄ (U (triphenylphosphine) palladium), Pd(PPh ₃ ) ₂ Cl ₂ (bis(triphenylphosphine) dichloropalladium), Pd(dba) ₂ (bis(dibenzylideneacetone) palladium), Pd ₂ (dba) ₃ (Shen (dibenzylideneacetone) dipalladium) ), Pd(Pt-Bu ₃ ) ₂ (bis(tris(t-butylphosphine)) palladium), Pd(OAc) ₂ (palladium acetate) and other palladium catalysts and the like. These catalysts can be used alone or in combination of two or more. In addition, these catalysts can also be used with well-known suitable ligands. Examples of such ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, and tributyl Phosphine, tri-t-butylphosphine, di-t-butyl(phenyl)phosphine, di-t-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphine ) Terane such as ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,1'-bis(diphenylphosphine)ferrocene , Tertiary phosphite such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc.

觸媒的用量，相對於式(H1)所示之三苯基胺衍生物1mol可取0.01～0.2mol左右，宜為0.1mol左右。 又，使用配位基時，相對於所用金屬錯合物(觸媒)，其用量可取0.1～5當量，宜為1～2當量。The amount of the catalyst may be about 0.01 to 0.2 mol, preferably about 0.1 mol, relative to 1 mol of the triphenylamine derivative represented by the formula (H1). In addition, when using a ligand, the amount of the metal complex (catalyst) used may be 0.1 to 5 equivalents, preferably 1 to 2 equivalents.

基於原料化合物全為固體時，或者有效獲得目標聚合物之觀點，上述各反應係於溶劑中進行。使用溶劑時，就其種類，只要不會對反應造成不良影響則不特別限制。作為具體例，可舉出脂肪族烴類(戊烷、n-己烷、n-辛烷、n-癸烷、十氫萘等)、鹵化脂肪族烴類(氯仿、二氯甲烷、二氯乙烷、四氯化碳等)、芳香族烴類(苯、硝基苯、甲苯、鄰二甲苯、間二甲苯、對二甲苯、均三甲苯等)、鹵化芳香族烴類(氯苯、溴苯、鄰二氯苯、間二氯苯、對二氯苯等)、醚類(二乙基醚、二異丙基醚、t-丁基甲基醚、四氫呋喃、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)、酮類(丙酮、甲基乙基酮、甲基異丁基酮、二-n-丁基酮、環己酮等)、醯胺類(N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等)、內醯胺及內酯類(N-甲基吡咯啶酮、γ-丁內酯等)、尿素類(N,N-二甲基咪唑啉酮、四甲基脲等)、亞碸類(二甲基亞碸、環丁碸等)、腈類(乙腈、丙腈、丁腈等)等，此等溶劑可單獨使用，亦可混合2種以上使用。From the viewpoint that the raw material compounds are all solid, or the target polymer is effectively obtained, the above reactions are carried out in a solvent. When a solvent is used, its type is not particularly limited as long as it does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, methylene chloride, dichloromethane) Ethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, Bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, 1,2- Dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc. ), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), lactamides and lactones (N-methylpyrrolidone, γ-butyrolactone Esters), ureas (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfonamides (dimethyl sulfoxide, cipros, etc.), nitriles (acetonitrile, propionitrile, butyl Nitrile, etc.) These solvents can be used alone or in combination of two or more.

反應溫度只要在所用溶劑的熔點至沸點的範圍適宜設定即可，尤以0～200℃左右，更佳為20～150℃。 反應結束後，依循常用方法實施後處理，可獲得目標聚合物。The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, particularly about 0 to 200°C, and more preferably 20 to 150°C. After the reaction is completed, post-treatment is carried out in accordance with common methods to obtain the target polymer.

本發明之聚合物的製造中所使用之式(A1)所示之三苯基胺衍生物可使用市售品，亦可依循下述所示路徑圖，依以下方法來製造。 根據周知之方法，使下述既定的苯胺衍生物與例如4-氟硝基苯反應而得到對應的二硝基化合物。然後，使所得之二硝基化合物的硝基，藉由使用例如Pd/C的氫化反應轉換成胺基。The triphenylamine derivative represented by the formula (A1) used in the production of the polymer of the present invention may be a commercially available product, or may be produced by the following method according to the route diagram shown below. According to a well-known method, the following predetermined aniline derivative is reacted with, for example, 4-fluoronitrobenzene to obtain the corresponding dinitro compound. Then, the nitro group of the obtained dinitro compound is converted into an amine group by, for example, hydrogenation reaction using Pd/C.

(式中，Ph及G表示與前述相同意義)。

(In the formula, Ph and G have the same meaning as described above).

本發明之聚合物的製造中所使用之式(H1)所示之三苯基胺衍生物可使用市售品，亦可依循下述所示路徑圖，將對應的三苯基胺衍生物鹵化或假鹵化。鹵化或假鹵化可依循通用方法，使用鹵化試劑或假鹵化試劑來進行。The triphenylamine derivative represented by the formula (H1) used in the production of the polymer of the present invention can be a commercially available product, or the corresponding triphenylamine derivative can be halogenated according to the route diagram shown below Or false halogenation. Halogenation or pseudohalogenation can be carried out using a halogenation reagent or pseudohalogenation reagent according to a general method.

(式中，Ph、G及X表示與前述相同意義)。

(In the formula, Ph, G and X have the same meaning as described above).

以下舉出本發明之聚合物的較佳之一例，但本發明不限定於此。The following is a preferred example of the polymer of the present invention, but the present invention is not limited thereto.

(k為表示重複單元之整數，係依據聚合物的分子量來決定)。

(k is an integer representing a repeating unit and is determined according to the molecular weight of the polymer).

本發明之聚合物係顯示對有機溶劑之良好的溶解性，藉由使本發明之聚合物作為電荷輸送性物質溶解於有機溶劑，可製造電荷輸送性組成物。The polymer of the present invention exhibits good solubility in organic solvents, and by dissolving the polymer of the present invention as a charge-transporting substance in an organic solvent, a charge-transporting composition can be produced.

作為此種有機溶劑，可使用能良好地溶解本發明之聚合物的高溶解性有機溶劑。 作為其具體例，可舉出氯仿、氯苯等氯系溶劑、甲苯、二甲苯、四氫萘、環己基苯、3-苯氧基甲苯等芳香族烴系溶劑等的低極性高溶解性有機溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基異丁醯胺、N-甲基吡咯啶酮、1,3-二甲基-2-咪唑啉酮等醯胺系溶劑、異佛爾酮、環己酮等酮系溶劑、乙酸乙酯、苯甲酸甲酯等酯系溶劑、乙二醇、二乙二醇等多元醇系溶劑、四氫呋喃、二噁烷、苯甲醚等醚系溶劑、二甲基亞碸等亞碸系溶劑等極性高溶解性有機溶劑。 此等有機溶劑可單獨使用1種或混合2種以上使用，其用量可取使用於電荷輸送性組成物之全部溶劑中的5～100質量%。As such an organic solvent, a highly soluble organic solvent that can dissolve the polymer of the present invention well can be used. Specific examples thereof include low-polarity and high-solubility organic solvents such as chlorine-based solvents such as chloroform and chlorobenzene, aromatic hydrocarbon-based solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and 3-phenoxytoluene. Solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, 1,3-dimethyl Acylamine solvents such as 2-methylimidazolidinone, ketone solvents such as isophorone and cyclohexanone, ester solvents such as ethyl acetate and methyl benzoate, polyhydric alcohols such as ethylene glycol and diethylene glycol Solvents, ether solvents such as tetrahydrofuran, dioxane, and anisole; benzene sulfonate solvents such as dimethyl sulfoxide; polar polar highly soluble organic solvents. These organic solvents may be used alone or in combination of two or more, and the amount may be 5 to 100% by mass in all solvents used in the charge transport composition.

又，前述有機溶劑亦可包含至少1種在25℃下具有10～200mPa・s，尤為35～150mPa・s的黏度，且在常壓(大氣壓)下沸點為50～300℃，尤為150～250℃的高黏度有機溶劑。藉由添加此種溶劑，便容易調整電荷輸送性組成物的黏度，可再現性良好地提供高平坦性的薄膜，且可隨所用塗佈方法來調製組成物。In addition, the aforementioned organic solvent may also include at least one kind having a viscosity of 10 to 200 mPa·s at 25°C, especially 35 to 150 mPa·s, and a boiling point of 50 to 300°C, especially 150 to 250 at normal pressure (atmospheric pressure). ℃ high viscosity organic solvent. By adding such a solvent, the viscosity of the charge transporting composition can be easily adjusted, a highly flat film can be provided with good reproducibility, and the composition can be prepared according to the coating method used.

作為高黏度有機溶劑，可舉出例如環己醇、乙二醇、乙二醇二環氧丙基醚、1,3-辛二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、丙二醇、己二醇等，但不限定於此等。高黏度有機溶劑亦可兼作高溶解性有機溶劑，其係依據屬電荷輸送性物質之聚合物的結構來決定。Examples of high-viscosity organic solvents include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and triethylene glycol. Propylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexanediol, etc. are not limited thereto. The high-viscosity organic solvent can also double as the high-solubility organic solvent, which is determined according to the structure of the polymer which is a charge transporting substance.

添加高黏度有機溶劑時，其添加比例較佳為不析出固體的範圍內；只要不析出固體，則較佳為使用於電荷輸送性組成物之全部溶劑中的5～90質量%。When a high-viscosity organic solvent is added, the addition ratio is preferably within a range where solids are not precipitated; as long as solids are not precipitated, it is preferably 5 to 90% by mass in all solvents used in the charge transport composition.

再者，以提升對基板之浸潤性、調整溶劑之表面張力、調整極性、調整沸點等為目的，亦能以使用於電荷輸送性組成物之全部溶劑中的1～90質量%，較佳為1～50質量%的比例混合其他溶劑。Furthermore, for the purpose of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., 1 to 90% by mass of all solvents used in the charge transport composition can also be used, preferably Mix other solvents in a ratio of 1 to 50% by mass.

作為此種溶劑，可舉出例如丙二醇單甲基醚、乙二醇單丁基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇二甲基醚、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二乙二醇單乙基醚、二丙酮醇、γ-丁內酯、乳酸乙酯、乙酸n-己酯等，但不限定於此等。此等溶劑可單獨使用1種或混合2種以上使用。此外，以同樣目的使用的溶劑有時兼具高溶解性有機溶劑之機能。Examples of such solvents include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, di Acetone alcohol, γ-butyrolactone, ethyl lactate, n-hexyl acetate, etc. are not limited thereto. These solvents can be used alone or in combination of two or more. In addition, the solvent used for the same purpose sometimes has the function of a highly soluble organic solvent.

本發明之電荷輸送性組成物，以提升所得電荷輸送性薄膜的電荷輸送性等為目的，亦可包含摻雜物質(電荷接受性物質)或摻雜物質前驅物(電荷接受性物質前驅物)。The charge-transporting composition of the present invention may include a doping substance (charge-receiving substance) or a doping substance precursor (charge-receiving substance precursor) for the purpose of improving the charge-transporting properties of the obtained charge-transporting thin film. .

就摻雜物質而言，只要是可溶解於使用於電荷輸送性組成物之至少一種溶劑者則不特別限定，作為有機系電荷接受性物質，由芳基磺酸、陰離子與其抗衡陽離子所構成的離子化合物、四氰基醌二甲烷衍生物或苯醌衍生物等有機系摻雜物質；芳基磺酸酯等有機系摻雜物質前驅物；磷鎢酸、磷鉬酸等無機系摻雜物質的任一種皆可使用。The doping substance is not particularly limited as long as it is soluble in at least one solvent used in the charge transporting composition, and it is composed of an arylsulfonic acid, an anion and its counter cation as an organic charge-accepting substance Organic dopants such as ionic compounds, tetracyanoquinodimethane derivatives or benzoquinone derivatives; precursors of organic dopants such as arylsulfonates; inorganic dopants such as phosphotungstic acid and phosphomolybdic acid Any of them can be used.

本發明中之較佳一例的電荷輸送性組成物係包含由式(1)所示之磺酸酯化合物所構成的摻雜物質前驅物。A preferred example of the charge-transporting composition in the present invention includes a dopant precursor composed of a sulfonate compound represented by formula (1).

R¹ 及R² 彼此獨立表示氫原子、或直鏈狀或者分支狀之一價脂肪族烴基，R³ 表示直鏈狀或者分支狀之一價脂肪族烴基。惟，R¹ 、R² 及R³ 之碳數的合計為6以上。R¹ 、R² 及R³ 之碳數的合計的上限不特別限定，較佳為20以下，更佳為10以下。R ¹ and R ² independently represent a hydrogen atom, or a linear or branched monovalent aliphatic hydrocarbon group, and R ³ represents a linear or branched monovalent aliphatic hydrocarbon group. However, the total carbon number of R ¹ , R ² and R ³ is 6 or more. The upper limit of the total number of carbon atoms of R ¹ , R ² and R ³ is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.

作為前述直鏈狀或者分支狀之一價脂肪族烴基，不特別限定，可舉出甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、t-丁基、n-己基、n-辛基、2-乙基己基、癸基等碳數1～18之烷基；乙烯基、1-丙烯基、2-丙烯基、異丙烯基、1-甲基-2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、己烯基等碳數2～18之烯基等。The linear or branched monovalent aliphatic hydrocarbon group is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. , N-hexyl, n-octyl, 2-ethylhexyl, decyl and other alkyl groups with 1 to 18 carbon atoms; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl- C2-C18 alkenyl groups such as 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, hexenyl, etc.

作為R¹ ，較佳為氫原子；作為R² 及R³ ，較佳為碳數1～6之烷基。此時，R² 及R³ 可相同或相異。R ^{1 is} preferably a hydrogen atom; and R ² and R ^{3 are} preferably C 1-6 alkyl groups. At this time, R ² and R ³ may be the same or different.

A¹ 表示-O-或-S-，較佳為-O-。A² 表示(n+1)價芳香族烴基。A³ 表示包含1個以上之芳香環的經取代或未取代之m價烴基。A ¹ represents -O- or -S-, preferably -O-. A ² represents a (n+1)-valent aromatic hydrocarbon group. A ³ represents a substituted or unsubstituted m-valent hydrocarbon group containing one or more aromatic rings.

A² 所示之(n+1)價芳香族烴基係由芳香族烴化合物之芳香環上移除(n+1)個氫原子而得到的基團。作為前述芳香族烴化合物，可舉出苯、甲苯、二甲苯、萘、蒽、菲等。此等當中，作為A² ，較佳為衍生自萘或蒽之基團，更佳為衍生自萘之基團。The (n+1)-valent aromatic hydrocarbon group shown in A ^{2 is a} group obtained by removing (n+1) hydrogen atoms from the aromatic ring of the aromatic hydrocarbon compound. Examples of the aromatic hydrocarbon compounds include benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. Among these, as A ² , a group derived from naphthalene or anthracene is preferred, and a group derived from naphthalene is more preferred.

A³ 所示之包含1個以上之芳香環的經取代或未取代之m價烴基係由包含1個以上之芳香環的經取代或未取代之烴化合物移除m個鍵結於碳骨架之原子或原子團而得到的基團。作為前述烴化合物，可舉出苯、甲苯、二甲苯、乙基苯、聯苯、萘、蒽、菲等，或此等基團的一部分或全部氫原子進一步經羥基、胺基、矽醇基、硫醇基、羧基、磺酸酯基、磷酸基、磷酸酯基、酯基、硫酯基、醯胺基、硝基、一價烴基、有機氧基、有機胺基、有機矽烷基、有機硫基、醯基、磺基、鹵素原子等取代者。The substituted or unsubstituted m-valent hydrocarbon group containing more than one aromatic ring shown in A ^{3 is} removed from the carbon skeleton by the substituted or unsubstituted hydrocarbon compound containing more than one aromatic ring A group derived from an atom or group of atoms. Examples of the aforementioned hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene, etc., or a part or all of the hydrogen atoms of these groups may further pass through a hydroxyl group, an amine group, or a silanol group. , Thiol group, carboxyl group, sulfonate group, phosphate group, phosphate group, ester group, thioester group, amide group, nitro group, monovalent hydrocarbon group, organic oxygen group, organic amine group, organic silane group, organic Thio, acetyl, sulfo, halogen atoms and other substitutions.

若考量提升式(1)所示之磺酸酯化合物的耐久性及提升電荷輸送性，作為A³ ，較佳為衍生自1,3,5-三嗪之二價或三價基團、衍生自經取代或未取代之苯之二價或三價基團、衍生自經取代或未取代之甲苯之二價或三價基團、衍生自經取代或未取代之對二甲苯之二價基團、衍生自經取代或未取代之萘之二價或三價基團、衍生自全氟聯苯基之二～四價基團等，較佳為二價全氟聯苯基。In consideration of enhancing the durability of the sulfonate compound represented by formula (1) and improving the charge transport property, as A ³ , it is preferably derived from a divalent or trivalent group derived from 1,3,5-triazine, derived Divalent or trivalent groups from substituted or unsubstituted benzene, divalent or trivalent groups derived from substituted or unsubstituted toluene, divalent groups derived from substituted or unsubstituted para-xylene The group, a divalent or trivalent group derived from substituted or unsubstituted naphthalene, a bi- to tetravalent group derived from perfluorobiphenyl, etc., preferably a divalent perfluorobiphenyl.

m表示滿足2≦m≦4之整數，較佳為2。n表示滿足1≦n≦4之整數，較佳為2。m represents an integer satisfying 2≦m≦4, preferably 2. n represents an integer satisfying 1≦n≦4, preferably 2.

式(1)所示之磺酸酯化合物亦可藉由國際公開第2017/217457號所記載之方法來合成。The sulfonate compound represented by formula (1) can also be synthesized by the method described in International Publication No. 2017/217457.

當本發明之電荷輸送性組成物包含摻雜物質或摻雜物質前驅物時，其含量係視彼等的種類或所期望的電荷輸送性等適宜決定，無法一概地規定；以質量比計，相對於本發明之聚合物1，摻雜物質與摻雜物質前驅物的合計為0.01～10的範圍內。When the charge-transporting composition of the present invention contains a dopant substance or a dopant substance precursor, its content is appropriately determined depending on their types or desired charge-transporting characteristics, etc., and cannot be specified in a general manner; in terms of mass ratio, With respect to the polymer 1 of the present invention, the total amount of dopant and dopant precursor is in the range of 0.01 to 10.

以下舉出本發明中較佳之摻雜物質或摻雜物質前驅物的具體例，但不限定於此等。Specific examples of the preferred doping substance or doping substance precursor in the present invention are given below, but are not limited thereto.

此外，電荷輸送性物質以及摻雜物質及摻雜物質前驅物係以完全溶解於前述溶劑，或呈均勻分散之狀態為佳，最佳為完全溶解。In addition, the charge transporting substance, the dopant substance and the dopant substance precursor are preferably completely dissolved in the aforementioned solvent or uniformly dispersed, and most preferably completely dissolved.

本發明之電荷輸送性組成物亦可包含水作為溶劑，而基於將由組成物所得之電荷輸送性薄膜作為有機EL元件之電洞注入層使用時可再現性良好地獲得高耐久性之元件之觀點，水的含量較佳為溶劑全體的10質量%以下，更佳為5質量%以下，最佳為僅使用有機溶劑作為溶劑。 此外，此時之「僅有有機溶劑」，係指作為溶劑使用者僅為有機溶劑之意，不否定微量地含於所用之有機溶劑或固體成分等的「水」之存在。 此外，本發明中所稱固體成分，係指電荷輸送性組成物所含之溶劑以外的成分。The charge-transporting composition of the present invention may contain water as a solvent, and it is based on the viewpoint that a highly durable device can be obtained with good reproducibility when the charge-transporting thin film obtained from the composition is used as a hole injection layer of an organic EL device The water content is preferably 10% by mass or less of the entire solvent, more preferably 5% by mass or less, and most preferably, only organic solvents are used as the solvent. In addition, "organic solvent only" at this time means that the user of the solvent is only an organic solvent, and does not deny the existence of "water" contained in a small amount in the organic solvent or solid components used. In addition, the solid content in the present invention refers to components other than the solvent contained in the charge transporting composition.

本發明中，就電荷輸送性組成物而言，基於可再現性良好地獲得平坦性更高的薄膜之觀點，係以使電荷輸送性物質溶解於有機溶劑後，使用亞微米級過濾器等加以過濾為宜。In the present invention, the charge-transporting composition is obtained by dissolving the charge-transporting substance in an organic solvent from the viewpoint of obtaining a thin film with higher flatness with good reproducibility. Filtration is appropriate.

本發明之電荷輸送性組成物中的固體成分濃度，基於可抑制電荷輸送性物質的析出並確保充分的膜厚之觀點，通常為0.1～20質量%左右，較佳為0.5～15質量%。The solid content concentration in the charge-transporting composition of the present invention is usually about 0.1 to 20% by mass, preferably 0.5 to 15% by mass from the viewpoint of suppressing the precipitation of the charge-transporting substance and ensuring a sufficient film thickness.

本發明之電荷輸送性組成物的黏度通常在25℃下為1～50mPa・s，表面張力通常在25℃下為20～50mN/m。 本發明之電荷輸送性組成物的黏度與表面張力，可考量所用塗佈方法、所期望的膜厚等各種要素，變更所用有機溶劑的種類或彼等的比率、固體成分濃度等來調整。The viscosity of the charge transporting composition of the present invention is usually 1 to 50 mPa·s at 25°C, and the surface tension is usually 20 to 50 mN/m at 25°C. The viscosity and surface tension of the charge-transporting composition of the present invention can be adjusted by taking into consideration various factors such as the coating method used, the desired film thickness, and the like, and changing the type or ratio of the organic solvent used, the solid content concentration, and the like.

本發明之電荷輸送性組成物可使本發明之聚合物溶解於有機溶劑來製造。亦可預先使本發明之聚合物溶解於有機溶劑，並對其依序添加其他有機溶劑，預先製作所用之全部溶劑的混合溶劑，並使本發明之聚合物溶解於其中。當本發明之電荷輸送性組成物包含本發明之聚合物與溶劑以外的成分時亦依循同樣的程序。 又，若有需要，亦可注意勿使組成物所含之成分分解或變質地加熱而促進聚合物等的溶解。The charge transporting composition of the present invention can be produced by dissolving the polymer of the present invention in an organic solvent. It is also possible to dissolve the polymer of the present invention in an organic solvent in advance and add other organic solvents in sequence to prepare a mixed solvent of all solvents used in advance and dissolve the polymer of the present invention therein. The same procedure is followed when the charge-transporting composition of the present invention contains components other than the polymer and the solvent of the present invention. In addition, if necessary, care can be taken not to decompose the components contained in the composition or change the texture to heat to promote the dissolution of the polymer or the like.

藉由將本發明之電荷輸送性組成物塗佈於基材上並進行燒成，可於基材上形成本發明之電荷輸送性薄膜。By applying the charge-transporting composition of the present invention to a substrate and firing it, the charge-transporting thin film of the present invention can be formed on the substrate.

作為電荷輸送性組成物之塗佈方法，可舉出浸漬法、旋轉塗佈法、轉印印刷法、輥塗法、毛刷塗佈、噴墨法、噴霧法、狹縫塗佈法等，但不限定於此等。較佳依據塗佈方法來調節電荷輸送性組成物的黏度及表面張力。Examples of the coating method of the charge transport composition include dipping method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spray method, slit coating method, etc. But it is not limited to this. Preferably, the viscosity and surface tension of the charge transport composition are adjusted according to the coating method.

又，燒成條件亦不特別限定，例如使用加熱板進行加熱燒成。一般而言，燒成溫度係於100～260℃的範圍內，燒成時間係於1分鐘～1小時的範圍內。燒成環境亦不特別限定，較佳為空氣下。 再者，亦可視需求以不同的2種以上之溫度進行多階段之燒成。In addition, the firing conditions are not particularly limited. For example, the firing is performed using a hot plate. Generally, the firing temperature is in the range of 100 to 260°C, and the firing time is in the range of 1 minute to 1 hour. The firing environment is also not particularly limited, preferably under air. In addition, multi-stage firing can be carried out at two or more different temperatures as required.

電荷輸送性薄膜的膜厚不特別限定，在作為有機EL元件之機能層使用時，較佳為5～300nm。作為改變膜厚之方法，有改變電荷輸送性組成物中的固體成分濃度，或改變塗佈時的液量等方法。The thickness of the charge transporting thin film is not particularly limited, and when used as a functional layer of an organic EL element, it is preferably 5 to 300 nm. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the charge-transporting composition or changing the amount of liquid at the time of coating.

本發明之有機EL元件係具有一對電極，且於此等電極之間具有上述本發明之電荷輸送性薄膜。 作為有機EL元件的代表性構造，可舉出以下(a)～(f)，但並不限定於此等。此外，下述構造中，亦可視需求在發光層與陽極之間設置電子阻擋層等、在發光層與陰極之間設置正孔(電洞)阻擋層等。又，電洞注入層、電洞輸送層或者電洞注入輸送層亦可兼備作為電子阻擋層等之機能，電子注入層、電子輸送層或者電子注入輸送層亦可兼備作為正孔(電洞)阻擋層等之機能。再者，亦可視需求於各層之間設置任意的機能層。 (a)陽極/電洞注入層/電洞輸送層/發光層/電子輸送層/電子注入層/陰極 (b)陽極/電洞注入層/電洞輸送層/發光層/電子注入輸送層/陰極 (c)陽極/電洞注入輸送層/發光層/電子輸送層/電子注入層/陰極 (d)陽極/電洞注入輸送層/發光層/電子注入輸送層/陰極 (e)陽極/電洞注入層/電洞輸送層/發光層/陰極 (f)陽極/電洞注入輸送層/發光層/陰極The organic EL device of the present invention has a pair of electrodes, and has the above-mentioned charge transport film of the present invention between these electrodes. As a typical structure of the organic EL element, the following (a) to (f) may be mentioned, but it is not limited thereto. In addition, in the following structure, an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a positive hole (hole) blocking layer or the like may be provided between the light emitting layer and the cathode as required. In addition, the hole injection layer, the hole transport layer, or the hole injection transport layer can also function as an electron blocking layer, etc., and the electron injection layer, electron transport layer, or electron injection transport layer can also function as a positive hole (hole) Functions such as barriers. Furthermore, any functional layer can be set between the layers according to the requirements. (a) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (b) Anode/hole injection layer/hole transport layer/light emitting layer/electron injection transport layer/cathode (c) Anode/hole injection transport layer/light emitting layer/electron transport layer/electron injection layer/cathode (d) Anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode (e) Anode/hole injection layer/hole transport layer/light emitting layer/cathode (f) Anode/hole injection transport layer/light emitting layer/cathode

「電洞注入層」、「電洞輸送層」及「電洞注入輸送層」係指形成於發光層與陽極之間的層，且具有將電洞由陽極輸送至發光層之機能者；在發光層與陽極之間設置1層電洞輸送性材料層時，其係「電洞注入輸送層」；在發光層與陽極之間設置2層以上之電洞輸送性材料層時，靠近陽極的層為「電洞注入層」，其以外的層則為「電洞輸送層」。尤其是電洞注入(輸送)層係使用來自陽極的電洞接受性且對電洞輸送(發光)層的電洞注入性亦優良的薄膜。 「電子注入層」、「電子輸送層」及「電子注入輸送層」係指形成於發光層與陰極之間的層，且具有將電子由陰極輸送至發光層之機能者；在發光層與陰極之間僅設置1層電子輸送性材料層時，其為「電子注入輸送層」；在發光層與陰極之間設置2層以上之電子輸送性材料層時，靠近陰極的層為「電子注入層」，其以外的層為「電子輸送層」。 「發光層」係指具有發光機能之有機層，採用摻雜系統時，係包含主體材料與摻雜物材料。此時，主體材料主要具有促進電子與電洞的再結合，並將激子侷限於發光層內之機能，摻雜物材料則具有使以再結合所得之激子有效地發光之機能。若為磷光元件時，主體材料主要具有將摻雜物所生成的激子侷限於發光層內之機能。The "hole injection layer", "hole transport layer" and "hole injection transport layer" refer to the layer formed between the light emitting layer and the anode, and have the function of transporting the hole from the anode to the light emitting layer; When a hole transporting material layer is provided between the light emitting layer and the anode, it is a "hole injection transporting layer"; when two or more hole transporting material layers are provided between the light emitting layer and the anode, the one close to the anode The layer is the "hole injection layer", and the other layers are the "hole transport layer". In particular, the hole injection (transport) layer uses a thin film that has hole acceptability from the anode and is excellent in hole injection property to the hole transport (luminescence) layer. "Electron injection layer", "electron transport layer" and "electron injection transport layer" refer to the layers formed between the light emitting layer and the cathode, and have the function of transporting electrons from the cathode to the light emitting layer; in the light emitting layer and the cathode When only one electron transporting material layer is provided between them, it is an "electron injection transporting layer"; when two or more electron transporting material layers are provided between the light emitting layer and the cathode, the layer close to the cathode is the "electron injection layer" ", the other layers are "electron transport layer". "Light-emitting layer" refers to an organic layer with light-emitting function. When a doping system is used, it includes a host material and a dopant material. At this time, the host material mainly has the function of promoting the recombination of electrons and holes, and confining excitons to the light emitting layer, and the dopant material has the function of making the exciton obtained by recombination effectively emit light. In the case of a phosphorescent element, the host material mainly has the function of confining the excitons generated by the dopant within the light-emitting layer.

本發明之電荷輸送性薄膜可適用於作為設於有機EL元件中之陽極與發光層之間的有機機能膜，更可適用於作為電洞注入層、電洞輸送層、電洞注入輸送層，更可適用於作為電洞注入層。The charge-transporting thin film of the present invention can be applied as an organic functional film provided between an anode and a light-emitting layer in an organic EL element, and can also be applied as a hole injection layer, a hole transport layer, and a hole injection transport layer. It is more suitable as a hole injection layer.

作為使用本發明之電荷輸送性組成物製作有機EL元件時的使用材料或製作方法，可舉出如下述者，但不限定於此等。Examples of materials used and methods for producing organic EL devices using the charge-transporting composition of the present invention include the following, but they are not limited thereto.

具有由本發明之電荷輸送性組成物所得之薄膜所構成的電洞注入層之OLED元件的製作方法之一例如下。此外，電極係以在不對電極造成不良影響的範圍內預先進行使用醇、純水等的洗淨或使用UV臭氧處理、氧-電漿處理等的表面處理。 在陽極基板上，藉由上述方法形成由本發明之電荷輸送性薄膜所構成的電洞注入層。將其導入於真空蒸鍍裝置內，依序蒸鍍電洞輸送層、發光層、電子輸送層、電子輸送層/正孔阻擋層、陰極金屬。或者，為了替代在該方法中以蒸鍍形成電洞輸送層與發光層，而使用包含電洞輸送性高分子的電洞輸送層形成用組成物與包含發光性高分子的發光層形成用組成物並藉由濕式製程來形成此等層。此外，可視需求在發光層與電洞輸送層之間設置電子阻擋層。An example of a method for manufacturing an OLED device having a hole injection layer composed of a thin film obtained from the charge transporting composition of the present invention is as follows. In addition, the electrode system is provided with a surface treatment such as washing with alcohol, pure water, or UV ozone treatment, oxygen plasma treatment, etc. in advance within a range that does not adversely affect the electrode. On the anode substrate, a hole injection layer composed of the charge-transporting thin film of the present invention is formed by the method described above. It is introduced into a vacuum evaporation device, and the hole transport layer, the light emitting layer, the electron transport layer, the electron transport layer/positive hole barrier layer, and the cathode metal are sequentially deposited. Alternatively, instead of forming the hole transport layer and the light emitting layer by vapor deposition in this method, a hole transport layer forming composition containing a hole transporting polymer and a light emitting layer forming composition containing a light emitting polymer are used These layers are formed by a wet process. In addition, an electron blocking layer may be provided between the light emitting layer and the hole transport layer according to requirements.

作為陽極材料，可舉出由以銦錫氧化物(ITO)、銦鋅氧化物(IZO)為代表之透明電極、以鋁為代表之金屬或此等的合金等所構成的金屬陽極，較佳為經過平坦化處理者。亦可使用具有高電荷輸送性的聚噻吩衍生物或聚苯胺衍生物。 此外，構成金屬陽極之其他金屬，可舉出金、銀、銅、銦或此等的合金等，但並不限定於此等。Examples of the anode material include a metal anode composed of a transparent electrode typified by indium tin oxide (ITO), indium zinc oxide (IZO), a metal typified by aluminum, or an alloy thereof, and the like is preferred. Those who have been flattened. Polythiophene derivatives or polyaniline derivatives having high charge transportability can also be used. In addition, other metals constituting the metal anode may include gold, silver, copper, indium, or these alloys, but are not limited thereto.

作為形成電洞輸送層之材料，可舉出(三苯基胺)二聚物衍生物、[(三苯基胺)二聚物]螺二聚物、N,N’-雙(萘-1-基)-N,N’-雙(苯基)-聯苯胺(α-NPD)、4,4’,4”-三[3-甲基苯基(苯基)胺基]三苯基胺(m-MTDATA)、4,4’,4”-三[1-萘(苯基)胺基]三苯基胺(1-TNATA)等三芳基胺類、5,5”-雙-{4-[雙(4-甲基苯基)胺基]苯基}-2,2’：5’,2”-第三噻吩(BMA-3T)等寡聚噻吩類等。Examples of the material for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spiro dimer, and N,N'-bis(naphthalene-1 -Yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4"-tri[1-naphthalene(phenyl)amino]triphenylamine (1-TNATA) and other triarylamines, 5,5"-bis-{4 -[Bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-third thiophene (BMA-3T) and other oligothiophenes and the like.

作為形成發光層之材料，可舉出對8-羥基喹啉之鋁錯合物等金屬錯合物、10-羥基苯并[h]喹啉之金屬錯合物、雙苯乙烯基苯衍生物、雙苯乙烯基伸芳基衍生物、(2-羥苯基)苯并噻唑之金屬錯合物、噻咯衍生物等低分子發光材料；聚(對苯乙烯)、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯乙烯]、聚(3-烷基噻吩)、聚乙烯基咔唑等高分子化合物混合發光材料與電子移動材料之系統等，但不限定於此等。 此外，以蒸鍍形成發光層時，亦可與發光性摻雜物進行共蒸鍍，作為發光性摻雜物，可舉出三(2-苯基吡啶)銥(III)(Ir(ppy)₃ )等金屬錯合物、或紅螢烯等并四苯衍生物、喹吖啶酮衍生物、苝等縮合多環芳香族環等，但不限定於此等。Examples of the material for forming the light-emitting layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, and bisstyrylbenzene derivatives , Bisstyryl aryl aryl derivatives, (2-hydroxyphenyl) benzothiazole metal complexes, silole derivatives and other low-molecular luminescent materials; poly (p-styrene), poly [2-methoxy -5-(2-ethylhexyloxy)-1,4-styrene], poly(3-alkylthiophene), polyvinylcarbazole and other polymer compounds mixed with luminescent materials and electronic mobile materials system, etc., But it is not limited to this. In addition, when the light-emitting layer is formed by vapor deposition, it may be co-evaporated with a light-emitting dopant. Examples of the light-emitting dopant include tris(2-phenylpyridine)iridium(III)(Ir(ppy) ₃ ) Condensed polycyclic aromatic rings such as metal complex compounds, naphthacene derivatives such as rubrene, quinacridone derivatives, and perylene, etc., but not limited thereto.

作為形成電子輸送層/正孔阻擋層之材料，可舉出噁二唑衍生物、***衍生物、啡啉衍生物、苯基喹喔啉衍生物、苯并咪唑衍生物、嘧啶衍生物等，但不限定於此等。Examples of the material for forming the electron transport layer/positive pore barrier layer include oxadiazole derivatives, triazole derivatives, morpholine derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives. , But not limited to this.

作為形成電子注入層之材料，可舉出氧化鋰(Li₂ O)、氧化鎂(MgO)、氧化鋁(Al₂ O₃ )等金屬氧化物、氟化鋰(LiF)、氟化鈉(NaF)金屬氟化物，但不限定於此等。 作為陰極材料，可舉出鋁、鎂-銀合金、鋁-鋰合金等，但不限定於此等。 作為形成電子阻擋層之材料，可舉出三(苯基吡唑)銥等，但不限定於此。Examples of the material for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (MgO), and aluminum oxide (Al ₂ O ₃ ), lithium fluoride (LiF), and sodium fluoride (NaF ) Metal fluoride, but not limited to these. Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like, but are not limited thereto. Examples of the material for forming the electron blocking layer include tris(phenylpyrazole)iridium and the like, but it is not limited thereto.

作為電洞輸送性高分子，可舉出聚[(9,9-二己基茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、聚[(9,9-二辛基茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,1’-伸聯苯基-4,4-二胺)]、聚[(9,9-雙{1’-戊烯-5’-基}茀基-2,7-二基)-co-(N,N’-雙{p-丁基苯基}-1,4-二胺基伸苯基)]、聚[N,N’-雙(4-丁基苯基)-N,N’-雙(苯基)-聯苯胺]-封端的聚倍半矽氧烷、聚[(9,9-雙二辛基茀基-2,7-二基)-co-(4,4’-(N-(p-丁基苯基))二苯基胺)]等。Examples of the hole transporting polymer include poly[(9,9-dihexyloxy-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1 ,4-diamino-phenylene)], poly[(9,9-dioctyl-chrysyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}- 1,1'-biphenyl-4,4-diamine)], poly[(9,9-bis{1'-pentene-5'-yl} stilbene-2,7-diyl)- co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylphenyl)], poly[N,N'-bis(4-butylphenyl)-N,N '-Bis(phenyl)-benzidine]-terminated polysilsesquioxanes, poly[(9,9-bisdioctyl stilbene-2,7-diyl)-co-(4,4' -(N-(p-butylphenyl))diphenylamine)] etc.

作為發光性高分子，可舉出聚(9,9-二烷基茀)(PDAF)等聚茀衍生物、聚(2-甲氧基-5-(2’-乙基己氧基)-1,4-伸苯基亞乙烯)(MEH-PPV)等聚伸苯基亞乙烯衍生物、聚(3-烷基噻吩)(PAT)等聚噻吩衍生物、聚乙烯基咔唑(PVCz)等。 [實施例]Examples of the light-emitting polymer include polyfluorene derivatives such as poly(9,9-dialkyl stilbene) (PDAF), poly(2-methoxy-5-(2'-ethylhexyloxy)- 1,4-phenylene vinylene) (MEH-PPV) and other polyphenylene vinylene derivatives, poly(3-alkylthiophene) (PAT) and other polythiophene derivatives, polyvinylcarbazole (PVCz) Wait. [Example]

以下根據實施例對本發明更具體地加以說明，惟本發明不限定於此。此外，使用之裝置如下： (1)基板洗淨：長州產業(股)製　基板洗淨裝置(減壓電漿方式) (2)組成物的塗佈：Mikasa(股)製　旋轉塗佈機MS-A100 (3)元件的製作：長州產業(股)製　多機能蒸鍍裝置系統C-E2L1G1-N (4)電流密度等的測定：EHC(股)製　多通道IVL測定裝置 (5)EL元件的壽命測定(半衰期的測定)：EHC(股)製　有機EL亮度壽命評定系統PEL-105S (6)重量平均分子量(Mw)及數量平均分子量(Mn)測定：島津製作所(股)製(管柱：SHODEX GPC KF-803L+GPC KF-804L、管柱溫度：40℃、檢測器：UV檢測器(254nm)及RI檢測器、沖提液：0.5%Et₃ N/THF、管柱流速：1.0mL/min.) (7)¹ H-NMR：Bruker公司製　Ascend500 (8)LC/MS：Waters公司製　ZQ2000The present invention will be described more specifically below based on examples, but the present invention is not limited thereto. In addition, the equipment used is as follows: (1) Substrate cleaning: Substrate cleaning device made by Changzhou Industry Co., Ltd. (reduced-pressure plasma method) (2) Coating of composition: Spin coater MS made by Mikasa Co., Ltd. -A100 (3) Production of components: Multi-function vapor deposition system C-E2L1G1-N manufactured by Changzhou Industry (Co., Ltd.) (4) Measurement of current density, etc.: Multi-channel IVL measurement equipment manufactured by EHC (Co) (5) EL device Lifetime measurement (half-life measurement): Organic EL brightness life evaluation system PEL-105S made by EHC (shares) (6) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn): Shimadzu Corporation (shares) (tube column) : SHODEX GPC KF-803L+GPC KF-804L, column temperature: 40℃, detector: UV detector (254nm) and RI detector, eluent: 0.5%Et ₃ N/THF, column flow rate: 1.0 mL/min.) (7) ¹ H-NMR: Ascend500 manufactured by Bruker (8) LC/MS: ZQ2000 manufactured by Waters

[1]原料化合物的合成 [合成例1]

[1] Synthesis of raw material compounds [Synthesis Example 1]

在三頸燒瓶內裝入4-s-丁基苯胺(4.48g,30mmol)與4-氟硝基苯(8.51g,60.3mmol)，進一步對其添加二甲基亞碸(45mL)與氟化銫(9.16g,60.3mmol)，以110℃進行加熱回流48小時。 將反應液冷卻至室溫後，將冷卻之反應液朝乙醇(750mL)滴下，濾取析出之固體，將所得過濾物用水(100mL)洗淨並加以乾燥，而得到化合物1(8.60g,73%)。¹ H-NMR(500MHz、CDCl3)：δ　0.87(t, J= 7.5Hz, 3H), 1.27(d, J= 7.0Hz, 3H), 1.62(quin, J= 7.5Hz, 2H), 2.65(sext, J= 7.0Hz, 1H), 7.08(d, J= 8.5Hz, 2H), 7.14(d, J= 9.0Hz, 4H), 7.23(d, J= 8.5Hz, 2H), 8.14(d, J= 9.0Hz, 4H).Into a three-necked flask was charged 4-s-butylaniline (4.48g, 30mmol) and 4-fluoronitrobenzene (8.51g, 60.3mmol), further added dimethyl sulfoxide (45mL) and fluorination Cesium (9.16g, 60.3mmol) was heated to reflux at 110°C for 48 hours. After the reaction liquid was cooled to room temperature, the cooled reaction liquid was dropped into ethanol (750 mL), and the precipitated solid was collected by filtration, and the resulting filtrate was washed with water (100 mL) and dried to obtain compound 1 (8.60 g, 73 %). ¹ H-NMR(500MHz, CDCl3): δ 0.87(t, J= 7.5Hz, 3H), 1.27(d, J= 7.0Hz, 3H), 1.62(quin, J= 7.5Hz, 2H), 2.65(sext , J = 7.0Hz, 1H), 7.08(d, J = 8.5Hz, 2H), 7.14(d, J = 9.0Hz, 4H), 7.23(d, J = 8.5Hz, 2H), 8.14(d, J = 9.0Hz, 4H).

[合成例2]

[Synthesis Example 2]

在三頸燒瓶內裝入化合物1(4.3g,11mmol)的乙醇懸浮液(65mL)，對其添加鈀碳(0.21g)與肼單水合物(6.5mL)，進行加熱回流5小時。 將反應液冷卻至室溫後，將冷卻之反應液進行矽藻土過濾，並將過濾物用乙醇(30mL)洗淨，回收此包含乙醇之濾液。 對回收之濾液添加水(400mL)並於0℃下攪拌30分鐘，濾取析出之固體並加以乾燥，而得到化合物2(3.00g,82%)。¹ H-NMR(500MHz、CDCl₃ )：δ　0.83(t,J= 7.5Hz, 3H), 1.19(d,J= 6.5Hz, 3H), 1.54(quin,J= 7.5Hz, 2H), 2.49(sext,J= 7.0Hz, 1H), 3.52(brs, 4H), 6.60(d,J= 8.5Hz, 4H), 6.83(d,J= 8.5Hz, 2H), 6.91-6.95(m, 6H). LC/MS(ESI⁺ )m/z；332[M+1]⁺ A three-necked flask was charged with an ethanol suspension (65 mL) of Compound 1 (4.3 g, 11 mmol), palladium carbon (0.21 g) and hydrazine monohydrate (6.5 mL) were added thereto, and the mixture was heated and refluxed for 5 hours. After the reaction solution was cooled to room temperature, the cooled reaction solution was filtered through celite, and the filtrate was washed with ethanol (30 mL) to recover the filtrate containing ethanol. Water (400 mL) was added to the recovered filtrate and stirred at 0°C for 30 minutes, and the precipitated solid was collected by filtration and dried to obtain Compound 2 (3.00 g, 82%). ¹ H-NMR(500MHz, CDCl ₃ ): δ 0.83(t, J= 7.5Hz, 3H), 1.19(d, J= 6.5Hz, 3H), 1.54(quin, J= 7.5Hz, 2H), 2.49( sext, J = 7.0Hz, 1H), 3.52(brs, 4H), 6.60(d, J = 8.5Hz, 4H), 6.83(d, J = 8.5Hz, 2H), 6.91-6.95(m, 6H). LC/MS(ESI ⁺ )m/z; 332[M+1] ⁺

[2]聚合物(polymer)的合成 [實施例1]

[2] Synthesis of polymer [Example 1]

在三頸燒瓶內裝入化合物2(1.50g,4.5mmol)、化合物3(1.72g,3.75mmol)、Pd(PPh₃ )₄ (0.43g,0.38mmol)及t-BuONa(0.86g,9mmol)，對其添加二甲苯(34mL)進行加熱回流4小時後，添加4-s-丁基苯胺(0.20g,1.35mmol)，進一步進行加熱回流3小時。 將反應液冷卻至室溫後，將冷卻之反應液與水(34mL)混合，並使用所得混合物與甲苯(17mL×2)進行分液處理，回收有機層並以硫酸鈉加以乾燥。 其次，濃縮乾燥之有機層，對所得濃縮物添加四氫呋喃(17mL)予以稀釋，將所得稀釋物朝甲醇(340mL)滴下並攪拌1小時。 其後，以抽吸過濾回收析出之粉末，使所得過濾物溶解於四氫呋喃(17mL)，將此溶液朝甲醇(340mL)滴下並攪拌1小時，以抽吸過濾回收析出之粉末並進行減壓乾燥，而得到聚合物A(2.20g)。 此外，化合物3係依循J.Mater.Chem., 2011,21,11800所記載之方法來合成。 Mw=3,871 Mn(GPC)=7,455 Mw/Mn=1.93A three-necked flask was charged with compound 2 (1.50 g, 4.5 mmol), compound 3 (1.72 g, 3.75 mmol), Pd(PPh ₃ ) ₄ (0.43 g, 0.38 mmol), and t-BuONa (0.86 g, 9 mmol) To this, xylene (34 mL) was added and heated to reflux for 4 hours, then 4-s-butylaniline (0.20 g, 1.35 mmol) was added, and heated and refluxed for 3 hours. After the reaction liquid was cooled to room temperature, the cooled reaction liquid was mixed with water (34 mL), and the resulting mixture was subjected to liquid separation treatment with toluene (17 mL×2), and the organic layer was recovered and dried over sodium sulfate. Next, the dried organic layer was concentrated, and the obtained concentrate was diluted with tetrahydrofuran (17 mL), and the resulting dilution was dropped into methanol (340 mL) and stirred for 1 hour. Thereafter, the precipitated powder was recovered by suction filtration, and the resulting filtrate was dissolved in tetrahydrofuran (17 mL). This solution was dropped into methanol (340 mL) and stirred for 1 hour. The precipitated powder was recovered by suction filtration and dried under reduced pressure. To obtain polymer A (2.20 g). In addition, compound 3 was synthesized according to the method described in J. Mater. Chem., 2011 , 21 , 11800. Mw=3,871 Mn(GPC)=7,455 Mw/Mn=1.93

[比較例1]

[Comparative Example 1]

在燒瓶內裝入4-s-丁基苯胺(1.51g,10.1mmol)、1,4-二溴苯(2.36g,10mmol)、Pd(dba)₄ (0.43g,0.38mmol)、[(t-Bu)₃ Ph]BF₄ (0.58g,2mmol)及t-BuONa (2.88g,30mmol)，對其添加甲苯(47mL)進行加熱回流3小時後，添加二苯基胺(0.34g,2mmol)，進一步進行加熱回流2小時。 將反應液冷卻至室溫後，將冷卻之反應液與水(50mL)混合，使用所得混合物與氯仿(50mL×2)進行分液處理，回收有機層並以硫酸鈉加以乾燥。 其次，濃縮乾燥之有機層，對所得濃縮物添加氯仿(50mL)予以稀釋，將所得稀釋物朝甲醇(470mL)滴下並攪拌1小時。 其後，以抽吸過濾回收析出之粉末，使所得過濾物溶解於氯仿(50mL)，將此溶液朝甲醇(470mL)滴下並攪拌1小時，以抽吸過濾回收析出之粉末並進行減壓乾燥，而得到聚合物X(1.88g)。 Mw=2,043　Mn=3,608　Mw/Mn=1.77Charge 4-s-butylaniline (1.51g, 10.1mmol), 1,4-dibromobenzene (2.36g, 10mmol), Pd(dba) ₄ (0.43g, 0.38mmol), ((t -Bu) ₃ Ph]BF ₄ (0.58g, 2mmol) and t-BuONa (2.88g, 30mmol), to which toluene (47mL) was added and heated to reflux for 3 hours, then diphenylamine (0.34g, 2mmol) was added , And further heated to reflux for 2 hours. After cooling the reaction liquid to room temperature, the cooled reaction liquid was mixed with water (50 mL), and the resulting mixture was subjected to liquid separation treatment with chloroform (50 mL×2), and the organic layer was recovered and dried over sodium sulfate. Next, the dried organic layer was concentrated, and the obtained concentrate was diluted with chloroform (50 mL), and the obtained dilution was dropped into methanol (470 mL) and stirred for 1 hour. Thereafter, the precipitated powder was recovered by suction filtration, and the resulting filtrate was dissolved in chloroform (50 mL). This solution was dropped into methanol (470 mL) and stirred for 1 hour. The precipitated powder was recovered by suction filtration and dried under reduced pressure. To obtain polymer X (1.88g). Mw=2,043 Mn=3,608 Mw/Mn=1.77

[3]電荷輸送性組成物的調製 [實施例2] 使聚合物A0.167g與下述之芳基磺酸酯化合物0.333g溶解於三乙二醇丁基甲基醚4.75g、苯甲酸丁酯2.85g及鄰苯二甲酸二甲酯1.90g之混合溶劑而得到電荷輸送性組成物。此外，下述之芳基磺酸酯化合物係依循國際公開第2017/217457號所記載之方法來合成。[3] Modulation of charge transport composition [Example 2] 0.167 g of polymer A and 0.333 g of the following arylsulfonate compound were dissolved in a mixed solvent of 4.75 g of triethylene glycol butyl methyl ether, 2.85 g of butyl benzoate and 1.90 g of dimethyl phthalate. A charge transporting composition is obtained. In addition, the following arylsulfonate compounds were synthesized according to the method described in International Publication No. 2017/217457.

[比較例2] 除使用聚合物X來替代聚合物A以外係以與實施例2同樣的方法嘗試調製組成物，惟固體溶解殘留，無法獲得足以製作電荷輸送性薄膜的均勻組成物。[Comparative Example 2] Except that the polymer X was used instead of the polymer A, the composition was tried in the same manner as in Example 2, but the solid was dissolved and remained, and a uniform composition sufficient to produce a charge-transporting thin film could not be obtained.

[4]單層元件的製作與特性評定 [實施例3] 將實施例2中所得之電荷輸送性組成物使用旋轉塗佈機塗佈於ITO基板後，於大氣下以120℃乾燥1分鐘，其次以230℃進行燒成15分鐘，而於ITO基板上形成40nm之均勻的薄膜。作為ITO基板，係使用表面形成有經圖型化之厚度50nm的銦錫氧化物(ITO)膜之25mm×25mm×0.7t的玻璃基板，於使用前係藉由O₂ 電漿洗淨裝置(150W、30秒)去除表面上的雜質。 其次，使用蒸鍍裝置(真空度1.0×10^-5 Pa)，以0.2nm/秒之條件於其上形成80nm的鋁膜，而得到單層元件。此外，為防止空氣中的氧、水等的影響而造成特性劣化，單層元件係藉由密封基板密封後，再評定其特性。密封係依以下程序進行。在氧濃度2ppm以下、露點-76℃以下的氮氣環境中，將元件收納於密封基板之間，並將密封基板藉由接著劑(MORESCO(股)製，MORESCO MOISTURECUT WB90US(P))予以貼合。此時，將捕水劑(DYNIC(股)製,HD-071010W-40)與元件共同收納於密封基板內。對經貼合之密封基板照射UV光(波長：365nm、照射量：6,000mJ/cm² )後，以80℃進行退火處理1小時而使接著劑硬化。[4] Preparation of single-layer device and evaluation of characteristics [Example 3] After applying the charge transport composition obtained in Example 2 to an ITO substrate using a spin coater, it was dried at 120°C for 1 minute in the atmosphere. Next, it was fired at 230°C for 15 minutes to form a 40 nm uniform thin film on the ITO substrate. As the ITO substrate, a glass substrate of 25 mm × 25 mm × 0.7 t with a patterned indium tin oxide (ITO) film with a thickness of 50 nm formed on the surface was used, and an O ₂ plasma cleaning device ( 150W, 30 seconds) to remove impurities on the surface. Next, using a vapor deposition apparatus (vacuum degree 1.0×10 ^-5 Pa), an 80-nm aluminum film was formed thereon at 0.2 nm/sec to obtain a single-layer device. In addition, in order to prevent the characteristic deterioration caused by the influence of oxygen, water, etc. in the air, the single-layer device is sealed with a sealing substrate, and then the characteristics are evaluated. Sealing is performed according to the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the components are housed between the sealing substrates, and the sealing substrates are bonded with an adhesive (MORESCO (MORESCO), MORESCO MOISTURECUT WB90US (P)). . At this time, the water-capturing agent (made by DYNIC Co., Ltd., HD-071010W-40) and the element were housed together in a sealed substrate. After the bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm ² ), annealing treatment was performed at 80° C. for 1 hour to harden the adhesive.

測定對所得元件施加5V的電壓時的電流密度。將結果示於表1。The current density when a voltage of 5V was applied to the obtained element was measured. The results are shown in Table 1.

如表1所示，由本發明之電荷輸送性組成物所得之薄膜係顯示優良的電荷輸送性。As shown in Table 1, the film obtained from the charge-transporting composition of the present invention shows excellent charge-transporting properties.

[5]有機EL元件的製作與特性評定 [實施例4] 除將膜厚作成50nm以外係以與實施例3同樣的方法，使用實施例2中所得之電荷輸送性組成物在ITO基板上形成薄膜。 其次，使用蒸鍍裝置(真空度1.0×10^-5 Pa)，於此形成之薄膜上以0.2nm/秒形成30nm的α-NPD膜，並於其上形成10nm關東化學公司製電子阻擋材料HTEB-01的膜。進一步於其上共蒸鍍新日鐵住金化學公司製發光層主體材料NS60與發光層摻雜物材料Ir(PPy)₃ 。共蒸鍍係以Ir(PPy)₃ 的濃度成為6%的方式控制蒸鍍速率，層合40nm。最後，依序層合Alq₃ 、氟化鋰及鋁之薄膜，而得到有機EL元件。此時，就蒸鍍速率，對於Alq₃ 及鋁係以0.2nm/秒、對於氟化鋰則以0.02nm/秒之條件來進行，膜厚係分別形成20nm、0.5nm及80nm。 此外，為防止空氣中的氧、水等的影響而造成特性劣化，係以與實施例3同樣的方法密封元件後，再評定其特性。[5] Fabrication and evaluation of characteristics of organic EL devices [Example 4] The charge transporting composition obtained in Example 2 was formed on an ITO substrate in the same manner as Example 3 except that the film thickness was 50 nm. film. Next, using a vapor deposition device (vacuum degree 1.0×10 ^-5 Pa), a 30-nm α-NPD film was formed on the thin film formed at 0.2 nm/sec, and a 10-nm electron blocking material HTEB manufactured by Kanto Chemical Co., Ltd. was formed thereon. -01 film. Further, a light emitting layer host material NS60 and a light emitting layer dopant material Ir(PPy) ₃ manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. were co-evaporated thereon. The co-deposition system controls the deposition rate so that the concentration of Ir(PPy) ₃ becomes 6%, and is laminated at 40 nm. Finally, thin films of Alq ₃ , lithium fluoride, and aluminum are sequentially laminated to obtain an organic EL device. At this time, the vapor deposition rate was 0.2 nm/sec for Alq ₃ and aluminum, and 0.02 nm/sec for lithium fluoride, and the film thickness was 20 nm, 0.5 nm, and 80 nm, respectively. In addition, in order to prevent the deterioration of characteristics caused by the influence of oxygen, water, etc. in the air, the elements were sealed in the same manner as in Example 3, and then the characteristics were evaluated.

測定以亮度10,000cd/m² 驅動所得元件時之驅動電壓、電流密度、發光效率及外部量子產率以及亮度的半衰期。將結果示於表2。The driving voltage, current density, luminous efficiency, external quantum yield, and luminance half-life when the resulting device was driven at a luminance of 10,000 cd/m ^{2 were} measured. The results are shown in Table 2.

如表2所示，具備由本發明之電荷輸送性組成物所得之電荷輸送性薄膜的有機EL元件可合宜地驅動，且耐久性亦優良。As shown in Table 2, the organic EL device provided with the charge-transporting thin film obtained from the charge-transporting composition of the present invention can be suitably driven, and has excellent durability.

Claims (8)

一種聚合物，其係包含式(P1)所示之重複單元；

[式中，Ph表示1,4-伸苯基，G表示式(A01)～(A18)之任一者所示之一價基團：

(式中，L⁰¹ 表示-S-、-O-、-CO-、-CH₂ -、-(CH₂ )₂ -、 -C(CH₃ )₂ -、-CF₂ -、-(CF₂ )₂ -、-C(CF₃ )₂ -或茀-9,9-二基， L⁰² 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基， L⁰³ 及L⁰⁴ 彼此獨立表示氫原子、可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基、可經氟原子取代之碳數2～20之炔基或可經R取代之碳數6～20之芳基， Z⁰¹ ～Z¹⁸ 表示取代為芳香環之取代基，彼此獨立表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或碳數2～20之炔基， R表示可經氟原子取代之碳數1～20之烷基、可經氟原子取代之碳數2～20之烯基或可經氟原子取代之碳數2～20之炔基， Ar表示式(S1)～(S6)之任一者所示之基，

a⁰¹¹ ～a¹⁸³ 彼此獨立為表示取代為芳香環之取代基數的整數， a⁰⁷¹ 、a⁰⁸¹ 、a⁰⁹¹ 、a¹⁰¹ 及a¹¹¹ 為0～3， a⁰⁵¹ 、a⁰⁶¹ 、a⁰⁷² 、a⁰⁸² 、a⁰⁹² 、a¹⁰² 、a¹¹² 、a¹¹³ 、a¹¹⁴ 、a¹²¹ 、a¹³¹ 、a¹⁴¹ 、a¹⁵¹ 、a¹⁶¹ 、a¹⁷¹ 、a¹⁸¹ 、a¹⁸² 及a¹⁸³ 為0～4， a⁰¹¹ 、a⁰⁵² 、a⁰⁶² 、a¹²² 、a¹²³ 及a¹³² 為0～5， a⁰²¹ 、a¹³³ 、a¹⁴² 、a¹⁴³ 、a¹⁵² 、a¹⁵³ 、a¹⁶² 及a¹⁶³ 為0～7， a⁰³¹ 及a⁰⁴¹ 為0～9)]。A polymer comprising repeating units represented by formula (P1);

[In the formula, Ph represents 1,4-phenylene, G represents a monovalent group represented by any one of formulas (A01) to (A18):

(In the formula, L ⁰¹ represents -S-, -O-, -CO-, -CH ₂ -, -(CH ₂ ) ₂ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -(CF ₂ ) ₂ -, -C(CF ₃ ) ₂ -or Fu-9-9,9-diyl, L ⁰² independently of each other represents a hydrogen atom, a C 1-20 alkyl group which may be substituted by a fluorine atom, and may be substituted by a fluorine atom Alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms which may be substituted with fluorine atoms or aryl having 6 to 20 carbon atoms which may be substituted with R, L ⁰³ and L ⁰⁴ independently represent a hydrogen atom, C 1-20 alkyl group which may be substituted with a fluorine atom, C 2-20 alkenyl group which may be substituted with a fluorine atom, C 2-20 alkynyl group which may be substituted with a fluorine atom or R may be substituted Aryl groups having 6 to 20 carbon atoms, Z ⁰¹ to Z ¹⁸ represent substituents substituted with aromatic rings, and independently represent alkyl groups having 1 to 20 carbon atoms which may be substituted by fluorine atoms, and 2 carbon atoms which may be substituted by fluorine atoms -20 alkenyl group or C 2-20 alkynyl group, R represents a C 1-20 alkyl group which may be substituted by a fluorine atom, a C 2-20 alkenyl group which may be substituted by a fluorine atom or fluorine An atom-substituted alkynyl group having 2 to 20 carbon atoms, Ar represents a group represented by any one of formulas (S1) to (S6),

a ⁰¹¹ to a ¹⁸³ are independently integers representing the number of substituents substituted into the aromatic ring, a ⁰⁷¹ , a ⁰⁸¹ , a ⁰⁹¹ , a ¹⁰¹ and a ¹¹¹ are 0 to 3, a ⁰⁵¹ , a ⁰⁶¹ , a ⁰⁷² , a ⁰⁸² , a ⁰⁹² , a ¹⁰² , a ¹¹² , a ¹¹³ , a ¹¹⁴ , a ¹²¹ , a ¹³¹ , a ¹⁴¹ , a ¹⁵¹ , a ¹⁶¹ , a ¹⁷¹ , a ¹⁸¹ , a ¹⁸² and a ¹⁸³ are 0-4, a ⁰¹¹ , a ⁰⁵² , a ⁰⁶² , a ¹²² , a ¹²³ and a ¹³² are 0 to 5, a ⁰²¹ , a ¹³³ , a ¹⁴² , a ¹⁴³ , a ¹⁵² , a ¹⁵³ , a ¹⁶² and a ¹⁶³ are 0 to 7, a ⁰³¹ and a ⁰⁴¹ is 0-9)]. 如請求項1之聚合物，其中前述G為式(A01-1)～(A01-3)之任一者所示之基：

(式中，Z⁰¹ 表示與前述相同意義)。The polymer according to claim 1, wherein the aforementioned G is a group represented by any one of formulas (A01-1) to (A01-3):

(In the formula, Z ⁰¹ represents the same meaning as described above). 一種聚合物，其係包含式(E1)所示之重複單元；

。A polymer comprising repeating units represented by formula (E1);

. 一種電荷輸送性組成物，其係包含由如請求項1～3中任一項之聚合物所構成的電荷輸送性物質及有機溶劑。A charge transporting composition comprising a charge transporting substance composed of the polymer according to any one of claims 1 to 3 and an organic solvent. 如請求項4之電荷輸送性組成物，其係進一步包含電荷接受性物質或電荷接受性物質前驅物。The charge-transporting composition according to claim 4 further contains a charge-receiving substance or a charge-receiving substance precursor. 一種電荷輸送性薄膜，其係由如請求項4或5之電荷輸送性組成物而得到。A charge transporting film obtained from the charge transporting composition according to claim 4 or 5. 一種有機電致發光元件，其係具有如請求項6之電荷輸送性薄膜。An organic electroluminescent device having the charge transport film as in claim 6. 一種如請求項1之聚合物的製造方法，其特徵為使式(A1)所示之三苯基胺衍生物與式(H1)所示之三苯基胺衍生物反應；

(式中，X彼此獨立表示氯原子、溴原子、碘原子或假鹵素基，Ph及G表示與前述相同意義)。A method for producing a polymer according to claim 1, characterized in that the triphenylamine derivative represented by formula (A1) is reacted with the triphenylamine derivative represented by formula (H1);

(In the formula, X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G have the same meanings as described above).