JP2004346312A - Organic polymeric light-emitting element material having structure of gold complex and organic polymeric light-emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric phosphorescent light-emitting material having high light-emitting efficiency, capable of being made to have a large area, capable of being mass-produced, and useful for a polychromatic and white light-emitting organic EL element. <P>SOLUTION: This organic polymeric light-emitting element material has a structure of a gold complex as a part of its side chain or crosslinking group, wherein formulae (5) and (8) (symbols in formulae are each defined in the specification) are each exemplified as the structure of the gold complex. The organic polymeric light-emitting element contains the organic polymeric light-emitting element material in its light-emitting layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer which emits light by electric energy and is used for an organic light emitting element (OLED) which can be used for a flat display panel and a backlight, an illumination light source, an electrophotograph, an optical device light source, a sign board, etc. The present invention relates to organic light-emitting device materials.

  The organic light emitting device was manufactured by Kodak Co., Ltd. in 1987. W. Since Tang et al. Showed high-luminance light emission (Appl. Phys. Lett., Vol. 51, pp. 913, 1987; Non-Patent Document 1), material development and improvement of the element structure have progressed rapidly and recently. Practical use began with displays for car audio and mobile phones. In order to further expand the use of the organic EL (electroluminescence), development of materials for improving luminous efficiency and durability, development of full-color display, and the like are being actively performed.

  Regarding the luminous efficiency, a fluorescent substance which emits light from the excited singlet state was used as the luminescent material because the generation ratio of the excited singlet state and the excited triplet state exciton in the electric excitation was 1: 3. The upper limit of the internal quantum efficiency of light emission in the organic EL is 25% (Monthly Display, October 1998, separate volume, “Organic EL Display”, p. 58; Non-Patent Document 2). In contrast, when a phosphorescent substance that emits light from an excited triplet state is used as a light-emitting material, the generated singlet state and the excited triplet state both contribute to light emission. Increase to 100%.

  Many of the phosphors are compounds containing heavy metal atoms, but Y. Ma et al. Have reported an organic EL device using a coordination compound having gold as a central metal as a light emitting material (Adv. Mater., Vol. 11, p. 852, 1999; non-patent document 3). Then V. W. -W. Yam et al. Also paid attention to the good phosphorescent property of the gold complex and used it as a light emitting material for an organic EL device (Chem. Commun., P. 53, 2000; Non-Patent Document 4).

  As for the method of manufacturing an organic EL device, a vacuum evaporation method has been used conventionally, but this method requires vacuum equipment, and it is difficult to form an organic thin film to a uniform thickness as the area becomes larger. There are problems such as the following. On the other hand, the ink-jet method and the printing method, which have been developed as a film-forming technique by coating, can form a film under normal pressure, and are excellent in increasing the area of the element and in mass productivity. In film formation by these methods, a low molecular compound which may cause layer separation or segregation cannot be used, and therefore, a polymer luminescent material which does not crystallize must be used.

  However, most of the compounds known to date as a polymer containing a gold complex have a structure in which gold is contained in the polymer main chain (Chem. Commun., P. 1055, 1998; Reference 5). Such a structure is difficult to control the concentration of gold in the polymer, it is difficult to obtain a multifunctional polymer having a luminescent site and a charge transporting site, etc. There are drawbacks such as the decomposition of molecules due to bond dissociation, and a compound having a polymer main chain composed of only organic groups is required as a light emitting material of an organic EL device.

  With regard to luminescent colors, in recent years, research and development of full color displays and white light sources using organic EL elements have been actively conducted, and even in phosphorescent materials with high luminous efficiency, multi-colors including short-wavelength blue luminescent colors have been developed. Development of a light emitting material has been an issue.

  As described above, in order to produce a large-area color / white organic EL device having high luminous efficiency as described above, development of a polymer material containing a phosphorescent light-emitting portion that allows easy control of luminescent color has been desired.

Appl. Phys. Lett. , 51, 913, 1987 Monthly Display, October 1998 Special Volume “Organic EL Display”, p. 58 Adv. Mater. , Vol. 11, p. 852, 1999 Chem. Commun. , 53 pages, 2000 Chem. Commun. , P. 1055, 1998

  It is an object of the present invention to provide a polymer-based phosphorescent material which can be used for mass-produced multicolor and white light-emitting organic EL devices, can have a high luminous efficiency, can have a large area, and can be mass-produced.

The present inventors have completed the present invention by using a polymer material that is a phosphorescent coordination compound having a gold complex structure (a phosphorescent gold complex).
That is, the present invention relates to the following organic polymer light emitting device material and an organic polymer light emitting device using the organic polymer light emitting device material.

〔式中、Ｒ¹〜Ｒ³はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わす。〕で示される前記４乃至６のいずれか一つに記載の有機高分子発光素子材料。
［８］有機リン化合物が式（２）

〔式中、Ｒ⁴〜Ｒ⁷はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わし、
Ｚ¹は二つのリン原子を架橋する有機基を表わし、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数３〜１５の環状構造を有するアルキレン基、または置換基を有していてもよい炭素数６〜２０のアリーレン基を表わす。〕で示される前記４乃至６のいずれか一つに記載の有機高分子発光素子材料。
［９］重合性金錯体が、式（３）

〔式中、Ｒ⁴〜Ｒ⁷およびＺ¹は前記８の記載と同じ意味を表わし、
Ｒ⁸〜Ｒ¹¹はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わし、
Ｚ²は二つのリン原子を架橋する有機基を表わし、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数３〜１５の環状構造を有するアルキレン基、または置換基を有していてもよい炭素数６〜２０のアリーレン基を表わし、Ａ^-は一価の陰イオンを表わす。
ただし、Ｒ⁴〜Ｒ¹¹およびＺ¹〜Ｚ²の少なくとも一つは重合性官能基を有する。〕
で示される構造を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１０］重合性金錯体が、式（４）

〔式中、Ｒ⁴〜Ｒ⁷およびＺ¹は前記８の記載と同じ意味を表わし、Ｈａｌはハロゲン原子を表わす。ただし、Ｒ⁴〜Ｒ⁷およびＺ¹の少なくとも一つは重合性官能基を有する。〕で示される構造を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１１］金錯体構造が、アルキニル配位子を少なくとも一つ有する前記１乃至４のいずれか一つに記載の有機高分子発光素子材料。
［１２］重合性金錯体が、式（５）

〔式中、Ｒ¹²は、水素原子、シアノ基、炭素数３〜２０のシリル基、置換基を有していてもよい炭素数１〜１５アルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、炭素数１〜１５のアシル基、カルボキシル基、炭素数２〜１５のアルコキシカルボニル基を表わし、
Ｒ¹³〜Ｒ¹⁵はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わし、
ｎは１〜５の整数を表わす。
ただし、Ｒ¹²〜Ｒ¹⁵の少なくとも一つは重合性官能基を有する。〕で示される構造を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１３］重合性金錯体が式（６）

〔式中、Ｒ¹⁶〜Ｒ¹⁹はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わし、
Ｚ³は二つのリン原子を架橋する有機基を表わし、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数３〜１５の環状構造を有するアルキレン基、または置換基を有していてもよい炭素数６〜２０のアリーレン基を表わし、
Ｒ²⁰〜Ｒ²¹はそれぞれ独立して、水素原子、シアノ基、炭素数３〜２０のシリル基、置換基を有していてもよい炭素数１〜１５アルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、炭素数１〜１５のアシル基、カルボキシル基、炭素数２〜１５のアルコキシカルボニル基を表わし、Ｒ²⁰とＲ²¹は架橋基を介して連結していてもよく、
ｎは１〜５の整数を表わす。
ただし、Ｒ¹⁶〜Ｒ²¹およびＺ³の少なくとも一つは重合性官能基を有する。〕で示される構造を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１４］重合性金錯体が式（７）

〔式中、Ｌ¹、Ｌ²は単座または二座の配位子を表わし、Ｌ¹とＬ²のうち少なくとも一つは前記７または８に記載の有機リン化合物であり、ｎは１〜５の整数を表わす。〕で示される構造を有する前記３、５、６のいずれか一つに記載の有機高分子発光素子材料。
［１５］重合性金錯体がチオラート配位子を少なくとも一つ有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１６］重合性金錯体が式（８）

〔式中、Ｒ²²〜Ｒ²⁵はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５のアルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数１〜１５のアルコキシ基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基、または置換基を有していてもよい炭素数６〜１５のアリールオキシ基を表わし、
Ｒ²⁶〜Ｒ²⁷はそれぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜１５アルキル基、置換基を有していてもよい環状構造を有する炭素数３〜１５のアルキル基、置換基を有していてもよい炭素数２〜１５のアルケニル基、置換基を有していてもよい炭素数６〜１５のアリール基、置換基を有していてもよい炭素数３〜１５のヘテロアリール基を表わし、Ｒ²⁶とＲ²⁷は架橋基を介して連結していてもよく、
Ｚ⁴は二つのリン原子を架橋する有機基を表わし、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有していてもよい炭素数３〜１５の環状構造を有するアルキレン基、または置換基を有していてもよい炭素数６〜２０のアリーレン基を表わす。
ただし、Ｒ²²〜Ｒ²⁷およびＺ⁴の少なくとも一つは重合性官能基を有する。〕で示される構造を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１７］重合性官能基がラジカル重合性を有する前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１８］重合性官能基が炭素−炭素二重結合を有する有機基である前記３乃至６のいずれか一つに記載の有機高分子発光素子材料。
［１９］一対の電極間に、前記１乃至１８のいずれか一つに記載の有機高分子発光素子材料からなる層が少なくとも一層挟持された有機高分子発光素子。
［２０］一対の電極間に、前記１乃至１８のいずれか一つに記載の有機発光素子材料を一種以上含む層が少なくとも一層挟持されてなる有機高分子発光素子。 [1] An organic polymer light emitting device material having a gold complex structure as a side chain or a part of a crosslinking group.
[2] The organic polymer light emitting device material according to [1], wherein the molecular weight of the organic polymer is 1,000 to 1,000,000.
[3] The organic polymer luminescence described in 1 or 2 above, which is obtained by polymerizing a composition containing a polymerizable gold complex in which at least one ligand has a polymerizable functional group as a substituent. Element material.
[4] The organic polymer light emitting device material according to [1], wherein the gold complex structure has an organic phosphorus compound as at least one of the ligands.
[5] The organic polymer light emitting device material according to the above item 3, wherein at least one of the ligands of the polymerizable gold complex is an organic phosphorus compound.
[6] The organic polymer light emitting device material according to [5], wherein at least one of the organic phosphorus compounds of the ligand has a polymerizable functional group as a substituent.
[7] An organic phosphorus compound represented by the formula (1)

[Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents ] The organic polymer light emitting device material according to any one of the above items 4 to 6, wherein
[8] The organic phosphorus compound represented by the formula (2)

[Wherein, R ^{4 to} R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
Z ¹ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms which may have a substituent. ] The organic polymer light emitting device material according to any one of the above items 4 to 6, wherein
[9] The polymerizable gold complex has the formula (3)

[Wherein, R ^{4 to} R ⁷ and Z ¹ represent the same meaning as described in the above item 8,
R ^{8 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having 3 to 15 carbon atoms having a cyclic structure which may have a substituent. An alkyl group, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, and a carbon atom which may have a substituent Represents an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent;
Z ² represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent. the alkylene group or substituent having an optionally arylene group having 6 to 20 carbon atoms, a, a ^- represents a monovalent anion.
However, at least one of R ^{4 to} R ¹¹ and Z ^{1 to} Z ² has a polymerizable functional group. ]
7. The organic polymer light emitting device material according to any one of the above items 3 to 6, having a structure represented by the following formula:
[10] The polymerizable gold complex has the formula (4)

[In the formula, R ^{4 to} R ⁷ and Z ¹ have the same meaning as described in the above item 8, and Hal represents a halogen atom. However, at least one of R ^{4 to} R ⁷ and Z ¹ has a polymerizable functional group. ] The organic polymer light emitting device material according to any one of the above items 3 to 6, having a structure represented by the following formula:
[11] The organic polymer light emitting device material according to any one of [1] to [4], wherein the gold complex structure has at least one alkynyl ligand.
[12] A polymerizable gold complex represented by the formula (5)

[Wherein, R ¹² represents a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a cyclic group which may have a substituent. An alkyl group having 3 to 15 carbon atoms having a structure, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an aryl group having 6 to 15 carbon atoms which may have a substituent, a substituent Represents a heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 15 carbon atoms,
R ^{13 to} R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having 3 to 15 carbon atoms having a cyclic structure which may have a substituent. An alkyl group, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, and a carbon atom which may have a substituent Represents an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent;
n represents an integer of 1 to 5.
However, at least one of R ^{12 to} R ¹⁵ has a polymerizable functional group. ] The organic polymer light emitting device material according to any one of the above items 3 to 6, having a structure represented by the following formula:
[13] The polymerizable gold complex has the formula (6)

[Wherein, R ^{16 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
Z ³ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Represents an alkylene group having, or an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ^{20 to} R ²¹ each independently represent a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a substituent. An alkyl group having 3 to 15 carbon atoms having a cyclic structure, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, and an aryl group having 6 to 15 carbon atoms which may have a substituent Represents an optionally substituted heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 15 carbon atoms, and R ²⁰ and R ²¹ represent It may be linked via a crosslinking group,
n represents an integer of 1 to 5.
However, at least one of R ^{16 to} R ²¹ and Z ³ has a polymerizable functional group. ] The organic polymer light emitting device material according to any one of the above items 3 to 6, having a structure represented by the following formula:
[14] The polymerizable gold complex has the formula (7)

Wherein, L ^1, L ² represents a ligand of monodentate or bidentate, at least one of L ¹ and L ² are organic phosphorus compound according to the 7 or 8, n is from 1 to 5 Represents an integer. ] The organic polymer light emitting device material according to any one of the above 3, 5 and 6, having a structure represented by the following formula:
[15] The organic polymer light emitting device material according to any one of the above items 3 to 6, wherein the polymerizable gold complex has at least one thiolate ligand.
[16] The polymerizable gold complex is represented by the formula (8)

[Wherein, R ^{22 to} R ²⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
R ^{26 to} R ²⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an alkyl group having 3 to 15 carbon atoms which has a cyclic structure which may have a substituent. Alkyl group, alkenyl group having 2 to 15 carbon atoms which may have a substituent, aryl group having 6 to 15 carbon atoms which may have a substituent, carbon number which may have a substituent 3 to 15 heteroaryl groups, and R ²⁶ and R ²⁷ may be linked via a bridging group;
Z ⁴ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms which may have a substituent.
Provided that at least one of R ²² to R ²⁷ and Z ⁴ having a polymerizable functional group. ] The organic polymer light emitting device material according to any one of the above items 3 to 6, having a structure represented by the following formula:
[17] The organic polymer light-emitting device material according to any one of the above items 3 to 6, wherein the polymerizable functional group has radical polymerizability.
[18] The organic polymer light emitting device material according to any one of [3] to [6], wherein the polymerizable functional group is an organic group having a carbon-carbon double bond.
[19] An organic polymer light emitting device in which at least one layer made of the organic polymer light emitting device material according to any one of 1 to 18 is sandwiched between a pair of electrodes.
[20] An organic polymer light-emitting device in which at least one layer containing at least one of the organic light-emitting device materials according to any one of 1 to 18 is sandwiched between a pair of electrodes.

  The organic polymer light emitting device using the phosphorescent material of the present invention can emit visible light from blue to red with high efficiency, and can easily produce a large area device by a coating method.

Hereinafter, the present invention will be described specifically.
The organic light emitting device material used for the organic light emitting device of the present invention is a coordination compound having gold as a central metal, that is, a polymer having a gold complex structure in a side chain or a cross-linking group portion. The polymer light emitting device material of the present invention may be used alone, or may be used as a composite material in which these materials are mixed with a material containing no gold complex.

  The polymer material having a gold complex structure in the present invention can be synthesized by polymerizing a polymerizable gold complex having a polymerizable functional group as a substituent alone or copolymerizing with a compound other than a polymerizable gold complex. Although preferred, it can also be obtained by introducing gold later into a polymer having an organic group capable of coordinating to gold as a part of a side chain.

  The valence of gold in the gold complex structure is not particularly limited, but is preferably monovalent to tetravalent, and more preferably monovalent and trivalent. Further, the gold complex may be an ionic complex having a charge on the central metal. In that case, there is a counter ion that neutralizes the charge.

  The polymerizable functional group in the polymerizable gold complex used in the synthesis of the polymer material of the present invention may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable. Radical polymerizable functional groups are preferred. As the polymerizable functional group, a group having a carbon-carbon double bond is preferable, and an alkenoyloxy group such as a vinyl group, an allyl group, an alkenyl group, an acryloyloxy group and a methacryloyloxy group, and a methacryloyloxyethyl carbamate group ( Examples of the substituent include a (meth) acryloyloxyalkyl carbamate group, a styryl group and a derivative thereof, and a substituent having a vinylamide group and a derivative thereof. Among these polymerizable functional groups, a styryl group, an acryloyloxy group, a methacryloyloxy group, and a (meth) acryloyloxyalkyl carbamate group are preferable from the viewpoint of the polymerizability.

The metal complex structure and the polymerizable metal complex of the present invention preferably include at least one of the organic phosphorus compounds represented by the following formulas (1) and (2) as a ligand.

R ^{1 to} R ⁷ are each independently
Hydrogen atom,
An alkyl group having 1 to 15 carbon atoms which may have a substituent,
An alkyl group having 3 to 15 carbon atoms having a cyclic structure which may have a substituent,
An alkenyl group having 2 to 15 carbon atoms which may have a substituent,
An alkoxy group having 1 to 15 carbon atoms which may have a substituent,
An aryl group having 6 to 15 carbon atoms which may have a substituent,
And represents an optionally substituted heteroaryl group having 3 to 15 carbon atoms or an optionally substituted aryloxy group having 6 to 15 carbon atoms.
Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, and a hexyl group. Examples of the substituent of the alkyl group include an aryl group such as a phenyl group, a tolyl group, and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. Can be

  The alkyl group having 3 to 15 carbon atoms having a cyclic structure includes a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, a cycloalkyl group substituted with a cycloalkyl group, and an alkyl group substituted with a cycloalkyl group. . Here, the cycloalkyl group includes not only a monocyclic group but also a bicyclic or higher polycyclic group. The polycyclic includes spirocyclic and bridged cyclic. Specific examples include a cyclopentyl group, a cyclohexyl group, a perhydronaphthyl group, a perhydroanthracenyl group, a cyclohexyl group substituted with an alkyl group having 1 to 4 carbon atoms, and a bicyclohexyl group. Examples of the substituent of the alkyl group having a cyclic structure include an aryl group such as a phenyl group, a tolyl group and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. And the like.

  Examples of the alkenyl group having 2 to 15 carbon atoms include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. Examples of the substituent of the alkenyl group include an aryl group such as a phenyl group, a tolyl group and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. Can be

  Examples of the alkoxy group having 1 to 15 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a tert-butoxy group. Examples of the substituent of the alkoxy group include an aryl group such as a phenyl group, a tolyl group and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. Can be

  Examples of the aryl group having 6 to 15 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the substituent of the aryl group include an alkyl group having 1 to 8 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 1 to 8 carbon atoms such as a vinyl group, an allyl group and an isopropenyl group; a methoxy group and an ethoxy group. And an aryl group such as an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a styryl group, a halogen atom, a hydroxyl group, a nitro group, and an amino group.

  The heteroaryl group having 3 to 15 carbon atoms is a monocyclic, bicyclic or tricyclic heterocyclic group containing 1 to 4 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Represents a pyridyl group, a pyrrolyl group, an imidazolyl group, a quinolyl group, an isoquinolyl group, a thienyl group, a benzothienyl group, a furyl group and the like. Examples of the substituent of the heteroaryl group include an alkyl group having 1 to 8 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 1 to 8 carbon atoms such as a vinyl group, an allyl group and an isopropenyl group; a methoxy group and an ethoxy group. And an aryl group such as an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a styryl group, a halogen atom, a hydroxyl group, a nitro group, an amino group, and the like.

  Examples of the aryloxy group having 6 to 15 carbon atoms include a phenyloxy group, a naphthyloxy group, and an anthracenyloxy group. Examples of the substituent of the aryloxy group include an alkyl group having 1 to 8 carbon atoms such as a methyl group and an ethyl group, an alkenyl group having 1 to 8 carbon atoms such as a vinyl group, an allyl group and an isopropenyl group, a methoxy group and an ethoxy group. And an aryl group such as an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a styryl group, a halogen atom, a hydroxyl group, a nitro group, an amino group, and the like.

  Among these, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 4 to 10 carbon atoms which may have a substituent, and a substituent may be present. An alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 4 to 10 carbon atoms which may have a substituent is preferable, and an alkyl group having 1 to 12 carbon atoms which may have a substituent, a substituent. And an aryl group having 6 to 10 carbon atoms which may have

Z ¹ represents an organic group bridging two phosphorus atoms,
An alkylene group having 1 to 20 carbon atoms which may have a substituent,
An alkylene group having a cyclic structure of 3 to 15 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms which may have a substituent.
Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group. Examples of the substituent of the alkylene group include an aryl group such as a phenyl group, a tolyl group and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. Can be

  The alkylene group having a cyclic structure having 3 to 15 carbon atoms includes a cycloalkylene group, a cycloalkylene group substituted with an alkyl group, a cycloalkylene group substituted with a cycloalkyl group, an alkylene group substituted with a cycloalkyl group, and cycloalkylene-cycloalkyl. It includes an alkylene group and an alkylene-cycloalkylene group. Here, the cycloalkylene group includes monocyclic groups, bicyclic groups and tricyclic groups. Specific examples include a cyclopentylene group, a cyclohexylene group, a perhydronaphthylene group, a perhydroanthracenylene group, a cyclohexylene group substituted with an alkyl group having 1 to 4 carbon atoms, a bicyclohexane-diyl group, And a methylene-cyclohexylene group. Examples of the substituent of the alkyl group having a cyclic structure include an aryl group such as a phenyl group, a tolyl group and a styryl group, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom, a hydroxyl group, a nitro group, and an amino group. And the like.

  Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, a naphthylene group, a binaphthylene group, and a ferrocenylene group. Examples of the substituent of the arylene group include an alkyl group having 1 to 8 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 1 to 8 carbon atoms such as a vinyl group, an allyl group and an isopropenyl group; a methoxy group and an ethoxy group. And an aryl group such as an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a styryl group, a halogen atom, a hydroxyl group, a nitro group, and an amino group.

Z ¹ is preferably an alkylene group having 1 to 4 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent, and may have a substituent. A good methylene group, an ethylene group which may have a substituent, and an o-phenylene group which may have a substituent are more preferable.

When the organic phosphorus compound represented by the formula (1) is included as a ligand of the polymerizable gold complex, any of R ^{1 to} R ³ can be a group containing a polymerizable functional group. When the organic phosphorus compound represented by the formula (2) is included as a ligand of the polymerizable gold complex, any ^one of R ^{4 to} R ⁷ and Z ¹ can be a group containing a polymerizable functional group.
When R ^{1 to} R ⁷ include a polymerizable functional group, R ^{1 to} R ⁷ are an alkenyl group having 2 to 15 carbon atoms, or an alkyl group, an alkoxy group, or an aryl having a substituent including the polymerizable functional group. And the like. When Z ¹ contains a polymerizable functional group, Z ¹ is an alkylene group having a substituent containing the polymerizable functional group, an arylene group, or the like. The substituent having a polymerizable functional group is preferably a group having a carbon-carbon double bond such as an alkenyl group such as vinyl and allyl, an alkenyl-substituted aryl group such as vinylphenyl, and an alkenyl-substituted aralkyl group such as vinylbenzyl.

  In the present invention, it is preferable to use a polymerizable metal complex having a ligand having a polymerizable functional group as a substituent when producing a polymer for an organic light emitting device material. The ligand referred to herein is a group consisting of an organic compound having 1 to 40 carbon atoms having a site capable of coordinating to gold, and includes an alkyl group, an alkynyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkoxy group, Anionic groups such as aryloxy group, alkylthio group, arylthio group, carboxylate group, dithiocarbamate group, neutral groups such as alkylphosphine, arylphosphine, alkylphosphite, arylphosphite, pyridine, nitrile, isocyanide, pyridylphenyl Group, Schiff base, diketonate group, anionic or neutral chelate compound such as bipyridine. Here, anionic or neutral means that the formal charge of the group bonded to gold is -1 and 0, respectively.

  As typical structures of the polymerizable gold complex, structures of the following formulas (3) to (8) can be shown.

The substituents R ^{4 to} R ¹¹ , R ^{13 to} R ¹⁹ and R ^{22 to} R ²⁵ in each formula independently represent the same meaning as R ^{1 to} R ³ described above.

R ¹² , R ²⁰ and R ²¹ are each independently:
Hydrogen atom,
Cyano group,
A silyl group having 3 to 20 carbon atoms,
An alkyl group having 1 to 15 carbon atoms which may have a substituent,
An alkyl group having 3 to 15 carbon atoms having a cyclic structure which may have a substituent,
An alkenyl group having 2 to 15 carbon atoms which may have a substituent,
An aryl group having 6 to 15 carbon atoms which may have a substituent,
A heteroaryl group having 3 to 15 carbon atoms which may have a substituent,
An acyl group having 1 to 15 carbon atoms,
Carboxyl group,
Represents an alkoxycarbonyl group having 2 to 15 carbon atoms.
Further, R ²⁰ and R ²¹ may be linked via a crosslinking group.

Examples of the silyl group having 3 to 20 carbon atoms include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.
Examples of the acyl group having 1 to 15 carbon atoms include a formyl group and an acetyl group.
Examples of the alkoxycarbonyl group having 2 to 15 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-ethylhexyloxycarbonyl group.

R ¹² , R ²⁰ and R ²¹ may optionally have a C 1-15 alkyl group which may have a substituent, C 3-15 alkyl group having a cyclic structure which may have a substituent, An alkenyl group having 2 to 15 carbon atoms which may have a group, an aryl group having 6 to 15 carbon atoms which may have a substituent, and 3 to 15 carbon atoms which may have a substituent Is the same as described for R ^{1 to} R ³ above.

  Among these, an alkyl group having 1 to 10 carbon atoms that may have a substituent, an aryl group having 4 to 10 carbon atoms that may have a substituent, and a substituent may be present. An acyl group having 1 to 10 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms which may have a substituent, An aryl group having 6 to 10 carbon atoms and an alkoxycarbonyl group having 2 to 10 carbon atoms are more preferable.

Examples of the cross-linking group represented by R ²⁰ and R ²¹ include the same as those described above for Z ^1, and among them, an alkylene group having 1 to 4 carbon atoms and an arylene group having 6 to 20 carbon atoms are preferable, and a propylene group, Butylene and naphthylene are particularly preferred.

R ^{26 to} R ²⁷ are each independently:
Hydrogen atom,
An alkyl group having 1 to 15 carbon atoms which may have a substituent,
An alkyl group having 3 to 15 carbon atoms having a cyclic structure which may have a substituent,
An alkenyl group having 2 to 15 carbon atoms which may have a substituent,
An aryl group having 6 to 15 carbon atoms which may have a substituent,
Represents an optionally substituted heteroaryl group having 3 to 15 carbon atoms, and R ²⁶ and R ²⁷ may be linked via a cross-linking group.
These groups R ²⁶ and R ²⁷ represent are the same as those described above for R ¹ to R ^3. The bridging groups represented by R ²⁶ and R ²⁷ are the same as those described above for R ²⁰ and R ²¹ .

Z ^{2 to} Z ⁴ each independently represent the same meaning as Z ¹ described above.

  Hal in the formula (4) represents a halogen atom, and among them, chlorine, bromine and iodine are preferable.

  In the formulas (5) to (7), n is a parameter that greatly contributes to the emission color of phosphorescence, and represents an integer of 1 to 5, preferably 1 to 4.

At least one of L ¹ and L ² in the formula (7) is an organophosphorus compound represented by the formula (1) or (2), preferably a monodentate or diphosphorus compound having an organic phosphorus compound having a polymerizable functional group. Is a ligand of the locus. The ligand other than the organic phosphorus compound is not particularly limited as long as it can form a complex with gold. For example, organic nitrogen-containing ligands (amine ligand, pyridine ligand, nitrile Ligand, phenylpyridine ligand, Schiff base, etc.), alkyl ligand, alkynyl ligand, carbonyl ligand, cyanide ligand, isocyanide ligand, diketonate ligand, carboxylate ligand , Dithiocarbamate ligands and the like.

  As the ligand L, an organic phosphorus compound is preferable, and particularly preferable are trialkylphosphine, triarylphosphine, trialkylphosphite, and triarylphosphite.

A ⁻ in the formula (3) represents a monovalent anion, and examples thereof include a halide ion, a carboxylate ion, a sulfonate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a perchlorate ion. Further, anions having a valence of two or more, such as carbonate ions, sulfate ions, and phosphate ions, may be present in such a ratio as to neutralize the charge of the gold complex.

The polymerizable gold complexes of the formulas (3) to (8) contain at least one polymerizable functional group in the structure. When any of R ^{4 to} R ²⁶ contains a polymerizable functional group, any of R ^{4 to} R ²⁶ is an alkenyl group having 2 to 15 carbon atoms or a substituent containing a polymerizable functional group. It is a group having a group. When any of Z ^{1 to} Z ⁴ contains a polymerizable functional group, any of Z ^{1 to} Z ⁴ is a group having a substituent containing a polymerizable functional group. As the substituent containing a polymerizable functional group, a group having a carbon-carbon double bond such as vinyl, allyl, vinylphenyl, and vinylbenzyl is preferable.

  The polymerizable gold complex in the present invention is obtained by coordinating a ligand having a polymerizable functional group to gold or coordinating a ligand having a reactive substituent to gold. It can be synthesized by reacting with a compound having a polymerizable functional group. In this case, examples of the reactive substituent include a halogenated alkyl group, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, and the like, but are not limited thereto. Examples of the compound having a polymerizable functional group to be reacted with these reactive substituents include a polymerizable acid halide, a polymerizable isocyanate, a polymerizable alcohol, and a polymerizable alkoxide, but are not limited thereto. Not something.

  The mononuclear and dinuclear gold complexes having a polymerizable functional group in the present invention can be produced by the method shown in Scheme 1, respectively. In the production of any gold complex, gold is first reduced using sodium chloroaurate (III) dihydrate as a starting material. As the reducing agent, thiodiglycol or the like is used, but when synthesizing a mononuclear gold complex, an organic phosphorus compound serving as a ligand can also serve as the reducing agent. Subsequently, by reacting the produced intermediate with an organic phosphorus compound, mononuclear and dinuclear gold chloride complexes (I) and (II) are obtained. Further, by replacing chlorine in the obtained gold complex with a ligand L selected from an organic phosphorus compound, acetylide and thiolate, complexes (III) and (IV) are obtained.

  If the polymerizable gold complex in the present invention has radical polymerizability, a thermal polymerization initiator such as 2,2′-azobis (isobutyronitrile) (AIBN) and benzoyl peroxide and an ultraviolet polymerization initiator such as benzophenone can be used. By using the agent, polymerization can be easily performed, and a polymer containing a gold complex portion can be provided.

  The polymer is a homopolymer of the polymerizable gold complex, a copolymer of two or more of the polymerizable gold complexes, one or more of the polymerizable gold complexes, and a polymerizable polymer other than the polymerizable gold complex. Any of copolymers with one or more compounds may be used. Here, as the polymerizable compound other than the polymerizable gold complex, a hole transporting compound such as vinyl carbazole, an electron transporting compound such as an oxadiazole derivative or a triazole derivative having a polymerizable functional group, methyl acrylate, methacrylic Examples thereof include compounds having no carrier transporting property, such as alkyl (meth) acrylates such as methyl acid ester, styrene and derivatives thereof, but are not limited thereto.

  The concentration of gold in the polymer can be arbitrarily adjusted by using a copolymer of one or more polymerizable gold complexes and one or more other polymerizable compounds. The concentration of gold in the polymer is not limited, and may be determined according to the purpose. When used as a light emitting device material, gold is preferably contained in an amount of 0.01 to 5% by mass, and a copolymerization ratio of the polymerizable gold complex is 0.1 to 10% by mol when the copolymer is used. Is preferred.

  FIG. 1 is a sectional view showing an example of the configuration of the organic light emitting device of the present invention, in which a hole transport layer, a light emitting layer, and an electron transport layer are sequentially provided between an anode and a cathode provided on a transparent substrate. Further, the configuration of the organic light emitting device of the present invention is not limited to the example shown in FIG. 1, and any one of 1) a hole transport layer / a light emitting layer and 2) a light emitting layer / an electron transport layer may be sequentially disposed between an anode and a cathode. And a layer containing a hole transporting material, a light emitting material, and an electron transporting material; 4) a layer containing a hole transporting material, a light emitting material; 5) a layer containing a light emitting material and an electron transporting material; Only one layer of the single layer of the light emitting material may be provided. Further, the light emitting layer is not limited to one layer shown in FIG. 1, and two or more layers may be stacked.

  When the light emitting device material according to the present invention is formed as a light emitting layer of an organic light emitting device, a polymer light emitting device material may be applied (coated), and the polymerizable composition containing the polymerizable gold complex according to the present invention may be used as a lower layer. After application on top, it may be polymerized. In the case of coating, a solution dissolved in an appropriate solvent may be applied, and then the solvent may be dried.

  The light emitting layer of the organic light emitting device of the present invention is a layer containing the polymer light emitting device material of the present invention as a light emitting material, but may contain other light emitting substances, hole transport substances, electron transport substances, and the like.

  In the organic light emitting device according to the present invention, by forming the hole transport layer and the electron transport layer on both sides or one side of the light emitting layer, it is possible to further improve the luminous efficiency and / or the durability.

  Examples of the hole transporting material forming the hole transporting layer include TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 ′ diamine), α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine) Known hole transport materials such as triphenylamine derivatives, polyvinylcarbazole, and poly (3,4-ethylenedioxythiophene) can be used, but are not particularly limited thereto. These hole transporting materials may be used alone or may be mixed with or laminated with different hole transporting materials. The thickness of the hole transporting layer depends on the electrical conductivity of the hole transporting layer and cannot be unequivocally limited, but is preferably from 10 nm to 10 μm, more preferably from 10 nm to 1 μm.

As the electron transporting material for forming the electron transporting layer, known electron transporting materials such as quinolinol derivative metal complexes such as Alq ₃ (tris aluminum quinolinol), oxadiazole derivatives, and triazole derivatives can be used. Never. These electron transporting materials may be used alone or may be mixed with or laminated with different electron transporting materials. The thickness of the electron transporting layer depends on the conductivity of the electron transporting layer and cannot be unconditionally limited, but is preferably from 10 nm to 10 μm, more preferably from 10 nm to 1 μm.

  The light emitting material, the hole transporting material, and the electron transporting material used for each of the above-described layers may be used alone, or may be used in combination with materials having different functions. In addition, each layer can be formed using a polymer material as a binder. The polymer material used for this purpose is not particularly limited, but examples include polymethyl methacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide.

  The film formation of the light emitting material, the hole transporting material, and the electron transporting material used for each of the above layers is not particularly limited, but includes resistance heating evaporation, electron beam evaporation, sputtering, coating, and solution coating. In the case of a low molecular compound, resistance heating evaporation and electron beam evaporation are mainly used, and in the case of a polymer material, a coating method is mainly used in many cases.

  The anode material of the organic light emitting device according to the present invention is not particularly limited, but may be a known anode material such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, or a conductive polymer such as polyaniline. A transparent conductive material can be used. The electrode made of the transparent conductive material preferably has a surface resistance of 1 to 50 Ω / □ (ohm / square). The method for forming the anode material is not particularly limited, but an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like can be used. The thickness of the anode is preferably 50 to 300 nm.

  Further, a buffer layer may be inserted between the anode and the hole transport layer or the organic layer laminated adjacent to the anode for the purpose of relaxing an injection barrier against hole injection. The buffer layer is not particularly limited, but a known material such as copper phthalocyanine is used.

  The cathode material of the organic light-emitting device according to the present invention is not particularly limited. Al, an MgAg alloy, an alkali metal such as Li and Cs, an alkaline earth metal such as Ca and Ba, and an Al such as AlCa. Known cathode materials, such as alkali metal alloys, can be used. The method for forming these cathode materials is not particularly limited, but a resistance heating evaporation method, an electron beam evaporation method, a sputtering method, an ion plating method, or the like can be used. The thickness of the cathode is preferably from 10 nm to 1 μm, more preferably from 50 to 500 nm. However, when using a highly active metal such as an alkali metal or an alkaline earth metal as the cathode, the thickness of the cathode is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm. In this case, an air-stable metal layer is further laminated thereon to protect the cathode metal. For this purpose, metals such as Al, Ag, Au, Pt, Cu, Ni and Cr are used. The thickness is preferably from 10 nm to 1 μm, more preferably from 50 to 500 nm.

  Further, an insulating layer having a thickness of 0.1 to 10 nm may be inserted between the cathode and the electron transporting layer or the organic layer laminated adjacent to the cathode for the purpose of improving electron injection efficiency. . The insulating layer is not particularly limited. For example, a known cathode material such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina can be used.

  Further, a hole blocking layer may be provided adjacent to the light emitting layer on the cathode side for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining with electrons in the light emitting layer. Although these materials are not particularly limited, known materials such as a triazole derivative and an oxadiazole derivative are used.

  As the substrate of the organic polymer light-emitting device according to the present invention, an insulating substrate transparent to the emission wavelength of the light-emitting material can be used, and is not particularly limited. In addition to glass, PET (polyethylene terephthalate) or Known materials such as polycarbonate and other transparent plastics can be used.

  The organic polymer light emitting device of the present invention can form a pixel by a matrix method or a segment method by a known method, and can be used as a backlight without forming a pixel.

  Hereinafter, the present invention will be described in more detail with reference to representative examples, but the present invention is not limited thereto. Although the organic polymer light-emitting device material of the present invention is a polymer material, since the polymerization process of the polymerizable composition containing the polymerizable gold complex was made the same, the synthesis of the polymerizable gold complex was first exemplified, and then Examples of the synthesis of polymers using the above compound were summarized.

The equipment used for the analysis in the following examples is as follows. Unless otherwise specified, commercial reagents (special grade) were used without purification.
1) Element analyzer CHNS-932 manufactured by LECO.
2) GPC measurement (molecular weight measurement)
Column: Shodex KF-G + KF804L + KF802 + KF801,
Eluent: tetrahydrofuran (THF),
Temperature: 40 ° C,
Detector: RI (Shodex RI-71).
3) ICP elemental analysis ICPS 8000 manufactured by Shimadzu Corporation.

塩化金（III）酸ナトリウムをチオジグリコールと反応させ、引き続き重合性官能基を有するビス（ジフェニルホスフィノ）メタンを反応させることによって重合性金錯体１を合成した。即ち、ビス（ジフェニルホスフィノ）メタン２.０ｇ（５.２ｍｍｏｌ）に２０ｍｌのテトラヒドロフラン（以下ＴＨＦと略す）を加え、氷冷しながらｎ−ブチルリチウムの１.６Ｍヘキサン溶液３.５ｍｌ（５.６ｍｍｏｌ）を滴下した。得られたスラリーにテトラクロロ銅（ＩＩ）酸リチウム１０ｍｇ（０.０５ｍｍｏｌ）のＴＨＦ溶液を加えた後、塩化４−ビニルベンジル０.８５ｇ（５.６ｍｍｏｌ）の１０ｍｌＴＨＦ溶液を滴下し、室温で３時間撹拌した。次に減圧で溶媒を留去し、ジクロロメタンで有機物を抽出後、減圧乾燥した。得られた固体をシリカゲルカラムクロマトグラフィー（溶出液：ジクロロメタン）で精製し、減圧乾燥することによって化合物Ａ １.２ｇ（２.４ｍｍｏｌ）を無色の固体として得た。
次いで塩化金（III）酸ナトリウム二水和物０.４０ｇ（１.０ｍｍｏｌ）の水５ｍｌ−メタノール７.５ｍｌ溶液を氷冷し、チオジグリコール０.３７ｇ（３.０ｍｍｏｌ）の５ｍｌメタノール溶液を加えた。次にこの溶液に化合物Ａ ０.２５ｇ（０.５０ｍｍｏｌ）のクロロホルム５ｍｌ−メタノール５ｍｌ溶液を加えて室温で２時間撹拌した。生成した無色沈殿を濾取し、メタノールで洗浄後、減圧乾燥した。得られた無色固体をジクロロメタン−メタノール混合溶液中から再結晶することにより、目的とする重合性金錯体１ ０.２５ｇ（０.３３ｍｍｏｌ）を無色の固体として得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₃₄Ｈ₃₀ＡｕＣｌ₂Ｐ₂として）： Ｃ ４２.３０、Ｈ ３.１３
実測値： Ｃ ４２.５７、Ｈ ３.１０
質量分析（ＦＡＢ＋）： ９６４ （Ｍ⁺） Example 1 Synthesis of Polymerizable Gold Complex 1

Polymerizable gold complex 1 was synthesized by reacting sodium chloroaurate (III) with thiodiglycol and subsequently reacting with bis (diphenylphosphino) methane having a polymerizable functional group. That is, 20 ml of tetrahydrofuran (hereinafter abbreviated as THF) was added to 2.0 g (5.2 mmol) of bis (diphenylphosphino) methane, and 3.5 ml of a 1.6 M hexane solution of n-butyllithium (5.5 ml) was added while cooling with ice. 6 mmol) was added dropwise. To the obtained slurry, a THF solution of 10 mg (0.05 mmol) of lithium tetrachlorocuprate (II) was added, and then a solution of 0.85 g (5.6 mmol) of 4-vinylbenzyl chloride in 10 ml of THF was added dropwise. Stirred for hours. Next, the solvent was distilled off under reduced pressure, the organic matter was extracted with dichloromethane, and dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (eluent: dichloromethane), and dried under reduced pressure to obtain 1.2 g (2.4 mmol) of compound A as a colorless solid.
Then, a solution of 0.40 g (1.0 mmol) of sodium chloroaurate (III) dihydrate in 7.5 ml of water and 7.5 ml of methanol was cooled on ice, and a solution of 0.37 g (3.0 mmol) of thiodiglycol in 5 ml of methanol was added. added. Next, a solution of 0.25 g (0.50 mmol) of compound A in 5 ml of chloroform and 5 ml of methanol was added to the solution, and the mixture was stirred at room temperature for 2 hours. The resulting colorless precipitate was collected by filtration, washed with methanol, and dried under reduced pressure. The obtained colorless solid was recrystallized from a dichloromethane-methanol mixed solution to obtain 0.25 g (0.33 mmol) of the objective polymerizable gold complex as a colorless solid. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (as C ₃₄ H ₃₀ AuCl ₂ P ₂ ): C 42.30, H 3.13
Found: C, 42.57; H, 3.10.
Mass spectrometry (FAB +): 964 (M ⁺ )

重合性金錯体１とビス（ジフェニルホスフィノ）メタンの反応によって重合性金錯体２を合成した。即ち、金錯体１ １５０ｍｇ（０.２０ｍｍｏｌ）を１０ｍｌのジクロロメタンに溶解し、ビス（ジフェニルホスフィノ）メタン７７ｍｇ（０.２０ｍｍｏｌ）とトリフルオロメタンスルホン酸銀１００ｍｇ（０.３９ｍｍｏｌ）を加えて室温で２時間撹拌した。得られた反応混合物から減圧で溶媒を留去し、ジクロロメタンで抽出後、減圧乾燥した。残渣を少量のジクロロメタンに溶解してさらにメタノールを加え、濃縮することによって得られた結晶を濾取して乾燥することにより目的とする重合性金錯体２ １１８ｍｇ（０.０９６ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₆₁Ｈ₅₂Ａｕ₂Ｆ₆Ｏ₆Ｐ₄Ｓ₂として）： Ｃ ４６.４６、Ｈ ３.３２
実測値： Ｃ ４６.８３、Ｈ ３.５９
質量分析（ＦＡＢ＋）： ６３９ （Ｍ²⁺） Example 2: Synthesis of polymerizable gold complex 2

Polymerizable gold complex 2 was synthesized by the reaction between polymerizable gold complex 1 and bis (diphenylphosphino) methane. That is, 150 mg (0.20 mmol) of gold complex 1 was dissolved in 10 ml of dichloromethane, and 77 mg (0.20 mmol) of bis (diphenylphosphino) methane and 100 mg (0.39 mmol) of silver trifluoromethanesulfonate were added. Stirred for hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, extracted with dichloromethane, and dried under reduced pressure. The residue was dissolved in a small amount of dichloromethane, further methanol was added, and the resulting crystals were collected by filtration and dried to obtain 118 mg (0.096 mmol) of the desired polymerizable gold complex 2. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (as C ₆₁ H ₅₂ Au ₂ F ₆ O ₆ P ₄ S ₂ ): C 46.46, H 3.32
Found: C, 46.83; H, 3.59.
Mass spectrometry (FAB +): 639 (M2 ⁺ ).

塩化金（III）酸ナトリウムと重合性官能基を有するトリフェニルホスフィンの反応によって得られた金錯体に、公知の方法（Ｐ．Ｃａｄｉｏｔ，Ｗ．Ｃｈｏｄｋｉｅｗｉｃｚ，“Ｃｈｅｍｉｓｔｒｙ ｏｆ Ａｃｅｔｙｌｅｎｅｓ”，Ｈ．Ｇ．Ｖｉｅｈｅ，Ｅｄ．，Ｍａｒｃｅｌ Ｄｅｋｋｅｒ，Ｎｅｗ Ｙｏｒｋ（１９６９））により合成したフェニルブタジインを反応させることによって重合性金錯体３−１を合成した。即ち、マグネシウム３４１ｍｇ（１４ｍｍｏｌ）に２０ｍｌの脱水ＴＨＦを加え、２.７０ｇの４−ブロモスチレン（１５ｍｍｏｌ）の１０ｍｌＴＨＦ溶液を滴下してグリニャール（Ｇｒｉｇｎａｒｄ）試薬を調製した。得られた溶液にクロロジフェニルホスフィン２.５０ｇ（１１ｍｍｏｌ）の１０ｍｌＴＨＦ溶液を滴下し、室温で１.５時間撹拌した。減圧で溶媒を留去した後、残渣をシリカゲルカラムクロマトグラフィーで精製し、ヘキサン溶液から再結晶させることによって（４−ビニルフェニル）ジフェニルホスフィン（化合物Ｂ）２.３０ｇ（８.３ｍｍｏｌ）を得た。
次いで塩化金（III）酸ナトリウム二水和物２５０ｍｇ（０.６３ｍｍｏｌ）を２.５ｍｌのアセトンと２.５ｍｌのエタノールの混合溶媒中に溶解し、化合物Ｂ ３６０ｍｇ（１.２５ｍｍｏｌ）の５ｍｌクロロホルム溶液を加えて室温で１５分間撹拌した。生じた沈殿をグラスフィルターで濾別し、得られた溶液を−２０℃に冷却することによって金錯体Ｃ ２５４ｍｇ（０.４９ｍｍｏｌ）を得た。
次いで金錯体Ｃ １００ｍｇ（０.１９ｍｍｏｌ）を５ｍｌのメタノールに懸濁させ、フェニルブタジイン３０ｍｇ（０.２４ｍｍｏｌ）とナトリウムメトキシド１５ｍｇ（０.２８ｍｍｏｌ）を加えて室温で１６時間撹拌した。減圧で溶媒を留去後、少量のジエチルエーテルを加えてグラスフィルターに通し、得られた溶液から再び減圧で溶媒を留去した。残渣をシリカゲルのカラムクロマトグラフィーで精製し、減圧乾燥することによって目的とする重合性金錯体３−１ ７９ｍｇ（０.１３ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₃₀Ｈ₂₂ＡｕＰとして）： Ｃ ５９.０３、Ｈ ３.６３
実測値： Ｃ ５８.８８、Ｈ ３.５９
質量分析（ＦＡＢ＋）： ６１０ （Ｍ⁺） Example 3: Synthesis of polymerizable gold complex 3-1

The gold complex obtained by the reaction of sodium chloroaurate (III) and triphenylphosphine having a polymerizable functional group is added to a gold complex by a known method (P. Cadiot, W. Chodkiewicz, “Chemistry of Acetylenes”, HG Viehe). , Ed., Marcel Dekker, New York (1969)) to synthesize a polymerizable gold complex 3-1. That is, 20 ml of dehydrated THF was added to 341 mg (14 mmol) of magnesium, and a solution of 2.70 g of 4-bromostyrene (15 mmol) in 10 ml of THF was added dropwise to prepare a Grignard reagent. To the resulting solution was added dropwise a solution of chlorodiphenylphosphine (2.50 g, 11 mmol) in 10 ml of THF, and the mixture was stirred at room temperature for 1.5 hours. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized from a hexane solution to obtain 2.30 g (8.3 mmol) of (4-vinylphenyl) diphenylphosphine (compound B). .
Next, 250 mg (0.63 mmol) of sodium chloroaurate (III) dihydrate is dissolved in a mixed solvent of 2.5 ml of acetone and 2.5 ml of ethanol, and a 360 ml (1.25 mmol) of compound B in 5 ml of chloroform is dissolved. Was added and stirred at room temperature for 15 minutes. The resulting precipitate was separated by filtration with a glass filter, and the obtained solution was cooled to −20 ° C. to obtain 254 mg (0.49 mmol) of gold complex C.
Next, 100 mg (0.19 mmol) of gold complex C was suspended in 5 ml of methanol, 30 mg (0.24 mmol) of phenylbutadiine and 15 mg (0.28 mmol) of sodium methoxide were added, and the mixture was stirred at room temperature for 16 hours. After evaporating the solvent under reduced pressure, a small amount of diethyl ether was added and the mixture was passed through a glass filter, and the solvent was distilled off again from the obtained solution under reduced pressure. The residue was purified by silica gel column chromatography, and dried under reduced pressure to obtain the desired polymerizable gold complex 3-179 mg (0.13 mmol). Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated value (as C ₃₀ H ₂₂ AuP): C 59.03, H 3.63
Found: C, 58.88; H, 3.59.
Mass spectrometry (FAB +): 610 (M ⁺ )

４−ブロモスチレンの代わりに４−（４−ブロモブチル）スチレンを用い、クロロジフェニルホスフィンの代わりにクロロジエチルホスフィンを用い、フェニルブタジインの代わりに１−エチニルナフタレンを用いて重合性金錯体３−１の合成と同様な操作により重合性金錯体３−２を合成した。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₂₈Ｈ₃₂ＡｕＰとして）： Ｃ ５６.３８、Ｈ ５.４１
実測値： Ｃ ５５.９１、Ｈ ５.７６
質量分析（ＦＡＢ＋）： ５９６ （Ｍ⁺） Example 4: Synthesis of polymerizable gold complex 3-2

Polymerizable gold complex 3-1 using 4- (4-bromobutyl) styrene in place of 4-bromostyrene, chlorodiethylphosphine in place of chlorodiphenylphosphine, and 1-ethynylnaphthalene in place of phenylbutadiyne The polymerizable gold complex 3-2 was synthesized by the same operation as in the synthesis of. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated value (as C ₂₈ H ₃₂ AuP): C 56.38, H 5.41
Obtained: C 55.91, H 5.76
Mass spectrometry (FAB +): 596 (M ⁺ )

重合性金錯体１とフェニルアセチレンの反応によって重合性金錯体４−１を合成した。即ち、重合性金錯体１ １０３ｍｇ（０.１１ｍｍｏｌ）を５ｍｌのメタノール中に懸濁させ、フェニルアセチレン２５ｍｇ（０.２４ｍｍｏｌ）とナトリウムメトキシド１５ｍｇ（０.２８ｍｍｏｌ）を加えて室温で２４時間撹拌した。減圧で溶媒を留去後、少量のジエチルエーテルを加えてグラスフィルターに通し、得られた溶液から再び減圧で溶媒を留去した。残渣をシリカゲルのカラムクロマトグラフィーで精製し、減圧乾燥することによって目的とする重合性金錯体４−１ ６０ｍｇ（０.０５５ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₅₀Ｈ₄₀Ａｕ₂Ｐ₂として）： Ｃ ５４.７６、Ｈ ３.６８
実測値： Ｃ ５５.０２、Ｈ ３.５５
質量分析（ＦＡＢ＋）： １０９６ （Ｍ⁺） Example 5: Synthesis of polymerizable gold complex 4-1

Polymerizable gold complex 4-1 was synthesized by the reaction between polymerizable gold complex 1 and phenylacetylene. That is, 103 mg (0.11 mmol) of the polymerizable gold complex 1 was suspended in 5 ml of methanol, 25 mg (0.24 mmol) of phenylacetylene and 15 mg (0.28 mmol) of sodium methoxide were added, and the mixture was stirred at room temperature for 24 hours. . After evaporating the solvent under reduced pressure, a small amount of diethyl ether was added and the mixture was passed through a glass filter, and the solvent was distilled off again from the obtained solution under reduced pressure. The residue was purified by silica gel column chromatography and dried under reduced pressure to obtain the desired polymerizable gold complex 4-160 mg (0.055 mmol). Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as _{C 50 H 40 Au 2 P 2} ): C 54.76, H 3.68
Found: C, 55.02; H, 3.55.
Mass spectrometry (FAB +): 1096 (M ⁺ )

Example 6-9: By combining the same operation as the alkyne H (C _{2) n} with R ¹⁰¹ polymerizable gold complex 4-1 in place of the synthetic phenylacetylene polymerizable gold complex 4-2 to 4-5 Polymerizable gold complexes 4-2 to 4-5 were synthesized.

重合性官能基を有する金錯体Ｃと公知の方法（Ｐ．Ｃａｄｉｏｔ，Ｗ．Ｃｈｏｄｋｉｅｗｉｃｚ，“Ｃｈｅｍｉｓｔｒｙ ｏｆ Ａｃｅｔｙｌｅｎｅｓ”，Ｈ．Ｇ．Ｖｉｅｈｅ，Ｅｄ．，Ｍａｒｃｅｌ Ｄｅｋｋｅｒ，Ｎｅｗ Ｙｏｒｋ（１９６９））により合成したビス（トリメチルシリル）オクタテトラインの反応によって重合性金錯体５−１を合成した。即ち、金錯体Ｃ ９８ｍｇ（０.１９ｍｍｏｌ）を１０ｍｌのメタノールに懸濁させ、１４ｍｇのナトリウムメトキシド（０.２６ｍｍｏｌ）と２４ｍｇのビス（トリメチルシリル）オクタテトライン（０.０９９ｍｍｏｌ）を加えて室温で８時間撹拌した。精製した褐色の沈殿をグラスフィルターで濾取し、メタノールで洗浄後、減圧乾燥することによって目的とする重合性金錯体５−１ ４９ｍｇ（０.０４６ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₄₈Ｈ₃₄Ａｕ₂Ｐ₂として）： Ｃ ５４.０５、Ｈ ３.２１
実測値： Ｃ ５４.４７、Ｈ ３.０３
質量分析（ＦＡＢ＋）： １０６６ （Ｍ⁺） Example 10: Synthesis of polymerizable gold complex 5-1

A gold complex C having a polymerizable functional group was synthesized with a known method (P. Cadiot, W. Chodkiewicz, "Chemistry of Acetylenes", HG Viehe, Ed., Marcel Dekker, New York (1969)). Polymerizable gold complex 5-1 was synthesized by the reaction of (trimethylsilyl) octatetrain. That is, 98 mg (0.19 mmol) of gold complex C was suspended in 10 ml of methanol, and 14 mg of sodium methoxide (0.26 mmol) and 24 mg of bis (trimethylsilyl) octatetrayne (0.099 mmol) were added thereto. Stir for 8 hours. The purified brown precipitate was collected by filtration with a glass filter, washed with methanol, and dried under reduced pressure to obtain 149 mg (0.046 mmol) of the desired polymerizable gold complex 5-1. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as _{C 48 H 34 Au 2 P 2} ): C 54.05, H 3.21
Found: C, 54.47; H, 3.03
Mass spectrometry (FAB +): 1066 (M ⁺ )

重合性官能基を有する金錯体（Ｃ）の代わりに実施例４で合成した重合性金錯体（Ｄ）を用い、ビス（トリメチルシリル）オクタテトラインの代わりにビス（トリメチルシリル）ブタジインを用いて重合性金錯体５−１と同様な操作により重合性金錯体５−２を合成した。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₃₆Ｈ₅₀Ａｕ₂Ｐ₂として）： Ｃ ４６.０６、Ｈ ５.３７
実測値： Ｃ ４５.７１、Ｈ ５.８０
質量分析（ＦＡＢ＋）： ９３８ （Ｍ⁺） Example 11: Synthesis of polymerizable gold complex 5-2

The polymerizable gold complex (D) synthesized in Example 4 was used in place of the gold complex (C) having a polymerizable functional group, and bis (trimethylsilyl) butadiyne was used in place of bis (trimethylsilyl) octatetraine. Polymerizable gold complex 5-2 was synthesized in the same manner as in gold complex 5-1. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (as C ₃₆ H ₅₀ Au ₂ P ₂ ): C 46.06, H 5.37
Found: C, 45.71; H, 5.80.
Mass spec (FAB +): 938 (M ⁺ )

重合性金錯体１と１，３−プロパンジチオールの反応によって重合性金錯体６−１を合成した。即ち、重合性金錯体１ １３１ｍｇ（０.１４ｍｍｏｌ）を１０ｍｌのジクロロメタンに溶解し、１５ｍｇの１，３−プロパンジチオール（０.１４ｍｍｏｌ）と１７ｍｇのエタノールアミン（０.２８ｍｍｏｌ）の２ｍｌエタノール溶液を加えて室温で２時間撹拌した。得られた反応混合物から減圧で溶媒を留去し、クロロホルム−メタノール混合溶媒から再結晶することにより目的とする重合性金錯体６−１ ７５ｍｇ（０.０７５ｍｍｏｌ）を薄黄色の固体として得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₃₇Ｈ₃₆Ａｕ₂Ｐ₂Ｓ₂として）： Ｃ ４４.４１、Ｈ ３.６３
実測値： Ｃ ４４.２５、Ｈ ３.８８
質量分析（ＦＡＢ＋）： １０００ （Ｍ⁺） Example 12: Synthesis of polymerizable gold complex 6-1

Polymerizable gold complex 6-1 was synthesized by the reaction between polymerizable gold complex 1 and 1,3-propanedithiol. That is, 131 mg (0.14 mmol) of polymerizable gold complex 1 was dissolved in 10 ml of dichloromethane, and a 2 ml ethanol solution of 15 mg of 1,3-propanedithiol (0.14 mmol) and 17 mg of ethanolamine (0.28 mmol) was added. And stirred at room temperature for 2 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, and the residue was recrystallized from a mixed solvent of chloroform-methanol to obtain the desired polymerizable gold complex 6-1 (75 mg, 0.075 mmol) as a pale yellow solid. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as _{C 37 H 36 Au 2 P 2} S 2): C 44.41, H 3.63
Found: C, 44.25; H, 3.88.
Mass spectrometry (FAB +): 1000 (M ⁺ )

１，３−プロパンジチオールの代わりにベンゼンチオールを用いて重合性金錯体６−１と同様な操作により重合性金錯体６−２を合成した。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₄₆Ｈ₄₀Ａｕ₂Ｐ₂Ｓ₂として）： Ｃ ４９.６５、Ｈ ３.６２
実測値： Ｃ ４９.２３、Ｈ ３.２９
質量分析（ＦＡＢ＋）： １１１２ （Ｍ⁺） Example 13: Synthesis of polymerizable gold complex 6-2

Polymerizable gold complex 6-2 was synthesized by the same operation as polymerizable gold complex 6-1 using benzenethiol instead of 1,3-propanedithiol. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (as C ₄₆ H ₄₀ Au ₂ P ₂ S ₂ ): C 49.65, H 3.62
Found: C, 49.23; H, 3.29
Mass spectrometry (FAB +): 1112 (M ⁺ )

公知の方法（Ｃ．Ａ．ＭｃＡｕｌｉｆｆｅ ｅｔ ａｌ．，Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｄａｌｔｏｎ Ｔｒａｎｓ．，１７３０（１９７９））に従って合成したクロロ（トリフェニルホスフィン）金（Ｉ）と公知の方法（Ａ．Ｈｉｒａｏ ｅｔ ａｌ．，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２６，６９８５（１９９３））により合成した４−（トリメチルシリルエチニル）スチレンの反応によって重合性金錯体７を合成した。即ち、クロロ（トリフェニルホスフィン）金（Ｉ）１００ｍｇ（０.２０ｍｍｏｌ）を５ｍｌのメタノール中に懸濁させ、４５ｍｇの４−（トリメチルシリルエチニル）スチレン（０.２２ｍｍｏｌ）と１５ｍｇのナトリウムメトキシド（０.２８ｍｍｏｌ）を加えて室温で２４時間撹拌した。減圧で溶媒を留去後、少量のジエチルエーテルを加えてグラスフィルターに通し、得られた溶液から再び減圧で溶媒を留去した。残渣をシリカゲルのカラムクロマトグラフィーで精製し、減圧乾燥することによって目的とする重合性金錯体７ ７２ｍｇ（０.１２ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₂₈Ｈ₂₂ＡｕＰとして）： Ｃ ５７.３５、Ｈ ３.７８
実測値： Ｃ ５６.９４、Ｈ ３.４５
質量分析（ＦＡＢ＋）： ５８６ （Ｍ⁺） Example 14: Synthesis of polymerizable gold complex 7

Chloro (triphenylphosphine) gold (I) synthesized according to a known method (CA McAuliffe et al., J. Chem. Soc., Dalton Trans., 1730 (1979)) and a known method (A. Hirao). et al., Macromolecules, 26, 6985 (1993)) to synthesize polymerizable gold complex 7 by the reaction of 4- (trimethylsilylethynyl) styrene. That is, 100 mg (0.20 mmol) of chloro (triphenylphosphine) gold (I) was suspended in 5 ml of methanol, and 45 mg of 4- (trimethylsilylethynyl) styrene (0.22 mmol) and 15 mg of sodium methoxide (0. .28 mmol) and stirred at room temperature for 24 hours. After evaporating the solvent under reduced pressure, a small amount of diethyl ether was added and the mixture was passed through a glass filter, and the solvent was distilled off again from the obtained solution under reduced pressure. The residue was purified by silica gel column chromatography, and dried under reduced pressure to obtain 772 mg (0.12 mmol) of the desired polymerizable gold complex. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated value (as C ₂₈ H ₂₂ AuP): C 57.35, H 3.78
Found: C, 56.94; H, 3.45.
Mass spectrometry (FAB +): 586 (M ⁺ )

塩化金酸ナトリウムとジオジグリコールの反応によって得られる金錯体と公知の方法（Ｙ．Ｃｈｏｊｉ ｅｔ ａｌ．，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，３２，７７３２（１９９９））により合成した４−ビニルベンゼンチオールの反応によって重合性金錯体８を合成した。即ち、塩化金（III）酸ナトリウム二水和物６００ｍｇ（１.５ｍｍｏｌ）の水５ｍｌ−メタノール７.５ｍｌ溶液を氷冷し、チオジグリコール０.５５ｇ（４.５ｍｍｏｌ）の５ｍｌメタノール溶液を加えた。次にこの溶液にビス（ジフェニルホスフィノ）メタン２８８ｍｇ（０.７５ｍｍｏｌ）のクロロホルム５ｍｌ−メタノール５ｍｌ溶液を加えて室温で２時間撹拌した。生成した無色沈殿を濾取し、メタノールで洗浄後、減圧乾燥した。得られた無色固体を１５ｍｌのジクロロメタンに溶解し、７９ｍｇの４−ビニルベンゼンチオール（０.５８ｍｍｏｌ）と３５ｍｇのエタノールアミン（０.５８ｍｍｏｌ）の２ｍｌエタノール溶液を加えて室温で２時間撹拌した。得られた反応混合物から減圧で溶媒を留去し、残渣をエタノールに再溶解して濾過した。濾液から減圧で溶媒を留去し、クロロホルム−メタノール混合溶液から再結晶することによって目的とする重合性金錯体８ １７５ｍｇ（０.１７ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、質量分析で行った。
計算値（Ｃ₄₁Ｈ₃₆Ａｕ₂Ｐ₂Ｓ₂として）： Ｃ ４６.９６、Ｈ ３.４６
実測値： Ｃ ４７.２２、Ｈ ３.４４
質量分析（ＦＡＢ＋）： １０４８ （Ｍ⁺） Example 15: Synthesis of polymerizable gold complex 8

Polymerizable gold is produced by the reaction of a gold complex obtained by the reaction of sodium chloroaurate and diodiglycol with 4-vinylbenzenethiol synthesized by a known method (Y. Choji et al., Macromolecules, 32, 7732 (1999)). Complex 8 was synthesized. That is, a solution of 600 mg (1.5 mmol) of sodium chloroaurate (III) dihydrate in 5 ml of water and 7.5 ml of methanol was cooled on ice, and a solution of 0.55 g (4.5 mmol) of thiodiglycol in 5 ml of methanol was added. Was. Next, a solution of 288 mg (0.75 mmol) of bis (diphenylphosphino) methane in 5 ml of chloroform and 5 ml of methanol was added to the solution, and the mixture was stirred at room temperature for 2 hours. The resulting colorless precipitate was collected by filtration, washed with methanol, and dried under reduced pressure. The obtained colorless solid was dissolved in 15 ml of dichloromethane, a 2 ml ethanol solution of 79 mg of 4-vinylbenzenethiol (0.58 mmol) and 35 mg of ethanolamine (0.58 mmol) was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, and the residue was redissolved in ethanol and filtered. The solvent was distilled off from the filtrate under reduced pressure, and the residue was recrystallized from a mixed solution of chloroform and methanol to obtain 8175 mg (0.17 mmol) of the desired polymerizable gold complex. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as _{C 41 H 36 Au 2 P 2} S 2): C 46.96, H 3.46
Obtained: C 47.22, H 3.44
Mass spectrometry (FAB +): 1048 (M ⁺ )

Examples 16 to 30: Synthesis of polymerizable gold complex-N-vinyl carbazole copolymer By copolymerizing polymerizable gold complexes 1 to 8 and N-vinyl carbazole, a light emitting function useful as an organic light emitting device material was obtained. Polymers 9 to 23 having a hole transport function were synthesized. That is, 1.55 g (8.0 mmol) of N-vinylcarbazole, 0.080 mmol of a polymerizable gold complex, and 13 mg (0.08 mmol) of AIBN were dissolved in 40 ml of dehydrated toluene, and argon was further blown for 1 hour. The temperature of the solution was raised to 80 ° C. to start the polymerization reaction, and the mixture was stirred for 8 hours. After cooling the reaction solution to room temperature, it was dropped into 250 ml of methanol to precipitate a polymer, which was recovered by filtration. Further, the recovered polymer was dissolved in 25 ml of chloroform, and the solution was purified by re-precipitation by dropping into 250 ml of methanol, followed by vacuum drying at 60 ° C. for 12 hours to obtain a target copolymer. Was. Table 2 shows the recovery, average molecular weight, molecular weight distribution, and gold complex content.

Examples 31 to 33: Production and Evaluation of Organic Light-Emitting Element A substrate with ITO (indium tin oxide) in which two 4 mm-wide ITO electrodes serving as anodes were formed in a stripe shape on one surface of a 25 mm square glass substrate. (Nippo Electric Co., Ltd.) to produce an organic light emitting device. First, poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid (manufactured by Bayer, trade name “Baytron P”) was coated on the ITO (anode) of the substrate with ITO by spin coating at 3,500 rpm. The coating was performed under the conditions of a coating time of 40 seconds and then dried at 60 ° C. for 2 hours under reduced pressure using a vacuum dryer to form an anode buffer layer. The thickness of the obtained anode buffer layer was about 50 nm. Next, a coating solution for forming a layer containing a light emitting material and an electron transporting material was prepared. 21.0 mg of the light-emitting material shown in Table 3 and 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD) (Tokyo Kasei Kogyo Co., Ltd.) Was dissolved in 2970 mg of chloroform (manufactured by Wako Pure Chemical Industries, Ltd., special grade), and the resulting solution was filtered through a filter having a pore size of 0.2 μm to obtain a coating solution. Next, on the anode buffer layer, the prepared coating solution was applied by spin coating under the conditions of a rotation speed of 3000 rpm and an application time of 30 seconds, and dried at room temperature (25 ° C.) for 30 minutes to obtain a luminescent material. A layer containing an electron transporting material was formed. The thickness of the obtained layer containing the light emitting material and the electron transporting material was about 100 nm. Next, the substrate on which the layer containing the light-emitting material and the electron transporting material is formed is placed in a vapor deposition apparatus, and calcium and aluminum are co-deposited at a weight ratio of 1:10, and are arranged in a stripe pattern of 3 mm in width. The cathode was formed so as to be orthogonal to the extending direction of the anode. The thickness of the obtained cathode was about 50 nm. Finally, in an argon atmosphere, lead wires (wiring) were attached to the anode and the cathode, and four organic light-emitting devices measuring 4 mm long × 3 mm wide were manufactured. A voltage was applied to the organic EL element using a programmable DC voltage / current source TR6143 manufactured by Advantest Co., Ltd. to emit light, and the emission luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. As a result, the emission color and the initial luminance at 15 V were as shown in Table 3 (average of four elements using each emission material).

The example of the sectional view of the organic polymer light emitting element of the present invention.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Anode 3 Hole transport layer 4 Light emitting layer 5 Electron transport layer 6 Cathode

Claims (20)

  An organic polymer light emitting device material having a gold complex structure as a part of a side chain or a crosslinking group.   The organic polymer light emitting device material according to claim 1, wherein the organic polymer has a molecular weight of 1,000 to 1,000,000.   3. The organic polymer light emitting device material according to claim 1, wherein at least one ligand is obtained by polymerizing a composition containing a polymerizable gold complex which is a ligand having a polymerizable functional group as a substituent. .   The organic polymer light emitting device material according to claim 1, wherein the gold complex structure has an organic phosphorus compound as at least one of the ligands.   The organic polymer light emitting device material according to claim 3, wherein at least one of the ligands of the polymerizable gold complex is an organic phosphorus compound.   The organic polymer light-emitting device material according to claim 5, wherein at least one of the ligand organic phosphorus compounds has a polymerizable functional group as a substituent. When the organic phosphorus compound has the formula (1)

[Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents The organic polymer light emitting device material according to any one of claims 4 to 6, wherein The organic phosphorus compound has the formula (2)

[Wherein, R ^{4 to} R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
Z ¹ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms which may have a substituent. The organic polymer light emitting device material according to any one of claims 4 to 6, wherein The polymerizable gold complex has the formula (3)

[Wherein, R ^{4 to} R ⁷ and Z ¹ represent the same meaning as described in claim 8,
R ^{8 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having 3 to 15 carbon atoms having a cyclic structure which may have a substituent. An alkyl group, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, and a carbon atom which may have a substituent Represents an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent;
Z ² represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent. the alkylene group or substituent having an optionally arylene group having 6 to 20 carbon atoms, a, a ^- represents a monovalent anion.
However, at least one of R ^{4 to} R ¹¹ and Z ^{1 to} Z ² has a polymerizable functional group. ]
The organic polymer light emitting device material according to any one of claims 3 to 6, having a structure represented by: The polymerizable gold complex has the formula (4)

[Wherein, R ^{4 to} R ⁷ and Z ¹ have the same meaning as described in claim 8, and Hal represents a halogen atom. However, at least one of R ^{4 to} R ⁷ and Z ¹ has a polymerizable functional group. The organic polymer light emitting device material according to any one of claims 3 to 6, which has a structure represented by the following formula:   The organic polymer light emitting device material according to any one of claims 1 to 4, wherein the gold complex structure has at least one alkynyl ligand. The polymerizable gold complex has the formula (5)

[Wherein, R ¹² represents a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a cyclic group which may have a substituent. An alkyl group having 3 to 15 carbon atoms having a structure, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an aryl group having 6 to 15 carbon atoms which may have a substituent, a substituent Represents a heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 15 carbon atoms,
R ^{13 to} R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having 3 to 15 carbon atoms having a cyclic structure which may have a substituent. An alkyl group, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, and a carbon atom which may have a substituent Represents an aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent;
n represents an integer of 1 to 5.
However, at least one of R ^{12 to} R ¹⁵ has a polymerizable functional group. The organic polymer light emitting device material according to any one of claims 3 to 6, which has a structure represented by the following formula: The polymerizable gold complex has the formula (6)

[Wherein, R ^{16 to} R ¹⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
Z ³ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Represents an alkylene group having, or an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ^{20 to} R ²¹ each independently represent a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a substituent. An alkyl group having 3 to 15 carbon atoms having a cyclic structure, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, and an aryl group having 6 to 15 carbon atoms which may have a substituent Represents an optionally substituted heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 15 carbon atoms, and R ²⁰ and R ²¹ represent It may be linked via a crosslinking group,
n represents an integer of 1 to 5.
However, at least one of R ^{16 to} R ²¹ and Z ³ has a polymerizable functional group. The organic polymer light emitting device material according to any one of claims 3 to 6, which has a structure represented by the following formula: The polymerizable gold complex has the formula (7)

Wherein, L ^1, L ² represents a ligand of monodentate or bidentate, at least one of L ¹ and L ² are organic phosphorus compound according to claim 7 or 8, n is 1 to Represents an integer of 5. The organic polymer light emitting device material according to any one of claims 3, 5, and 6, which has a structure represented by the following formula:   The organic polymer light emitting device material according to any one of claims 3 to 6, wherein the polymerizable gold complex has at least one thiolate ligand. The polymerizable gold complex has the formula (8)

[Wherein, R ^{22 to} R ²⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon atom having a cyclic structure which may have a substituent. An alkyl group having 3 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms which may have a substituent, an alkoxy group having 1 to 15 carbon atoms which may have a substituent, An aryl group having 6 to 15 carbon atoms, a heteroaryl group having 3 to 15 carbon atoms which may have a substituent, or an aryloxy group having 6 to 15 carbon atoms which may have a substituent Represents
R ^{26 to} R ²⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an alkyl group having 3 to 15 carbon atoms which has a cyclic structure which may have a substituent. Alkyl group, alkenyl group having 2 to 15 carbon atoms which may have a substituent, aryl group having 6 to 15 carbon atoms which may have a substituent, carbon number which may have a substituent 3 to 15 heteroaryl groups, and R ²⁶ and R ²⁷ may be linked via a bridging group;
Z ⁴ represents an organic group bridging two phosphorus atoms, an alkylene group having 1 to 20 carbon atoms which may have a substituent, and a cyclic structure having 3 to 15 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms which may have a substituent.
Provided that at least one of R ²² to R ²⁷ and Z ⁴ having a polymerizable functional group. The organic polymer light emitting device material according to any one of claims 3 to 6, which has a structure represented by the following formula:   The organic polymer light emitting device material according to any one of claims 3 to 6, wherein the polymerizable functional group has radical polymerizability.   The organic polymer light emitting device material according to any one of claims 3 to 6, wherein the polymerizable functional group is an organic group having a carbon-carbon double bond.   An organic polymer light emitting device having at least one layer made of the organic polymer light emitting device material according to any one of claims 1 to 18 sandwiched between a pair of electrodes. An organic polymer light emitting device comprising at least one layer containing at least one of the organic light emitting device materials according to claim 1, between a pair of electrodes.

Images