JP4666338B2 - Organic polymer light emitting device material having gold complex structure and organic polymer light emitting device - Google Patents

Description

  The present invention is a polymer used in organic light emitting devices (OLEDs) that emit light by electrical energy and can be used in flat display panels and backlights, illumination light sources, electrophotography, optical device light sources, sign boards, and the like. The present invention relates to an organic light emitting device material.

  The organic light-emitting device was manufactured by Kodak C.I. W. Since Tang et al. Showed light emission with high brightness (Appl. Phys. Lett., 51, 913, 1987; Non-Patent Document 1), material development and device structure improvements have rapidly progressed recently. Practical use has begun with displays for car audio and mobile phones. In order to further expand the applications of organic EL (electroluminescence), development of materials for improving luminous efficiency and durability, development of full-color display, and the like are being actively carried out.

  Regarding the light emission efficiency, since the generation ratio of excitons in the excited singlet state and excited triplet state in electrical excitation is 1: 3, a fluorescent substance that emits light from the excited singlet state is used as the light emitting material. 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”, page 58; Non-Patent Document 2). On the other hand, when a phosphorescent material that emits light from the excited triplet state is used as the light emitting material, both the excited singlet state and the excited triplet state that are generated contribute to light emission, so the upper limit of the internal quantum efficiency is Improve to 100%.

  Many of the phosphors are compounds containing heavy metal atoms. 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., 11, 852, 1999; Non-Patent Document 3). V. W. -W. Yam et al. Pay attention to the good phosphorescent property of the gold complex, and use it as a light emitting material of an organic EL element (Chem. Commun., P. 53, 2000; Non-Patent Document 4).

  Conventionally, a vacuum deposition method has been used as a method for manufacturing an organic EL element. However, this method requires a vacuum facility, and it is difficult to form an organic thin film with a uniform thickness as the area increases. It has problems such as. On the other hand, the ink-jet method and printing method that have been developed as a film-forming technique by coating can form a film under normal pressure, and are excellent in device enlargement and mass productivity. In film formation by these methods, a low molecular compound that may cause layer separation or segregation cannot be used, and therefore, a polymer light emitting material that does not crystallize must be used.

  However, most of the compounds known so far as polymers containing gold complexes have a structure in which gold is contained in the polymer main chain (Chem. Commun., 1055, 1998; non-patent Reference 5). In such a structure, it is difficult to control the gold concentration in the polymer, it is difficult to obtain a multifunctional polymer having a light emitting portion and a charge transporting portion, There are drawbacks such as decomposition of molecules due to bond dissociation, and a light-emitting material for an organic EL element requires a compound in which the polymer main chain is composed only of organic groups.

  With regard to the emission color, in recent years, research and development of full-color displays and white light sources using organic EL elements have been actively conducted. Even in phosphorescent materials with high emission efficiency, there are many colors including blue emission colors with short wavelengths. The development of luminescent materials has been an issue.

  As described above, in order to produce a color / white organic EL device having a high luminous efficiency and a large area, it has been desired to develop a polymer material including a phosphorescent light-emitting portion that can easily control the emission color.

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

  An object of the present invention is to provide a polymer phosphorescent light-emitting material that is useful for a multicolor and white light-emitting organic EL device that can have a large area with high luminous efficiency and can be mass-produced.

The inventors have completed the present invention by using a polymer material that is a phosphorescent coordination compound having a gold complex structure (phosphorescent gold complex).
That is, the present invention relates to the following organic polymer light-emitting element material and organic polymer light-emitting element using the organic polymer light-emitting element 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 as described in 1 above, wherein the molecular weight of the organic polymer is 1,000 to 1,000,000.
[3] The organic polymer light-emitting device according to 1 or 2 obtained by polymerizing a composition containing a polymerizable gold complex in which at least one ligand is a ligand having a polymerizable functional group as a substituent. Element material.
[4] The organic polymer light-emitting device material as described in 1 above, wherein the gold complex structure has an organic phosphorus compound as at least one ligand.
[5] The organic polymer light-emitting device material as described in 3 above, 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 as described in 5 above, wherein at least one of the organic phosphorus compounds of the ligand has a polymerizable functional group as a substituent.
[7] The organophosphorus compound is represented by the formula (1)

[Wherein, R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 element material as described in any one of 4 to 6 above.
[8] The organophosphorus compound is represented by the formula (2)

[Wherein, R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 that bridges 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 element material as described in any one of 4 to 6 above.
[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 8,
R ^{8 to} R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted cyclic structure having 3 to 15 carbon atoms. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted alkoxy group having 1 to 15 carbon atoms, and an optionally substituted carbon 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 that bridges two phosphorus atoms, an optionally substituted alkylene group having 1 to 20 carbon atoms, and an optionally substituted cyclic structure having 3 to 15 carbon atoms Represents an alkylene group having a carbon number, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and 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 3 to 6, which has a structure represented by:
[10] The polymerizable gold complex has the formula (4)

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

[Wherein R ¹² is a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted cyclic group. 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, and a substituent; A heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 15 carbon atoms,
R ^{13 to} R ¹⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms, or a cyclic structure optionally having substituents having 3 to 15 carbon atoms. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted alkoxy group having 1 to 15 carbon atoms, and an optionally substituted carbon 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. 7. The organic polymer light-emitting device material according to any one of 3 to 6, which has a structure represented by
[13] The polymerizable gold complex has the formula (6)

[Wherein, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 that bridges two phosphorus atoms, an optionally substituted alkylene group having 1 to 20 carbon atoms, and an optionally substituted cyclic structure having 3 to 15 carbon atoms Or an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ^{20 to} R ²¹ each independently have a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, 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 And an optionally substituted heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 15 carbon atoms, R ²⁰ and R ²¹ are 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. 7. The organic polymer light-emitting device material according to any one of 3 to 6, which has a structure represented by
[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. ] Organic polymer light emitting element material as described in any one of said 3, 5 and 6 which has a structure shown by these.
[15] The organic polymer light-emitting device material according to any one of 3 to 6, wherein the polymerizable gold complex has at least one thiolate ligand.
[16] The polymerizable gold complex has the formula (8)

[Wherein, R ^{22 to} R ²⁵ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 are each independently a hydrogen atom, a C 1-15 alkyl group which may have a substituent, or a C 3-15 having a cyclic structure which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted carbon number 3 to 15 heteroaryl groups, R ²⁶ and R ²⁷ may be linked via a bridging group;
Z ⁴ represents an organic group that bridges 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.
However, at least one of R ^{22 to} R ²⁷ and Z ⁴ has a polymerizable functional group. 7. The organic polymer light-emitting device material according to any one of 3 to 6, which has a structure represented by
[17] The organic polymer light-emitting device material according to any one of 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 one or more 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 not only emit visible light from blue to red with high efficiency, but also can easily produce a large area device by a coating method.

Hereinafter, the present invention will be specifically described.
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 crosslinking group portion. The polymer light-emitting device material of the present invention may be used alone or as a composite material obtained by mixing these materials and a material not containing a 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 by copolymerizing with a compound other than a polymerizable gold complex. Although it is preferable, it can also be obtained by later introducing gold into a polymer having an organic group capable of coordinating with gold as part of the side chain.

  Although the valence of gold in the gold complex structure is not particularly limited, monovalent to tetravalent are preferable, and monovalent and trivalent are more preferable. 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 for 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, A radical polymerizable functional group is 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, a methacryloyloxyethyl carbamate group, etc. Examples thereof include a substituent having a (meth) acryloyloxyalkyl carbamate group, a styryl group and a derivative thereof, a vinylamide group and a derivative thereof, and the like. Among these polymerizable functional groups, a styryl group, an acryloyloxy group, a methacryloyloxy group, and a (meth) acryloyloxyalkylcarbamate group are preferable from the viewpoint of polymerizability.

The metal complex structure and polymerizable metal complex of the present invention preferably contain at least one organophosphorus compound represented by the following formulas (1) and (2) as a ligand.

R ^{1 to} R ⁷ are each independently
Hydrogen atom,
An optionally substituted alkyl group having 1 to 15 carbon atoms,
A C3-C15 alkyl group having a cyclic structure which may have a substituent,
An alkenyl group having 2 to 15 carbon atoms which may have a substituent,
A C1-C15 alkoxy group which may have a substituent,
An aryl group having 6 to 15 carbon atoms which may have a substituent,
It represents 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.
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 aryl groups such as phenyl group, tolyl group and styryl group, alkoxy groups having 1 to 8 carbon atoms such as methoxy group and ethoxy group, halogen atom, hydroxyl group, nitro group and amino group. It is done.

  The C3-C15 alkyl group having a cyclic structure includes a cycloalkyl group, a cycloalkyl group substituted by an alkyl group, a cycloalkyl group substituted by a cycloalkyl group, and an alkyl group substituted by a cycloalkyl group . Here, the cycloalkyl group includes a bicyclic or polycyclic group in addition to a monocyclic group. 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, a bicyclohexyl group, and the like. Examples of substituents for alkyl groups having a cyclic structure include aryl groups such as phenyl, tolyl and styryl groups, alkoxy groups having 1 to 8 carbon atoms such as methoxy and ethoxy groups, halogen atoms, hydroxyl groups, nitro groups and amino groups. Groups and the like.

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

  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 tertiary butoxy group. Examples of the substituent of the alkoxy group include aryl groups such as phenyl group, tolyl group and styryl group, alkoxy groups having 1 to 8 carbon atoms such as methoxy group and ethoxy group, halogen atom, hydroxyl group, nitro group and amino group. It is done.

  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. C1-C8 alkoxy groups, phenyl groups, tolyl groups, styryl groups and other aryl groups, halogen atoms, hydroxyl groups, nitro groups, amino groups, and the like.

  The heteroaryl group having 3 to 15 carbon atoms is a cyclic group containing 1 to 4 heteroatoms selected from a monocyclic, bicyclic or tricyclic nitrogen atom, oxygen atom and sulfur atom. Includes 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 for 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 a phenyl group, a tolyl group and a styryl group, a halogen atom, a hydroxyl group, a nitro group and an amino group.

  Examples of the aryloxy group having 6 to 15 carbon atoms include a phenyloxy group, a naphthyloxy group, and an anthracenyloxy group. As a substituent of the aryloxy group, 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 C1-C8 alkoxy groups, such as phenyl groups, tolyl groups, styryl groups and other aryl groups, halogen atoms, hydroxyl groups, nitro groups, amino groups, and the like.

  Among these, the alkyl group having 1 to 12 carbon atoms which may have a substituent, the aryl group having 4 to 10 carbon atoms which may have a substituent, and the substituent may be included. A C1-C10 alkoxy group and a C4-C10 aryloxy group which may have a substituent are preferable, A C1-C12 alkyl group and substituent which may have a substituent An aryl group having 6 to 10 carbon atoms, which may have a hydrogen atom, is more preferable.

Z ¹ represents an organic group that bridges two phosphorus atoms,
An alkylene group having 1 to 20 carbon atoms which may have a substituent;
It represents an alkylene group having 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.
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 aryl groups such as phenyl group, tolyl group and styryl group, alkoxy groups having 1 to 8 carbon atoms such as methoxy group and ethoxy group, halogen atom, hydroxyl group, nitro group and amino group. It is done.

  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 a cycloalkylene-cyclo Including alkylene group and alkylene-cycloalkylene group. Here, the cycloalkylene group includes a bicyclic group and a tricyclic group in addition to a monocyclic group. 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 substituents for alkyl groups having a cyclic structure include aryl groups such as phenyl, tolyl and styryl groups, alkoxy groups having 1 to 8 carbon atoms such as methoxy and ethoxy groups, halogen atoms, hydroxyl groups, nitro groups and amino groups. Groups 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 for 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. C1-C8 alkoxy groups, phenyl groups, tolyl groups, styryl groups and other aryl groups, halogen atoms, hydroxyl groups, nitro groups, amino groups, and the like.

Z ¹ is preferably an alkylene group having 1 to 4 carbon atoms which may have a substituent, or 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 organophosphorus compound represented by the formula (1) is contained as a ligand of the polymerizable gold complex, any one of R ^{1 to} R ³ can be used as a group containing a polymerizable functional group. When the organophosphorus compound represented by the formula (2) is contained as a ligand of the polymerizable gold complex, any of R ^{4 to} R ⁷ and Z ¹ can be used as a group containing a polymerizable functional group.
When R ^{1 to} R ⁷ contain a polymerizable functional group, R ^{1 to} R ⁷ are an alkenyl group having 2 to 15 carbon atoms, or an alkyl group, alkoxy group, aryl having a substituent containing a polymerizable functional group Group. When Z ¹ contains a polymerizable functional group, Z ¹ is an alkylene group, an arylene group or the like having a substituent containing a polymerizable functional group. The substituent containing a polymerizable functional group is preferably a group having a carbon-carbon double bond such as an alkenyl group such as vinyl or allyl, an alkenyl-substituted aryl group such as vinylphenyl, or 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 here is a group composed of an organic compound having 1 to 40 carbon atoms having a site capable of coordinating with 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 group such as alkylphosphine, arylphosphine, alkylphosphite, arylphosphite, pyridine, nitrile, isocyanide, pyridylphenyl Represents an anionic or neutral chelate compound such as a group, Schiff base, diketonate group, bipyridine and the like. Here, anionic or neutral means that the formal charges of the group bonded to gold are −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 the above R ^{1 to} R ³ .

R ¹² , R ²⁰ and R ²¹ are each independently
Hydrogen atom,
A cyano group,
A silyl group having 3 to 20 carbon atoms,
An optionally substituted alkyl group having 1 to 15 carbon atoms,
A C3-C15 alkyl group 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,
An optionally substituted heteroaryl group having 3 to 15 carbon atoms,
An acyl group having 1 to 15 carbon atoms,
Carboxyl group,
An alkoxycarbonyl group having 2 to 15 carbon atoms is represented.
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 formyl group and 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.

An alkyl group having 1 to 15 carbon atoms which may have a substituent represented by R ¹² , R ²⁰ and R ^21; 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 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. The heteroaryl group is the same as described above for R ^{1 to} R ³ .

  Among these, an alkyl group having 1 to 10 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 included. A C1-C10 acyl group, a carboxyl group, and a C2-C10 alkoxycarbonyl group are preferable, and a C1-C6 alkyl group which may have a substituent may have a substituent. A good aryl group having 6 to 10 carbon atoms and an alkoxycarbonyl group having 2 to 10 carbon atoms are more preferable.

Examples of the bridging group represented by R ²⁰ and R ²¹ include those similar to Z ¹ above. Among them, an alkylene group having 1 to 4 carbon atoms and an arylene group having 6 to 20 carbon atoms are preferable, a propylene group, A butylene group and a naphthylene group are particularly preferred.

R ^{26 to} R ²⁷ are each independently
Hydrogen atom,
An optionally substituted alkyl group having 1 to 15 carbon atoms,
A C3-C15 alkyl group 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,
Substituted represents a heteroaryl group carbon atoms which may 3 to 15, R ²⁶ and R ²⁷ may be linked via a bridging group.
These groups represented by R ²⁶ and R ²⁷ 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 Formula (4) represents a halogen atom, and among them, chlorine, bromine and iodine are preferable.

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

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

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

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, an anion having a valence of two or more, such as carbonate ion, sulfate ion, and phosphate ion, may be present in such a ratio as to neutralize the charge of the gold complex.

The polymerizable gold complex of the formulas (3) to (8) contains at least one polymerizable functional group in its structure. If any of the groups R ⁴ to R ²⁶ is a polymerizable functional group, any group of R ⁴ to R ²⁶ contains an alkenyl group or, or a polymerizable functional group having from 2 to 15 carbon atoms substituted A group having a group. If any of the groups Z ¹ to Z ⁴ is a polymerizable functional group, any group 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, vinylbenzyl and the like is preferable.

  The polymerizable gold complex in the present invention is obtained by coordinating a ligand having a polymerizable functional group to gold, or by 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, and a carboxyl group, but are not limited thereto. Examples of the compound having a polymerizable functional group to be reacted with these reactive substituents include polymerizable acid halides, polymerizable isocyanates, polymerizable alcohols, and polymerizable alkoxides, but are not limited thereto. It is not a thing.

  The mononuclear and binuclear 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 chloride (III) chloride dihydrate as a starting material. As the reducing agent, thiodiglycol or the like is used, but in the case of synthesizing a mononuclear gold complex, an organophosphorus compound serving as a ligand can also serve as the reducing agent. Subsequently, an organophosphorus compound is allowed to act on the produced intermediate to obtain mononuclear and binuclear gold chloride complexes (I) and (II). Further, by replacing chlorine of the obtained gold complex with a ligand L selected from an organic phosphorus compound, acetylide, and thiolate, complexes (III) and (IV) can be obtained.

  If the polymerizable gold complex in the present invention has radical polymerizability, thermal polymerization initiators such as 2,2′-azobis (isobutyronitrile) (AIBN) and benzoyl peroxide and ultraviolet polymerization initiation such as benzophenone are initiated. Polymerization can be easily performed by using an agent, 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, and one or more of the polymerizable gold complexes and a polymerizable other than the polymerizable gold complex. It may be any copolymer with one or more compounds. Here, examples of the polymerizable compound other than the polymerizable gold complex include 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 acid. Examples thereof include, but are not limited to, compounds having no carrier transport properties such as (meth) acrylic acid alkyl esters such as methyl acrylate, styrene and derivatives thereof.

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

  FIG. 1 is a cross-sectional view showing an example of the structure 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. In addition, the organic light-emitting device configuration of the present invention is not limited to the example of FIG. 1, and any one of 1) hole transport layer / light-emitting layer and 2) light-emitting layer / electron transport layer is sequentially formed between the anode and the cathode. 3) hole transport material, light emitting material, layer containing electron transport material, 4) hole transport material, layer containing light emitting material, 5) layer containing light emitting material, electron transport material, 6) Any one of the single layers 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 laminated.

  When the light emitting device material in the present invention is formed as a light emitting layer of an organic light emitting device, the polymer light emitting device material may be applied (coated), and the polymerizable composition containing the polymerizable gold complex in the present invention is used as a lower layer. It may be polymerized after coating on it. In the case of application | coating, what was melt | dissolved in the suitable solvent can be apply | coated, and a solvent can also be dried after that.

  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 materials, hole transport materials, electron transport materials and the like.

  In the organic light-emitting device according to the present invention, the luminous efficiency and / or durability can be further improved by forming the hole transport layer and the electron transport layer on both sides or one side of the light-emitting layer.

  As a hole transport material for forming the hole transport layer, 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 such as polyvinylcarbazole and poly (3,4-ethylenedioxythiophene) can be used, but are not particularly limited thereto. These hole transport materials may be used alone, but may be mixed or laminated with different hole transport materials. Although the thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be generally limited, it is preferably 10 nm to 10 μm, more preferably 10 nm to 1 μm.

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

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

  The film formation of the light emitting material, hole transport material, and electron transport material used for each of the above layers is not particularly limited, but resistance heating vapor deposition method, electron beam vapor deposition method, sputtering method, coating method, solution coating method, etc. In the case of a low molecular weight compound, resistance heating vapor deposition and electron beam vapor deposition 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 known materials such as conductive polymers such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, and polyaniline. A transparent conductive material can be used. The surface resistance of the electrode made of this transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). A method for forming these anode materials is not particularly limited, and an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, and 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 the injection barrier against hole injection. The buffer layer is not particularly limited, and 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, but Al, MgAg alloy, alkali metals such as Li and Cs, alkaline earth metals such as Ca and Ba, and Al such as AlCa Known cathode materials such as alkali metal alloys can be used. The film formation method for these cathode materials is not particularly limited, and a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ion plating method, and the like can be used. The thickness of the cathode is preferably 10 nm to 1 μm, and more preferably 50 to 500 nm. However, when a highly active metal such as an alkali metal or alkaline earth metal is used as the cathode, the thickness of the cathode is preferably 0.1 to 100 nm, and more preferably 0.5 to 50 nm. In this case, a metal layer that is more stable to the atmosphere is further laminated thereon for the purpose of protecting these cathode metals. For this purpose, metals such as Al, Ag, Au, Pt, Cu, Ni and Cr are used. The thickness is preferably 10 nm to 1 μm, and more preferably 50 to 500 nm.

  In addition, an insulating layer having a thickness of 0.1 to 10 nm may be inserted between the cathode and the electron transport layer or the organic layer stacked adjacent to the cathode for the purpose of improving electron injection efficiency. . Although it does not specifically limit as an insulating layer, For example, known cathode materials, such as lithium fluoride, magnesium fluoride, magnesium oxide, an alumina, can be used.

  Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer in order to prevent holes from passing through the light emitting layer and to efficiently recombine with electrons in the light emitting layer. These materials are not particularly limited, and known materials such as triazole derivatives and oxadiazole derivatives 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, but besides glass, PET (polyethylene terephthalate) or Known materials such as transparent plastics such as polycarbonate 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 also be used as a backlight without forming a pixel.

  Hereinafter, representative examples of the present invention will be shown and more specifically described, but the present invention is not limited to these. 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 subsequently those The synthesis example of the polymer using these compounds was summarized.

The apparatus used for analysis in the following examples is as follows. Unless otherwise specified, commercially available products (special grade) were used without purification.
1) Elemental analyzer CHNS-932 type 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

Polymeric gold complex 1 was synthesized by reacting sodium chloroaurate (III) with thiodiglycol and subsequently reacting 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 (5. 5 ml) of a 1.6 M hexane solution of n-butyllithium was added while cooling with ice. 6 mmol) was added dropwise. To the obtained slurry was added a THF solution of 10 mg (0.05 mmol) of lithium tetrachlorocopper (II), and then a 10 ml THF solution of 0.85 g (5.6 mmol) of 4-vinylbenzyl chloride was added dropwise at room temperature. Stir for hours. Next, the solvent was distilled off under reduced pressure, and the organic substance 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.
Next, a solution of sodium gold chloride (III) dihydrate 0.40 g (1.0 mmol) in water 5 ml-methanol 7.5 ml was ice-cooled, and thiodiglycol 0.37 g (3.0 mmol) in 5 ml methanol was added. added. Next, a solution of 0.25 g (0.50 mmol) of Compound A in 5 ml of chloroform-5 ml of methanol was added to this solution and stirred at room temperature for 2 hours. The formed 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 target polymerizable gold complex 1 as a colorless solid. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as C ₃₄ H ₃₀ AuCl ₂ P ₂ ): C 42.30, H 3.13
Actual value: 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

A polymerizable gold complex 2 was synthesized by a reaction between the 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, 77 mg (0.20 mmol) of bis (diphenylphosphino) methane and 100 mg (0.39 mmol) of silver trifluoromethanesulfonate were added, and 2 at room temperature was added. Stir for hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, extracted with dichloromethane, and then dried under reduced pressure. The residue was dissolved in a small amount of dichloromethane, methanol was further added, and the crystals obtained by concentration were collected by filtration and dried to obtain 118 mg (0.096 mmol) of the target polymerizable gold complex 2. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as _{C 61 H 52 Au 2 F 6} O 6 P 4 S 2): C 46.46, H 3.32
Actual value: C 46.83, H 3.59
Mass spectrometry (FAB +): 639 (M ²⁺ )

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

A gold complex obtained by the reaction of sodium gold chloride (III) with triphenylphosphine having a polymerizable functional group is converted into a known method (P. Cadiot, W. Chodkiewicz, “Chemistry of Acetylenes”, HG Viehe. , Ed., Marcel Dekker, New York (1969)) was reacted with phenylbutadiyne 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 70 ml THF solution of 2.70 g of 4-bromostyrene (15 mmol) was added dropwise to prepare a Grignard reagent. To the obtained solution, a 10 ml THF solution of 2.50 g (11 mmol) of chlorodiphenylphosphine was added dropwise and 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 gold chloride (III) dihydrate was dissolved in a mixed solvent of 2.5 ml of acetone and 2.5 ml of ethanol, and 360 mg (1.25 mmol) of Compound B in a 5 ml chloroform solution. And stirred at room temperature for 15 minutes. The resulting precipitate was filtered off with a glass filter, and the resulting 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 phenylbutadiyne and 15 mg (0.28 mmol) of sodium methoxide were added, and the mixture was stirred at room temperature for 16 hours. After the solvent was distilled off under reduced pressure, a small amount of diethyl ether was added and passed through a glass filter, and the solvent was again distilled off from the resulting solution under reduced pressure. The residue was purified by column chromatography on silica gel and dried under reduced pressure to obtain 79 mg (0.13 mmol) of the target polymerizable gold complex 3-1. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (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 instead of 4-bromostyrene, chlorodiethylphosphine instead of chlorodiphenylphosphine, and 1-ethynylnaphthalene instead of phenylbutadiyne A 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 values (as C ₂₈ H ₃₂ AuP): C 56.38, H 5.41
Actual value: 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

A polymerizable gold complex 4-1 was synthesized by a reaction between the 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 the solvent was distilled off under reduced pressure, a small amount of diethyl ether was added and passed through a glass filter, and the solvent was again distilled off from the resulting solution under reduced pressure. The residue was purified by column chromatography on silica gel and dried under reduced pressure to obtain 60 mg (0.055 mmol) of the target polymerizable gold complex 4-1. 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
Actual value: C 55.02, H 3.55
Mass spectrometry (FAB +): 1096 (M ⁺ )

Examples 6 to 9: Synthesis of polymerizable gold complex 4-2 to 4-5 By using alkyne H (C ₂ ) _n R ¹⁰¹ instead of phenylacetylene, the same operation as the synthesis of polymerizable gold complex 4-1 was performed. 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

The gold complex C having a polymerizable functional group was synthesized by a known method (P. Cadiot, W. Chodkiewicz, “Chemistry of Acetylenes”, HG Viehe, Ed., Marcel Dekker, New York (1969)). A polymerizable gold complex 5-1 was synthesized by a 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) octatetrain (0.099 mmol) were added at room temperature. 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 49 mg (0.046 mmol) of the target 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
Actual value: 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) octatetrain. A polymerizable gold complex 5-2 was synthesized by the same operation as that of the gold complex 5-1. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (as C ₃₆ H ₅₀ Au ₂ P ₂ ): C 46.06, H 5.37
Actual value: C 45.71, H 5.80
Mass spectrometry (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

A polymerizable gold complex 6-1 was synthesized by a reaction between the 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 solution of 15 mg of 1,3-propanedithiol (0.14 mmol) and 17 mg of ethanolamine (0.28 mmol) in 2 ml of ethanol was added. And stirred at room temperature for 2 hours. The solvent was distilled off from the resulting reaction mixture under reduced pressure, and recrystallization from a chloroform-methanol mixed solvent gave 75 mg (0.075 mmol) of the target polymerizable gold complex 6-1 as a pale yellow solid. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated values (as C ₃₇ H ₃₆ Au ₂ P ₂ S ₂ ): C 44.41, H 3.63
Actual value: 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

A polymerizable gold complex 6-2 was synthesized in the same manner as the 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
Actual value: 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 McAulife et al., J. Chem. Soc., Dalton Trans., 1730 (1979)) and a known method (A. Hirao et al., Macromolecules, 26, 6985 (1993)), a polymerizable gold complex 7 was synthesized by reaction of 4- (trimethylsilylethynyl) styrene. Namely, 100 mg (0.20 mmol) of chloro (triphenylphosphine) gold (I) was suspended in 5 ml of methanol, 45 mg of 4- (trimethylsilylethynyl) styrene (0.22 mmol) and 15 mg of sodium methoxide (0 .28 mmol) was added and stirred at room temperature for 24 hours. After the solvent was distilled off under reduced pressure, a small amount of diethyl ether was added and passed through a glass filter, and the solvent was again distilled off from the resulting solution under reduced pressure. The residue was purified by column chromatography on silica gel and dried under reduced pressure to obtain 72 mg (0.12 mmol) of the target polymerizable gold complex. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated (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 by reaction of 4-vinylbenzenethiol synthesized by a known method (Y. Choji et al., Macromolecules, 32, 7732 (1999)) with a gold complex obtained by the reaction of sodium chloroaurate and geodiglycol. Complex 8 was synthesized. That is, 600 ml (1.5 mmol) of sodium chloroaurate (III) dihydrate in water (5 ml) -methanol (7.5 ml) was ice-cooled, and thiodiglycol (0.55 g, 4.5 mmol) in 5 ml of methanol was added. It was. Next, bis (diphenylphosphino) methane (288 mg, 0.75 mmol) in chloroform (5 ml) -methanol (5 ml) was added to the solution, and the mixture was stirred at room temperature for 2 hours. The formed 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, and 79 mg of 4-vinylbenzenethiol (0.58 mmol) and 35 mg of ethanolamine (0.58 mmol) in 2 ml of ethanol were 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 redissolved in ethanol and filtered. The solvent was distilled off from the filtrate under reduced pressure, and recrystallization from a chloroform-methanol mixed solution gave 175 mg (0.17 mmol) of the target polymerizable gold complex 8. Identification was performed by CHN elemental analysis and mass spectrometry.
Calculated value (as C ₄₁ H ₃₆ Au ₂ P ₂ S ₂ ): C 46.96, H 3.46
Actual value: C 47.22, H 3.44
Mass spectrometry (FAB +): 1048 (M ⁺ )

Examples 16 to 30: Synthesis of polymerizable gold complex-N-vinylcarbazole copolymer By copolymerizing polymerizable gold complexes 1 to 8 and N-vinylcarbazole, each has a light emitting function useful as an organic light emitting device material. 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 blown for another hour. This solution was heated to 80 ° C. to initiate the polymerization reaction and stirred as it was for 8 hours. The reaction solution was cooled to room temperature and then dropped into 250 ml of methanol to precipitate a polymer, which was collected by filtration. Further, the recovered polymer was dissolved in 25 ml of chloroform and purified by dripping the solution again into 250 ml of methanol, followed by vacuum drying at 60 ° C. for 12 hours to obtain the desired copolymer. It was. Table 2 shows the recovery rate, average molecular weight, molecular weight distribution, and gold complex content.

Examples 31 to 33: Production and Evaluation of Organic Light-Emitting Element Substrate with ITO (Indium Tin Oxide) in which two ITO electrodes having a width of 4 mm serving as anodes are formed in stripes on one surface of a 25 mm square glass substrate (Nippo Electric Co., Ltd., Nippon Electric Co., LTD.) Was used to produce an organic light emitting device. First, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (trade name “Vitron P” manufactured by Bayer Co., Ltd.) on the ITO (anode) of the substrate with ITO is rotated at 3500 rpm. After coating under the condition of a coating time of 40 seconds, drying was performed at 60 ° C. for 2 hours under reduced pressure in a vacuum dryer to form an anode buffer layer. The film 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 transport 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 Chemical Industry) as an electron transport material 9.0 mg) was dissolved in 2970 mg chloroform (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), and the obtained solution was filtered through a filter having a pore size of 0.2 μm to obtain a coating solution. Next, the prepared coating solution is applied onto the anode buffer layer by a spin coating method under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds, and dried at room temperature (25 ° C.) for 30 minutes. A layer containing an electron transport material was formed. The thickness of the layer containing the obtained light emitting material and electron transporting material was about 100 nm. Next, a substrate on which a layer containing a light-emitting material and an electron transport material is formed is placed in a vapor deposition apparatus, and calcium and aluminum are co-deposited at a weight ratio of 1:10. Two cathodes were formed so as to be orthogonal to the extending direction of the anode. The film thickness of the obtained cathode was about 50 nm. Finally, in an argon atmosphere, lead wires (wirings) were attached to the anode and the cathode to produce four organic light emitting elements having a length of 4 mm and a width of 3 mm. A voltage was applied to the organic EL element by using a programmable DC voltage / current source TR6143 manufactured by Advantest Co., Ltd. to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. As a result, the luminescent color and the initial luminance at 15 V were as shown in Table 3 (average of four elements using each luminescent material).

The example of sectional drawing of the organic polymer light emitting element of this invention.

Explanation of symbols

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

Claims (12)

Having a gold complex structure as part of a side chain or bridging group, and at least one ligand is vinyl, allyl, alkenyl, alkenoyloxy, (meth) acryloyloxyalkylcarbamate, styryl, or It is obtained by radical polymerization of a composition containing a polymerizable gold complex that is a ligand having an organic group having a carbon-carbon double bond selected from a vinylamide group as a substituent. Formula (3)

[Wherein, R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 has an alkylene group of carbon atoms which may 20 have a location substituent, an alkylene group or a substituent having a ring structure of carbon atoms which may 3-15 substituted Represents an arylene group having 6 to 20 carbon atoms,
R ^{8 to} R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted cyclic structure having 3 to 15 carbon atoms. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted alkoxy group having 1 to 15 carbon atoms, and an optionally substituted carbon 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 has an alkylene group of carbon atoms which may 20 have a location substituent, an alkylene group or a substituent having a ring structure of carbon atoms which may 3-15 substituted Represents an optionally substituted arylene group having 6 to 20 carbon atoms, and A ⁻ represents a monovalent anion.
However, at least one of R ^{4 to} R ¹¹ and Z ^{1 to} Z ² has a carbon-carbon double bond as a polymerizable functional group. ] A structure represented by
Formula (4)

[Wherein, R ^{4 to} R ⁷ and Z ¹ represent the same meaning as described above, and Hal represents a halogen atom. However, at least one of R ^{4 to} R ⁷ and Z ¹ has a carbon-carbon double bond as a polymerizable functional group. ] A structure represented by
Formula (5)

[Wherein R ¹² is a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted cyclic group. 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, and a substituent; A heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 15 carbon atoms,
R ^{13 to} R ¹⁵ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 15 carbon atoms, or a cyclic structure optionally having substituents having 3 to 15 carbon atoms. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted alkoxy group having 1 to 15 carbon atoms, and an optionally substituted carbon 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 carbon-carbon double bond as a polymerizable functional group. ] A structure represented by
Formula (6)

[Wherein, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 has an alkylene group of carbon atoms which may 20 have a location substituent, an alkylene group or a substituent having a ring structure of carbon atoms which may 3-15 substituted Represents an arylene group having 6 to 20 carbon atoms,
R ^{20 to} R ²¹ each independently have a hydrogen atom, a cyano group, a silyl group having 3 to 20 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, 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 And an optionally substituted heteroaryl group having 3 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 15 carbon atoms, R ²⁰ and R ²¹ are An alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkylene group having a cyclic structure having 3 to 15 carbon atoms which may have a substituent, or a substituent. It may be linked via an arylene group having 6 to 20 carbon atoms . The
n represents an integer of 1 to 5.
However, at least one of R ^{16 to} R ²¹ and Z ³ has a carbon-carbon double bond as a polymerizable functional group. ] A structure represented by
Formula (7)

Wherein, L ^1, L ² represents a ligand of monodentate or bidentate, at least one formula of L ¹ and L ² (1)

{In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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. } Or formula (2)

{Wherein R ^{4 to} R ⁷ and Z ¹ represent the same meaning as described above. }, N represents an integer of 1 to 5. However, at least one of L ¹ and L ² has a carbon-carbon double bond as a polymerizable functional group. Or a structure represented by formula (8)

[Wherein, R ^{22 to} R ²⁵ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or a carbon 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, and 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 are each independently a hydrogen atom, a C 1-15 alkyl group which may have a substituent, or a C 3-15 having a cyclic structure which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted carbon number Represents a 3-15 heteroaryl group, R ²⁶ and R ²⁷ each optionally have a C 1-20 alkylene group, and optionally have a C 3-15 cyclic group. It may be linked via an alkylene group having a structure, or an arylene group having 6 to 20 carbon atoms which may have a substituent ,
Z ⁴ has an alkylene group of carbon atoms which may 20 have a location substituent, an alkylene group or a substituent having a ring structure of carbon atoms which may 3-15 substituted And an arylene group having 6 to 20 carbon atoms which may be present.
However, at least one of R ^{22 to} R ²⁷ and Z ⁴ has a carbon-carbon double bond as a polymerizable functional group. ] Organic polymer light emitting element material which has either of the structures shown. The polymerizable gold complex has the following structural formula (a1)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a2)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a3-1)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a4-1)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a5-1)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a6-1)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a7)

The organic polymer light-emitting device material according to claim 1 represented by: The polymerizable gold complex has the following structural formula (a8)

The organic polymer light-emitting device material according to claim 1 represented by: The organic polymer light emitting element material according to any one of claims 1 to 9, wherein the organic polymer has a molecular weight of 1,000 to 1,000,000. The organic polymer light emitting element by which the layer which consists of organic polymer light emitting element material as described in any one of Claims 1-10 was pinched | interposed between a pair of electrodes. An organic polymer light-emitting device in which at least one layer containing one or more organic polymer light-emitting device materials according to any one of claims 1 to 10 is sandwiched between a pair of electrodes.

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