JPWO2013089217A1 - Organic electroluminescence device - Google Patents

Abstract

Organic electroluminescent element or anode comprising an anode, a cathode, and a light emitting layer interposed between these electrodes, and an organic electric field comprising two or more functional layers including a cathode and a light emitting layer interposed between these electrodes A light-emitting element, wherein the light-emitting layer includes a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at room temperature with a gelling agent, or a carrier transport material and a light-emitting material, and at least one of these materials is at room temperature A light emitting layer obtained by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent, and at least one of the other functional layers is a liquid carrier transporting material at room temperature Is a gel functional layer formed by gelling with a gelling agent, or a gel functional layer comprising a carrier transporting material that is liquid at normal temperature, and gelling a carrier transporting composition that is liquid at normal temperature with a gelling agent as a whole Organic electric field To provide an optical element.

Description

  The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device including a gel light emitting layer.

An organic electroluminescence element (organic light-emitting element) (hereinafter referred to as an organic EL element) has a configuration in which a thin film organic layer (light-emitting layer) containing at least one light-emitting organic compound is sandwiched between a cathode and an anode. Electrons and holes are injected into and transported into this thin film and recombined to generate excitons, and light emission when this exciton is deactivated (fluorescence / phosphorescence) This is an element that emits light using
Since this organic EL element is a light-emitting element using a light-emitting organic compound in a light-emitting layer, it is expected to be applied as a display that is lightweight, flexible, inexpensive, and capable of large-area full-color display.

The light-emitting layer used in this organic EL device is driven by three processes: transport of both holes and electrons (charge), formation of excitons by recombination of these carriers, and light emission.
Therefore, a material satisfying these three functions is indispensable for the light-emitting layer. Usually, the material includes a carrier-transporting light-emitting material that exhibits these three functions, and a plurality of types to supplement these three functions. A carrier transport material / light emitting material mixed with an organic substance is used.

When the carrier transporting material / luminescent material is used for the light emitting layer, the light emitting material is diluted with the carrier transporting material, so that concentration quenching is suppressed and an organic EL device having high luminous efficiency is expected to be obtained. . For this reason, intensive research has been conducted on a wide variety of combinations of light-emitting materials and carrier transport materials.
By the way, it is not necessary to simply use a material having a desired fluorescence wavelength and a high quantum yield as a light emitting material for a light emitting layer, and it is necessary to select a carrier transport material suitable for a specific fluorescent dye. . This is because the carriers transported into the carrier transport material recombine and the excitation energy generated there induces the emission of the fluorescent dye doped in the carrier transport material.
Therefore, it is indispensable to select the mutual relationship between the HOMO / LUMO energy levels of each component of the light emitting material / carrier transport material or a combination of their efficient energy transfer.

Besides the selection of the carrier transport material / light emitting material combination, as a means for improving the light emission efficiency of the organic EL element, there is known a method of separating a material that promotes carrier injection, transport, and recombination into a plurality of layers. It has been.
This originated from a functionally separated thin film stacked organic EL device (hereinafter referred to as a thin film stacked organic EL device) reported by Kodak's Tang et al. In 1987. Currently, it is a cathode / electron injection layer / electron transport. The development of thin-film stacked organic EL devices in which multiple layers of materials such as layers, hole blocking layers, light emitting layers, electron blocking layers, hole transport layers, hole injection layers, and anodes are laminated Has been promoted.
In this thin-film stacked organic EL device, it is necessary to pile up materials having various functions, and from the viewpoint of the convenience of the process, the vapor deposition process has been mainly studied as a method for fabricating the device rather than the wet process. ing.
Thus, in the current organic EL device, it is necessary to select a light-emitting material / carrier transport material for the light-emitting layer, and also to select a functional separation thin film including the light-emitting layer. ing.

Currently, one of the important problems in organic EL devices is deterioration called baking. This phenomenon is considered to be caused by the fact that impurities are decomposed or modified by applying impurities to the organic EL element for a long time.
In order to prevent this deterioration, it is necessary to remove moisture and oxygen on the electrode surface and slight impurities contained in the organic thin film to be formed.
As a specific method, a method of sealing a desiccant or the like is used in order to improve the purity and stability of the organic substance constituting the organic EL element and to prevent the entry of oxygen and moisture from the outside.

However, from the practical viewpoint, the lifetime of the organic EL element is at least 100 cd / m ² and 100,000 hours are required, and it can be said that the degradation of the element due to the decomposition of the organic substances and the generated impurities during that period is inevitable.
In the existing organic EL element described above, the baking of each organic layer causes deterioration of the element, and if one of the organic layers constituting the organic EL element deteriorates, the lifetime of the entire element is greatly increased. Affect.
If this deteriorated organic layer has a structure that can be replaced by, for example, a cartridge, a new organic layer can be continuously supplied. As a result, the organic EL element can be driven semipermanently.
However, most of the existing organic EL elements described above use a solid organic thin film, and it is very difficult to replace only the deteriorated organic layer.

In recent years, technologies that lead to the solution of the above problems are being developed. For example, Patent Document 1 and Non-Patent Documents 1 and 2 report organic EL elements in which a light emitting layer is liquefied. By making the light emitting layer liquefied or semisolid, it can be said that the deteriorated liquid light emitting layer is easier to replace than the solid thin film layer, and at least the light emitting layer is considered to be a replaceable light emitting element. .
However, it is difficult to say that the organic EL element using the liquid light emitting layer disclosed in Patent Document 1 and Non-Patent Documents 1 and 2 is an organic EL element having such high characteristics that it can be replaced with an existing illumination or display. The liquid light emitting layer and device structure needed to be optimized.

One of the reasons why an organic EL element using a liquid light-emitting layer has lower characteristics than existing solid organic EL elements is that only one type of carrier transport material is included in the liquid light-emitting layer. In this case, the balance between holes injected from the anode and electrons injected from the cathode is poor, and the probability of recombination of holes and electrons in the light emitting layer (carrier recombination balance) decreases. In other words, this means that the internal quantum yield is poor, and the luminous efficiency of the device is reduced.
Furthermore, when trying to increase the injection efficiency of one carrier, the other carrier injection efficiency is lowered, and the voltage at which both carriers start to be injected increases. Since light emission is a phenomenon caused by injection of both carriers, this increase in the carrier injection start voltage results in an increase in the drive voltage of the device.
Therefore, in order to increase the carrier recombination balance in the liquid light emitting layer containing a single carrier transport material, it is necessary to control the dense electrode interface using the carrier block layer and the carrier injection layer.

In addition to the carrier injection efficiency, a factor that greatly contributes to device characteristics is control of the distance between the electrodes.
The liquid light emitting layer is manufactured by sandwiching a liquid light emitting material between the anode and the cathode, and the distance between the two electrodes is controlled by the thickness of the spacer and the amount of the liquid light emitting material. It is difficult to precisely control the thickness to 1 μm or less, and as a result, the drive voltage increases.
Moreover, since it is a liquid, the influence of the nonuniformity of the distance between electrodes resulting from the unevenness | corrugation of the electrode substrate surface is remarkable, and it was difficult to produce the element of the same performance with sufficient reproducibility.
In an EL element that is required to have a large area and an improvement in yield, the element manufacturing process sandwiched between two electrodes is inefficient, and application to a large-area element is difficult.

International Publication No. 2011/010656 JP 2009-224747 A

Appl. Phys. Lett. , 95, 053304 (2009) Adv. Mater. , 23, 889 (2011) Materials, 3, 3729 (2010)

  The present invention has been made in view of such circumstances, and provides an organic EL element having a high luminance and a low driving voltage in which the distance between electrodes is controlled in a wide range and the yield in manufacturing is improved. For the purpose.

The present inventors have found a light-emitting layer that is liquid at room temperature and can maintain a liquid state during both driving and non-driving, and has already reported an organic electroluminescence device (organic EL device) provided with this light-emitting layer. However, this organic EL element has room for further improvement in terms of luminance and driving voltage as described above.
Accordingly, the present inventors have conducted extensive studies to further improve the luminance and lower the driving voltage of an organic EL element having a liquid light emitting layer, and to improve the yield during manufacturing. It has been found that by using a gel light emitting layer, control of the film thickness by the coating process, that is, control of the distance between the electrodes becomes easy, and an organic electroluminescence device having high luminance and low driving voltage can be obtained. Furthermore, the present inventors have made the light emitting layer a gel light emitting layer, and at least one of the other functional layers is a gel functional layer, thereby controlling the film thickness of the light emitting layer by the coating process, that is, controlling the distance between the electrodes. As a result, it was found that an organic electroluminescence device having a high luminance and a low driving voltage with good carrier recombination balance was obtained, and the present invention was completed.
In Patent Document 2 and Non-Patent Document 3, electroluminescence from a gel-like substance having an ionic liquid is observed, but a gel light-emitting material using a liquid light-emitting material or a carrier transport material at room temperature is disclosed. It has not been. Moreover, since the gel-like substances of these documents contain a high concentration of electrolyte, there is a drawback that the device lifetime is low.

（式中、Ｒ¹〜Ｒ³は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、若しくはフェニル基を表すか、又はＲ¹とＲ²若しくはＲ²とＲ³とが互いに結合して形成される炭素数４〜１０のシクロアルキル基若しくはシクロアルケニル基を表し、Ｘ¹は、エーテル結合、アミド結合、又はエステル結合を含んでいてもよい炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基を表し、Ａ¹はエーテル結合、エステル結合、アミド結合を含んでいてもよい炭素数１〜２０の直鎖状、分岐状又は環状のアルキレン基を表し、ｎ₁及びｎ₂は、繰り返し単位構造の数であって互いに独立して２〜１００，０００の整数を表す。）
１１．前記非導電性高分子が、式（３）及び（４）から選ばれる１種又は２種以上である１０の有機電界発光素子、

（式中、ｎ₁及びｎ₂は、前記と同じ意味を表す。）
１２．前記導電性高分子が、式（５）及び（６）から選ばれる１種又は２種以上である９の有機電界発光素子、

（式中、Ｒ⁴〜Ｒ⁶は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、若しくはフェニル基を表すか、又はＲ⁴とＲ⁵若しくはＲ⁴とＲ⁶とが互いに結合して形成される炭素数４〜１０のシクロアルキル基若しくはシクロアルケニル基を表し、Ａｒ¹は、カルバゾール誘導体基、トリアリールアミン誘導体基、スターバーストアミン、チアントレン誘導体基、フェノチアジン誘導体基、アゼピン誘導体基、フェニレンジアミン誘導体基、トリフェニルメタン誘導体基、フルオレン誘導体基、スチルベン誘導体基、ポリアニリン誘導体基、シラン誘導体基、ピロール誘導体基、ポルフィリン誘導体基、炭素縮合環系化合物基、金属若しくは無金属のフタロシアニン誘導体基、ジフェニレンスルホン（ジベンゾチオフェン５，５−ジオキシド）誘導体基、オキサジアゾール誘導体基、トリアゾール誘導体基、トリアジン誘導体基、フェナントロリン誘導体基、イミダゾール誘導体基、オキサゾール誘導体基、フルオレノン誘導体基、シロール誘導体基、トリアリールホスフィンオキシド誘導体基、トリアリールボラン誘導体基、フラン誘導体基、及び電子輸送性金属錯体基から選ばれる１種又は２種以上の基を表し、Ｂ¹は、単結合、並びに２価の、ベンゼン誘導体基、ナフタレン誘導体基、アントラセン誘導体基、ピレン誘導体基、チオフェン誘導体基、フラン誘導体基、ピロール誘導体基、カルバゾール誘導体基、トリアリールアミン誘導体基、スターバーストアミン、チアントレン誘導体基、フェノチアジン誘導体基、アゼピン誘導体基、フェニレンジアミン誘導体基、トリフェニルメタン誘導体基、フルオレン誘導体基、スチルベン誘導体基、ポリアニリン誘導体基、シラン誘導体基、ポルフィリン誘導体基、金属若しくは無金属のフタロシアニン誘導体基、ジフェニレンスルホン（ジベンゾチオフェン５，５−ジオキシド）誘導体基、オキサジアゾール誘導体基、トリアゾール誘導体基、トリアジン誘導体基、フェナントロリン誘導体基、イミダゾール誘導体基、オキサゾール誘導体基、フルオレノン誘導体基、キナクリドン誘導体基、ピラゾロン誘導体基、シロール誘導体基、トリアリールホスフィンオキシド誘導体基、トリアリールボラン誘導体基、及び電子輸送性金属錯体基から選ばれる１種又は２種以上を表し、Ｃ¹は、炭素数１〜２０の直鎖状、分岐状若しくは環状の２価共役系脂肪族炭化水素基、又は単結合を表し、ただし、Ｂ¹及びＣ¹が同時に単結合となることはない、ｎ₃及びｎ₄は、繰り返し単位構造の数であって互いに独立して２〜１００，０００の整数を表す。）
１３．前記導電性高分子が、式（７）及び（８）から選ばれる１種又は２種以上である１２の有機電界発光素子、

（式中、Ｒ⁷〜Ｒ¹⁸は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、又はフェニル基を表し、ｎ₃及びｎ₄は、前記と同じ意味を表す。）
１４．前記導電性高分子が、式（９）〜（１１）から選ばれる１種又は２種以上である１３の有機電界発光素子、

（式中、ｎ₃及びｎ₄は、前記と同じ意味を表す。）
１５．常温で液体の半導体を含む液状組成物を、高分子ゲル化剤でゲル化させてなるゲル、
１６．弾性を有する１５のゲル、
１７．陽極と、陰極と、これら各極間に介在するゲル発光層とを備える有機電界発光素子の製造方法であって、
（Ａ１）常温で液体の発光材料とゲル化剤とを含み、全体として常温で液体の組成物、又は（Ａ２）キャリア輸送材料、発光材料及びゲル化剤を含み、前記キャリア輸送材料及び発光材料のうち少なくとも１つが常温で液体であるとともに、全体として常温で液体の組成物から、塗布法によって前記ゲル発光層を形成することを特徴とする有機電界発光素子の製造方法、
１８．陽極と、陰極と、これら各極間に介在するゲル発光層を含む２層以上のゲル機能層を備える有機電界発光素子の製造方法であって、
（Ａ１）常温で液体の発光材料とゲル化剤とを含み、全体として常温で液体の組成物、又は（Ａ２）キャリア輸送材料、発光材料及びゲル化剤を含み、前記キャリア輸送材料及び発光材料のうち少なくとも１つが常温で液体であるとともに、全体として常温で液体の組成物から、塗布法によって前記ゲル発光層を形成し、
（Ｂ）常温で液体のキャリア輸送材料とゲル化剤とを含み、全体として常温で液体の組成物から、塗布法によって少なくとも１層の前記ゲル機能層を形成することを特徴とする有機電界発光素子の製造方法、
１９．前記ゲル発光層を冷却した状態で、当該ゲル発光層上に前記陰極を蒸着する１７又は１８の有機電界発光素子の製造方法
を提供する。That is, the present invention
1. An organic electroluminescent device comprising an anode, a cathode, and a light emitting layer interposed between these electrodes,
The light-emitting layer includes (A1) a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at normal temperature with a gelling agent, or (A2) a carrier transporting material and a light-emitting material, and at least one of these materials is normal temperature An organic electroluminescent device characterized in that it is a gel light emitting layer formed by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent,
2. One organic electroluminescent element, wherein the carrier transport material is at least one selected from a hole transport material, an electron transport material, and a material having both a hole transport capability and an electron transport capability;
3. An organic electroluminescent device comprising an anode, a cathode, and two or more functional layers including a light emitting layer interposed between these electrodes,
The light-emitting layer includes (A1) a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at normal temperature with a gelling agent, or (A2) a carrier transporting material and a light-emitting material, and at least one of these materials is normal temperature And a gel light emitting layer formed by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent,
At least one of the other functional layers includes (B1) a gel functional layer obtained by gelling a carrier transport material that is liquid at normal temperature with a gelling agent, or (B2) a carrier transport material that is liquid at normal temperature, An organic electroluminescent device characterized in that it is a gel functional layer formed by gelling a carrier transport composition that is liquid at room temperature as a whole with a gelling agent,
4). 3. The organic electroluminescence device according to 3, wherein the carrier transport material contained in the gel light emitting layer is at least one selected from a hole transport material, an electron transport material, and a material having both hole transport capability and electron transport capability;
5. The organic electroluminescence device according to 3 or 4, wherein the carrier transport material contained in the gel functional layer is a hole transport material, an electron transport material, or a material having both a hole transport capability and an electron transport capability,
6). The organic electroluminescent element according to any one of 3 to 5, wherein the gel functional layer is an electron block layer laminated in a manner in contact with the gel light emitting layer between the gel light emitting layer and the anode,
7). The organic electroluminescent element according to any one of 1 to 6, wherein the gelling agent is a polymer material,
8). The polymer material is selected from poly (meth) acrylates, polyacrylonitriles, polyolefins, polystyrenes, polyamides, polyesters, polyimides, polyalkoxyoxides, polysiloxanes, and biopolymers 1 The organic electroluminescent device according to 7, which is a seed or two or more kinds of non-conductive polymers,
9. The polymer material is one or more conductive polymers selected from polyvinyl carbazoles, polythiophenes, polyphenylene vinylenes, polyacetylenes, polydiacetylenes, polyanilines, polypyrroles, and carbons. Organic electroluminescent elements,
10. 8 organic electroluminescent elements, wherein the nonconductive polymer is one or more selected from formulas (1) and (2);

(Wherein R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, or R ¹ and R ² or R ² and R ³ ; Represents a cycloalkyl group having 4 to 10 carbon atoms or a cycloalkenyl group formed by bonding to each other, and X ¹ is a straight chain having 1 to 20 carbon atoms which may contain an ether bond, an amide bond, or an ester bond. Represents a chain, branched or cyclic alkyl group, and A ¹ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond or an amide bond, n ₁ and n ₂ are the number of repeating unit structures and each independently represent an integer of 2 to 100,000.)
11. 10 organic electroluminescent elements, wherein the nonconductive polymer is one or more selected from formulas (3) and (4);

(In the formula, n ₁ and n ₂ represent the same meaning as described above.)
12 9 organic electroluminescent elements, wherein the conductive polymer is one or more selected from formulas (5) and (6);

(Wherein R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, or R ⁴ and R ^5, or R ⁴ and R ^6, and Represents a C 4-10 cycloalkyl group or cycloalkenyl group formed by bonding each other, Ar ¹ is a carbazole derivative group, a triarylamine derivative group, a starburst amine, a thianthrene derivative group, a phenothiazine derivative group, Azepine derivative group, phenylenediamine derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline derivative group, silane derivative group, pyrrole derivative group, porphyrin derivative group, carbon condensed ring compound group, metal or non-metal Phthalocyanine derivative group, diphenylene sulfone (dibenzothiophene) , 5-dioxide) derivative group, oxadiazole derivative group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imidazole derivative group, oxazole derivative group, fluorenone derivative group, silole derivative group, triarylphosphine oxide derivative group, tria Represents one or more groups selected from a reelborane derivative group, a furan derivative group, and an electron transporting metal complex group, and B ¹ is a single bond and a divalent benzene derivative group, naphthalene derivative group, Anthracene derivative group, pyrene derivative group, thiophene derivative group, furan derivative group, pyrrole derivative group, carbazole derivative group, triarylamine derivative group, starburst amine, thianthrene derivative group, phenothiazine derivative group, azepine derivative group, phenylenediametic Derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline derivative group, silane derivative group, porphyrin derivative group, metal or metal-free phthalocyanine derivative group, diphenylene sulfone (dibenzothiophene 5,5-dioxide ) Derivative group, oxadiazole derivative group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imidazole derivative group, oxazole derivative group, fluorenone derivative group, quinacridone derivative group, pyrazolone derivative group, silole derivative group, triarylphosphine oxide derivative group, one or more selected triaryl borane derivative group, and the electron transporting metal complex groups, C ¹ is a straight, divalent conjugated branched or cyclic Fat Family hydrocarbon group, or a single bond, however, never B ¹ and C ¹ is a single bond simultaneously, n ₃ and n _4, and the number of repeating unit structures each independently from 2 to 100 Represents an integer of 1,000. )
13. 12 organic electroluminescent elements wherein the conductive polymer is one or more selected from formulas (7) and (8);

(In the formula, R ^{7 to} R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and n ₃ and n ₄ represent the same meaning as described above. )
14 13 organic electroluminescent elements, wherein the conductive polymer is one or more selected from formulas (9) to (11);

(Wherein n ₃ and n ₄ represent the same meaning as described above.)
15. A gel obtained by gelling a liquid composition containing a semiconductor that is liquid at room temperature with a polymer gelling agent;
16. 15 gels with elasticity,
17. A method for producing an organic electroluminescent device comprising an anode, a cathode, and a gel light emitting layer interposed between these electrodes,
(A1) A light emitting material and a gelling agent which are liquid at normal temperature, and a composition which is liquid at normal temperature as a whole, or (A2) a carrier transporting material, a light emitting material and a gelling agent, and the carrier transporting material and the light emitting material And at least one of them is liquid at normal temperature, and the gel light emitting layer is formed by a coating method from a composition that is liquid at normal temperature as a whole, a method for producing an organic electroluminescent device,
18. A method for producing an organic electroluminescent device comprising an anode, a cathode, and two or more gel functional layers including a gel light emitting layer interposed between these electrodes,
(A1) A light emitting material and a gelling agent which are liquid at normal temperature, and a composition which is liquid at normal temperature as a whole, or (A2) a carrier transporting material, a light emitting material and a gelling agent, and the carrier transporting material and the light emitting material At least one of them is liquid at room temperature, and the gel light emitting layer is formed by a coating method from a composition that is liquid at room temperature as a whole,
(B) Organic electroluminescence comprising a carrier transport material and a gelling agent which are liquid at normal temperature, and forming at least one gel functional layer by a coating method from a composition which is liquid at normal temperature as a whole. Device manufacturing method,
19. A method for producing an organic electroluminescent device according to 17 or 18, wherein the cathode is deposited on the gel light emitting layer in a state where the gel light emitting layer is cooled.

According to the present invention, by adopting a gel light emitting layer and a plurality of gel functional layers including a gel light emitting layer, the yield during production can be improved, the distance between the two electrodes can be controlled over a wide range, and the carrier can be regenerated. It is possible to provide an organic electroluminescence device having a high luminance and a low driving voltage with a good coupling balance.
The gel light emitting layer and gel functional layer of this organic electroluminescent element are composed of a liquid light emitting material and / or a carrier transport material and a gelling agent, and maintain a semi-solid (gel) state when driven and not driven. Can do. By using this gel light emitting layer, it is possible to provide an organic electroluminescent device that can maintain the device shape at around room temperature and has high flexibility. Further, when the liquid light emitting material or the carrier transporting material is deteriorated, it is possible to exchange them (for example, cartridge, extraction / reinjection by circulation).
The organic electroluminescent device of the present invention can be manufactured using a coating process, and since the gel light emitting layer is used, the distance between electrodes can be accurately controlled even in a large-area lighting device. Yes, yield is also good.
Furthermore, since the gel light emitting layer used in the organic electroluminescent element of the present invention does not require the use of an electrolyte unlike the gel-like substance described in Patent Document 2 and Non-Patent Document 3, it is possible to extend the life of the element.
In addition, by using a gel light emitting layer and a gel functional layer excellent in stretchability, and making an organic EL element using a stretchable electrode, it is possible to emit light while being stretched, and against excessive bending However, it is possible to realize a flexible light source that is not damaged.

It is a schematic sectional drawing which shows the 1st organic EL element which concerns on this invention. 6 is a schematic cross-sectional view showing an organic EL element produced in Comparative Example 1. FIG. 2 is a diagram showing a ¹ H-NMR spectrum of TEGPy obtained in Synthesis Example 1. FIG. 6 is a graph showing current density-voltage-luminance characteristics of an EL element manufactured in Example 1. FIG. FIG. 3 is a diagram showing EL external quantum efficiency-current density characteristics of the EL element produced in Example 1. It is the photograph (Upper: At the time of UV light non-irradiation, The lower: At the time of UV light irradiation, visual observation) which shows the transparent gel-like film produced in Example 22. It is a photograph which shows the extending | stretching-shrinking behavior of the gel-like film produced in Example 22. It is a figure which shows the repetitive stress-strain curve of the gel-like film produced in Example 22. It is the photograph (Upper: At the time of UV light non-irradiation, The lower: At the time of UV light irradiation, visual observation) which shows the cloudy gel-like film produced in Example 29. It is a figure which shows the thermal-analysis result of the transparent gel-like film obtained in Examples 39-45. It is a figure which shows the thermal-analysis result of the cloudy gel-like film obtained in Example 46. It is a schematic sectional drawing which shows the 2nd organic EL element which concerns on this invention. It is a schematic sectional drawing which shows the organic EL element produced by Comparative Examples 7-13. 14 is a graph showing current density-voltage-luminance characteristics of an EL element manufactured in Example 47. FIG. 42 is a graph showing EL external quantum efficiency-current density characteristics of an EL element manufactured in Example 47. FIG. 10 is a graph showing current density-voltage-luminance characteristics of an EL element manufactured in Comparative Example 7. FIG. 10 is a diagram showing EL external quantum efficiency-current density characteristics of an EL element manufactured in Comparative Example 7. FIG. 6 is a graph showing current density-voltage-luminance characteristics of an EL element produced in Example 52. FIG. 42 is a graph showing EL external quantum efficiency-current density characteristics of an EL element manufactured in Example 52. FIG. 10 is a graph showing current density-voltage-luminance characteristics of an EL element manufactured in Comparative Example 8. FIG. 10 is a graph showing EL external quantum efficiency-current density characteristics of an EL element manufactured in Comparative Example 8. FIG.

Hereinafter, the present invention will be described in more detail.
A first organic electroluminescent device according to the present invention includes an anode, a cathode, and a light emitting layer interposed between these electrodes, and the light emitting layer is (A1) a light emitting material that is liquid at room temperature with a gelling agent. A gel light-emitting layer formed by gelation, or (A2) a carrier transport material and a light-emitting material, and at least one of these materials is liquid at room temperature, and the light-emitting composition that is liquid at room temperature as a whole is a gelling agent. It is characterized by being a gel light emitting layer formed by gelation.
The second organic electroluminescent device according to the present invention comprises two or more functional layers including an anode, a cathode, and a light emitting layer interposed between these electrodes, and the light emitting layer is (A1) at room temperature. A gel light-emitting layer obtained by gelling a liquid light-emitting material with a gelling agent, or (A2) a carrier transport material and a light-emitting material, and at least one of these materials is liquid at room temperature, and at room temperature as a whole It is a gel light emitting layer formed by gelling a liquid light emitting composition with a gelling agent, and at least one of the other functional layers is (B1) gelled with a gelling agent at a room temperature. It is a gel functional layer or (B2) a gel functional layer containing a carrier transporting material which is liquid at normal temperature, and gelling a carrier transporting composition which is liquid at normal temperature with a gelling agent as a whole. To do.
Here, normal temperature means a range of 20 ° C. ± 15 ° C. (5-35 ° C.) defined by JIS Z 8703.

First, the gelling agent will be described.
The gelling agent used in the present invention is not particularly limited as long as it can gel a liquid luminescent material or the like, and can be appropriately selected from materials conventionally used as a gelling agent. A polymer material is preferred.
The polymer material may be either a non-conductive polymer or a conductive polymer, but a conductive polymer is more preferable in consideration of enhancing the characteristics of the organic EL element to be obtained.

Non-conductive polymers include poly (meth) acrylates, polyacrylonitriles, polyolefins, polystyrenes, polyamides, polyesters, polyimides, polyalkoxyoxides, polysiloxanes, biopolymers, etc. It is done.
Examples of poly (meth) acrylates include polymethyl methacrylate (polymer represented by the formula (3)).
Examples of polyacrylonitriles include polyacrylonitrile.
Examples of polyolefins include polyethylene, polypropylene, polybutadiene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and the like.
Examples of polystyrenes include polystyrene, polystyrene sulfonic acid, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-styrene copolymer.
Examples of polyamides include nylon-6 and nylon 66.
Examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid (PLA), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate, and the like. It is done.
Examples of polyalkoxyoxides include polyethylene oxide (polymer represented by the formula (4)), polypropylene oxide, polybutylene oxide, and the like.
Examples of biopolymers include gelatin and sugar.

  Among these, nonconductive polymers represented by the formulas (1) and (2) are preferable.

Here, R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, or R ¹ and R ² or R ² and R ³ are mutually bonded. Represents a cycloalkyl group having 4 to 10 carbon atoms or a cycloalkenyl group formed by bonding, and X ¹ is a straight chain having 1 to 20 carbon atoms which may contain an ether bond, an amide bond or an ester bond, Represents a branched or cyclic alkyl group, and A ¹ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond or an amide bond, and n ₁ and n ₂ is the number of repeating unit structures and represents an integer of 2 to 100,000 independently of each other.
Incidentally, an ether bond in X ^1, an amide bond, an ester bond may be present in the connecting portion between the carbon atoms and X ^1.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, c-propyl, n-butyl, i-butyl, s-butyl, t-butyl, c-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, c-pentyl, 2-methyl-c-butyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, c-hexyl, 1-methyl-c-pentyl, 1-ethyl-c-butyl, 1,2-dimethyl-c-butyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl group Etc.

Specific examples of the cycloalkyl group having 4 to 10 carbon atoms include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups.
Examples of the cycloalkenyl group having 4 to 10 carbon atoms include cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, and cyclodecenyl groups.

Specific examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether bond include n-undecyl and n-dodecyl in addition to the alkyl group having 1 to 10 carbon atoms. Alkyl groups having 11 to 20 carbon atoms such as n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl group, and -CH ₂ OCH ₃ , —CH ₂ OCH ₂ CH ₃ , —CH ₂ O (CH ₂ ) ₂ CH ₃ , —CH ₂ OCH (CH ₃ ) ₂ , —CH ₂ O (CH ₂ ) ₃ CH ₃ , —CH ₂ OCH ₂ CH ( _{CH 3) 2, -CH 2 OC} (CH 3) 3, -CH 2 O (CH 2) 4 CH 3, -CH 2 OCH (CH 3) (CH 2) 2 CH 3, -CH 2 OCH 2 CH ( _{CH 3), - CH 2 O} (CH 2) 2 CH (C _{3), - CH 2 OCH (} CH 3) (CH 2) 3 CH 3, -CH 2 O (CH 2) 5 CH 3, -CH 2 OCH 2 CH (CH 3) (CH 2) 2 CH 3, - _{CH 2 O (CH 2) 2} CH (CH 3) CH 2 CH 3, -CH 2 O (CH 2) 3 CH (CH 3), - CH 2 OC (CH 3) 2 (CH 2) 2 CH 3, _{-CH 2 OCH (CH 2 CH 3} ) (CH 2) 2 CH 3, -CH 2 OC (CH 3) 2 CH (CH 3), - CH 2 O (CH 2) 6 CH 3, -CH 2 O ( _{CH 2) 7 CH 3, -CH} 2 OCH 2 CH (CH 2 CH 3) (CH 2) 3 CH 3, -CH 2 O (CH 2) 8 CH 3, -CH 2 O (CH 2) 9 CH 3 , —CH ₂ O (CH ₂ ) ₁₀ CH ₃ , —CH ₂ O (CH ₂ ) ₁₁ CH ₃ , —CH ₂ O (CH ₂ ) ₁₂ CH ₃ , —CH ₂ O (CH ₂ ) ₁₃ CH ₃ , − CH ₂ O (C _{2) 14 CH 3, -CH 2} O (CH 2) 15 CH 3, -CH 2 O (CH 2) 16 CH 3, -CH 2 O (CH 2) 17 CH 3, -CH 2 O (CH 2) ₁₈ CH ₃ , —CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₂ CH ₃ , —CH ₂ CH ₂ OCH (CH ₃ ) ₂ , —CH ₂ CH ₂ O (CH ₂ ) ₃ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) ₂ , —CH ₂ CH ₂ OC (CH ₃ ) ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₄ CH ₃ , —CH ₂ CH ₂ OCH (CH ₃ ) (CH ₂ ) ₂ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH (CH ₃ ), —CH ₂ CH ₂ O (CH ₂ ) ₂ CH (CH ₃ ), _{-CH 2 CH 2 OC (CH 3} ), - CH 2 CH 2 OCH (CH 3) (CH 2) 3 CH 3, -CH 2 CH 2 O (CH 2) 5 CH 3, -CH 2 CH ₂ OCH (CH ₃ ) (CH ₂ ) ₃ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) (CH ₂ ) ₂ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₂ CH (CH ₃ ) _{CH 2 CH 3, -CH 2 CH} 2 O (CH 2) 3 CH (CH 3), - CH 2 CH 2 OC (CH 3) 2 (CH 2) 2 CH 3, -CH 2 CH 2 OCH (CH 2 _{CH 3) (CH 2) 2} CH 3, -CH 2 CH 2 OC (CH 3) 2 CH (CH 3), - CH 2 CH 2 O (CH 2) 6 CH 3, -CH 2 CH 2 O (CH _{2) 7 CH 3, -CH 2} CH 2 OCH 2 CH (CH 2 CH 3) (CH 2) 3 CH 3, -CH 2 CH 2 O (CH 2) 8 CH 3, -CH 2 CH 2 O (CH _{2) 9 CH 3, -CH 2} CH 2 O (CH 2) 10 CH 3, -CH 2 CH 2 O (CH 2) 11 CH 3, -CH 2 CH 2 O (CH 2) 12 CH 3, -C _{2 CH 2 O (CH 2)} 13 CH 3, -CH 2 CH 2 O (CH 2) 14 CH 3, -CH 2 CH 2 O (CH 2) 15 CH 3, -CH 2 CH 2 O (CH 2) ₁₆ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₁₇ CH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH _{2) 2} CH _{3,
-CH 2 CH 2 CH 2 OCH (} CH 3) 2, -CH 2 CH 2 CH 2 O (CH 2) 3 CH 3, -CH 2 CH 2 CH 2 OCH 2 CH (CH 3) 2, -CH 2 CH ₂ CH ₂ OC (CH ₃ ) ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₄ CH ₃ , —CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) (CH ₂ ) ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH (CH ₃ ), —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₂ CH (CH ₃ ), —CH ₂ CH ₂ CH ₂ OC (CH ₃ ), —CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) (CH ₂ ) ₃ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₅ CH ₃ , —CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) (CH ₂ ) ₃ CH ₃ , − _{CH 2 CH 2 CH 2 OCH 2} CH (CH 3) (CH 2) 2 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 2 CH (CH 3) CH 2 C _{3, -CH 2 CH 2 CH 2} O (CH 2) 3 CH (CH 3), - CH 2 CH 2 CH 2 OC (CH 3) 2 (CH 2) 2 CH 3, -CH 2 CH 2 CH 2 OCH _{(CH 2 CH 3) (CH} 2) 2 CH 3, -CH 2 CH 2 CH 2 OC (CH 3) 2 CH (CH 3), - CH 2 CH 2 CH 2 O (CH 2) 6 CH 3, - _{CH 2 CH 2 CH 2 O (} CH 2) 7 CH 3, -CH 2 CH 2 CH 2 OCH 2 CH (CH 2 CH 3) (CH 2) 3 CH 3, -CH 2 CH 2 CH 2 O (CH 2 ₈ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₉ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₀ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) _{11 CH 3, -CH 2 CH 2 CH} 2 O (CH 2) 12 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 13 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 14 _{CH 3, -CH 2 CH 2 CH} 2 O (CH 2) 15 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 16 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 3, -CH 2 CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _{2 CH 2 OCH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ ,- CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _{2 OCH 2 CH 3, -CH 2 CH} 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 group, and the like.
Specific examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ester bond include at least one oxygen atom (O) of the ether group-containing alkyl group described above, Examples include a group in place of C (O) O or OC (O).

Examples of the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain an ether bond include — (CH ₂ ) _m such as methylene, ethylene, trimethylene, tetramethylene and pentamethylene groups. -(M = 1-20) group, a propylene group, the bivalent group etc. which remove | eliminate one terminal hydrogen atom of the ether group containing alkyl group mentioned above, etc. are mentioned.
As the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain an ester bond or an amide bond, at least one oxygen atom (O) of the ether group-containing alkylene group described above is used. Examples include a group replaced with C (O) O or OC (O), a group replaced with NHC (O) or C (O) NH, and the like.

  Among these, nonconductive polymers represented by the formulas (3) and (4) are more preferable.

（式中、ｎ₁及びｎ₂は、前記と同じ意味を表す。）

(In the formula, n ₁ and n ₂ represent the same meaning as described above.)

On the other hand, examples of the conductive polymer include polyvinyl carbazoles, polythiophenes, polyphenylene vinylenes, polyacetylenes, polydiacetylenes, polyanilines, polypyrroles, carbons and the like.
Examples of polyvinyl carbazoles include polymers represented by formula (7) or formula (9).
Examples of polythiophenes include polythiophene, poly (ethylenedioxythiophene), p-toluenesulfonic acid / poly (ethylenedioxythiophene), and the like.
Examples of polyphenylene vinylenes include compounds represented by formula (8), poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene) (MEHPPV, polymer represented by formula (10)). , Poly (2-methoxy-5- (4- (2-ethylhexyloxy) phenyl) -1,4-phenylenevinylene) (MEHPPPV, polymer represented by the formula (11)), and the like.
Examples of carbons include carbon nanotubes.

  Among these, the conductive polymer represented by Formula (5) and Formula (6) is preferable.

Here, R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, or R ⁴ and R ⁵ or R ⁴ and R ⁶ are Represents a cycloalkyl group or a cycloalkenyl group having 4 to 10 carbon atoms formed by bonding, Ar ¹ is a carbazole derivative group, a triarylamine derivative group, a starburst amine, a thianthrene derivative group, a phenothiazine derivative group, an azepine derivative Group, phenylenediamine derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline derivative group, silane derivative group, pyrrole derivative group, porphyrin derivative group, carbon condensed ring system compound group, metal or metal-free phthalocyanine Derivative group, diphenylene sulfone (dibenzothiophene 5 5-dioxide) derivative group, oxadiazole derivative group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imidazole derivative group, oxazole derivative group, fluorenone derivative group, silole derivative group, triarylphosphine oxide derivative group, triaryl It represents one or more groups selected from a borane derivative group, a furan derivative group, and an electron transporting metal complex group, and B ¹ is a single bond and a divalent benzene derivative group, naphthalene derivative group, anthracene. Derivative group, pyrene derivative group, thiophene derivative group, furan derivative group, pyrrole derivative group, carbazole derivative group, triarylamine derivative group, starburst amine, thianthrene derivative group, phenothiazine derivative group, azepine derivative group, phenylenediamine Derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline derivative group, silane derivative group, porphyrin derivative group, metal or metal-free phthalocyanine derivative group, diphenylene sulfone (dibenzothiophene 5,5-dioxide) Derivative group, oxadiazole derivative group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imidazole derivative group, oxazole derivative group, fluorenone derivative group, quinacridone derivative group, pyrazolone derivative group, silole derivative group, triarylphosphine oxide derivative Represents one or more selected from a group, a triarylborane derivative group, and an electron-transporting metal complex group, and C ¹ is a linear, branched or cyclic divalent conjugated system having 1 to 20 carbon atoms. fat Hydrocarbon group, or a single bond (B ¹ and C ¹ does not become a single bond simultaneously), n ₃ and n ₄ is the number of repeating unit structures independently of one another 2～100,000 Represents an integer.

Examples of the halogen atom, the alkyl group having 1 to 10 carbon atoms, the cycloalkyl group having 4 to 10 carbon atoms, and the cycloalkenyl group include those described above.
Examples of the linear, branched or cyclic divalent conjugated aliphatic hydrocarbon group having 1 to 20 carbon atoms include — (CH═CR) _k —, — (C≡C) ₁ —, — (CR═CR -C≡C) _m- (wherein, k and l are integers of 1 to 10, and m is an integer of 1 to 5).
As the binding mode of C ¹ and B ^1, embodiment C ¹ to the annular site of the B ¹ is connected directly, or the polyaniline derivative include aspects attached to the NH group.

（式中、Ｒ⁷〜Ｒ¹⁸は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜１０のアルキル基又はフェニル基を表し、ｎ₃及びｎ₄は、前記と同じ意味を表す。）In particular, the conductive polymers represented by the formulas (7) and (8) are preferable, and the conductive polymers represented by the formulas (9) to (11) are more preferable. In consideration of improving quantum efficiency and the like, polyvinylcarbazoles represented by the formulas (7) and (9) having a conductive moiety in the side chain are preferable.
In addition, the gelling agent demonstrated above may be used individually, respectively, or may be used in combination of 2 or more types.

(Wherein R ^{7 to} R ¹⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n ₃ and n ₄ represent the same meaning as described above.)

（式中、ｎ₃及びｎ₄は、前記と同じ意味を表す。）

(Wherein n ₃ and n ₄ represent the same meaning as described above.)

The components constituting the gel light-emitting layer used together with the above-described gelling agent may be any material that exhibits liquid properties without the addition of the gelling agent. The carrier transporting material and the light-emitting material that are constituent materials of the light-emitting layer may be used. While at least one is liquid, the whole composition constituting the light emitting layer can be liquid.
That is, only a light emitting material that is liquid at room temperature is used, and this is treated with a gelling agent to form a gel light emitting layer, including a carrier transport material and a light emitting material, and at least one of these materials is liquid at room temperature. The light emitting composition that is liquid at room temperature as a whole may be treated with a gelling agent to form a gel light emitting layer.
Depending on the substance, both functions of carrier transport ability and light emission ability cannot be clearly separated. For example, some carbazoles, triarylamines, carbon condensed ring dyes, etc. have both functions.
In the present invention, such a substance having both functions can be used, and any substance showing a liquid state can be used alone.

In the present invention, as the liquid luminescent material and / or carrier transport material, the compound represented by the formula (12) can be preferably used.

  Here, X is a carrier transport and / or light emission (dye) part, and is a carbazole derivative, thianthrene derivative, phenothiazine derivative, azepine derivative, triazole derivative, imidazole derivative, oxadiazole derivative, arylcycloalkene derivative, triaryl. Amine derivatives, phenylenediamine derivatives, silole derivatives, triarylborane derivatives, stilbene derivatives, oxazole derivatives, triphenylmethane derivatives, pyrazolone derivatives, fluorenone derivatives, polyaniline derivatives, silane derivatives, pyrrole derivatives, porphyrin derivatives, quinacridone derivatives, triarylphosphine Carbon such as oxide derivatives, anthracene derivatives, tetracene derivatives, pyrene derivatives, rubrene derivatives, decacyclene derivatives, perylene derivatives Fused dyes, xanthene dyes, cyanine dyes, coumarin dyes, quinacridone dyes, squalium dyes, styryl dyes, phenoxazone dyes, metal or metal-free phthalocyanines, benzidines, iridium complexes, Al, Zn, Be Or the metal complex comprised from the central metal and ligand which consist of rare earth metals is represented.

  Among these, carbazole derivatives are preferable from the viewpoint of carrier transport ability, and carbon condensed ring dyes, particularly rubrene derivatives and pyrene derivatives are preferable from the viewpoint of light emission ability.

On the other hand, Y is at least one substituent linked to X, and represents an alkyl group having 1 to 30 carbon atoms or a coordinating substituent.
In this case, the alkyl group may be linear, branched, or cyclic, but when a linear alkyl group is used, the crystallinity may be improved due to intermolecular interactions such as packing of alkyl chains. A branched alkyl group is more preferable because of an increase in viscosity.
Specific examples of such an alkyl group having 1 to 30 carbon atoms include those similar to those exemplified above for the alkyl group having 1 to 20 carbon atoms.

On the other hand, the coordinating substituent is not particularly limited as long as it is a substituent containing a coordinating element, but is preferably a nonionic substituent.
Note that a coordinating element refers to an element having an electron pair (lone electron pair) not involved in a covalent bond and capable of coordinating with a Lewis acidic substance or the like by this electron pair.

In the present invention, the preferred coordinating element is preferably one or more selected from oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic and antimony, and a coordinating substituent containing these elements. Can be suitably used.
Among them, a coordinating substituent containing one or more coordinating elements selected from oxygen, sulfur, nitrogen and phosphorus is preferable, and a coordinating substituent containing oxygen is particularly preferable.
Specifically, an alkyl group having 1 to 30 carbon atoms having an ether bond, a thioether bond, an ester bond, a carbonic acid ester bond or an amide bond, a coordinating substituent containing a polyether structure, and the like can be given.
In this case as well, an ether bond, a thioether bond, an ester bond, a carbonate ester bond, and an amide bond may exist at the connecting portion between X and Y.

Here, specific examples of the alkyl group having 1 to 30 carbon atoms, which may include an ether bond and an ester bond, include those exemplified for the alkyl group having 1 to 20 carbon atoms, and —CH ₂ O (CH _{2) 19 CH 3, -CH 2} CH 2 O (CH 2) 18 CH 3, -CH 2 CH 2 O (CH 2) 19 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 17 CH 3, _{-CH 2 CH 2 CH 2 O (} CH 2) 18 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 19 CH 3, -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH _{2 CH 2 OCH 2 CH 2 CH} 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 _{H 2 OCH 2 CH 2 CH 2} OCH 3, -CH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH _{2 CH 2 CH 2 CH 2 OCH 2} CH 2 CH 2 CH 2 OCH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 group, etc. Or a group represented by the following formula, And groups in which the oxygen atom (O) of these groups is replaced with C (O) O or OC (O).

Specific examples of the alkyl group containing a thioether bond include a group in which at least one oxygen atom (O) of the above-described ether bond-containing alkyl group is replaced with a sulfur atom (S).
Specific examples of the alkyl group containing a carbonic acid ester bond include a group in which at least one oxygen atom (O) of the ether bond-containing alkyl group described above is replaced with OC (O) O.
Specific examples of the alkyl group containing an amide bond include a group in which at least one oxygen atom (O) of the above-described ether bond-containing alkyl group is replaced with C (O) NH or NHC (O). Can be mentioned.

Among these, a substituent having 6 to 30 carbon atoms is preferable from the viewpoint of easily becoming a liquid. Specifically, c-hexyl, 1-methyl-c-pentyl, 1-ethyl-c-butyl, 1, 2-dimethyl-c-butyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- hexadecyl, n- heptadecyl, n- octadecyl, n- nonadecyl, n- eicosyl _{group, -CH 2 O (CH 2)} 5 CH 3, -CH 2 OCH (CH 3) (CH 2) 3 CH 3, -CH 2 _{OCH 2 CH (CH 3) (} CH 2) 2 CH 3, -CH 2 O (CH 2) 2 CH (CH 3) CH 2 CH 3, -CH 2 O (CH 2) 3 CH (CH 3) CH 3 , -CH ₂ OC (CH _{3 2 (CH 2) 2 CH 3} , -CH 2 OCH (CH 2 CH 3) (CH 2) 2 CH 3, -CH 2 OC (CH 3) 2 CH (CH 3) CH 3, -CH 2 O (CH _{2) 6 CH 3, -CH 2} O (CH 2) 7 CH 3, -CH 2 OCH 2 CH (CH 2 CH 3) (CH 2) 3 CH 3, -CH 2 O (CH 2) 8 CH 3, _{-CH 2 O (CH 2) 9} CH 3, -CH 2 O (CH 2) 10 CH 3, -CH 2 O (CH 2) 11 CH 3, -CH 2 O (CH 2) 12 CH 3, -CH ₂ O (CH ₂ ) ₁₃ CH ₃ , —CH ₂ O (CH ₂ ) ₁₄ CH ₃ , —CH ₂ O (CH ₂ ) ₁₅ CH ₃ , —CH ₂ O (CH ₂ ) ₁₆ CH ₃ , —CH ₂ O _{(CH 2) 17 CH 3,} -CH 2 O (CH 2) 18 CH 3, -CH 2 O (CH 2) 19 CH 3, -CH 2 CH 2 O (CH 2) 5 CH 3, -CH 2 CH ₂ OCH (CH _{3 (CH 2) 3 CH 3,} -CH 2 CH 2 OCH 2 CH (CH 3) (CH 2) 2 CH 3, -CH 2 CH 2 O (CH 2) 2 CH (CH 3) CH 2 CH 3, - _{CH 2 CH 2 O (CH 2} ) 3 CH (CH 3) CH 3, -CH 2 CH 2 OC (CH 3) 2 (CH 2) 2 CH 3, -CH 2 CH 2 OCH (CH 2 CH 3) ( _{CH 2) 2 CH 3, -CH} 2 CH 2 OC (CH 3) 2 CH (CH 3) CH 3, -CH 2 CH 2 O (CH 2) 6 CH 3, -CH 2 CH 2 O (CH 2) ₇ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH (CH ₂ CH ₃ ) (CH ₂ ) ₃ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₈ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) _{9 CH 3, -CH 2 CH 2} O (CH 2) 10 CH 3, -CH 2 CH 2 O (CH 2) 11 CH 3, -CH 2 CH 2 O (CH 2) 12 CH 3, -CH 2 _{H 2 O (CH 2) 13} CH 3, -CH 2 CH 2 O (CH 2) 14 CH 3, -CH 2 CH 2 O (CH 2) 15 CH 3, -CH 2 CH 2 O (CH 2) 16 CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₁₇ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₁₈ CH ₃ , —CH ₂ CH ₂ O (CH ₂ ) ₁₉ CH ₃ , —CH ₂ CH _{2 CH 2 O (CH 2) 5} CH 3, -CH 2 CH 2 CH 2 OCH (CH 3) (CH 2) 3 CH 3,
_{-CH 2 CH 2 CH 2 OCH 2} CH (CH 3) (CH 2) 2 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 2 CH (CH 3) CH 2 CH 3, -CH 2 CH 2 _{CH 2 O (CH 2) 3} CH (CH 3) CH 3, -CH 2 CH 2 CH 2 OC (CH 3) 2 (CH 2) 2 CH 3, -CH 2 CH 2 CH 2 OCH (CH 2 CH 3 _{) (CH 2) 2 CH 3} , -CH 2 CH 2 CH 2 OC (CH 3) 2 CH (CH 3) CH 3, -CH 2 CH 2 CH 2 O (CH 2) 6 CH 3, -CH 2 CH ₂ CH ₂ O (CH ₂ ) ₇ CH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH (CH ₂ CH ₃ ) (CH ₂ ) ₃ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₈ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₉ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₀ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₁ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₂ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₃ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₄ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₅ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₆ CH ₃ , —CH ₂ CH ₂ CH ₂ O (CH ₂ ) ₁₇ CH ₃ , _{-CH 2 CH 2 CH 2 O (} CH 2) 18 CH 3, -CH 2 CH 2 CH 2 O (CH 2) 19 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 3, -CH 2 CH 2 OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _{2 OCH 3, -CH 2 CH 2} OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 _{H 2 OCH 3, -CH 2 CH} 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH _{2 CH 2 CH 2 CH 2 OCH 3} , -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH _{2 CH 2 CH 2 OCH 3, -CH} 2 CH 2 OCH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 _{CH 2 OCH 2 CH 2 OCH 2} CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH ₂ CH ₂ O CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ groups, etc., as well as oxygen atoms (O) of these groups to sulfur Group replaced with atom (S), group replaced with C (O) O or OC (O), group replaced with OC (O) O, group replaced with C (O) NH or NHC (O), etc. Is preferred.

More preferably, —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , --CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , --CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH _{2 CH 2 CH 2 CH 2 OCH 3} , -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 3, -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ C It is a ₂ OCH ₃ groups and the like.

On the other hand, as a coordinating substituent containing a (poly) ether structure, for example, — (AO) _n — (wherein A represents a divalent organic group and n represents an integer of 1 to 100). And a group containing a structure represented by:
Here, the divalent organic group includes an alkylene group having 1 to 30 carbon atoms, which may include an ether bond, a thioether bond, an ester bond, a carbonic acid ester bond or an amide bond, an unsubstituted or substituted group. A divalent aromatic ring which may be present, or a divalent heterocyclic ring which may be unsubstituted or substituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.
Examples of the divalent aromatic ring which may be unsubstituted or include a substituent include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,6-naphthylene, 1,7-naphthylene, , 6-naphthylene, 2,7-naphthylene group and the like.
Similarly, examples of the divalent heterocyclic ring include an imidazole ring, a pyridine ring, a pyrimidine ring, an indole ring, a quinoline ring, a furan ring, and a thiophene ring.
Examples of the halogen atom are the same as those described above.

Further, the alkylene group having 1 to 30 carbon atoms may be linear, branched or cyclic, and examples thereof include a — (CH ₂ ) _o — (o = 1 to 30) group and a propylene group. It is done.
The C1-C30 alkylene group containing an ether bond, a thioether bond, an ester bond, a carbonate ester bond or an amide bond includes those having these bonds at any position of the alkylene group as described above. Specific examples include the following substituents.

Examples of the alkylene group containing an ether _{bond, -CH 2 CH 2 OCH 2 CH} 2 OCH 2 -, - CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 2 -, - CH 2 CH 2 OCH 2 CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , --CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , --CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , --CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , --CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ O _{H 2 -, - CH 2 CH} 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 -, - CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 CH 2 CH ₂ OCH ₂ —, —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ —, —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH _2- , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH _2- , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH _{2 CH 2 CH 2 OCH 2 CH 2} C _{2 OCH 2 CH 2 CH 2 OCH} 2 CH 2 CH 2 OCH 2 CH 2 CH 2 OCH 2 - group, and the like are preferable.

Specific examples of the alkylene group containing a thioether bond include a group in which the oxygen atom (O) of the alkylene group containing an ether bond is replaced with a sulfur atom (S).
Specific examples of the alkylene group containing an ester bond include groups in which the oxygen atom (O) of the alkylene group containing an ether bond is replaced with C (O) O or OC (O).
Specific examples of the alkylene group containing a carbonic acid ester bond include groups in which the oxygen atom (O) of the alkylene group containing an ether bond is replaced with OC (O) O.
Specific examples of the alkylene group having 1 to 30 carbon atoms containing an amide bond include a group in which the oxygen atom (O) of the alkylene group containing an ether bond is replaced with C (O) NH or NHC (O). Etc.

  More specifically, for example, the following carbazole (13), N, N-disubstituted or N, N, N-trisubstituted arylamine (14) and the like can be mentioned.

In the above formula, Y ^{1 to} Y ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether, an ester bond, a carbonate ester bond, an amide bond, or the like (provided that , At least one of Y ^{1 to} Y ³ and at least one of Y ^{4 to} Y ⁶ is the alkyl group), E ¹ and E ² represent a single bond or a substituted or unsubstituted aromatic ring.
Examples of the aromatic ring include a benzene ring and a naphthalene ring.

In the present invention, in order to prevent an increase in viscosity due to an increase in molecular weight, it is more preferable that Y ¹ , Y ² , Y ⁴ and Y ⁵ are hydrogen atoms, Y ³ and Y ⁶ are alkyl groups, and further, E ¹ , E ² is preferably a benzene ring or a single bond.
From these points, the following compound (15) is preferable, the compound (16) is more preferable, and the compound (17) is more preferable, but is not limited thereto.

（式中、Ｙ¹、Ｙ²及びＹ³は前記と同じ意味を表す。）

(Wherein Y ¹ , Y ² and Y ³ represent the same meaning as described above.)

  Moreover, the carbazole derivative which has the (poly) ether structure which is a coordinating substituent on a nitrogen atom shown by Formula (18) can also be used suitably.

（式中、Ｂは１価の有機基を表し、Ａ及びｎは前記と同じ意味を表す。）

(In the formula, B represents a monovalent organic group, and A and n have the same meaning as described above.)

In said Formula (18), 1-10 are preferable and, as for n, 1-5 are more preferable.
The monovalent organic group may include an ether bond, a thioether bond, an ester bond, a carbonic acid ester bond or an amide bond, an alkyl group having 1 to 30 carbon atoms, an unsubstituted or substituted group. And a good aromatic ring or a heterocyclic ring which may be unsubstituted or substituted.
Examples of the aromatic ring include a benzene ring and a naphthalene ring.
Examples of the heterocyclic ring include an imidazole ring, a pyridine ring, a pyrimidine ring, an indole ring, a quinoline ring, a furan ring, and a thiophene ring.
Examples of the alkyl group having 1 to 30 carbon atoms which may contain an ether bond and the like are the same as those described above.

Among them, those represented by the formulas (19) to (21) are preferable, but are not limited thereto.
In Formula (19), a compound in which n is 2 to 4 is preferable. In Formula (20), a compound in which n is 1 is preferable. In Formula (21), a compound in which n is 3 is preferable.

（式中、ｎは前記と同じ意味を表す。）

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

  Moreover, the compound shown below can also be used suitably.

（式中、Ｙ⁴〜Ｙ¹¹は、それぞれ独立に、水素原子、又はエーテル結合、チオエーテル、エステル結合、炭酸エステル結合若しくはアミド結合等を含んでもよい炭素数１〜３０のアルキル基を表し（ただし、Ｙ⁴〜Ｙ⁶の少なくとも１つ、Ｙ⁷及びＹ⁸の少なくとも１つ、Ｙ⁹〜Ｙ¹¹の少なくとも１つは前記アルキル基であり、アルキル基の具体例としては、前記Ｙと同様のものが挙げられる。）

(Wherein Y ^{4 to} Y ¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may contain an ether bond, a thioether, an ester bond, a carbonate ester bond, an amide bond, or the like (provided that , At least one of Y ^{4 to} Y ⁶ , at least one of Y ⁷ and Y ⁸ , and at least one of Y ^{9 to} Y ¹¹ are the alkyl group. Specific examples of the alkyl group are the same as those of Y Can be mentioned.)

（式中、Ｒ¹⁹〜Ｒ²²は互いに独立して、炭素数１〜３０のアルキル基を示す。）

(Wherein, R ¹⁹ to R ²² independently of one another, represent an alkyl group having 1 to 30 carbon atoms.)

  In the present invention, the following pyrene derivative (31), which is a carbon condensed ring dye having excellent light emission characteristics, can also be used as the liquid light emitting material.

In the above formulas, W ^{1 to} W ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms that may contain an ether bond, a thioether, an ester bond, a carbonate ester bond, an amide bond, or the like (provided that And at least one of W ^{1 to} W ⁴ is the alkyl group), F ^{1 to} F ^{4 each} represents a single bond or a substituted or unsubstituted aromatic ring. Here, specific examples of the alkyl group include those similar to the above Y, and specific examples of the aromatic ring include those similar to the above.

Also in this case, in order to prevent an increase in viscosity accompanying an increase in molecular weight, a compound in which F ^{1 to} F ⁴ are single bonds, that is, a compound (32) in which W ^{1 to} W ⁴ are directly bonded to a carbon condensed ring is preferable. Furthermore, it is more preferable that at least one of W ^{1 to} W ⁴ is a hydrogen atom, particularly, three is a hydrogen atom.
From these points, the following compound (33) is preferable, but is not limited thereto.

  Furthermore, a pyrene dye having a (poly) ether structure which is a coordinating substituent represented by the formula (34) can also be suitably used as the liquid light emitting material.

（式中、Ｚは２価の有機基を表し、Ａ、Ｂ及びｎは前記と同様の意味を表す。）

(In the formula, Z represents a divalent organic group, and A, B, and n have the same meaning as described above.)

  Examples of the divalent organic group Z include the same as those described in the above A, and in particular, 2 represented by -QC (O) O- (wherein Q represents an alkylene group). A valent organic group is preferable, and therefore, a pyrene dye represented by the formula (35) is preferable.

Here, the alkylene group Q includes an alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples of these alkylene groups The same as those mentioned above.
Specific examples of the more preferable liquid compound include those represented by the formula (36), but are not limited thereto.
In the formula (36), a compound in which n is 3 is preferable.

（式中、ｎは前記と同じ意味を表す。）

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

In addition, as long as it becomes liquid as the whole luminescent composition, a solid thing can be used at normal temperature as a carrier transport material or a luminescent material, or they can further be mix | blended with a liquid material.
Such a carrier transport material may be appropriately selected from conventionally known materials. For example, (triphenylamine) dimer derivative (TPD), (α-naphthyldiphenylamine) dimer (α-NPD), [(triphenyl Amine) dimer] triarylamines such as spiro-dimer (Spiro-TAD); 4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′ , 4 "-tris [1-naphthyl (phenyl) amino] triphenylamine (1-TNATA) and other starburst amines; 5,5" -bis- {4- [bis (4-methylphenyl) amino] phenyl } -2,2 ′: Hole transport materials such as oligothiophenes such as 5 ′, 2 ″ -terthiophene (BMA-3T); Alq ₃ , BAlq, DPVBi, (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole) (t-BuPBD), triazole derivative (TAZ), bathocuproine (BCP) ), Electron transport materials such as silole derivatives.

Such a light emitting material may be appropriately selected from conventionally known materials. For example, tris (8-quinolinolato) aluminum (III) (Alq ₃ ), bis (8-quinolinolato) zinc (II) (Znq ₂ ), Bis (2-methyl-8-quinolinolate) (p-phenylphenolate) aluminum (III) (BAlq), 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), and the like.

In the first and second organic electroluminescent devices of the present invention, (A1) includes a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at room temperature with a gelling agent, (A2) a carrier transport material and a light-emitting material. At least one of the materials is liquid at room temperature, and in any case of a gel light emitting layer obtained by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent, a combination of the gelling agent and the liquid material The ratio can be about gelling agent: liquid material (total amount) = 1: 99 to 99: 1 (mass ratio, the same applies hereinafter).
In particular, 10:90 to 90:10 are preferable, 20:80 to 80:20 are more preferable, and 30:70 to 70:30 are still more preferable in consideration of further improving the characteristics of the obtained organic EL element. 40:60 to 65:35 is optimal.
In addition, regarding the blending ratio of the liquid material and the gelling agent for further enhancing the physical properties such as the stretch properties and flexibility of the gel light emitting layer, it strongly affects the physical properties such as the molecular weight and viscosity of the liquid material and the gelling agent. Therefore, although not particularly limited, gelling agent: liquid material (total amount) = 1: 99 to 90:10 is more preferable, 1:99 to 60:40 is more preferable, and 20:80 to 50:50 is Is optimal.
From these viewpoints, the mixing ratio of the gelling agent and the liquid material in the gel light emitting layer requires selection of the mixing ratio of the gelling agent and the liquid material from both the characteristics of the EL element and the physical properties.

In the gel light-emitting layer of (A2), the mixing ratio of the carrier transport material and the light-emitting material is not particularly limited as long as the entire composition is a liquid, and the carrier transport material: the light-emitting material can be used in a mass ratio. = 99.99: 0.01 to 0.01: 99.99, but preferably 99: 1 to 1:99.
The carrier transport material may be appropriately selected from a hole transport material, an electron transport material, and a material having both a hole transport capability and an electron transport capability. In the present invention, the electron transport material and the hole transport material are used in combination. In addition, it is preferable to use a material having both hole transporting ability and electron transporting ability. However, when the light emitting material has hole transporting ability, an embodiment using only the electron transporting material is also suitable.
In this case, in consideration of increasing the external quantum efficiency of the obtained organic electroluminescent device, an electron transport material or a material having both a hole transport capability and an electron transport capability is included in the composition (gel light-emitting layer). In an organic electroluminescent element, it is preferable to use 2-30 mass%, and in a 2nd organic electroluminescent element, it is preferable to use 2-50 mass%. Moreover, in any organic electroluminescent element, it is more preferable to use at 5-20 mass%.

In any of the gel light emitting layers (A1) and (A2), the gel for the light emitting layer can be prepared by mixing the components in any order.
At this time, ketone solvents such as cyclohexanone, acetone and methyl ethyl ketone; aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene; alcohol solvents such as methanol, ethanol and isopropanol; chloroform, methylene chloride, ethylene dichloride, Halogenated hydrocarbon solvents such as carbon tetrachloride; ether solvents such as diethyl ether, diisopropyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether; ethyl acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate Using an organic solvent such as an amide solvent such as N, N-dimethylformamide, N-methylpyrrolidone, etc. Liquid or dispersion may be prepared and then the organic solvent was evaporated to prepare a gel.

  However, in the second organic electroluminescent element of the present invention, when the gel light emitting layer is laminated on the gel functional layer by a coating method such as spin coating, it is necessary to use a solvent that does not easily erode the gel functional layer, For example, in the case of a gel functional layer using PVK as a gelling agent, acetone, ethanol, methanol, isopropanol, toluene and the like are suitable. In the case of a gel functional layer using PMMA as a gelling agent, Isopropanol, ethanol, methanol, toluene and the like are preferable.

The solid content concentration at the time of preparing the solution (dispersion) is not particularly limited, but is preferably 0.001 to 50% by mass, and 0.3 to 10% by mass in consideration of film formability and drying property. Is more preferable.
In the organic electroluminescent element of the present invention, the thickness of the gel light emitting layer is not particularly limited and can be about 1 to 500 nm, preferably about 10 to 250 nm, and more preferably about 20 to 150 nm.

On the other hand, in the gel functional layer of the second organic electroluminescence device of the present invention, (B1) a gel functional layer obtained by gelling a carrier transporting material which is liquid at room temperature with a gelling agent, and (B2) liquid at room temperature. In any case of the gel functional layer containing the carrier transporting material and gelling the carrier transporting composition which is liquid at room temperature as a whole with the gelling agent, the blending ratio of the gelling agent and the liquid material is determined as follows: Liquid material (total amount) = 1: 99 to 99: 1 (mass ratio, hereinafter the same).
In particular, 10:90 to 90:10 are preferable, 20:80 to 80:20 are more preferable, and 30:70 to 70:30 are even more preferable in consideration of further improving the characteristics of the obtained organic EL element.
Also in this case, regarding the blending ratio of the liquid material and the gelling agent for further enhancing the physical properties such as the stretch properties and flexibility of the gel functional layer, the physical properties such as the molecular weight and viscosity of the liquid material and the gelling agent are considered. Since it strongly influences, it is not particularly limited, but gelling agent: liquid material (total amount) = 1: 99 to 90:10 is more preferable, 1:99 to 60:40 is more preferable, and 20:80 to 50:50 is optimal.

In the gel functional layer (B2), a carrier transport material that is solid at room temperature as exemplified above may be used as long as the carrier transport composition is liquid as a whole.
As the carrier transport material used in the gel functional layer, an electron transport material, a hole transport material, an electron transport material, and a material having both hole transport capability and electron transport capability may be appropriately selected and used according to the intended function. Good.
In the second organic electroluminescent element of the present invention, the gel functional layer can be provided at an arbitrary position between the anode and the cathode of the element, but is preferably provided in contact with the gel light emitting layer.
In particular, in consideration of increasing the external quantum efficiency of the obtained organic EL element, it is preferable to provide a gel functional layer having an electronic blocking function between the gel light emitting layer and the anode.

In both (B1) and (B2), the gel for the functional layer can be prepared by mixing the components in any order.
In this case, a gel may be prepared by once preparing a solution or a dispersion using an organic solvent as exemplified above, and then evaporating the organic solvent. When a gel light emitting layer is laminated on the gel functional layer by a coating method such as spin coating, it is necessary to use a solvent that does not easily erode the gel light emitting layer.
The solid content concentration at the time of preparing the solution (dispersion) is not particularly limited, but is preferably 0.001 to 50% by mass, and 0.3 to 10% by mass in consideration of film formability and drying property. Is more preferable.

  In the second organic electroluminescent element of the present invention, the thickness of the gel functional layer is not particularly limited, but is preferably about 1 to 100 nm in consideration of increasing the external quantum efficiency of the obtained organic electroluminescent element. 5 to 70 nm is more preferable, and about 10 to 50 nm is even more preferable.

The organic electroluminescent element of the present invention is characterized by the gel light emitting layer and the gel functional layer described above, and there are no particular restrictions on the constituent members of the other elements, and conventionally known elements can be appropriately employed.
For example, as the anode material, a transparent electrode typified by indium tin oxide (ITO) or indium zinc oxide (IZO), a polythiophene derivative having high charge transportability, a polyaniline derivative, or the like can be used.
As the cathode material, aluminum, magnesium-silver alloy, aluminum-lithium alloy, silver, lithium, sodium, potassium, calcium, cesium, cesium-added ITO, or the like can be used.

Moreover, the organic electroluminescent element of this invention may be equipped with the various solid functional layers generally used for an organic electroluminescent element other than an anode, a cathode, a gel light emitting layer, and a gel functional layer.
Examples of such a solid functional layer include a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a carrier block layer, and the like.

The hole transport layer is a layer that is provided between the anode and the light emitting layer and has a function of transporting holes injected from the anode to the light emitting layer. The same thing as the hole transport material illustrated by (5) is mentioned.
The hole injection layer is a layer that is provided between the hole transport layer and the anode and has a function of increasing the hole injection efficiency from the anode.
Examples of the material for forming the hole injection layer include copper phthalocyanine, 4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), and the like.

The electron transport layer is a layer that is provided between the cathode and the light emitting layer and has a function of transporting electrons injected from the cathode to the light emitting layer. Examples of the material include the carrier transport material that is solid at room temperature. Examples thereof are the same as those described above.
The electron injection layer is a layer that is provided between the electron transport layer and the cathode and has a function of increasing the efficiency of electron injection from the cathode.
As a material for forming such an electron injection layer, lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), Examples thereof include strontium fluoride (SrF ₂ ), Li (acac), lithium acetate, and lithium benzoate.

The carrier block layer is a layer for controlling the light emitting region, and can be formed between any of the above-described layers.
Examples of the material for forming such a carrier block layer include t-BuPBD, TAZ, and BCP.

Next, the electroluminescent element of the present invention will be described with reference to the drawings.
FIG. 1 shows an organic EL element 1 which is a first organic electroluminescent element according to the present invention.
The organic EL element 1 includes an anode 10, a cathode 20, a gel light emitting layer 30 and a hole injection layer 50 interposed between the electrodes 10 and 20.

In the present embodiment, the anode 10 is composed of a glass substrate 11 and an ITO substrate 12 formed thereon.
On the other hand, the cathode 20 is composed of a Ca layer 14 and an Ag layer 13 formed thereon.
The gel light emitting layer 30 is composed of a liquid light emitting material and a gelling agent.
The hole injection layer 50 is made of PEDOT-PSS.

Although there is no restriction | limiting in particular as a preparation method of the organic EL element 1 comprised as mentioned above, For example, the following methods can be used.
First, the glass substrate 10 with ITO 12 is spin-coated with PEDOT: PSS, and then heated to produce the hole injection layer 50.
Subsequently, a solution in which a liquid light emitting material and a gelling agent are dissolved in cyclohexanone is spin-coated on the hole injection layer 50 to form a film, and then heated to produce the gel light emitting layer 30.
On the gel light emitting layer 30, Ca and Ag are sequentially deposited to obtain the organic EL element 1.
The conditions during metal deposition may be set as appropriate according to the material constituting the gel light emitting layer, but the temperature during deposition is preferably lower than the melting point of the liquid material. Although the temperature differs depending on the type of liquid material, it cannot be defined unconditionally. For example, the temperature is preferably 200 K or less, more preferably 150 K or less, and even more preferably 100 K or less.

FIG. 12 shows an organic EL element 3 which is a second organic electroluminescent element according to the present invention.
The organic EL element 3 includes a cathode 100, an anode 200, a gel light emitting layer 300 interposed between the respective electrodes 100 and 200, and a form in contact with the gel light emitting layer 300 between the gel light emitting layer 300 and the anode 200. And a gel electron blocking layer 400 serving as a gel functional layer provided in step (1) and a hole injection layer 103.

In this embodiment, the anode 200 is composed of a glass substrate 105 and an ITO substrate 104 formed thereon.
On the other hand, the cathode 100 is composed of a Ca layer 102 and an Ag layer 101 formed thereon.
The gel light emitting layer 300 is composed of a liquid hole transport material, an electron transport material, a liquid light emitting material, and a gelling agent.
The gel functional layer 400 is composed of a liquid hole transport material and a gelling agent.
The hole injection layer 103 is made of PEDOT-PSS.

Although there is no restriction | limiting in particular as a preparation method of the organic EL element 3 comprised as mentioned above, For example, the following methods can be used.
First, PEDOT: PSS is spin-coated on the glass substrate 105 with ITO 104 to form a film, and then heated to produce the hole injection layer 103.
On the other hand, a solution in which a liquid hole transport material and a gelling agent are dissolved in cyclohexanone is spin-coated on the hole injection layer 103 to form a film, and then heated as necessary to produce the gel electron blocking layer 400. To do.
Subsequently, a solution in which a liquid hole transport material, an electron transport material, a liquid light emitting material, and a gelling agent are dissolved in toluene is spin-coated on the gel electron block layer 400, and then heated as necessary. Thus, the gel light emitting layer 300 is produced.
On this gel light emitting layer 300, the Ca layer 102 and the Ag layer 101 are sequentially deposited to form the cathode 100, whereby the organic EL element 3 is obtained.
The conditions at the time of metal vapor deposition are as described in the manufacture of the organic EL element 1.

In the two embodiments, the material constituting each layer is not limited to the material used in the above embodiment, and may be appropriately selected from the various materials exemplified above as long as the function of each layer is exhibited. Can be used.
In addition, the method for forming each layer is not limited to the method of the above embodiment, and a known method such as an evaporation method, a spray method, an ink jet method, or a sputtering method can be appropriately employed depending on the material used. .
Furthermore, if necessary, other gel functional layers may be provided, or a solid hole block layer, a hole injection layer, or the like may be formed.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In addition, the measuring apparatuses used in the examples are as follows.
(1) Current-Voltage-Luminance Characteristics Measurement was performed with a semiconductor parameter analyzer with a photo detector (Agilent, B1500A) and an optical power meter (Newport, 1930C).
(2) EL emission spectrum It measured with the multichannel spectrometer (PMA-11, Hamamatsu Photonics Co., Ltd. product).
(3) ¹ H-NMR
Apparatus: AVANCE 500, manufactured by Bruker (4) Absorption spectrum apparatus: Infrared ultraviolet visible absorption spectrum apparatus (Lambda 950-PKA, manufactured by PerkinElmer)
(5) DSC
Apparatus: Phoenix DSC204 F1, manufactured by NETZSCH (6) Micrometer apparatus: MDH-25M, manufactured by Mitutoyo Corporation (7) Tensile tester apparatus: small desktop tensile tester, EZ-L manufactured by Shimadzu Corporation

[Synthesis Example 1] Synthesis of TEGPy

4- (1-pyrenyl) butyric acid (3.5 g, 11.8 mmol), [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] p-toluenesulfonate (TEG-Ts, 4.6 g, 14.7 mmol) Aldrich) and sodium hydride (50% oily, 0.70 g, 14.6 mmol) were added to DMF (40 mL) and stirred at 80 ° C. for 6 hours. After the solvent was distilled off under reduced pressure, chloroform (100 mL) was added, and the insoluble material was filtered off. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (chloroform / ethyl acetate = 100/0 to 95/5 (v / v)) to obtain TEGPy (4.2 g, 83%) as a yellow liquid. Obtained. Identification was performed by ¹ H-NMR spectrum (500 MHz, TMS, DMSO-d ₆ , rt). ^{The 1} H-NMR spectrum is shown in FIG.

[1] Production of first organic EL element [Example 1]
In a washed sample bottle, 4 parts by mass of polymethyl methacrylate (PMMA, molecular weight 350,000, manufactured by Aldrich), 6 parts by mass of TEGPy obtained in Synthesis Example 1, and 160 parts by mass of cyclohexanone were placed, and PMMA was added at 70 ° C. And TEGPy were completely dissolved in cyclohexanone to prepare a composition (ink) for a gel light emitting layer.
On the other hand, a glass substrate 11 with an ITO layer 12 that was ultrasonically cleaned in the order of surfactant, pure water, and isopropanol and subjected to UV / ozone treatment (manufactured by Filgen, UV253S) for 12 minutes was prepared.
An aqueous solution (CLEVIOS ^™ PVP AI4083, HC, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS) on the ITO layer 12 side on the glass substrate 11 with ITO. Stark Co., Munich, Germany) was added dropwise, spin coated at 3000 rpm for 60 seconds to form a PEDOT: PSS layer, and heated at 200 ° C. for 10 minutes to obtain a hole injection layer 50 having a thickness of 30 nm. . After returning this substrate to room temperature, the ink prepared above was dropped onto the hole injection layer 50 and spin-coated for 60 seconds under the condition of 2000 rpm, thereby producing the gel light emitting layer 30.

  Since the gel light emitting layer 30 is very soft and its film thickness cannot be measured with a direct-core type film thickness measuring device (Dectac II), the film thickness was relatively evaluated by the following method. First, a thin film having a thickness of 100 nm composed of 99 parts by mass of PMMA and 1 part by mass of coumarin 6 represented by the following formula was prepared, and the absorbance at 440 nm corresponding to the absorption of coumarin 6 was measured. Next, an ink composed of 4 parts by mass of PMMA, 6 parts by mass of TEGPy, 1 part by mass of coumarin 6 and 160 parts by mass of cyclohexanone is spin-coated at 2000 rpm for 60 seconds, and 1% by mass of coumarin 6 is doped into the gel light emitting layer 30. A thin film was obtained. In this case, since the concentration of coumarin 6 is remarkably smaller than the concentrations of PMMA and TEGPy, it was assumed that the film thickness shows the same value regardless of whether coumarin 6 is doped or undoped. The absorbance of this film was measured at 440 nm, and it was confirmed that the film thickness of the gel light emitting layer 30 was 100 nm by comparing the absorbance of a sample with a thickness of 100 nm in which PMMA was doped with 1% by mass of coumarin 6. .

This substrate was set in a vacuum deposition chamber and evacuated to 1 × 10 ⁻⁴ Pa or less at room temperature.
Thereafter, the temperature of the substrate was cooled to 20K by a cryostat installed in the vacuum chamber. A film of Ca was deposited on the gel light emitting layer 30 of the cooled substrate by a vapor deposition method at a rate of 0.30 nm / s and a thickness of 50 nm, and Ag was deposited on the Ca layer by a vapor deposition method at a rate of 0.10 nm / s. A cathode layer 20 was formed by forming a film with a thickness of 100 nm.
This element was moved into a glove box in a state where the inert atmosphere was not broken, and sealed to obtain an EL element 1. The element area was 2 mm × 2 mm.

FIG. 4 shows the current density-voltage-luminance characteristics of the fabricated EL element, and FIG. 5 shows the EL external quantum efficiency-current density characteristics.
As shown in FIG. 4, light emission was observed at 8.0 V or higher, and a current density of 126 mA / cm ² and a maximum luminance of 886 cd / m ² were obtained at a voltage of 24 V. Further, as shown in FIG. 5, a maximum EL external quantum efficiency of 0.12% was obtained at 18.4 V and 10 mA / cm ² .

[Example 2]
An EL device was prepared in the same manner as in Example 1 except that 8 parts by mass of PMMA, 2 parts by mass of TEGPy, and 320 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 3]
An EL device was prepared in the same manner as in Example 1 except that 7 parts by mass of PMMA, 3 parts by mass of TEGPy, and 280 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 4]
An EL device was prepared in the same manner as in Example 1 except that 6 parts by mass of PMMA, 4 parts by mass of TEGPy, and 240 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 5]
An EL device was prepared in the same manner as in Example 1 except that 5 parts by mass of PMMA, 5 parts by mass of TEGPy, and 200 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 6]
An EL device was prepared in the same manner as in Example 1 except that 3 parts by mass of PMMA, 7 parts by mass of TEGPy, and 120 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 7]
An EL device was prepared in the same manner as in Example 1 except that 2 parts by mass of PMMA, 8 parts by mass of TEGPy, and 80 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 8]
An EL device was produced in the same manner as in Example 1 except that 1 part by mass of PMMA, 9 parts by mass of TEGPy, and 40 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Comparative Example 1]
A glass substrate 11 with ITO 12 (anode 10) and a glass substrate 15 with ITO 16 (cathode 60) which were subjected to ultrasonic cleaning in the order of surfactant, pure water and isopropanol, and subjected to UV / ozone treatment (manufactured by Filgen, UV253S) for 12 minutes. ) Was prepared.
In the glove box, a small amount of TEGPy is dropped on the cathode 60 (ITO 16) and fixed with a clip (not shown) from the outside of the laminate obtained by being sandwiched by the anode 10, as shown in FIG. An EL element 2 comprising glass substrate / ITO (anode) / liquid light emitter layer / ITO (cathode) / glass substrate was produced. The element area was 2 mm × 2 mm.

Table 1 shows the evaluation of the devices prepared in Examples 1 to 8 and Comparative Example 1. Table 1 also shows the carrier recombination balance γ calculated from the obtained measurement data according to the following formula.
In the following formula, EQE is the external emission quantum yield determined by measurement, Φ _PL is the fluorescence or phosphorescence quantum yield of the liquid light-emitting layer determined by measurement, η _ext is the light extraction efficiency, and the theoretical value of 0.2 is used , Η _r is the exciton generation efficiency, and the theoretical value of 0.25 is used for the element using the fluorescent material, and 1 which is the maximum theoretical value is used for the element using the phosphorescent material.

It can be seen that when the concentration of TEGPy is 40 to 80% by mass, the maximum external quantum yield and the carrier recombination balance both show good values.
More specifically, in the region where the concentration of TEGPy is 20% by mass to 70% by mass, both the maximum external quantum yield and the carrier recombination balance are increased. In the region where the concentration of TEGPy exceeds 70% by mass, the maximum external quantum yield and the carrier recombination balance decrease.
The reason for this is that while PMMA is an insulator, TEGPy has a content of 20% by mass to 70% by mass in order to exhibit better carrier injection characteristics, transport characteristics and light emission characteristics than PMMA. In the region, the external quantum efficiency and carrier recombination balance are thought to improve.
On the other hand, in the region where the concentration of TEGPy exceeds 70% by mass, innumerable cracks of micrometer size were confirmed on the cathode, and it was observed that Ca was clouded. From this, it is considered that Ca is oxidized. After the device was fabricated, sealing was performed in the glove box without taking it out to the atmosphere, but it is considered that the Ca electrode was oxidized by a small amount of oxygen present in the glove box. For this reason, it is considered that electrons are not efficiently injected, and the maximum external quantum yield and the carrier recombination balance are broken.

Further, from the results of Examples 1, 3 to 8 and Comparative Example 1, in comparison with Comparative Example 1 in which only TEGPy was used for the light emitting layer, although PMMA which is insulating in Example was added to TEGPy, It can be seen that low voltage emission and large external quantum efficiency and carrier recombination balance are achieved.
This is because the thickness of the light emitting layer of Examples 1, 3-8 is thinner than that of Comparative Example 1, and in Examples 1, 3-8, Ca is used for the cathode, whereas in Comparative Example, It relies heavily on the use of ITO.
That is, in the case of an embodiment with a thin film thickness, carriers are easily injected at a low voltage. Further, Ca (2.9 eV) having a low work function is used for the cathode, and electrons are easily injected because the energy barrier with respect to the LUMO level (2.6 eV) of TEGPy is small. Therefore, a low voltage and high efficiency external quantum efficiency and carrier recombination balance are achieved.
On the other hand, since the element of Comparative Example 1 has a thickness of 1570 nm, which is thicker than that of the example, a high voltage is required for carrier injection. Furthermore, since ITO (4.7 eV) having a high work function is used for the cathode, electron injection is difficult to occur, and both the external quantum efficiency and the carrier recombination balance remain low.

In the said Examples 1-8, the organic EL element which has a gel structure using PMMA which is a nonelectroconductive polymer was evaluated. Subsequently, an EL element using a single-layer gel using a conductive polymer was evaluated.
Examples of the conductive polymer used include polyvinyl carbazole (PVK, manufactured by Tokyo Chemical Industry Co., Ltd.) which is a pendant type conductive polymer, and poly (( 2-methoxy-5- (4- (2-ethylhexyloxy) phenyl) -1,4-phenylenevinylene) (MEHPPV, molecular weight of 100,000 or more, manufactured by American Dye Source), and poly represented by the formula (10) (2-Methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene) (MEHPPPV, molecular weight of 100,000 or more, manufactured by American Dice Source) was used.

[Example 9]
EL as in Example 1 except that 5 parts by mass of PVK, 5 parts by mass of TEGPy, and 300 parts by mass of cyclohexanone were used instead of PMMA, and the gel light-emitting layer was formed by spin coating at 3000 rpm for 60 seconds. A device was fabricated and its characteristics were evaluated.
The film thickness of this gel light emitting layer was also relatively evaluated by the following method. First, a thin film having a thickness of 100 nm composed of 99 parts by mass of PVK and 1 part by mass of coumarin 6 was prepared, and the absorbance at 440 nm corresponding to the absorption of coumarin 6 was measured. Next, an ink composed of 5 parts by mass of PVK, 5 parts by mass of TEGPy, 1 part by mass of coumarin 6 and 300 parts by mass of cyclohexanone is spin-coated at 1000 rpm for 60 seconds, and 1% by mass of coumarin 6 is doped in the gel light emitting layer. A thin film was obtained. In this case, since the concentration of coumarin 6 is significantly smaller than the concentration of PVK or TEGPy, it is assumed that the film thickness shows the same value regardless of whether the coumarin 6 is doped or not. The absorbance of this film was measured at 440 nm, and the thickness of the gel light emitting layer was confirmed to be 100 nm by comparing the absorbance of a sample with a thickness of 100 nm in which 1% by mass of coumarin 6 was doped into PVK.

[Example 10]
An EL device was prepared in the same manner as in Example 9 except that 4 parts by mass of PVK, 6 parts by mass of TEGPy, and 240 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 11]
An EL device was prepared in the same manner as in Example 9 except that 3 parts by mass of PVK, 7 parts by mass of TEGPy, and 180 parts by mass of cyclohexanone were used, and the characteristics thereof were evaluated.

[Example 12]
Except that 6 parts by mass of MEHPPPV instead of PMMA, 4 parts by mass of EHPy instead of TEGPy, and 1740 parts by mass of chloroform instead of cyclohexanone, the gel light emitting layer was formed by spin coating at 3000 rpm for 60 seconds. Then, an EL element was produced in the same manner as in Example 1, and its characteristics were evaluated.
The film thickness of this gel light emitting layer was also relatively evaluated by the following method. First, a MEHPPPV thin film having a thickness of 100 nm was prepared, and the absorbance at 450 nm corresponding to the absorption of MEHPPPV was measured. Next, an ink of 6 parts by mass of MEHPPPV, 4 parts by mass of EHPy, and 1740 parts by mass of chloroform was spin-coated at 3000 rpm for 60 seconds, and the absorbance at 450 nm of the gel light emitting layer was measured. By comparing with the absorbance of the thin film sample, it was confirmed that the film thickness of the gel light emitting layer was 100 nm.

[Example 13]
An EL device was prepared in the same manner as in Example 12 except that 3 parts by mass of MEHPPPV, 7 parts by mass of EHPy, and 1125 parts by mass of chloroform were used, and the characteristics thereof were evaluated.

[Example 14]
Except that 6 parts by mass of MEHPPV instead of PMMA, 4 parts by mass of EHPy instead of TEGPy, and 2520 parts by mass of chloroform instead of cyclohexanone, the gel light emitting layer was formed by spin coating at 3000 rpm for 60 seconds. Then, an EL element was produced in the same manner as in Example 1, and its characteristics were evaluated.
The film thickness of this gel light emitting layer was also relatively evaluated by the following method. First, a MEHPPV thin film having a thickness of 100 nm was prepared, and the absorbance at 500 nm corresponding to the absorption of MEHPPV was measured. Next, an ink of 6 parts by mass of MEHPPV, 4 parts by mass of EHPy, and 2520 parts by mass of chloroform was spin-coated at 3000 rpm for 60 seconds, and the absorbance of the gel light-emitting layer was measured at 450 nm. MEHPPV having a film thickness of 100 nm By comparing with the absorbance of the thin film sample, it was confirmed that the film thickness of the gel light emitting layer was 100 nm.

[Example 15]
An EL device was prepared in the same manner as in Example 14 except that 3 parts by mass of MEHPPV, 7 parts by mass of EHPy, 1406 parts by mass of chloroform, and spin-coated for 60 seconds at 3500 rpm to form a gel light emitting layer. The characteristics were evaluated.

  EHPy was synthesized according to the method described in International Publication No. 2011/010656.

  Table 2 shows the evaluation of the devices produced in Examples 9-15. Table 2 also shows the carrier recombination balance γ calculated according to the above equation from the obtained measurement data.

It was found that the EL devices manufactured in Examples 9 to 15 can realize low voltage driving and high external quantum efficiency and carrier balance as compared with Comparative Example 1.
From the results of Examples 9 to 15, it was shown that the conductive polymer is a good gelling agent as well as the non-conductive polymer.

In Examples 1 to 15, devices were manufactured using a liquid fluorescent host material. Subsequently, for the purpose of further improving the external light emission efficiency, an element composed of a host-guest combination in which a phosphorescent material was mixed as a guest material with a liquid host material was fabricated and evaluated.
The materials used are DEGCz which is a liquid hole transporting host material (p-type semiconductor) represented by the following formula, PMMA or PVK which is a gelling agent, and t-BuPBD which is an electron transporting material (n-type semiconductor). (Manufactured by Tokyo Chemical Industry Co., Ltd.) and Ir (ehppy) ₃ which is a phosphorescent material were used.
The structures of DEGCz, t-BuPBD, and Ir (ehppy) ₃ are shown below. DEGCz was synthesized with reference to the method described in Synthetic Metals, 89 (3), 171 (1997), and Ir (ehppy) ₃ was synthesized according to the method described in International Publication No. 2011/010656.

[Example 16]
An EL element was produced in the same manner as in Example 1 except that 2.6 parts by mass of PMMA, 6 parts by mass of DEGCz as a liquid host material instead of TEGPy, and 104 parts by mass of cyclohexanone were evaluated. .

[Example 17]
Other than 2.6 parts by mass of PMMA, 6 parts by mass of DEGCz which is a liquid host material instead of TEGPy, 1.4 parts by mass of t-BuPBD which is an n-type host material, and 104 parts by mass of cyclohexanone Produced an EL element in the same manner as in Example 1 and evaluated its characteristics.

[Example 18]
2.4 parts by mass of PMMA, 5.8 parts by mass of DEGCz which is a liquid host material instead of TEGPy, 1.3 parts by mass of t-BuPBD which is an n-type host material, and Ir which is a phosphorescent material ( ehppy) ₃ was added in an amount of 0.5 parts by mass, and except that cyclohexanone was changed to 112 parts by mass, an EL device was produced in the same manner as in Example 1, and its characteristics were evaluated.

[Example 19]
An EL device was prepared in the same manner as in Example 1 except that 2.6 parts by mass of PVK instead of PMMA, 6 parts by mass of DEGCz as a liquid host material instead of TEGPy, and 104 parts by mass of cyclohexanone were prepared. Characteristics were evaluated.

[Example 20]
2.6 parts by mass of PVK instead of PMMA, 6 parts by mass of DEGCz as a liquid host material instead of TEGPy, 1.4 parts by mass of t-BuPBD as an n-type host material, and 104 parts by mass of cyclohexanone An EL element was produced in the same manner as in Example 1 except that the part was used, and its characteristics were evaluated.

[Example 21]
Instead of PMMA, 2.4 parts by mass of PVK, 5.8 parts by mass of DEGCz which is a liquid host material instead of TEGPy, 1.3 parts by mass of t-BuPBD which is an n-type host material, and phosphorescent material An EL element was prepared in the same manner as in Example 1 except that 0.5 part by mass of Ir (ehppy) ₃ and 0.5 part by mass of cyclohexanone were added, and the characteristics thereof were evaluated.

  Table 3 shows the evaluation of the devices prepared in Examples 16-21. Table 3 also shows the carrier recombination balance γ calculated from the obtained measurement data according to the above equation.

  From the comparison between Example 16 and Example 17 and the comparison between Example 19 and Example 20, the device to which t-BuPBD was added had a lower emission start voltage, improved maximum external quantum yield, carrier It can be seen that an improvement in recombination balance is observed. This is presumably because the electron injection and transport properties are improved as a result of adding t-BuPBD, which is an electron transport material.

From the comparison between Example 17 and Example 18 and the comparison between Example 20 and Example 21, the device added with Ir (eppy) ₃ further improved the maximum external quantum yield and carrier recombination balance. Is observed. About the maximum external quantum yield improvement, since Example 18 and Example 21 use the phosphorescent guest, the number of excitons contributing to light emission becomes larger than that in the case of using a fluorescent material. It is thought that it is derived from that. The improvement of the carrier recombination balance is considered to be derived from the fact that the phosphorescent guest acts as an effective trap of holes and electrons.

As described above, the EL characteristics of the gel light emitting layer were evaluated. Subsequently, the stretching property of the gel light emitting layer was examined. The tensile test was measured using a small desktop tensile tester, and the film thickness was measured using a micrometer.
[2] Elastic properties of gel film using non-conductive polymer gelling agent [Example 22]
4 parts by mass of polymethyl methacrylate (PMMA, molecular weight 350,000, manufactured by Aldrich) and 6 parts by mass of TEGPy obtained in Synthesis Example 1 are added to 80 parts by mass of methylene chloride, and PMMA and TEGPy are completely dissolved in methylene chloride at room temperature. The composition for gel light emitting layer (ink) was prepared. This ink was applied on a watch glass and dried in air at room temperature for 24 hours to volatilize methylene chloride to obtain a transparent gel-like film (thickness: 191 μm) in which PMMA and TEGPy were compatible. Next, this film was cut out into 1 cm x 5 cm, and the tension test was done.

[Example 23]
A transparent gel-like film (thickness: 361 μm) was produced in the same manner as in Example 22 except that 3 parts by mass of PMMA and 7 parts by mass of TEGPy were used, and a tensile test was performed.

[Example 24]
A transparent gel-like film (thickness 255 μm) was produced in the same manner as in Example 22 except that 5 parts by mass of PMMA and 5 parts by mass of TEGPy were used, and a tensile test was performed.

[Example 25]
A transparent gel film (thickness: 102 μm) was prepared in the same manner as in Example 22 except that 6 parts by mass of PMMA and 4 parts by mass of TEGPy were used, and a tensile test was performed.

[Example 26]
A transparent gel-like film (thickness: 106 μm) was prepared in the same manner as in Example 22 except that 7 parts by mass of PMMA and 3 parts by mass of TEGPy were used, and a tensile test was performed.

[Example 27]
A transparent gel-like film (thickness 72 μm) was produced in the same manner as in Example 22 except that 8 parts by mass of PMMA and 2 parts by mass of TEGPy were used, and a tensile test was performed.

[Example 28]
A transparent gel-like film (thickness 120 μm) was prepared in the same manner as in Example 22 except that 9 parts by mass of PMMA and 1 part by mass of TEGPy were used, and a tensile test was performed.

[Comparative Example 2]
4 parts by mass of polymethyl methacrylate (PMMA, molecular weight 350,000, manufactured by Aldrich) was added to 80 parts by mass of methylene chloride, and stirred at room temperature until PMMA was completely dissolved in methylene chloride to prepare a composition (ink). This ink was applied on a watch glass and dried in the air at room temperature for 24 hours to volatilize methylene chloride to obtain a transparent film (thickness 111 μm) of PMMA.

[3] Stretching properties of gel-like film using liquid material incompatible with non-conductive polymer [Example 29]
5 parts by mass of polymethyl methacrylate (PMMA, molecular weight 350,000, manufactured by Aldrich) and 5 parts by mass of EHPy are added to 100 parts by mass of methylene chloride, and stirred at room temperature until PMMA and EHPy are completely dissolved in methylene chloride. A composition (ink) was prepared. This ink was applied on a watch glass and dried in the air at room temperature for 24 hours to volatilize methylene chloride to obtain a cloudy gel-like film (thickness 220 μm).

Table 4 shows the tensile test results of the films prepared in Examples 22 to 29 and Comparative Example 2.
In Table 4, Examples 22 to 25 are from a stress-strain curve in a strain region of 0% to 100%, and Examples 26 to 29 and Comparative Example 2 are from a stress-strain curve in a strain region of 0% to 0%. The elastic modulus of each film was calculated. The reversible stretchability was determined to be reversible when it returned to its original length after applying 100% tensile strain, and irreversible when it did not return.

As shown in Table 4, a film made of PMMA having a normal glass transition temperature of room temperature or higher produced in Comparative Example 2 shows a high elastic modulus and a small strain at breakage of about several percent, and therefore does not show stretch properties. I understand that.
On the other hand, it turns out that the gel-like film produced in Examples 22-25 has a low elasticity modulus and a large fracture strain compared with the comparative example 2. For example, the gel-like film produced in Example 22 shows an elastic modulus of 1/300 or less as compared with the film produced in Comparative Example 2, and the breaking strain is as large as 75 times.
In this respect, since the film obtained in Example 22 is transparent as shown in FIG. 6, PMMA as a gelling agent and a liquid semiconductor are compatible, and PMMA contributes to gelation. I understand that.
Such a gel-like film not only has a low elastic modulus and a large breaking strain, but also has stretch properties as shown in FIG. Further, as shown in FIG. 8, this expansion / contraction characteristic is reversible, and the expansion / contraction can be repeated many times.
Such a reversible expansion / contraction characteristic is a mechanical characteristic that is not found in normal PMMA. Furthermore, as shown in FIGS. 4 and 5, the gel film of Example 22 exhibits conductivity and electroluminescence characteristics that are not found in PMMA when it is used as a light emitting layer of an organic EL element.
In addition, from the comparison of Examples 22 to 28 shown in Table 4, the stretch characteristics of the gel film described above are improved with an increase in the concentration of TEGPy, which is a liquid semiconductor, in the range of the blending ratio of Examples 22 to 28. I understand that

On the other hand, as in Examples 22 to 28, even when PMMA and liquid EHPy are mixed, the gel-like film obtained in Example 29 has a high elastic modulus, a small breaking strain, and exhibits stretch properties. Absent.
In this regard, since the film obtained in Example 29 is cloudy as shown in FIG. 9, it can be seen that PMMA and liquid EHPy are not compatible.

[4] Elastic properties of gel-like film using conductive polymer gelling agent [Example 30]
4 parts by weight of polyvinylcarbazole (PVK, molecular weight 1.1 million, manufactured by Aldrich) and 6 parts by weight of TEGCz are added to 120 parts by weight of methylene chloride and stirred at room temperature until PVK and TEGCz represented by the following structure are completely dissolved in methylene chloride. Then, a composition (ink) for gel light emitting layer was prepared. This ink was applied on a watch glass and dried in the air at room temperature for 24 hours to volatilize methylene chloride to obtain a transparent gel film (thickness: 231 μm) in which PVK and TEGCz were compatible. Next, this film was cut out into 1 cm x 5 cm, and the tension test was done.
TEGCz was synthesized with reference to the method described in Synthetic Metals, 89 (3), 171 (1997).

[Example 31]
A transparent gel-like film (thickness: 382 μm) was produced in the same manner as in Example 30 except that 2 parts by mass of PVK and 8 parts by mass of TEGCz were used, and a tensile test was performed.

[Example 32]
A transparent gel-like film (thickness: 280 μm) was produced in the same manner as in Example 30 except that 3 parts by mass of PVK and 7 parts by mass of TEGCz were used, and a tensile test was performed.

[Example 33]
A transparent gel-like film (thickness: 199 μm) was prepared in the same manner as in Example 30 except that PVK was changed to 5 parts by mass and TEGCz was changed to 5 parts by mass, and a tensile test was performed.

[Example 34]
A transparent gel-like film (thickness: 101 μm) was produced in the same manner as in Example 30 except that 6 parts by mass of PVK and 4 parts by mass of TEGCz were used, and a tensile test was performed.

[Example 35]
A transparent gel-like film (thickness 90 μm) was produced in the same manner as in Example 30 except that 7 parts by mass of PVK and 3 parts by mass of TEGCz were used, and a tensile test was performed.

[Example 36]
A transparent gel-like film (thickness 84 μm) was produced in the same manner as in Example 30 except that 8 parts by mass of PVK and 2 parts by mass of TEGCz were used, and a tensile test was performed.

[Example 37]
A transparent gel-like film (thickness: 137 μm) was prepared in the same manner as in Example 30 except that 9 parts by mass of PVK and 1 part by mass of TEGCz were used, and a tensile test was performed.

[5] Elastic properties of conductive polymer [Comparative Example 3]
4 parts by mass of polyvinyl carbazole (PVK, molecular weight 1.1 million, manufactured by Aldrich) was added to 120 parts by mass of methylene chloride, and the mixture was stirred at room temperature until PVK was completely dissolved in methylene chloride to prepare a composition (ink). This ink was applied on a watch glass and dried in air at room temperature for 24 hours to volatilize methylene chloride to obtain a transparent film (thickness 92 μm) of PVK. Next, this film was cut out into 1 cm x 5 cm, and the tension test was done.

[Comparative Example 4]
1 part by mass of poly (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene) (MEHPPPV, molecular weight of 100,000 or more, manufactured by American Daisers) is added to 100 parts by mass of methylene chloride, and at room temperature. The composition (ink) was prepared by stirring until MEHPPPV was completely dissolved in methylene chloride. This ink was applied on a watch glass and dried in air at room temperature for 24 hours to volatilize methylene chloride to obtain a MEHPPPV red transparent film (thickness 35 μm). Next, this film was cut out into 1 cm x 5 cm, and the tension test was done.

[6] Stretch characteristics of a cloudy gel film using a liquid that is incompatible with the conductive polymer [Comparative Example 5]
A white turbid film (thickness: 388 μm) was produced in the same manner as in Example 33 except that 5 parts by mass of n-dodecane was used instead of TEGCz, and a tensile test was performed.

[Comparative Example 6]
A white turbid film (thickness of 278 μm) was prepared in the same manner as in Example 33 except that 5 parts by mass of triethylene glycol dimethyl ether was used instead of TEGCz, and a tensile test was performed.

As shown in Table 5, the film made of PVK made in Comparative Example 3 and the film made of MEHPPPV made in Comparative Example 4 both show a high elastic modulus, and the strain at breakage is as small as several percent. It can be seen that the characteristics are not exhibited.
On the other hand, it turns out that the gel-like film produced in Examples 30-37 has a low elastic modulus, a big fracture | rupture distortion compared with Comparative Examples 3 and 4, and shows the mechanical characteristic which PVK and MEHPPPV do not have. For example, the gel-like film produced in Example 33 shows an elastic modulus of 1/1000 or less and the breaking strain is 200 times or more larger than the film produced in Comparative Examples 3 and 4.
Moreover, from the comparison of Examples 30 to 37, it can be seen that the stretch properties of the gel film described above improve with an increase in the concentration of TEGCz, which is a liquid semiconductor, in the range of the blending ratio of Examples 30 to 37.
In addition, the gel-like films obtained in Examples 30 to 33 also show reversible expansion / contraction characteristics as in Example 22.
On the other hand, even when PVK and a liquid material are mixed as in Example 33 as in Comparative Examples 5 and 6, if they are not compatible, they have a high elastic modulus, a small breaking strain, and do not exhibit stretch properties.

[7] Elastic properties of gel-like film provided with phosphorescent material and electron transport material [Example 38]
PVK (molecular weight 1.1 million, manufactured by Aldrich) 28 parts by mass, TEGCz 58 parts by mass, t-BuPBD 12 parts by mass, represented by the following structure (bis (2- (9,9-dibutylfluorenyl) -1-pyridine) acetyl 2 parts by weight of acetonate) iridium (III) (DBPAI, manufactured by American Dice Source) are added to 840 parts by weight of methylene chloride, and stirred at room temperature until PVK, TEGCz, t-BuPBD and DBPAI are completely dissolved in methylene chloride. Then, a composition (ink) for gel light emitting layer was prepared. This ink was applied on a watch glass and dried in air at room temperature for 24 hours to volatilize methylene chloride to obtain a transparent gel-like film (thickness: 189 μm) in which each material was compatible. Next, this film was cut out into 1 cm x 5 cm, and the tension test was done. The results are shown in Table 6.

  As shown in Table 6, the gel-like film containing the phosphorescent conductive material as in Example 38 also has a low elastic modulus and a large breaking strain, and has a reversible stretching property. This gel-like film not only has a reversible expansion / contraction function, but also has the same semiconductor characteristics and phosphorescence as in Examples 19-21.

[8] Thermal analysis of gel film [Example 39]
4 parts by mass of polymethyl methacrylate (PMMA, molecular weight 350,000, manufactured by Aldrich) and 6 parts by mass of TEGPy obtained in Synthesis Example 1 are added to 150 parts by mass of methylene chloride, and PMMA and TEGPy are completely dissolved in methylene chloride at room temperature. The composition for gel light emitting layer (ink) was prepared. This ink was applied on a watch glass and dried in the atmosphere at room temperature for 24 hours to volatilize methylene chloride to produce a transparent gel film in which PMMA and TEGPy were compatible.

[Example 40]
A transparent gel-like film was produced in the same manner as in Example 39 except that 2 parts by mass of PMMA and 8 parts by mass of TEGPy were used.

[Example 41]
A transparent gel film was produced in the same manner as in Example 39 except that 3 parts by mass of PMMA and 7 parts by mass of TEGPy were used.

[Example 42]
A transparent gel film was prepared in the same manner as in Example 39 except that 5 parts by mass of PMMA and 5 parts by mass of TEGPy were used, and the material was subjected to thermal analysis.

[Example 43]
A transparent gel-like film was produced in the same manner as in Example 39 except that 6 parts by mass of PMMA and 4 parts by mass of TEGPy were used.

[Example 44]
A transparent gel-like film was produced in the same manner as in Example 39 except that 7 parts by mass of PMMA and 3 parts by mass of TEGPy were used.

[Example 45]
A transparent gel-like film was produced in the same manner as in Example 39 except that 8 parts by mass of PMMA and 2 parts by mass of TEGPy were used.

[Example 46]
Add 5 parts by weight of polyethylene glycol (PEO, molecular weight 100,000, manufactured by Aldrich) and 5 parts by weight of EHPy to 150 parts by weight of methylene chloride, and stir at room temperature until PEO and EHPy are completely dissolved in methylene chloride. A product (ink) was prepared. This ink was applied on a watch glass and dried in the air at room temperature for 24 hours to volatilize methylene chloride to produce a cloudy gel film.

10 mg of the film produced in Examples 39 to 46 was cut out, placed in an aluminum sample pan, and the material was subjected to thermal analysis by DSC.
The thermal analysis results of the films obtained in Examples 39 to 45 are shown in FIG. 10, and the thermal analysis results of the films obtained in Example 46 are shown in FIG. FIG. 10 also shows the thermal analysis results of PMMA alone and TEGPy alone, and FIG. 11 shows the thermal analysis results of EHPy alone and PEO alone.

Since the films obtained in Examples 39 to 45 are transparent gel-like films as in Example 22 (see FIG. 6), TEGPy and PMMA are compatible with each other at least in the size of the visible range or less. I can ask.
In this regard, as shown in FIG. 10, it can be seen that the Tg peak of PMMA near 110 ° C. disappears by doping TEGPy into PMMA. Furthermore, it is observed that as the concentration of TEGPy increases, the melting point of the compatible film approaches the melting point peak of TEGPy itself. From this, it can be seen that TEGPy is compatible with PMMA at any concentration.
On the other hand, the film obtained in Example 46 is a cloudy gel-like film as in Example 29 (see FIG. 9). However, as shown in FIG. 11, the peak of PEO around 60 ° C. Is not lost by the introduction of EHPy, and it can be seen that EHPy is phase-separated from PEO.

[9] Production of second organic EL device [Example 47]
(1) Preparation of composition for gel electronic block layer In a washed sample bottle, 3 parts by mass of polyvinylcarbazole (PVK, Aldrich, molecular weight 1.1 million), 7 parts by mass of TEGCz represented by the following formula, and cyclohexanone 300 parts by mass was added and stirred at 70 ° C. until PVK and TEGCz were completely dissolved in cyclohexanone to prepare a composition for gel electron blocking layer (ink 1).
(2) Preparation of composition for gel light emitting layer In the washed sample bottle, 4 parts by mass of polymethyl methacrylate (PMMA, Aldrich, molecular weight 350,000), 6 parts by mass of TEGPy obtained in Synthesis Example 1, 400 parts by mass of toluene was added and stirred at 70 ° C. until PMMA and TEGPy were completely dissolved in toluene to prepare a composition for gel light emitting layer (ink 2).

(3) Production of EL device A glass substrate 105 with an ITO layer 104 was prepared by ultrasonic cleaning in the order of surfactant, pure water, and isopropanol, and subjected to UV / ozone treatment (manufactured by Filgen, UV253S) for 12 minutes. On the ITO layer 104 side on the glass substrate 105 with ITO, an aqueous solution (CLEVIOS ^™ PVP AI4083, HC) of poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS). (Starck, Munich, Germany) was added dropwise and spin coated at 3000 rpm for 60 seconds to form a PEDOT: PSS layer and heated at 200 ° C. for 10 minutes to obtain a hole injection layer 103 with a thickness of 30 nm. It was.
After returning the substrate to room temperature, the ink 1 prepared above was dropped onto the hole injection layer 103 and spin-coated at 1000 rpm for 60 seconds to form the gel electron blocking layer 400 on the hole injection layer 103. .
Since this gel electron block layer 400 is very soft and its film thickness cannot be measured with a direct-core type film thickness measuring device (Dectac II), the film thickness was relatively evaluated by the following method.
First, a thin film having a thickness of 100 nm composed of 99 parts by mass of PVK and 1 part by mass of coumarin 6 represented by the following formula was prepared, and the absorbance at 440 nm corresponding to the absorption of coumarin 6 was measured.
Next, an ink composed of 30 parts by mass of PVK, 70 parts by mass of TEGCz, 1 part by mass of coumarin 6 and 3000 parts by mass of cyclohexanone is spin-coated at 1000 rpm for 60 seconds, and 1% by mass of coumarin 6 is doped into the gel electron block layer 400. A thin film was obtained. In this case, since the concentration of coumarin 6 is remarkably smaller than the concentration of PVK or TEGCz, it is assumed that the film thickness shows the same value regardless of whether coumarin 6 is doped or undoped. The film thickness of the gel electron blocking layer 400 was calculated by measuring the absorbance of this film at 440 nm and comparing the absorbance of a sample with a film thickness of 100 nm in which PVK was doped with 1% by mass of coumarin 6.
The film thickness of the gel electron block layer 400 calculated in this way was 122 nm.

Next, the ink 2 prepared above was dropped on the gel electron blocking layer 400 and spin-coated at 4000 rpm for 60 seconds to form the gel light emitting layer 300 on the gel electron blocking layer 400.
Since the gel light emitting layer 300 has a very soft film thickness, the film thickness was relatively evaluated by the following method as in the gel electron block layer 400.
First, a thin film having a thickness of 100 nm composed of 99 parts by mass of PMMA and 1 part by mass of DCM represented by the following formula was prepared, and the absorbance at 500 nm corresponding to the absorption of DCM was measured.
Next, an ink composed of 40 parts by mass of PMMA, 60 parts by mass of TEGPy, 1 part by mass of DCM, and 4000 parts by mass of toluene is spin-coated at 4000 rpm for 30 seconds, and the gel light emitting layer 300 is doped with 1% by mass of DCM. Got. In this case, since the concentration of DCM is significantly smaller than the concentration of PVK or TEGCz, it is assumed that the film thickness shows the same value regardless of whether the DCM is doped or not. Since the absorption at 500 nm of this film does not overlap with the absorption of the material of the gel electron block layer 400 or the absorption of coumarin 6, the absorbance at 500 nm is measured, and the absorbance of a sample with a thickness of 100 nm in which 1% by mass of DCM is doped into PVK. By comparing these, the film thickness of the gel light emitting layer 300 can be calculated.
The film thickness of the gel light emitting layer 300 thus calculated was 60 nm.
Furthermore, after the gel light emitting layer 300 was formed, the absorbance of the coumarin 6 was measured, and the film thickness of the gel electron blocking layer 400 was calculated again. As described above, the film thickness of the gel electron blocking layer 400 was reduced from 122 nm to 44 nm by toluene used in forming the gel light emitting layer.

Next, the substrate 200 on which the hole injection layer 103, the gel electron blocking layer 400, and the gel light emitting layer 300 are formed is set in a vacuum deposition chamber and evacuated until it becomes 1 × 10 ⁻⁴ Pa or less at room temperature. It was.
Thereafter, the temperature of the substrate 200 was cooled to 20K by a cryostat installed in the vacuum chamber. Ca is deposited on the gel light emitting layer 300 of the cooled substrate 200 at a rate of 0.30 nm / s by a vapor deposition method to a thickness of 50 nm, and Ag is deposited on the Ca layer at a rate of 0.10 nm / s. To form a cathode layer 100 with a thickness of 100 nm.
This element was moved into the glove box in a state where the inert atmosphere was not broken, and sealed to obtain an EL element 3. The element area was 2 mm × 2 mm.

  The structures of TEGCz, Coumarin 6 (manufactured by Sigma Aldrich), and DCM (manufactured by Sigma Aldrich) used in the above examples are shown below. TEGCz was synthesized with reference to the method described in Synthetic Metals, 89 (3), 171 (1997).

FIG. 14 shows the current density-voltage-luminance characteristics of the EL element produced in Example 47, and FIG. 15 shows the EL external quantum efficiency-current density characteristics.
As shown in FIG. 14, light emission was observed at 4.6 V or higher, and a current density of 0.95 mA / cm ² and a maximum luminance of 35 cd / m ² were obtained at 10 V. Further, as shown in FIG. 15, a maximum EL external quantum efficiency of 1.4% was obtained at 7.7 V, 0.22 mA / cm ² .

[Comparative Example 7]
An EL as shown in FIG. 13 was performed in the same manner as in Example 47 except that the gel light-emitting layer 300 was directly formed on the hole injection layer 103 using the ink 2 without forming the gel electron blocking layer 400. Element 4 was produced.
FIG. 16 shows the current density-voltage-luminance characteristics of the EL element produced in Comparative Example 7, and FIG. 17 shows the EL external quantum efficiency-current density characteristics.
As shown in FIG. 16, light emission was observed at 4.8 V or higher, and a current density of 38.9 mA / cm ² and a maximum luminance of 155 cd / m ² were obtained at 20.6 V.
Further, as shown in FIG. 17, a maximum EL external quantum efficiency of 0.11% was obtained at 19.8 V and 28.0 mA / cm ² .

In any of the EL elements produced in Example 47 and Comparative Example 7, light emission is emitted only from the gel light emitting layer.
In the case of the device manufactured in Comparative Example 7, it is considered that the external quantum efficiency remains low as a result of the large proportion of holes and electrons injected into the gel light-emitting layer not leaking to the anode or cathode without recombination. .
On the other hand, in the case of the device manufactured in Example 47, TEGPy was conducted because the LUMO level (2.6 eV) of TEGPy was larger than the LUK level (2.3 eV) of PVK or TEGCz of the gel electron block layer. Electrons are efficiently blocked by the gel electron block layer. At this time, electrons are accumulated on the gel light emitting layer side at the interface between the gel electron blocking layer and the gel light emitting layer, and the holes conducted through the gel electron blocking layer are injected therein, so that the holes and electrons are efficiently recombined. It is thought that an improvement in external quantum efficiency was observed.

[Example 48]
An element was fabricated in the same manner as in Example 47, except that the spin coating speed of ink 1 during the formation of the electronic block layer was 2000 rpm, and the characteristics thereof were evaluated.
The film thickness of the gel electron block layer before the formation of the gel light emitting layer was 96 nm. On the other hand, after the gel light emitting layer was formed on the gel electron blocking layer with a thickness of 60 nm, the total film thickness of the gel electron blocking layer and the gel light emitting layer was 82 nm. Therefore, the film thickness of the gel electron blocking layer decreased from 96 nm to 22 nm before and after the formation of the gel light emitting layer.
In the EL device manufactured in Example 48, light emission was observed at 3.6 V or higher, and a current density of 1.58 mA / cm ² and a maximum luminance of 52 cd / m ² were obtained at 8.8 V. In addition, a maximum EL external quantum efficiency of 1.29% was obtained at 7.4 V and 0.74 mA / cm ² .

[Example 49]
An element was fabricated in the same manner as in Example 47 except that the spin coating speed of ink 1 during the formation of the electronic block layer was set to 3000 rpm, and the characteristics thereof were evaluated.
In addition, the film thickness of the gel electron block layer before gel light emitting layer film-forming was 71 nm. On the other hand, after the gel light emitting layer was formed on the gel electron blocking layer with a thickness of 60 nm, the total film thickness of the gel electron blocking layer and the gel light emitting layer was 80 nm. Therefore, the film thickness of the gel electron blocking layer decreased from 71 nm to 20 nm before and after the formation of the gel light emitting layer.
In the EL device manufactured in Example 49, light emission was observed at 3.0 V or higher, and a current density of 2.0 mA / cm ² and a maximum luminance of 62 cd / m ² were obtained at 9.2 V. Moreover, the maximum EL external quantum efficiency of 1.16% was obtained at 7.0 V and 0.60 mA / cm ² .

[Example 50]
An element was fabricated in the same manner as in Example 47 except that the spin coating speed of ink 1 during the formation of the electronic block layer was set to 4000 rpm, and its characteristics were evaluated.
In addition, the film thickness of the gel electronic block layer before gel light emitting layer film-forming was 60 nm. On the other hand, after the gel light emitting layer was formed on the gel electron blocking layer with a thickness of 60 nm, the total film thickness of the gel electron blocking layer and the gel light emitting layer was 75 nm. Therefore, the film thickness of the gel electron blocking layer decreases from 60 nm to 15 nm before and after the formation of the gel light emitting layer.
In the EL device manufactured in Example 50, light emission was observed at 3.4 V or higher, and a current density of 5.37 mA / cm ² and a maximum luminance of 74 cd / m ² were obtained at 10.6 V. In addition, a maximum EL external quantum efficiency of 1.02% was obtained at 6.6 V, 0.89 mA / cm ² .

[Example 51]
An element was prepared in the same manner as in Example 47 except that the spin coating speed of ink 1 during the formation of the electronic block layer was 8000 rpm, and the characteristics thereof were evaluated.
The film thickness of the gel electron block layer before the formation of the gel light emitting layer was 39 nm. On the other hand, after the gel light emitting layer was formed on the gel electron blocking layer with a thickness of 60 nm, the total film thickness of the gel electron blocking layer and the gel light emitting layer was 69 nm. Therefore, the film thickness of the gel electron blocking layer is reduced from 39 nm to 9 nm before and after the formation of the gel light emitting layer.
In the EL device manufactured in Example 51, light emission was observed at 4.4 V or higher, and a current density of 5.37 mA / cm ² and a maximum luminance of 74 cd / m ² were obtained at 10.2 V. In addition, a maximum EL external quantum efficiency of 0.61% was obtained at 6.6 V, 0.89 mA / cm ² .

Table 7 shows the evaluation of the devices prepared in Examples 47 to 51 and Comparative Example 7. Table 7 also shows the carrier recombination balance γ calculated from the obtained measurement data according to the following formula.
In the following formula, EQE is the external emission quantum yield determined by measurement, Φ _PL is the fluorescence or phosphorescence quantum yield of the liquid light-emitting layer determined by measurement, η _ext is the light extraction efficiency, and the theoretical value of 0.2 is used , Η _r is the exciton generation efficiency, and the theoretical value of 0.25 is used for the element using the fluorescent material, and 1 which is the maximum theoretical value is used for the element using the phosphorescent material.

As shown in Table 7, when Examples 47 to 51 are compared with Comparative Example 7, it can be seen that the carrier recombination balance is greatly improved by introducing the gel electron blocking layer.
Further, from the results of Examples 47 to 51, as the film thickness of the gel electron blocking layer increases, the leakage of electrons to the anode side is suppressed, and as a result, the carrier recombination balance is increased. This shows that the gel electron block layer actually exhibits the electron block function.

[Example 52]
(1) Preparation of composition for gel light emitting layer In a washed sample bottle, 27 parts by mass of PVK (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 400,000), 59 parts by mass of TEGCz, and electron transport material (n-type) Semiconductor) t-BuPBD (manufactured by Tokyo Chemical Industry Co., Ltd.), 12 parts by mass, phosphorescent material (bis (2- (9,9-dibutylfluorenyl) -1-pyridine) acetylacetonate ) 2 parts by mass of iridium (III) (manufactured by American Dye Source) and 2700 parts by mass of toluene, and stirred at 70 ° C. until PVK and TEGCz are completely dissolved in toluene. 3) was prepared.

(2) Production of EL Element In the same manner as in Example 47, a hole injection layer 103 made of PEDOT: PSS was formed on the glass substrate 105 with the ITO layer 104.
After returning the substrate to room temperature, the ink 1 produced in Example 47 was dropped on the hole injection layer 103 and spin-coated at 4000 rpm for 60 seconds, and the gel electron blocking layer 400 was formed on the hole injection layer 103 at 60 nm. The thickness was formed.
Next, the ink 3 prepared above was dropped on the gel electron blocking layer 400 and spin-coated for 60 seconds under the condition of 3000 rpm, and the gel light emitting layer 300 was formed on the gel electron blocking layer 400.
The film thickness of the gel light emitting layer 300 was also relatively evaluated by the following method.
A thin film having a film thickness of 100 nm comprising 98 parts by mass of PVK and 2 parts by mass of (bis (2- (9,9-dibutylfluorenyl) -1-pyridine) acetylacetonate) iridium (III) was prepared, and (bis ( The absorbance at 430 nm corresponding to the absorption of 2- (9,9-dihexylfulrenyl) -1-pyridine) acetylacetonate) iridium (III) was measured. The film thickness of the gel light emitting layer 300 was calculated by comparing the absorbance at 430 nm with the light absorption at 430 nm of the gel light emitting layer 300, which was 70 nm.
Furthermore, after the gel light emitting layer 300 was formed, the film thickness of the gel electron blocking layer 400 was calculated again and found to be 15 nm. As described above, the thickness of the electron blocking layer 400 was reduced from 60 nm to 15 nm by toluene used in forming the gel light emitting layer.
Subsequently, an EL element 3 was produced in the same manner as in Example 1 except that the substrate 20 on which the gel electron blocking layer 400 and the gel light emitting layer 300 obtained as described above were used. The element area was 2 mm × 2 mm.

  The structures of bis (2- (9,9-dibutylfluorenyl) -1-pyridine) acetylacetonate) iridium (III) (Ir complex) and t-BuPBD used in Example 52 are shown below.

FIG. 18 shows the current density-voltage-luminance characteristics of the EL element produced in Example 52, and FIG. 19 shows the EL external quantum efficiency-current density characteristics.
As shown in FIG. 18, light emission was observed at 2.8 V or higher, and a current density of 149 mA / cm ² and a maximum luminance of 15900 cd / m ² were obtained at 21.0 V.
Further, as shown in FIG. 19, a maximum EL external quantum efficiency of 5.72% was obtained at 13.4 V and 4.84 mA / cm ² .

[Comparative Example 8]
The EL as shown in FIG. 13 is performed in the same manner as in Example 52 except that the gel light-emitting layer 300 is formed directly on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400. Element 4 was produced.
FIG. 20 shows the current density-voltage-luminance characteristics of the EL element produced in Comparative Example 8, and FIG. 21 shows the EL external quantum efficiency-current density characteristics.
As shown in FIG. 20, light emission was observed at 2.8 V or higher, and a current density of 215 mA / cm ² and a maximum luminance of 12600 cd / m ² were obtained at 18.6 V.
Further, as shown in FIG. 21, a maximum EL external quantum efficiency of 2.12% was obtained at 12.8 V and 14.4 mA / cm ² .

In any of the EL elements produced in Example 52 and Comparative Example 8, light emission is emitted only from the gel light emitting layer.
In the case of the device manufactured in Comparative Example 8, it is considered that the external quantum efficiency remains low as a result of the large proportion of holes and electrons injected into the gel light-emitting layer leaking to the anode and cathode without recombination. .
On the other hand, in the case of the device manufactured in Example 52, the LUMO level (2.9 eV) of t-BuPBD is larger than the LUK level (2.3 eV) of PVK or TEGCz of the gel electron block layer 400. -The electrons conducted through BuPBD are efficiently blocked by the gel electron block layer 400. At this time, electrons are accumulated on the gel light emitting layer side at the interface between the gel electron blocking layer and the gel light emitting layer, and the holes conducted through the gel electron blocking layer are injected therein, so that the holes and electrons are efficiently recombined. It is thought that an improvement in external quantum efficiency was observed.

[Example 53]
An element was prepared in the same manner as in Example 52 except that the composition of the ink 3 was changed to 39 parts by mass of PVK, 0 parts by mass of t-BuPBD, and 3900 parts by mass of toluene, and the characteristics thereof were evaluated. The film thickness of the gel light emitting layer was 77 nm, and the film thickness of the gel electron blocking layer after the gel light emitting layer was formed was 17 nm.
In the EL device manufactured in Example 53, light emission was observed at 5.4 V or higher, and a current density of 232 mA / cm ² and a maximum luminance of 3810 cd / m ² were obtained at 22.0 V. A maximum EL external quantum efficiency of 0.89% was obtained at 13.4 V and 2.25 mA / cm ² .

[Comparative Example 9]
An EL device was prepared in the same manner as in Example 53 except that the gel light-emitting layer 300 was formed directly on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400, and the characteristics were evaluated. did.
In the EL device manufactured in Comparative Example 9, light emission was observed at 2.7 V or higher, and a current density of 168 mA / cm ² and a maximum luminance of 3680 cd / m ² were obtained at 14.5 V. Moreover, the maximum EL external quantum efficiency of 0.61% was obtained at 11.7 V and 30.5 mA / cm ² .

[Example 54]
An element was prepared in the same manner as in Example 52 except that the composition of the ink 3 was changed to 33 parts by mass of PVK, 6 parts by mass of t-BuPBD, and 3300 parts by mass of toluene, and the characteristics thereof were evaluated. The film thickness of the gel light emitting layer was 79 nm, and the film thickness of the gel electron blocking layer after the gel light emitting layer was formed was 16 nm.
In the EL device manufactured in Example 54, light emission was observed at 3.8 V or higher, and at 21.8 V, a current density of 133 mA / cm ² and a maximum luminance of 7900 cd / m ² were obtained. A maximum EL external quantum efficiency of 4.73% was obtained at 12.6 V and 1.86 mA / cm ² .

[Comparative Example 10]
An EL element was prepared in the same manner as in Example 54 except that the gel light-emitting layer 300 was formed directly on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400, and the characteristics were evaluated. did.
In the EL device manufactured in Comparative Example 10, light emission was observed at 2.4 V or higher, and at 18.6 V, a current density of 190 mA / cm ² and a maximum luminance of 11600 cd / m ² were obtained. In addition, a maximum EL external quantum efficiency of 2.40% was obtained at 13.8 V and 26.4 mA / cm ² .

[Example 55]
An element was prepared in the same manner as in Example 52 except that the composition of the ink 3 was changed to 21 parts by mass of PVK, 18 parts by mass of t-BuPBD, and 2100 parts by mass of toluene, and the characteristics thereof were evaluated. The film thickness of the gel light emitting layer was 87 nm, and the film thickness of the gel electron blocking layer after the gel light emitting layer was formed was 15 nm.
In the EL device manufactured in Example 55, light emission was observed at 3.4 V or higher, and at 23.8 V, a current density of 128 mA / cm ² and a maximum luminance of 17700 cd / m ² were obtained. In addition, a maximum EL external quantum efficiency of 5.68% was obtained at 15.2 V, 3.52 mA / cm ² .

[Comparative Example 11]
An EL device was prepared in the same manner as in Example 55 except that the gel light-emitting layer 300 was formed directly on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400, and the characteristics were evaluated. did.
In the EL device manufactured in Comparative Example 11, light emission was observed at 3.0 V or higher, and at 24.8 V, a current density of 37.7 mA / cm ² and a maximum luminance of 1340 cd / m ² were obtained. A maximum EL external quantum efficiency of 0.83% was obtained at 21.6 V and 15.1 mA / cm ² .

[Example 56]
An element was prepared in the same manner as in Example 52 except that the composition of the ink 3 was changed to 15 parts by mass of PVK, 24 parts by mass of t-BuPBD, and 1500 parts by mass of toluene, and the characteristics thereof were evaluated. The film thickness of the gel light emitting layer was 87 nm, and the film thickness of the gel electron blocking layer after the gel light emitting layer was formed was 15 nm.
In the EL device manufactured in Example 56, light emission was observed at 3.6 V or higher, and a current density of 87.1 mA / cm ² and a maximum luminance of 9090 cd / m ² were obtained at 31.6 V. In addition, a maximum EL external quantum efficiency of 0.61% was obtained at 6.6 V, 0.89 mA / cm ² .

[Comparative Example 12]
An EL device was prepared in the same manner as in Example 56 except that the gel light-emitting layer 300 was directly formed on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400, and the characteristics were evaluated. did.
In the EL device manufactured in Comparative Example 12, light emission was observed at 4.2 V or higher, and at 28.4 V, a current density of 105 mA / cm ² and a maximum luminance of 238 cd / m ² were obtained. A maximum EL external quantum efficiency of 0.043% was obtained at 16.0 V and 2.91 mA / cm ² .

[Example 57]
An element was prepared in the same manner as in Example 52 except that the composition of Ink 3 was changed to 9 parts by mass of PVK, 30 parts by mass of t-BuPBD, and 900 parts by mass of toluene, and the characteristics thereof were evaluated. The film thickness of the gel light-emitting layer was 105 nm, and the film thickness of the gel electron blocking layer after the gel light-emitting layer was formed was 16 nm.
In the EL device manufactured in Example 57, light emission was observed at 2.4 V or higher, and a current density of 20.4 mA / cm ² and a maximum luminance of 3180 cd / m ² were obtained at 46.8 V. In addition, a maximum EL external quantum efficiency of 4.80% was obtained at 38.2 V and 2.37 mA / cm ² .

[Comparative Example 13]
An EL device was produced in the same manner as in Example 57, except that the gel light-emitting layer 300 was formed directly on the hole injection layer 103 using the ink 3 without forming the gel electron blocking layer 400, and the characteristics were evaluated. did.
In the EL device manufactured in Comparative Example 13, light emission was observed at 11.0 V or higher, and a current density of 7.50 mA / cm ² and a maximum luminance of 4.36 cd / m ² were obtained at 38.8 V. A maximum EL external quantum efficiency of 0.012% was obtained at 38.8 V, 7.50 mA / cm ² .

  Table 8 summarizes the light emission starting voltage, the maximum external quantum yield, the fluorescence quantum yield, and the carrier recombination balance of the EL devices prepared in Examples 52 to 57 and Comparative Examples 8 to 13.

As shown in Table 8, when Examples 52 to 57 and Comparative Examples 8 to 13 are compared, it can be seen that the carrier recombination balance is greatly improved by introducing the gel electron blocking layer.
Further, from the results of Comparative Examples 8 to 13, in the EL element having a single-layer gel structure, even when the concentration of t-BuPBD that is an electron transport material is adjusted with respect to the concentration of PVK or TEGCz that is a hole transport material. It can be seen that it is difficult to improve the carrier recombination balance.
On the other hand, it can be seen from the results of Examples 52 to 57 that when the gel electron blocking layer is used, the carrier recombination balance is improved as the concentration of t-BuPBD which is an electron transporting material is increased. This is because the LUMO level (2.9 eV) of t-BuPBD is larger than the PVK or TEGCz LUMO level (2.3 eV) of the gel electron block layer, so that the electrons conducting t-BuPBD are the gel electron block. Are efficiently blocked, and electrons are accumulated on the side of the gel light emitting layer at the interface between the gel electron blocking layer and the gel light emitting layer. Holes conducted through the gel electron blocking layer are injected there, and the holes and electrons are efficiently regenerated. It is thought to be for joining.

1, 3 Organic EL device (electroluminescent device)
DESCRIPTION OF SYMBOLS 10 Anode 20 Cathode 30 Gel light emitting layer 50 Hole injection layer 100 Cathode 200 Anode 300 Gel light emitting layer 400 Gel electron block layer (gel functional layer)

Claims (19)

An organic electroluminescent device comprising an anode, a cathode, and a light emitting layer interposed between these electrodes,
The light-emitting layer includes (A1) a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at normal temperature with a gelling agent, or (A2) a carrier transporting material and a light-emitting material, and at least one of these materials is normal temperature An organic electroluminescent device characterized by being a gel light emitting layer obtained by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent.   The organic electroluminescence device according to claim 1, wherein the carrier transport material is at least one selected from a hole transport material, an electron transport material, and a material having both a hole transport capability and an electron transport capability. An organic electroluminescent device comprising an anode, a cathode, and two or more functional layers including a light emitting layer interposed between these electrodes,
The light-emitting layer includes (A1) a gel light-emitting layer obtained by gelling a light-emitting material that is liquid at normal temperature with a gelling agent, or (A2) a carrier transporting material and a light-emitting material, and at least one of these materials is normal temperature And a gel light emitting layer formed by gelling a light emitting composition that is liquid at room temperature as a whole with a gelling agent,
At least one of the other functional layers includes (B1) a gel functional layer obtained by gelling a carrier transport material that is liquid at normal temperature with a gelling agent, or (B2) a carrier transport material that is liquid at normal temperature, An organic electroluminescence device characterized in that it is a gel functional layer formed by gelling a carrier transport composition that is liquid at room temperature as a whole with a gelling agent.   The organic electroluminescent device according to claim 3, wherein the carrier transport material contained in the gel light emitting layer is at least one selected from a hole transport material, an electron transport material, and a material having both a hole transport capability and an electron transport capability.   The organic electroluminescent element according to claim 3 or 4, wherein the carrier transport material contained in the gel functional layer is a hole transport material, an electron transport material, or a material having both a hole transport capability and an electron transport capability.   The organic electroluminescent element according to any one of claims 3 to 5, wherein the gel functional layer is an electron block layer laminated in a form in contact with the gel light emitting layer between the gel light emitting layer and the anode. .   The organic electroluminescent element according to claim 1, wherein the gelling agent is a polymer material.   The polymer material is selected from poly (meth) acrylates, polyacrylonitriles, polyolefins, polystyrenes, polyamides, polyesters, polyimides, polyalkoxyoxides, polysiloxanes, and biopolymers 1 The organic electroluminescent element according to claim 7, wherein the organic electroluminescent element is a seed or two or more kinds of non-conductive polymers.   The polymer material is one or more conductive polymers selected from polyvinyl carbazoles, polythiophenes, polyphenylene vinylenes, polyacetylenes, polydiacetylenes, polyanilines, polypyrroles, and carbons. Item 8. The organic electroluminescent device according to Item 7. The organic electroluminescent element according to claim 8, wherein the nonconductive polymer is one or more selected from the formulas (1) and (2).

(Wherein R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, or R ¹ and R ² or R ² and R ³ ; Represents a cycloalkyl group or cycloalkenyl group having 4 to 10 carbon atoms formed by bonding to each other;
X ¹ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether bond, an amide bond or an ester bond,
A ¹ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms which may contain an ether bond, an ester bond or an amide bond;
n ₁ and n ₂ are the number of repeating unit structures and each independently represent an integer of 2 to 100,000. ) The organic electroluminescent element according to claim 10, wherein the non-conductive polymer is one or more selected from formulas (3) and (4).

(In the formula, n ₁ and n ₂ represent the same meaning as described above.) The organic electroluminescent element according to claim 9, wherein the conductive polymer is one or more selected from formulas (5) and (6).

(Wherein R ^{4 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, or R ⁴ and R ^5, or R ⁴ and R ^6, and Represents a cycloalkyl group or cycloalkenyl group having 4 to 10 carbon atoms formed by bonding to each other;
Ar ¹ is carbazole derivative group, triarylamine derivative group, starburst amine, thianthrene derivative group, phenothiazine derivative group, azepine derivative group, phenylenediamine derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline Derivative group, silane derivative group, pyrrole derivative group, porphyrin derivative group, carbon condensed ring system compound group, metal or metal-free phthalocyanine derivative group, diphenylene sulfone (dibenzothiophene 5,5-dioxide) derivative group, oxadiazole derivative Group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imidazole derivative group, oxazole derivative group, fluorenone derivative group, silole derivative group, triarylphosphine oxide derivative Body group, a triaryl borane derivative group, a furan derivative group, and one or more groups selected from electron transporting metal complex groups,
B ¹ is a single bond as well as a divalent benzene derivative group, naphthalene derivative group, anthracene derivative group, pyrene derivative group, thiophene derivative group, furan derivative group, pyrrole derivative group, carbazole derivative group, triarylamine derivative group, Starburst amine, thianthrene derivative group, phenothiazine derivative group, azepine derivative group, phenylenediamine derivative group, triphenylmethane derivative group, fluorene derivative group, stilbene derivative group, polyaniline derivative group, silane derivative group, porphyrin derivative group, metal or none Metal phthalocyanine derivative group, diphenylenesulfone (dibenzothiophene 5,5-dioxide) derivative group, oxadiazole derivative group, triazole derivative group, triazine derivative group, phenanthroline derivative group, imida One group selected from a benzene derivative group, an oxazole derivative group, a fluorenone derivative group, a quinacridone derivative group, a pyrazolone derivative group, a silole derivative group, a triarylphosphine oxide derivative group, a triarylborane derivative group, and an electron transporting metal complex group Or represents 2 or more types,
C ¹ represents a linear, branched or cyclic divalent conjugated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a single bond, provided that B ¹ and C ¹ simultaneously become a single bond. Absent,
n ₃ and n ₄ are the number of repeating unit structures and each independently represents an integer of 2 to 100,000. ) The organic electroluminescent element according to claim 12, wherein the conductive polymer is one or more selected from formulas (7) and (8).

(In the formula, R ^{7 to} R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and n ₃ and n ₄ represent the same meaning as described above. ) The organic electroluminescent element according to claim 13, wherein the conductive polymer is one or more selected from formulas (9) to (11).

(Wherein n ₃ and n ₄ represent the same meaning as described above.)   A gel obtained by gelling a liquid composition containing a semiconductor that is liquid at room temperature with a polymer gelling agent.   The gel according to claim 15, which has elasticity. A method for producing an organic electroluminescent device comprising an anode, a cathode, and a gel light emitting layer interposed between these electrodes,
(A1) A light emitting material and a gelling agent that are liquid at normal temperature, and a composition that is liquid at normal temperature as a whole, or (A2) a carrier transporting material, a light emitting material, and a gelling agent. A method for producing an organic electroluminescent device, wherein at least one of them is liquid at room temperature, and the gel light emitting layer is formed by a coating method from a composition liquid at room temperature as a whole. A method for producing an organic electroluminescent device comprising an anode, a cathode, and two or more gel functional layers including a gel light emitting layer interposed between these electrodes,
(A1) A light emitting material and a gelling agent which are liquid at normal temperature, and a composition which is liquid at normal temperature as a whole, or (A2) a carrier transporting material, a light emitting material and a gelling agent, and the carrier transporting material and the light emitting material At least one of them is liquid at room temperature, and the gel light emitting layer is formed by a coating method from a composition that is liquid at room temperature as a whole,
(B) Organic electroluminescence comprising a carrier transport material and a gelling agent which are liquid at normal temperature, and forming at least one gel functional layer by a coating method from a composition which is liquid at normal temperature as a whole. Device manufacturing method.   The method for producing an organic electroluminescent element according to claim 17 or 18, wherein the cathode is deposited on the gel light emitting layer in a state where the gel light emitting layer is cooled.

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