WO2007148649A1

WO2007148649A1 - Organic electroluminescent device, process for producing organic electroluminescent device, illuminator, and display

Info

Publication number: WO2007148649A1
Application number: PCT/JP2007/062225
Authority: WO
Inventors: Tatsuo Tanaka; Hideo Taka; Rie Katakura; Hiroshi Kita; Hiroto Itoh
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2006-06-21
Filing date: 2007-06-18
Publication date: 2007-12-27

Abstract

An organic EL device which is free from separation at a bonding interface obtained by laminating and gives a high carrier mobility, a luminance, and a luminescent life. The organic EL device is characterized in that: (A) it comprises an anode, a cathode, and organic layers disposed therebetween, one of the electrodes has, formed thereon, a first organic layer comprising an organic compound having a reactive substituent, and the other electrode has a second organic layer formed thereon, the first and second organic layers having been laminated face to face to produce the device; (B) the film thickness (T) (EM) (nm) of a luminescent layer satisfies a given relationship, the luminescent layer comprises a phosphorescent material, and at least one of the organic layers is formed by laminating; (C) one of the organic layers comprises a phosphorescent compound, the two bonding surfaces of the organic layers to be laminated have a surface roughness (Ra) of 0.05-10 nm, and the ratio of the surface roughness between the two laminating surfaces is 0.5-2.0; and (D) at least one of the organic layers comprises a phosphorescent compound and the laminated surfaces have a peel strength of 10 N/m or higher.

Description

Specification

ORGANIC ELECTRIC LIGHT EMITTING ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTRIC LIGHT EMITTING ELEMENT, LIGHTING DEVICE, AND DISPLAY DEVICE

Technical field

TECHNICAL FIELD [0001] The present invention relates to an organic electoluminescence device, a method for manufacturing an organic electroluminescence device, an illumination device, and a display device.

[0002] In addition, the laminating process reduces the load on the stack and reduces the adhesion of the laminating surface. The luminous efficiency is high, and no dark spots are generated. In addition, the present invention relates to a manufacturing method thereof, and an illumination device and a display device using the organic electret luminescence element.

Furthermore, the present invention relates to an organic electroluminescent device and a method for manufacturing the same, and to an organic electroluminescent device formed by bonding an electrode substrate after forming an organic layer on the electrode substrate, and a method for manufacturing the organic electroluminescent device.

Background

[0004] An organic electoluminescence device (hereinafter also referred to as an organic EL device) is an all-solid device composed of a film of an organic material having a thickness of about 0. Lm between electrodes. This technology is expected as next-generation flat display and illumination because light emission can be achieved at a relatively low voltage of about 2 to 20V.

[0005] In addition, organic EL devices that use phosphorescence, which was recently discovered, can achieve a light emission efficiency that is approximately four times that of previous methods that use fluorescence. At the beginning, research and development of light-emitting element layer configurations and electrodes are being carried out around the world.

[0006] In addition, the structure of the organic EL element is simple as an organic layer is sandwiched between a transparent electrode and a counter electrode, and the number of parts is overwhelming compared to a liquid crystal display that is a typical flat display. However, the manufacturing cost should be kept low, but at the present time, liquid crystal displays are largely drained in terms of performance and cost. Poor productivity is thought to be a factor in cost. [0007] Most of the organic ELs currently commercialized! Are manufactured by a so-called vapor deposition method in which a low molecular material is deposited on a substrate to form a film. This vapor deposition method is very efficient in terms of efficiency and life because it can be applied to low-molecular compounds that are easy to purify and high-purity materials are easy to obtain. , the other hand, for example, for performing a vapor deposition under high vacuum conditions of 10- ⁴ Pa or less, joined by constraints apparatus for forming, in fact can not be applied to a substrate power of small area, further comprising when a plurality of layers stacked formation The disadvantage is that the membrane is time consuming and the throughput is low. In particular, lighting applications are problematic when applied to large-area electronic displays, and OLED is one of the reasons that is not practical for such applications.

[0008] Although a polymer system can form an organic layer by a coating process, it is advantageous in terms of large area, uneven light emission, etc., and in terms of cost, but the purity is difficult to increase, and the light emission performance is superior to a vapor deposition system. The disadvantage is that it does not.

[0009] Further, focusing on the manufacturing method itself, (A) a method of sequentially forming a thin film on an electrode substrate (sequential film formation method), (B) two methods, an electrode substrate and a counter electrode substrate. There is a method of bonding after forming a thin film appropriately (bonding method). The advantages of the bonding method are as follows: (1) In the sequential film forming method, the counter electrode to be finally formed can be prepared in advance ( 2) Use of a film for the substrate enables continuous production by a roll-to-roll system, and (3) The organic layers can be easily laminated if the bonding surfaces are made of organic layers. In particular, (1) and (2) will be the driving force for dramatically improving productivity, and it will be possible to significantly reduce the manufacturing cost of organic EL devices.

[0010] Further, in the sequential film forming method that is usually applied, the counter electrode is formed after the organic layer is formed. For example, in the case of a cathode using a metal having a small work function, the counter electrode is already formed. There is also a problem that the organic layer is damaged, and the light emitting characteristics and life of the organic EL element are greatly deteriorated. From this viewpoint, the bonding method in which the electrode film is formed first is preferable.

[0011] As described above, the bonding method is an effective technical means for innovatively improving productivity. However, at present, the bonding surface when bonded is not necessarily in close contact at the molecular level. As a result, the carrier moves smoothly to the line, and the bonding surface is peeled off. Problems such as failure of function are listed. In particular, peeling of the joint surface may be a major manufacturing problem in the roll roll method.

[0012] Several techniques for improving the bonding failure at the time of pasting have been disclosed.

For example, a technology that improves the adhesion between layers by making both bonding layers made of the same material (see, for example, Patent Document 1), and two bonding surfaces were produced by a wet method. Although a technique for bonding a film that has not been completely dried (see, for example, Patent Document 2) has been introduced, both of them have insufficient adhesion at the joint surface, which is a fundamental solution. There is not.

[0013] In addition, a technique (for example, see Patent Document 3) that improves the adhesiveness of the bonding surface by allowing a polymer binder to be present on the bonding surface and bonding or fusing around the element is also similar. technology combined to make a light-emitting layer in the transfer method of the technical idea, even phosphorescent discloses that that can be applied (e.g., see Patent Document 4.) with ₀ tooth force, the Rukoto be bonded around Although reducing the adverse effects of moisture and oxygen during device driving and improving the light emission lifetime contributes, it is not a technical means that can fundamentally solve the above-mentioned peeling of the joint surface.

[0014] Further, connected by covalent bonds interlayer of organic EL elements, techniques for improving the adhesion between the layers is shown open (e.g., Patent Document 5 reference.) The film in ₀ this technical idea sequential deposition method This is a technique for forming a covalent bond at the interface of the organic layer during or after film formation, and not a means of interfacial adhesion in the bonding method.

[0015] The bonding method can be an innovative method that is good both in terms of performance and manufacturing process, as long as the defects on the joint surface are improved.

Inventions (A) and (C) have been made based on these backgrounds.

[0017] Although a system using a polymer material can form an organic compound layer of an organic EL element by a coating process, it can be manufactured by a coating process such as spin coating, ink jet, printing, and spraying.

[0018] This is possible because it can be manufactured under atmospheric pressure, so that it can be manufactured at a low cost. At the same time, it is necessary to use organic materials for organic EL elements when forming organic layers. (Or, low molecular weight materials) are prepared as a solution and applied in a thin film, so multiple organic materials can be mixed precisely (for example, the adjustment of dopants to the light-emitting host material, etc.) Although it is characterized by the fact that uneven light emission is difficult to occur even with a large area, and is very advantageous in terms of manufacturing cost, the counter electrode formed after forming an organic layer in a general manufacturing process is Since it is produced by vacuum processes such as vapor deposition or sputtering, this process eventually becomes a bottleneck and can be an innovative production process.

[0019] Further, in contrast to the above-described vapor deposition system, the fact is that the purity of the polymer material cannot be increased and lamination is difficult. There is also the problem of being cunning.

[0020] The above is the difference in the manufacturing method mainly due to the material, but focusing on the method of forming the element itself,

(a) a method of sequentially forming a thin film on an electrode substrate (sequential film formation method);

(b) There is a method (bonding method) in which a thin film is appropriately formed on an electrode substrate and a counter electrode substrate and then bonded.

[0021] The advantage of the bonding method is

(1) In the sequential deposition method, the last counter electrode to be deposited can be prepared in advance.

(2) Use of a film for the substrate enables continuous production in a roll-to-roll system.

(3) The organic layer can be easily laminated if the bonding surfaces are made of organic layers, and the like.

[0022] In particular, (1) and (2) are the driving force for dramatically improving productivity, and if the technology is completed, it is possible to significantly reduce the manufacturing cost, which was the biggest problem of organic EL. It seems that On the other hand, the technology of the roll-to-roll method is disclosed even in a method other than the bonding method.

[0023] For example, a method of continuously forming a hole transport material on an electrode substrate wound in a ribbon shape on a reel by an inkjet method has been described (for example, see Patent Document 6). As described in the polymer coating method, since the formation of the counter electrode eventually becomes a vacuum process, the merit of the roll-to-roll method is greatly diminished, and the productivity is not substantially improved. There are problems.

[0024] As described above, the bonding method is an effective technical means for innovatively improving productivity. At present, organic EL devices fabricated using this method have problems in performance and are still in the process of being developed because no accurate breakthrough has been found.

[0025] There are several reasons for this, but considering the principle, the bonding surface when bonded is not necessarily in close contact at the molecular level, and as a result, carrier movement is not smooth, and the bonding surface peels off. It is expected that there will be problems such as the fact that it will soon not function as a light emitting element.

[0026] In particular, the peeling of the joint surface is the same as in the roll-to-roll method, and there is a winding process. When a flexible substrate is used, if the element is destroyed during use, V, and if it becomes a fatal defect, there is a problem.

[0027] Some techniques for improving the bonding failure at the time of bonding are also disclosed.

[0028] For example, by making both the bonding layers made of the same material, a technique for improving the adhesion between the layers (for example, see Patent Document 1) and two bonding surfaces are produced by a wet method. However, both of them have introduced a technology for bonding a film that is not completely dry (see, for example, Patent Document 2). It is not.

[0029] In addition, there is a technique (for example, refer to Patent Document 3) in which a polymer noinder is present on the bonding surface, and the adhesion of the bonding surface is improved by bonding or fusing around the element. It is described that the same technical idea can be applied to phosphorescence emission by combining with a technique for forming a light emitting layer by a transfer method (see, for example, Patent Document 4).

[0030] Adhering the surroundings contributes to reducing the adverse effects of moisture and oxygen during driving of the element and improving the light emission lifetime, but it is a technical means that can fundamentally solve the above-mentioned peeling of the joint surface. There is a problem of ecstatic ヽ.

[0031] Further, peeling of the thin film interface is not a problem only by the bonding method! ,.

[0032] The organic EL elements that are currently commercialized! / The power that is a non-flexible light emitting element that is made of glass as a substrate is the all-solid-state organic EL element as described above. A major feature is that it can be applied to flexible substrates such as films (so-called flexible displays). [0033] At present, it is said that the flexible substrate has insufficient gas noria, which delays its practical application. However, as another problem, there is a problem between the organic layer and the counter electrode layer. Peeling is also a major issue.

[0034] Since this is an inflexible element at present, this issue has not been taken up as an obvious issue. However, in principle, the adhesion between the organic substance and the metal forming the counter electrode is low. It is a serious problem.

[0035] Further, in the sequential deposition method that is usually applied, after forming an organic layer such as a light emitting layer and a carrier transport / injection layer, a counter electrode (usually a cathode, specifically A1, Ca, Ba, etc.) is formed. However, if the organic layer already formed is damaged, the emission characteristics and lifetime of the organic EL element will be greatly degraded. There is a problem that.

In other words, it is impossible to form the counter electrode in a strong energy state in order to increase the adhesion between the counter electrode and the organic layer interface. There is no choice but to deposit the film by means of notching.

[0037] As a means for solving this problem, a technique of providing a buffer layer made of a semiconductor material or a metal cover on an organic layer closest to the counter electrode (see, for example, Patent Document 7 and Patent Document 8). Is disclosed.

[0038] Certainly, it is possible to reduce the damage at the time of film formation of the counter electrode by interposing such a buffer layer in between. This increases the load in the manufacturing process and increases the productivity. I never liked it!

[0039] On the other hand, as a measure for improving the light emission efficiency and extending the life of organic EL elements using phosphorescence, multilayering of the element structure can be mentioned. In the coating method, the upper layer of the organic layer is applied. Since the lower layer film surface may be dissolved by the liquid solvent and the lower layer film may be disturbed, it is extremely difficult to form a stack of a plurality of organic layers.

[0040] On the other hand, a technique of laminating without dissolving the upper layer material in a solvent outside the solubility range of the solubility parameter of the main material of the lower layer without disturbing the surface of the lower layer thin film is disclosed.

(For example, see Patent Document 9).

[0041] In addition, a solvent (poor solvent) outside the solubility range of the solubility parameter of the lower layer main material may be removed from the upper layer. Disclosed is a technique in which a material is dissolved in a mixed solvent of a solvent (good solvent) and a poor solvent within the solubility range of the solubility parameter, and the solubility is lowered (for example, see Patent Document 10).

[0042] In an element having three or more organic layers having functional layers such as a hole transport layer and an electron transport layer before and after a light emitting layer optimal for an organic EL element using phosphorescence, If the above method is used for manufacturing, the restrictions on the organic EL element material will increase drastically, making it difficult to apply to any organic EL material, and the benefits of multi-layering will be lost. There are challenges.

[0043] The invention (B) has been made based on the background as described above.

[0044] Considering the manufacturing process of the bonding method from the viewpoint of the productivity of the manufacturing process.

[0045] Since the bonding is performed after forming all necessary layers, the transparent electrode and the counter electrode are formed first.

[0046] When forming a film of metal or metal oxide, it is desirable to apply high energy during deposition or after film formation in order to form a film, but this is possible with the bonding method It can also be considered as a means of achieving this.

[0047] In other words, if the bonding surfaces for bonding are organic layers, the transparent electrode and the counter electrode can be formed in advance by a method most suitable in terms of performance and productivity, respectively.

[0048] If an organic layer is appropriately laminated thereon and pasted at the end, it can be an innovative method that is good in terms of performance and manufacturing process as long as the defect on the joint surface is improved. Is.

[0049] The invention (D) has been made based on such a background.

Patent Document 1: Japanese Patent Laid-Open No. 2002-203675

Patent Document 2: Japanese Patent Laid-Open No. 9-306667

Patent Document 3: Japanese Patent Laid-Open No. 9 7736

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-79300

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-103401

Patent Document 6: Japanese Patent Laid-Open No. 2005-327677 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2005-243411

Patent Document 8: Japanese Unexamined Patent Application Publication No. 2005-183013

Patent Document 9: Japanese Unexamined Patent Application Publication No. 2002-299061

Patent Document 10: Japanese Patent Application Laid-Open No. 2005-259523

Disclosure of the invention

Problems to be solved by the invention

[0050] Therefore, the objects of the inventions (A) and (C) are to improve the adhesion at the bonding surface of the organic EL device produced by the bonding method, the bonding surface does not peel off, and the carrier moves. An object of the present invention is to provide an organic EL element that is enhanced and has high emission luminance and emission lifetime, a manufacturing method thereof, and a lighting device and a display apparatus using the organic EL element.

[0051] Further, the object of the invention (B) is to provide a production method for producing an organic-electric-luminescence device having high luminous efficiency and a long lifetime at a low cost, and the organic method produced by the production method is provided. It is an object to provide an electroluminescence device, an illumination device, and a display device.

[0052] In addition, the object of the invention (D) is to produce an organic electoluminescence that is formed by forming an organic layer including a light emitting layer on at least one of a pair of counter electrodes, and then bonding the counter electrodes to each other. In the method, an organic electoluminescence device having a high durability with a high bonding strength on a bonding surface and a good light emitting performance and life is provided.

Means for solving the problem

[0053] The above object of the invention (A) is achieved by the following means 1 to 12.

[0054] 1. An organic electoluminescence device having a plurality of organic layers between an anode and a cathode, wherein at least a first organic layer containing an organic compound having a reactive substituent is formed on one electrode. One layer is formed, at least one second organic layer is formed on the other electrode, and the first organic layer and the second organic layer are bonded to face each other. Mouth luminescence element.

[0055] 2. The organic electroluminescent device according to 1 above, wherein the second organic layer contains an organic compound having a reactive substituent.

[0056] 3. At least one of the plurality of organic layers contains a phosphorescent light-emitting compound. 3. The organic electroluminescence device according to 1 or 2 above, wherein

[0057] 4. The organic electroluminescent device according to any one of 1 to 3 above, wherein the reactive substituent is a reactive substituent selected from the following substituent group.

[0058] [Chemical 1] Rc Rll

O

— NCO — NCS One ^

O

[0059] (In the reactive substituent, A is represented by the following general formula (a), a linking group having at least one selected from the group of linking groups consisting of 1 O and S force, or a plurality of combinations of the linking groups) Represents a divalent linking group represented by a combination, and B represents a hydrogen atom or a substituent.

[0060] [Chemical formula 2] General formula (a)

[In the formula, R and R ′ each represent a hydrogen atom or a substituent, and n represents an integer of 1 or more.]

5. The force according to any one of 1 to 4 above, wherein the first organic layer and the second organic layer are bonded to face each other to form a bond between the organic compounds having a reactive substituent 1 The organic electoluminescence device according to item.

[0062] 6. The organic electroluminescent device according to any one of 1 to 5 above, wherein the bond is formed at an interface between the first organic layer and the second organic layer.

[0063] 7. The organic electr as described in 5 or 6 above, wherein the bond is a covalent bond Tronoreminence element.

[0064] 8. The first organic layer and the second organic layer have the same composition, and the bond is formed below the glass transition temperature (Tg) of the first organic layer and the second organic layer. The organic-electric-mouth luminescence element according to any one of claims 5 to 7, wherein:

[0065] 9. The organic electroluminescent device according to any one of 1 to 8, wherein at least one of the organic layers is formed by a wet method.

[0066] 10. The method of manufacturing an organic electoluminescence device according to any one of 1 to 9 above, wherein the organic electroluminescence device has a plurality of organic layers between an anode and a cathode, Forming at least one organic layer, forming at least one second organic layer on the other electrode, and bonding the first organic layer and the second organic layer opposite to each other. The manufacturing method of the organic electoluminescence device characterized by having.

[0067] 11. An illuminating device using the organic electoluminescence element according to any one of 1 to 9 above.

[0068] 12. A display device using the organic-electric-luminescence element according to any one of 1 to 9.

[0069] Further, the above object of the invention (B) has been achieved by the following structures 13 to 22.

[0070] 13. In a method for producing an organic electoluminescence device having at least an anode and a cathode on a support substrate, and an organic layer including at least one light emitting layer between the anode and the cathode.

The total thickness T (EM) (nm) of the light emitting layer satisfies the following relational expression (1), at least one of the light emitting layers has a phosphorescent light emitting material, and at least one of the organic layers has The manufacturing method of the organic electoluminescence device characterized by having the process formed by bonding of the layer A and the layer B.

[0071] Relational expression (1)

40nm <T (EM) ≤ lOOnm

14. The method for producing an organic electroluminescent device according to 13, wherein the organic layer has three or more layers.

[0072] 15. The layer A and the layer B each contain a compound having the same structure as a main component. 15. A method for producing an organic electoluminescence device as described in 13 or 14 above.

[0073] 16. The method for producing an organic electoluminescence device according to any one of the above 13 to 15, wherein either the layer A or the layer B contains a phosphorescent material.

[0074] 17. The method of producing an organic electoluminescence device according to any one of items 13 to 15, wherein the layer A and the layer B each contain a phosphorescent material.

[0075] 18. The method of producing an organic electroluminescent device according to 17 above, wherein the layer A and the layer B are layers containing the same phosphorescent material.

[0076] 19. The method for producing an organic electroluminescent device according to any one of 13 to 18, wherein the phosphorescent material is an iridium complex or a platinum complex.

[0077] 20. An organic electoluminescence device produced by the method for producing an organic electroluminescence device according to any one of the items 13 to 19, described above.

[0078] 21. An illumination device comprising the organic-electric-mouth luminescence element as described in 20 above.

[0079] 22. A display device comprising the organic-electric-luminescence element as described in 20 above.

[0080] The above object of the invention (C) is achieved by the following configurations 23 to 31.

[0081] 23. A first electrode substrate having at least n (n≥0) organic layers, and at least m layers (m

+ n≥1) In an organic letter-light-emitting element produced by bonding a second electrode substrate having an organic layer facing each other, the organic layer contains at least one S phosphorescent compound of the organic layer, The surface roughness (Ra) of the two laminated surfaces is in the range of 0.05 to: LOnm, and the ratio of the surface roughness of the two laminated surfaces is within 0.5 to 2.0 An organic-elect mouth luminescence device characterized by

[0082] 24. The organic electroluminescent device according to 23 above, wherein the two laminated surfaces to be bonded together are organic layers.

[0083] 25. Organic compound having reactive substituents on at least one of two laminated surfaces to be bonded 25. The organic electroluminescent mouth luminescence device as described in 23 or 24 above, which contains a product.

[0084] 26. The organic electroluminescent device according to any one of 23 to 25 above, which contains an organic compound having a reactive substituent on both of the laminated surfaces to be bonded.

[0085] 27. The organic electoluminescence device as described in 25 or 26 above, wherein the reactive substituent is represented by the following general formula.

[0086] [Chemical 3] ^ ~ ≡ — NH ₂ —OH

[0087] 28. The organic electroluminescent device according to any one of 23 to 27 above, wherein the organic layer is laminated by a wet method.

[0088] 29. a first electrode substrate having at least n (n≥0) organic layers, and at least m layers (m

+ n≥1) is a method for producing an organic electroluminescent device, wherein a second electrode substrate having an organic layer facing each other is bonded, wherein at least one of the organic layers contains a phosphorescent light-emitting compound, The surface roughness (Ra) of two opposing laminated surfaces is in the range of 0.05 to 1 Onm, and the ratio of the surface roughness of the two laminated surfaces is within 0.5 to 2.0. The manufacturing method of the organic electoluminescence device characterized by these.

[0089] 30. An illuminating device comprising the organic-electric-luminescence element according to 23 to 28!

[0090] 31. A display device comprising the organic electoluminescence element according to any one of 23 to 28 above.

Further, the object of the invention (D) could be solved by the following configurations 32 to 40.

[0092] 32. A first electrode substrate having at least n (n≥0) organic layers, and at least m layers (m In an organic electoluminescence element formed by laminating a second electrode substrate having an organic layer of ≥0), a phosphorescent light-emitting compound is formed on at least one of the organic layers (m + n≥l). An organic electoluminescence element characterized in that the peel strength of the bonded surface is lONZm or more.

[0093] 33. The organic electroluminescent device according to 32 above, wherein the surfaces to be bonded together are organic layers.

[0094] 34. The organic electroluminescent device according to 32 or 33 above, which contains an organic compound having a reactive substituent on at least one of the surfaces to be bonded.

[0095] 35. The organic electroluminescent device according to any one of 32 to 34 above, which contains an organic compound having a reactive substituent on both surfaces to be bonded.

[0096] 36. The organic electroluminescent device according to 34 or 35, wherein the reactive substituent is represented by the following general formula (1):

[0097] [Chemical 4]

[0098] 37. The organic electoluminescence device according to any one of 32 to 36 above, wherein the organic layer is formed by a wet method.

[0099] 38. In the method of manufacturing an organic electoluminescence device for producing an organic electroluminescence device according to any one of 32 to 37, at least of the organic layer.

A method for producing an organic electoluminescence device, characterized in that the phosphorescent light-emitting compound is contained in one and the peel strength of the bonded surface is lONZm or more.

[0100] 39. An illuminating device comprising the organic electoluminescence element according to any one of 32 to 37 above. [0101] 40. A display device comprising the organic electoluminescence element according to any one of 32 to 37 above.

The invention's effect

[0102] (A) The invention described in claims 1 to 12 improves the adhesion at the bonding surface of the organic EL element produced by the bonding method, and the bonding surface peels off. It was possible to provide an organic EL element capable of achieving high light emission luminance and light emission lifetime, and a manufacturing method thereof, and an illumination device and a display device using the organic EL element.

[0103] (B) According to the invention described in claims 13 to 22, there is provided a production method for producing an organic electoluminescence device having high luminous efficiency and long life at low cost, and It was possible to provide an organic electoluminescence element, a lighting device, and a display device manufactured by the manufacturing method.

[0104] (C) According to the invention described in claims 23 to 31, an organic electoluminescence (EL) element material whose luminous efficiency is increased by a bonding method, and the organic EL element material We were able to provide the organic EL elements, lighting devices and display devices used. Furthermore, it was possible to provide an organic EL element material having a long life, an organic EL element using the organic EL element material, an illumination device, and a display device.

[0105] (D) According to the invention described in claims 32 to 40, the manufacturing is easy, the strength of the adhesive surface can be increased, the durability is excellent, and the light emission performance and the light emission lifetime are improved. We were able to provide excellent organic EL devices. Furthermore, it was possible to provide a material for an organic EL element having a high adhesive surface strength and a long life, an organic EL element using the material for an organic EL element, a lighting device, and a display device.

Brief Description of Drawings

[0106] Fig. 1 is a schematic diagram showing an example of a display device that also has organic EL element power.

FIG. 2 is a schematic diagram of a display unit.

FIG. 3 is a schematic diagram of a pixel.

FIG. 4 is a schematic view of a lighting device.

FIG. 5 is a cross-sectional view of the lighting device. Explanation of symbols

[0107] 1 display

3 pixels

5 scan lines

6 Data line

7 Power line

10 Organic EL devices

11 Switching transistor

12 Ma District Motion Transistor

13 Capacitor

A Display section

B Control unit

107 Glass substrate with transparent electrode

106 OLED layer

105 cathode

102 Glass cover

108 nitrogen gas

109 Water catcher

BEST MODE FOR CARRYING OUT THE INVENTION

[0108] Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

First, a best mode for carrying out the invention (A) described in claims 1 to 12 will be described below.

[0110] The invention (A) described in claims 1 to 12 is the above-mentioned defect when an organic EL device is obtained by a bonding method, that is, the bonded bonding surface is not necessarily adhered at the molecular level. As a result, the present invention provides an organic EL device that solves the problems such as the carrier movement not smoothly moving to the line and the bonded surface peeling off and immediately becoming unable to function as a light emitting device. In the present invention, bonding is synonymous with bonding. [0111] In the invention (A) according to claims 1 to 12, on one electrode (for example, cathode) of an organic EL device having a plurality of organic layers between an anode and a cathode. At least one first organic layer containing an organic compound having a reactive substituent is formed on the other electrode (eg, anode), and at least one second organic layer is formed on the first organic layer. The organic EL element is formed by laminating the layer and the second organic layer facing each other. The second organic layer may also contain an organic compound having a reactive substituent. When the organic EL element is formed by bonding the first organic layer and the second organic layer to face each other, the first organic layer and the second organic layer are made to face each other and contact each other. In order to form a bond between organic compounds having reactive substituents, and preferably to form a bond at the bonded adhesive layer interface, energy such as electron beam, ultraviolet irradiation, or heat may be applied. Alternatively, a bond may be formed by using, as a polymerization initiator, a cation radical or a cation radical generated in the light emitting layer when the light emitting element is energized.

[0112] Further, in the invention (A) according to claims 1 to 12, the organic compounds having reactive substituents that form a bond may be different from each other even if they are the same compound. It may be. The bond to be formed is preferably a covalent bond.

[0113] Here, the reactive substituent in the organic compound having a reactive substituent represents a substituent capable of causing an organic chemical reaction that forms a new bond between two or more substituents. Examples of the organic compound having a group include polymerizable monomers. Specific examples of reactive substituents include the substituents shown in Chemical Formula 1 and trichlorosilane, and groups capable of cycloaddition reactions such as photo2 + 2 reaction and Diels-Alder reaction. It is not limited to.

[0114] Also, the first organic layer and the second organic layer to be bonded may have the same or different functions.

[0115] As a member on the cathode side, for example, a cathode made of aluminum or the like is formed on a support (for example, a glass substrate) by vacuum deposition or the like, and, for example, an electron transport material layer is applied thereon or It is formed by vapor deposition. On the other hand, as a member on the anode side, for example, a hole transport layer and a light emitting layer are sequentially formed on a glass substrate on which a thin film such as ITO is formed as an anode by coating or vapor deposition. These two members on the cathode side and anode side An organic EL device can be obtained by bonding and bonding the mechanical layers (the electron transport layer and the light emitting layer).

[0116] The laminated surface to be bonded may be any layer of each functional layer of the organic EL element, but the laminated surfaces to be bonded are preferably organic layers. Bonding between organic layers is preferred because it is easy to bond and adhere, and is difficult to peel off after bonding, and since it is easy to adjust the surface roughness in the case of an organic layer.

[0117] It is preferable to react at or below the glass transition temperature (Tg: ° C) of the organic layer to be bonded. When the organic layer to be bonded is different, the glass transition temperature is low. U, preferably conducted below the Tg of the organic layer.

[0118] The glass transition temperature (Tg: ° C) was measured by sealing a layer sample of about 10 mg in an aluminum pan for measurement and attaching it to a differential calorimeter (eg, DuPont V4. OB2000 type DSC). Measure by raising the temperature from 25 ° C to 20 ° CZ.

[0119] In addition, emission unevenness due to non-uniformity in the plane of carrier movement due to defects in the bonded laminated surface is a phosphorescence emission method that has a light emitting region inside the emission layer rather than a fluorescence emission method that emits light at the organic layer interface. Is relatively less likely to appear, especially when the relative thickness ratio of the entire organic layer of the light-emitting layer is increased, or when the film thickness of the light-emitting layer is increased, or when the light-emitting layers are joined to each other. Since the phosphorescent light emitting method containing a phosphorescent light emitting compound can reduce unevenness of light emission to the extent that it does not cause any inconvenience, the manufacturing method by bonding of the present invention is suitable for the phosphorescent light emitting method.

[0120] In the invention (A) according to claims 1 to 12, each organic layer of the organic EL element is formed on one electrode and on the other electrode, for example, a cathode side member, Then, it is laminated and formed as a positive electrode member, but there is no particular limitation on the method of forming the organic thin film for forming each functional layer of these organic EL elements.

[0121] Almost all of the organic EL device formations currently being promoted are so-called vapor deposition methods in which a low molecular material is vapor-deposited, but these vapor deposition methods are also used relatively frequently in polymer materials. The method of producing the organic layer by a coating (wet) process such as spin coating, ink jet, printing, spraying, etc. may be misaligned.

[0122] At the same time, it can be manufactured under atmospheric pressure and at a low cost. In addition, the necessary materials (polymeric material and Z or low molecular weight material) are prepared in a solution and applied in a thin film, so that multiple organic materials can be mixed precisely (for example, the preparation of a dopant for a light-emitting host material is possible). In addition, there is a feature that light emission unevenness is difficult to occur even when the device has a large area, and a wet method is preferable. In addition, if a film substrate on which a counter electrode is formed in advance is prepared, continuous production by a roll-to-roll method is possible and organic layers can be easily bonded. In this case, it is preferable that at least one of the organic layers is formed by a wet method. Furthermore, it is more preferable that at least one of the first organic layer and the second organic layer is formed by a wet method. In the present invention, the organic layer is preferably at least three layers.

[0123] When forming an electrode made of metal or metal oxide in the process of manufacturing an organic EL element, it is desirable to apply high energy in order to obtain a film with good performance. In this method, the electrode layer is formed at the end, so damage to the organic thin film is a concern, and in reality, it is only possible to form the film by vacuum evaporation or sputtering under mild conditions. In the bonding method, after this is performed in advance, the layers of each organic layer are stacked, so there is no damage to the organic layer that has already been formed, compared to the sequential method in which the sequential organic layer is formed. (The light emission characteristics and lifetime of the organic EL element are greatly deteriorated), and an electrode film with good performance can be formed.

[0124] The pressurizing and heating means for adhering and bonding the cathode side member and the anode side member are not particularly limited as long as they can be pressurized or pressurized without being mixed with bubbles. Can be used. For example, in between the cathode-side member and the anode-side member, under reduced pressure, ^{e.g., 0. 1 X 10- 2 ~1} . 0 X 10- & under vacuum environment to the extent a pressing force 0. IMPa a pressure of about Crimp and adhere.

[0125] In addition, a press machine including a pressing unit and a gantry can be used as a joining jig, and a method in which the cathode side member and the anode side member are sandwiched and pressed between the pressing unit and the gantry can be used. In this case, the pressure is usually 0.5 to: LOONZcm ² , preferably 5 to 50 NZcm, and the pressurization time is usually about 0.1 to 300 seconds.

[0126] When using a pressure roll such as a laminator, the pressure is usually 1 to 200 N / cm ² , preferably 5 to 100 NZcm ² , and the conveyance speed is usually 0.1 to 200 mmZ seconds, preferably 0.5 ~: If it is about LOOmmZ seconds, it can be adhered without bubbles and the like.

[0127] In addition, when applying a temperature that can be heated together with pressure in any case during bonding

The heating temperature is usually in the range of 60 to 200 ° C, preferably 100 to 150 ° C.

[0128] In addition, actinic rays or the like can be used at the time of bonding. Examples of actinic rays include electron beams and ultraviolet rays, and examples of ultraviolet light sources include ultraviolet lamps (for example, low pressure, medium pressure, high pressure mercury lamps having an operating pressure of 0.5 kPa to lMPa), xenon lamps, tungsten A lamp, a halogen lamp or the like is used, and ultraviolet rays having an intensity of about 5000 to 8000 μWZcm ² are preferably irradiated. The amount of energy required for curing ranges from 0.02 to ²⁰ kjZcm ² .

[0129] It is preferable to preheat the substrate of the cathode side member and the substrate of Z or the anode side member because the productivity is improved.

[0130] <Covalent bond formation at bonding interface>

Further, in a preferred embodiment of the present invention, the bonded interface is bonded at the molecular level, and thus it is found that forming a covalent bond between the interfaces after bonding is a very effective means. It was.

[0131] A technique for covalently connecting the layers of organic EL is disclosed in Patent Document 5, but in the present invention, this technique is applied as means for interfacial adhesion in the bonding method.

That is, an organic compound having a reactive substituent is contained in at least one of the laminated surfaces to be bonded. Such substituents cause chemical changes due to active species generated inside the device and heat at the time of bonding, and form a covalent bond to improve adhesion at the molecular level between the bonded organic layers.

[0133] In addition, when an organic compound having these reactive substituents is contained, a reaction (chemical change) between the compounds proceeds due to driving Joule heat (that is, when current flows in the element). As a result, we have discovered that even if the adhesion at the molecular level is improved and the light emission performance and the light emission lifetime are improved, it is a new phenomenon.

[0134] In the so-called "phosphorescent device" in which the light emitting layer of the organic EL device normally utilizes phosphorescent light emission, a phosphorescent light emitting compound is mixed with the light emitting host in a mass ratio of about 1 to 20%. Is considered to be effective in terms of luminous efficiency, and phosphorescent light emission is used in the present invention. In such a case, it is preferable to use a luminescent host in combination. For such a chemical change, a chemical reaction between the luminescent host material and a phosphorescent luminescent compound having reactivity thereto may be used.

[0135] For example, when the light emitting layers are bonded to each other or when the light emitting layer is composed of a light emitting compound and a light emitting host, the chemical change of the phosphorescent light emitting compound is caused by (condensation with the light emitting host). When a chemical reaction with a luminescent host that uses a reaction (e.g., polymerization) is used, the phosphorescent luminescent compound emits a reactive substituent that can react with a specific reactive group. It is preferably introduced into the host.

[0136] For example, when the phosphorescent light-emitting compound is substituted with a hydroxyl group (—OH), select a material with an isocyanate group (—NCO) or isothiocyanate group (—NCS) introduced as the light-emitting host. If the vinyl group is substituted on the phosphorescent light emitting compound, a light emitting host having a radically polymerizable bur group introduced thereto is selected.

[0137] In the present invention, most preferably, in an embodiment, at least one material substituted with a vinyl group is present in both the phosphorescent light-emitting compound and the light-emitting host in the same layer, and the light-emitting element is formed. By energization, a chain-like and Z- or network-like polymer is formed by using a cation radical or a cationic radical generated in the light emitting layer as a polymerization initiator.

[0138] Even when the surface layer of the cathode side member is an electron transport layer and the surface layer of the anode side member is a light emitting layer, for example, an electron transport layer having a reactive substituent such as a vinyl group, and -Polymerization is performed between the layers by bonding the members each having a light-emitting host or a light-emitting layer containing a dopant material having a reactive substituent such as a ruthel group, and adhesion between the bonded organic layers is improved. improves. Similarly, when the outermost layer of the cathode side substrate is a light emitting layer and the outermost layer of the anode side substrate is a hole transport layer, a hole transport layer containing a hole transport material having a reactive group may be used. Oh ,.

Accordingly, it is preferable that at least one of the two laminated surfaces to be bonded contains an organic compound having a reactive substituent, and at least one of the two laminated surfaces to be bonded has a reactive substituent. If it contains an organic compound and, on the other hand, a material having a group that reacts with it, it can strengthen the adhesion by reacting with each other, eliminate peeling of the joint surface, and facilitate carrier movement. it can. [0140] In addition, it is preferable to have an organic compound having a reactive substituent on both of the laminated surfaces to be bonded, because the adhesion of the laminated surfaces can be further enhanced.

[0141] Further, in a preferred embodiment of the invention (A) according to claims 1 to 12, a phosphorescent light emitting compound or a light emitting host, a hole transport material, an electron transport material and the like are bonded. When each organic layer contains at least one material substituted with a carbon-carbon double bond-containing substituent such as a vinyl group, a vinyl ether group, or the like, the light emitting element is generated in the light emitting layer by energization. Can be used as a polymerization initiator to form chain and Z or network polymers, and the light emitting device is more robust than the initial state due to polymerization within the layer. Thus, it is possible to realize a light emitting element that gradually increases in durability while being energized (driven). Of course, a normal polymerization initiator can be used together with an organic compound having a reactive substituent.

[0142] Examples of the reactive species generated inside the device and the reactive substituents that cause a chemical change due to Joule heat during driving include the following groups including the above-described groups.

[0143] [Chemical 5]

OH — SH

[0144] In the above reactive substituent, A is a linking group having at least one selected from the following general formula (a), a linking group consisting of -O and -S force, or a plurality of the linking groups. It represents a divalent linking group represented by a combination, and B represents a hydrogen atom or a substituent.

[0145] [Chemical 6] General formula (a>

R

R '

[0146] In the formula, R and R ^ each represents a hydrogen atom or a substituent, and n represents an integer of 1 or more.

[0147] The substituents represented by R and R 'each include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tbutyl group, a pentyl group, a hexyl group, an octyl group, Decyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, bur group, aryl group, 1 propylene group). -L group, 2 butur group, 1,3 butagel group, 2 pentyl group, isopropenyl group, etc.), alkyl group (for example, etulyl group, pronorgyl group, etc.), aromatic hydrocarbon group (Also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azuleyl group, acenaphthenyl group, fluorene group, etc. -Lu, Hue Enthryl group, indur group, pyrenyl group, bif ヱ -ryl group, etc.), aromatic heterocyclic group (for example, furyl group, chael group, pyridyl group, pyridazyl group, pyrimidyl group, pyradyl group, Triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (One of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom. ), Heterocyclic groups (eg pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl etc.), alkoxy groups (eg methoxy, ethoxy, propyloxy, pentyloxy, Hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, Clopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) Group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, Methyloxycarbonyl group, ethyloxycarbo- Group, butyoxycarbonyl group, octyloxycarbol group, dodecyloxy group, etc.), aryloxyl group (for example, phenylcarboxyl group, naphthyloxy group) Carboyl group, etc.), acyl group (for example, acetyl group, ethyl carbonyl group, propyl carbo yl group, pentyl carbo ol group, cyclohexyl carbonyl group)

, Octyl carbo yl group, 2-ethyl hexyl carbo yl group, dodecyl carbo ol group, phenol carbo ol group, naphthyl carbo ol group, pyridyl carbo ol group, etc.), acyl oxy group (for example, acetyl oxy group, Ethylcarboxoxy group, butylcarboxoxy group, octylcarboxoxy group, dodecylcarboxoxy group, phenylcarbonyloxy group, etc.), strong rubamoyl group (for example, aminocarbonyl group, methylaminocarboxyl group, dimethylamino group) Minocarbol group, propylaminocarbol group, pentylaminocarbol group, cyclohexylaminocarbol group, octylaminocarbol group, 2-ethylhexylaminocarbol group , Dodecylaminocarbol group, phenylaminocarbol group, naphthylaminocarbol group, 2-pyridylaminocarbol Group), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenol group) Etc.), cyano group, hydroxy group, mercapto group and the like.

[0148] n is a force that represents an integer greater than or equal to 1. Its upper limit is 5.

[0149] Among the reactive substituents described above, a substituent containing a carbon-carbon double bond, more preferably a vinyl group, a allyl group, or a vinyl ether group. Furthermore, the organic compound having a reactive substituent preferably has two or more reactive substituents.

[0150] When a cross-linking reaction with a reactive substituent is used for adhesion at the time of bonding, heat, active light, or the like can be used. In the case of heating, in the range of 60 to 200 ° C for 1 second to 5 hours, if it is actinic light, for example, the above-mentioned ultraviolet light source can also be used, and the intensity is about 5000-8000 μW / cm ² If irradiated with ultraviolet rays, As the amount of energy required for the reaction, a range of 0.02 to 20 kj / cm ² is used.

[0151] Although similar prior art has been considered as an example so far, there is the following as a publicly known document that high molecular weight is generated after film formation as a technology, and its crosslinking reaction is as follows. Can be used in the present invention. [0152] For example, JP-A-5-271166 describes a bifunctional triphenylamine derivative having two bur groups in the molecule. It is disclosed that a dimensionally cross-linked polymer is formed. Japanese Patent Application Laid-Open No. 2001-297882 discloses a technique of adding a material having two or more bur groups to a plurality of layers. In this case, the polymerization reaction is performed before the organic layer is laminated on the cathode. At the time of film formation, irradiation is performed with ultraviolet rays or heat. In JP-A-2003-73666, AIBN, which is a radical generator, is added to a mixture of comonomer having a vinyl group in the same manner as a material having a vinyl group at the end of a phosphorescent light-emitting compound to form a film. A production method for allowing the polymerization reaction to proceed is disclosed. Further, JP-A-2003-86371 describes a production method in which a Diels-Alder reaction is caused between two molecules in the same layer to crosslink.

[0153] Confirmation of the progress of the organic interface reaction is, for example, when the organic compound having a reactive substituent is a monomer having a beryl group substitution, and measuring the distribution of double bonds in the bull group using the following analytical method: It is possible to know by doing.

[0154] First, it is necessary to secure an analysis area that can be analyzed by a general microregion analysis method. For that purpose, it is an effective means to cut the thin film obliquely. The area is enlarged by 1 / cos θ (Θ is the value obtained by subtracting the angle of the cutting surface from the surface normal force) compared to the case where the cross section is created perpendicular to the surface by cutting diagonally.

[0155] To give an example, a method of tilting a glass knife using an ultramicrotome commonly used in the industry, or a surface cut obliquely using a Dybla-Wintes Cycus NN04 model You can mention how to create.

[0156] The double bond is measured after the analysis area is secured, but there are several methods for measuring the double bond. For example, microscopic infrared spectroscopic analysis, Raman spectroscopic analysis, or a double bond is labeled with a labeling reagent that reacts specifically with a double bond and has a specific element, and an electron beam probe microanalyzer, X Preferred examples include a method of measuring the distribution of the labeling element with a line photoelectron spectrometer, an auger electron spectrometer, a time-of-flight secondary ion mass spectrometer, and the like.

[0157] Next, the best mode for carrying out the invention (B) described in claims 13 to 22 Explain the state.

[0158] The invention according to Claims 13 to 22 (B) In the method of manufacturing an organic electroluminescent device according to any one of Claims 13 to 19, any one of Claims 13 to 19 Therefore, the present invention provides a manufacturing method for manufacturing an organic electroluminescent device having a high luminous efficiency and a long lifetime at a low cost, and the organic electroluminescent device manufactured by the manufacturing method. An element, a lighting device, and a display device could be provided.

Next, details of each component according to the invention (B) described in claims 13 to 22 will be sequentially described.

[0160] <Method for producing organic electoluminescence device>

The invention (B) described in claims 13 to 22 will be described with respect to the manufacturing method of the organic electroluminescence device related to this invention.

[0161] The invention (B) according to claims 13 to 22 of the invention (B) is a method for producing an organic electroluminescent device with an organic electroluminescence element on a support substrate as described in claim 13. In the method for producing an organic electoluminescence device having at least an anode and a cathode and an organic layer including at least one light emitting layer between the anode and the cathode, the film thickness T (EM) (nm) of the light emitting layer ) Satisfies the following relational expression (1), at least one of the light emitting layers has a phosphorescent light emitting material, and at least one layer of the organic layer is formed by bonding layers A and B This is a feature.

[0162] <Light emitting layer thickness T (EM)>

The film thickness T (EM) of the light emitting layer of the invention (B) according to the invention described in claims 13 to 22 represents the following relational expression (1).

[0163] In order to obtain the effects described in the invention (B) according to claims 13 to 22, the film thickness T of at least one light emitting layer of the organic EL element of the present invention is determined. (EM) must satisfy the relational expression (1). Furthermore, the organic EL device of the present invention has a reduced emission starting voltage, an improved power saving effect, a reduced non-emission point of the emission layer, and uneven emission. From the viewpoint of obtaining a sufficient effect of reducing the occurrence of the above, it is preferable to satisfy the relational expression represented by the following relational expression (2). [0164] Relational expression (1)

40nm <T (EM) ≤ lOOnm

Relational expression (2)

45nm <T (EM) ≤ lOOnm

It is preferable that the organic layer of the invention (B) according to the invention described in claims 13 to 22 has three or more organic layers, and at least one layer of the organic layer is preferable. Is formed by bonding with the layer A and the layer B, and it is preferable that the layer A and the layer B each contain a compound having the same structure as the main component.

[0165] In addition, it is preferable that any of the forces of the layer A and the layer B includes a phosphorescent material to improve the device characteristics of the organic EL device of the present invention. The phosphorescent light emitting material will be described in detail in the constituent layers of the organic EL element described later.

[0166] << Structure of Organic Layer and Film Thickness of Total Light-Emitting Layer T (EM) >>

In particular, when layer A is a light-emitting film, layer B is a light-emitting film, and at least one light-emitting layer is formed by laminating the layer A and the layer B, for example, ITO described later When layer B is provided on a cathode side substrate (also referred to as cathode side member) such as layers A and A1 on the anode side substrate (also referred to as anode side member) (layer A is the cathode side substrate) Layer B, which may be provided on top, may be provided on the anode side substrate ヽ),

The thickness of layer A on the anode side substrate and the thickness of layer B on the cathode side substrate both exceed 20 nm, and the total light emitting layer thickness T (EM) force Onm <T (EM) ≤ lOOnm It is preferable to satisfy the relational expression.

[0167] From the viewpoint of light emission unevenness, when the film thickness of the organic layer (also referred to as an organic compound layer) is T (org) and the film thickness of the total light emission layer is T (EM), the light emission unevenness is suppressed. From the point of view

It is preferable that the relational expression of 0.3≤T (EM) / T (org) ≤0.8 is satisfied.

[0168] «Formation of organic EL element component layers by bonding method (simply bonding! ヽぅ)»

The process for forming the constituent layers of the organic EL element by bonding according to the invention (B) described in claims 13 to 22 will be described.

[0169] For the bonding, all the layers necessary for the configuration of the organic EL element are formed in advance (for example, an anode side substrate, Therefore, the film formation of the transparent electrode (the anode side substrate such as ITO) and the counter electrode (the cathode side substrate such as A1) is performed first.

[0170] When a metal or metal oxide film is formed, it is desirable to apply high energy when depositing or after film formation in order to obtain a film with good performance. It can also be considered as a means of achieving this.

[0171] In other words, if the bonding surface when bonding is made of organic layers, the transparent electrode and the counter electrode can be formed in advance by a method most suitable in terms of performance and productivity, respectively.

[0172] If an organic layer is laminated and bonded as appropriate, it is an innovative method that is good in terms of performance and manufacturing process as long as the defect on the joint surface is improved.

[0173] Compatibility of phosphorescence method

As a problem of the bonding method, the problem on the joint surface was mentioned earlier. As a result of diligent investigation of this problem, for example, when organic layers are bonded to each other, the carrier movement at the bonding interface is not uniform over the entire surface, and it is easy to create a portion where carriers can flow locally and a portion where flow is difficult. I've come to power.

[0174] In particular, it has been found that the fluorescence method of emitting light at the interface of the organic layer has a remarkable behavior and is likely to cause uneven light emission.

[0175] On the other hand, the phosphorescence method, unlike the fluorescence method, has a light emitting region inside the light emitting layer, and this phenomenon is relatively difficult to occur. When increasing the thickness ratio, increasing the thickness of the light-emitting layer, or using two light-emitting layers that join the light-emitting layers together, light emission unevenness can be suppressed to the extent that there is no weakness even under microscopic observation. I found that it was possible.

[0176] This is a technology that effectively utilizes the phenomenon of slow carrier movement at the bonding interface, which is the biggest difficulty of the bonding method, and is an unprecedented breakthrough discovery. It can be said that.

[0177] The constituent layer of the organic EL element using the bonding method (particularly, the formation of the organic layer (organic compound layer)) is a very effective means for solving such problems.

[0178] As a result of our investigation, we have determined that the organic EL element has high luminous efficiency and long life. At the same time as the above-mentioned “use of phosphorescence emission, multilayering of elements (having a plurality of organic layers for separating functions)”, the thickness of the light emitting layer of the element was found to be an important factor. The

[0179] In particular, when the relative film thickness ratio of the entire organic layer of the light-emitting layer is increased, or when the film thickness of the light-emitting layer is increased, the light-emitting layers are joined together, that is, two light-emitting layers. When using a single light-emitting layer, it was found that it was possible to produce an organic EL device with high emission efficiency by suppressing light emission unevenness to the extent that there was no weakness even under microscopic observation.

[0180] <Method for forming organic layer other than bonding>

The method of manufacturing an organic EL element according to the invention (B) according to claims 13 to 22 includes a layer A and a cathode substrate provided with at least one organic layer as a constituent layer on the anode substrate side. It is characterized in that an organic EL element is manufactured through a process of bonding with layer B provided on the side.

[0181] The constituent layer of the organic EL element will be described in detail in the constituent layer of the organic EL element described later. For example, as a constituent example of the organic EL element, an anode Z hole injection layer Z hole transport Layer Z light-emitting layer Z electron transport layer Z electron injection layer An organic EL device consisting of a Z cathode will be described as an example. The layer formed by bonding layers A and B is a hole injection layer, a positive layer Any of a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer may be used.

[0182] In addition to the organic layer formed by bonding, conventionally known methods such as coating methods, vapor deposition, and sputtering can be used as appropriate. Of course, a bonding method can be used in combination as appropriate. is there.

[0183] As a method for forming each layer of the organic layer other than the bonding method, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) as described above, but a homogeneous film can be obtained. In the present invention, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable from the viewpoint that pinholes are not easily generated.

[0184] Examples of the liquid medium for dissolving or dispersing the organic EL material used for forming the organic layer include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, and dichlorobenzene. Halogenated hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, and other aromatic hydrocarbons, cyclohexane, decalin, Aliphatic hydrocarbons decane, _D MF, it is possible to use an organic solvent such as DMSO. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

[0185] Next, the best mode for carrying out the invention (C) described in claims 23 to 31 will be described.

[0186] The invention (C) according to claims 23 to 31 is the above-mentioned disadvantage when an organic EL element is obtained by a bonding method, that is, the bonded surface is not necessarily at the molecular level. This provides a method for manufacturing an organic EL device that solves the problems such as non-adherence and as a result, carrier movement does not move smoothly, and the bonding surface peels off and immediately does not function as a light emitting device. .

[0187] In the invention (C) according to claims 23 to 31, a member provided with an organic layer on a first electrode substrate (for example, a cathode) and a second electrode substrate (for example, an anode) ) Each member having an organic layer formed thereon is prepared, the organic layers are opposed to each other, and the members are bonded together to form an organic EL element.

[0188] As a member on the cathode side, for example, a cathode made of aluminum or the like is formed on a support (for example, a glass substrate) by vacuum deposition or the like, and an electron transport material layer is applied thereon or by evaporation or the like. Form.

[0189] On the other hand, as a member on the anode side, for example, a hole transport layer and a light emitting layer are sequentially formed by coating or vapor deposition on a glass substrate formed with a thin film such as ITO as an anode.

[0190] An organic EL element is obtained by adhering these two members on the cathode side and the anode side to each other with the organic layers (the electron transport layer and the light emitting layer), and in the present invention. It is characterized in that the surface roughness of the two organic layers to be bonded is kept in a predetermined relationship.

[0191] This solves the problems such as the above-mentioned bonding surface peels off and does not function as a light emitting element immediately, and the carrier movement is not smooth due to weak adhesion at the molecular level at the bonded bonding surface. The present invention provides a method for manufacturing an organic EL device having a high emission efficiency and an improved emission lifetime.

[0192] The organic EL device according to the invention (C) according to claims 23 to 31 includes at least a first electrode substrate having at least n layers (n≥0) organic layers, m layer (m + n≥ 1) In an organic EL device produced by bonding a second electrode substrate having an organic layer facing each other, the organic layer contains at least one light-emitting light emitting compound of the organic layer, and the surface roughness of the two facing stacked layers is (Ra) is in the range of 0.05 to: LOnm, respectively, and the ratio of the surface roughness of the two laminated surfaces is within the range of 0.5 to 2.0.

[0193] The laminated surface to be bonded may be any layer of each functional layer of the organic EL element, but the laminated surfaces to be bonded are preferably organic layers. Bonding of the organic layer is preferred because it is easy to bond and adhere, and is difficult to peel off after bonding, and in the case of an organic layer, it is easy to adjust the surface roughness.

[0194] In addition, light emission irregularity due to non-uniformity in the plane of carrier movement due to defects in the bonded laminated surface is a phosphorescent light emitting method with a light emitting region inside the light emitting layer rather than a fluorescent light emitting method that emits light at the organic layer interface. It is relatively less likely to appear, especially when the relative film thickness ratio of the entire organic layer of the light emitting layer is increased or when the thickness of the light emitting layer is increased, or when the light emitting layers are joined together. For example, when two layers are used, a phosphorescent light-emitting method that contains a phosphorescent light-emitting compound is sufficient to prevent uneven light emission.

Therefore, the manufacturing method by bonding according to the present invention is suitable for the phosphorescence emission method.

[0195] When the organic layer is formed by a coating method such as spin coating, the surface roughness of the organic layer to be bonded is adjusted by adjusting the viscosity of the organic material solution, the coating temperature, etc. However, a method for adjusting the surface roughness that does not depend on the film formation method involves so-called typing, in which the organic layer is pressed (heated) with a metal roll having a specific surface roughness. It is possible to do this.

[0196] As a method of molding, a metal roll having a predetermined surface roughness (Ra) is applied to a temperature of 50 to 150 ° C, a linear pressure of 150 to 1,500 NZcm, and a linear velocity of about 0.1 to 30 mZ seconds. An embodiment in which a pressure-bonding process is performed is mentioned. If the linear pressure is 150 NZcm or more, a uniform and faithful response can be obtained. In particular, 400 NZcm or more is preferable. Also, if it is less than 1500NZcm, the organic layer itself will not break (crack or crack).

Further, when the temperature is 50 to 150 ° C., there is no modification of the surface of the organic film and no significant deformation of the film.

[0198] In the invention (C) according to claims 23 to 31, the surfaces of the two organic layers to be bonded to each other have a centerline surface roughness (Ra) of 0. 05 ~: LOnm And the ratio of the surface roughness of the two laminated surfaces is adjusted to be within the range of 0.5 to 2.0.

[0199] The centerline average surface roughness Ra (nm) of the surface in the invention (C) according to claims 23 to 31 is a value obtained according to JIS B601 (1994). Yes, it represents a minute uneven state in a minute area. In the present invention, a value obtained by an atomic force microscope (AFM) is used.

[0200] Atomic Force Microscopy (AFM) is a piezo scanner that uses a SPI3800N probe station and SPA400 multifunctional unit manufactured by Seiko Instruments Inc. Set on the upper horizontal sample stage, approach the cantilever to the sample surface, reach the region where the atomic force works, scan in the XY direction, and the unevenness of the sample at that time of the piezo in the Z direction Capture by displacement. Use a piezo scanner that can scan XY20 m and Z2 m. The cantilever is a silicon cantilever SI-DF20 manufactured by Seiko Instruments Inc., which has a resonance frequency of 120 to 150 kHz and a panel constant of 12 to 20 NZm, and is measured in DFM mode (Dynamic Force Mode). Measurement area Measure 2m square with 1 (or2) field of view and scanning frequency 1Hz.

[0201] The centerline average roughness (Ra) is determined by extracting the portion of the measured length L in the direction of the centerline from the obtained roughness curve. When the direction of (perpendicular to the X axis) is the Y axis and the roughness curve is Y = F (X),

[0202] [Equation 1]

Ra J ^L _o IF (X) I dX

It is defined as the value given in [0203].

[0204] In this way, the surface to be bonded is a smooth surface with minute irregularities, and the surface roughness between the opposing organic layers is not so large that the adhesion between the layers is improved. In addition, the bonded joint surface is difficult to peel off.

[0205] In the invention (C) according to claims 23 to 31, each organic layer of the organic EL element is formed on the first electrode substrate and on the second electrode substrate, respectively. , Cathode side The material and the member for the anode are laminated and formed, but there is no particular limitation on the method for forming the organic thin film for forming each functional layer of these organic EL elements.

[0206] Most of the organic EL devices currently being promoted are V-type vapor deposition methods in which a low molecular material is vapor-deposited to form a film. A method of manufacturing a relatively frequently used organic compound layer by a coating (wet) process such as spin coating, ink jet, printing, spraying, etc. may be displaced! /.

[0207] While being able to manufacture under atmospheric pressure, low cost is possible, and at the same time, the necessary materials (polymer material and Z or low molecular material) are prepared into a solution to form a thin film. Because it is coated, it is possible to precisely mix a plurality of organic materials (for example, to adjust dopants to the light-emitting host material, etc.), and to prevent uneven light emission even if the device has a large area. And a wet process is preferred. In addition, if a film substrate with a counter electrode formed in advance is prepared, the wet process is preferred because it can be continuously produced in a roll-to-roll system and the organic layer can be easily bonded.

[0208] When forming an electrode made of metal or metal oxide in the process of manufacturing an organic EL element, force is required to apply high energy in order to make a film with good performance. In the method, since the electrode layer is formed last, there is a concern about the damage of the organic thin film, and it is practically the situation that the film can only be formed by vacuum evaporation or sputtering under mild conditions. In the bonding method, since this is performed in advance, each organic layer is laminated, so that the organic layer that has already been formed is not damaged as compared with the sequential method in which the sequential organic layer is formed. (The emission characteristics and emission lifetime of the organic EL element are greatly deteriorated.) It is also preferable because a high performance electrode film can be formed.

[0209] In the invention (C) according to claims 23 to 31, the organic layers formed on the respective members on the cathode side and the anode side have the above-mentioned surface roughness. After being prepared, each organic layer is faced and bonded to form an organic EL element.

[0210] The pressurizing and heating means for closely adhering and bonding the cathode side member and the anode side member are not particularly limited as long as they can be pressurized or pressurized without being mixed with bubbles. It can be used. [0211] For example, in between the cathode-side member and the anode-side member, under reduced pressure, for example, 0. 1 X 10 -1. 0 X 10- & degree of pressure of about pressing force 0. IMPa in a reduced pressure environment Crimp and stick with

[0212] Further, as a joining jig, a press machine including a pressing unit and a gantry can be used, and a method in which the cathode side member and the anode side member are sandwiched between the pressing unit and the gantry can be used. . In this case, the pressure is usually 0.5 to: LOONZcm ² , preferably 5 to 50 NZcm, and the pressurization time is usually about 0.1 to 300 seconds.

[0213] When using a pressure roll such as a laminator, the pressure is usually 1 to 200 N / cm ² , preferably 5 to 100 NZcm ² , and the conveyance speed is usually 0.1 to 200 mmZ seconds, preferably 0.5. ~: If it is about LOOmmZ seconds, it is possible to adhere without bubble mixing.

[0214] Also, in any case, when applying a temperature that can be heated together with pressure in any case, the heating temperature is usually in the range of 60 to 200 ° C, preferably 100 to 150 ° C. .

[0215] In addition, actinic rays or the like can be used at the time of bonding. Examples of actinic rays include electron beams and ultraviolet rays, and examples of ultraviolet light sources include ultraviolet lamps (for example, low pressure, medium pressure, and high pressure mercury lamps having an operating pressure of 0.5 kPa to lMPa), xenon lamps, tungsten lamps, A halogen lamp or the like is used, and ultraviolet rays having an intensity of about 5000 to 8000 μWZcm ² are preferably irradiated. The amount of energy required for curing ranges from 0.02 to ²⁰ kjZcm2.

[0216] It is preferable to preheat the substrate of the cathode side member and the substrate of Z or the anode side member because the productivity is improved.

In the preferred embodiment of the invention (C) described in claims 23 to 31, the bonded interface is bonded at the molecular level so that it is shared between the interfaces after bonding. We found that forming a bond is a very effective means.

[0218] A technique for connecting organic EL layers by covalent bonding is disclosed in Patent Document 5, but in the present invention, this technique is applied as means for interfacial adhesion in the bonding method.

[0219] That is, an organic compound having a reactive substituent is included in both of the laminated surfaces to be bonded. The

Such a substituent improves the adhesion at the molecular level between the bonded organic layers by causing a chemical change due to the active species generated inside the device and the heat at the time of bonding, and forming a covalent bond.

[0220] In addition, when an organic compound having these reactive substituents is contained, a reaction (chemical change) between the compounds proceeds due to driving Joule heat (that is, when an electric current flows in the device). We have discovered even new phenomena when adhesion at the molecular level is improved and luminous performance and lifetime are improved.

[0221] The light emitting layer of an organic EL element usually uses phosphorescent light emission. In so-called "phosphorescent elements", a phosphorescent material (phosphorescent dopant) is used in a mass ratio of 1 to 20 with respect to a light emitting host. It is said that mixing in the order of about% is effective from the viewpoint of luminous efficiency. In the case of using phosphorescent light emission in the present invention, it is preferable to use a luminescent host together. Utilizing a chemical reaction between the light emitting host material and a phosphorescent light emitting material (phosphorescent dopant) having reactivity therewith.

[0222] For example, when the light emitting layers are bonded to each other, or when the light emitting layer is composed of a light dopant and a light emitting host, the chemical change of the phosphorescent light emitting material (phosphorescent dopant) changes with the light emitting host. When using a chemical reaction with a luminescent host that may utilize a reaction (condensation or polymerization, etc.), it emits a reactive substituent that can react with a specific reactive group substituted on the phosphorescent material. Preferred to introduce to the host.

[0223] For example, when a phosphorescent material is substituted with a hydroxyl group (one OH), a material into which an isocyanate group (-NCO) or an isothiocyanate group (-NCS) is introduced is selected as the light-emitting host. Alternatively, when a bur group is substituted in the phosphor luminescent material, a luminescent host in which a vinyl group capable of radical polymerization is introduced is selected.

[0224] In the present invention, in the most preferred embodiment, at least one material having a bur group substituted on both the phosphorescent light emitting material and the light emitting host is present in the same layer to emit light. When the device is energized, chain-like and Z- or net-like polymers are formed by using as a polymerization initiator a key-on radical or a cation radical generated in the light-emitting layer. [0225] Even when the surface layer of the cathode side member is an electron transport layer and the surface layer of the anode side member is a light emitting layer, for example, an electron transport layer having a reactive substituent such as a vinyl group, and -By laminating members each having a light-emitting host or a light-emitting layer containing a dopant material having a reactive substituent such as a ruthel group, polymerization is performed between the layers, and adhesion between the bonded organic layers is improved. improves. Similarly, when the outermost layer of the cathode side substrate is a light emitting layer and the outermost layer of the anode side substrate is a hole transport layer, a hole transport layer containing a hole transport material having a reactive group may be used. Oh ,.

Accordingly, it is preferable that at least one of the two laminated surfaces to be bonded contains an organic compound having a reactive substituent, and at least one of the two laminated surfaces to be bonded has a reactive substituent. If it contains an organic compound and a material having a group that reacts with the other, it can strengthen the adhesion by reacting with each other, eliminate peeling of the joint surface, and facilitate carrier movement. I can do it.

[0227] In addition, it is preferable to have a material having a reactive substituent on both of the laminated surfaces to be bonded because the adhesion of the laminated surface can be further enhanced.

[0228] Further, in a preferred embodiment of the invention (C) according to claims 23 to 31, a phosphorescent compound, a light emitting host, a hole transport material, an electron transport material, etc. By making at least one material substituted with a bulu group present in each organic layer, the light-emitting element is energized to use a cation radical or a cation radical generated in the light emitting layer as a polymerization initiator. Chain and Z or network polymers can be formed, and the polymerization within the layer makes the light-emitting device more robust than the initial state, and while energized (driven), It is also possible to realize a light-emitting element that gradually increases in durability.

[0229] Examples of the reactive species generated inside the device and reactive substituents that cause a chemical change due to Joule heat during driving include the following groups including the above-described groups.

[0230] [Chemical 7] -^ ⁵ ^ ~~ = —NH, —OH — SH

[0231] When a cross-linking reaction using a reactive substituent is used for adhesion at the time of bonding, heat, active light rays, or the like can be used. In the case of heating, it is 1 second to 5 hours in the range of 60 to 200 ° C, and if it is an active light beam, for example, the above-mentioned ultraviolet light source can also be used, and the intensity is about 5000 to 8000 W Zcm ^2. If you irradiate with ultraviolet rays. The amount of energy required for the reaction is in the range of 0.02 to ²⁰ kjZcm2.

[0232] Although there is no example of a similar conventional technique so far, as a close technique, there is the following known literature that increases the molecular weight after film formation, and the crosslinking reaction is as follows. It can be used in the present invention.

[0233] For example, Japanese Patent Application Laid-Open No. 5-271166 describes a bifunctional triphenylamine derivative having two bur groups in the molecule, and the compound is formed into a three-dimensional film by irradiation with ultraviolet rays. It is disclosed that a crosslinked polymer is formed. Also, JP-A-2001-297882 has disclosed a technique for adding a material having two or more vinyl groups to a plurality of layers, and in this case, the polymerization reaction is performed before the cathode is laminated. At the time of layer formation, UV and heat irradiation is used. In JP 2003-73666, AIBN, a radical generator, is added to a mixture of comonomers having a bur group in the same manner as a material having a vinyl group at the end of a phosphorescent dornonto, and a polymerization reaction proceeds during film formation. The manufacturing method to be used is disclosed. Furthermore, JP-A-2003-86371 describes a production method in which a Diels-Alder reaction is caused between two molecules in the same layer to crosslink.

[0234] Next, the invention (D) according to claims 32 to 40 will be described in detail.

[0235] As described above, problems with the bonding method include defects such as bonding strength and uniformity at the bonding surface. As a result of diligent investigation on this problem, for example, organic layers are joined together In this case, the carrier movement at the bonding interface is not uniform over the entire surface, and it is easy to carry the carrier locally, and it is difficult for the part to flow and the part is easily formed.

[0236] In particular, it has been found that the fluorescence method of emitting light at the interface of the organic layer has a remarkable behavior and easily causes uneven light emission.

[0237] On the other hand, the phosphorescence method differs from the fluorescence method in that it has a light emitting region inside the light emitting layer, and this phenomenon is relatively difficult to occur. When increasing the thickness ratio, increasing the thickness of the light-emitting layer, or using two light-emitting layers that join the light-emitting layers together, light emission unevenness can be suppressed to the extent that there is no weakness even under microscopic observation. I found that it was possible.

[0238] This is a technology that makes effective use of the phenomenon of slow carrier movement at the bonding interface, which is the biggest difficulty of the bonding method, and is a groundbreaking discovery that has never been seen before. It can be said that.

[0239] As a means for bringing the bonding interface into close contact at the molecular level, the present inventors have studied various methods.

[0240] Among them, forming a covalent bond between the interfaces after bonding has proved to be a very effective means.

[0241] Japanese Unexamined Patent Application Publication No. 2004-103401 discloses a technique for connecting organic EL layers with a covalent bond. The technical idea of this patent is a technique for forming a covalent bond at the interface of an organic layer during or after film formation in a sequential film formation method, which is a similar technique, but in the present invention, a bonding method. As a means of interfacial adhesion in Japan, it is a new discovery to apply this technology as a role like a fastener, and it is not a technology that can be easily imagined.

[0242] In addition, when a special reactive substituent is present at the interface between two layers to be bonded in order to form a covalent bond, the light emitting element is driven (that is, when current flows in the element). ) We found a new phenomenon when a covalent bond was formed, and as a result, adhesion at the molecular level was obtained, and the luminescence performance and luminescence lifetime were improved.

[0243] Hereinafter, the best mode for carrying out the invention (D) described in claims 32 to 40 will be described. [0244] In the invention (D) according to claims 32 to 40, the above-mentioned disadvantage when the organic EL element is obtained by the bonding method, ie, the bonded bonding surface is not necessarily at the molecular level. This provides a method for manufacturing an organic EL device that solves the problems such as non-adherence and as a result, carrier movement does not move smoothly, and the bonding surface peels off and immediately does not function as a light emitting device. .

[0245] In the invention (D) according to claims 32 to 40, a member in which an organic layer is provided on a first electrode substrate (for example, a cathode) and a second electrode substrate (for example, an anode) ) Each member having an organic layer formed thereon is prepared, the organic layers are opposed to each other, and the members are bonded together to form an organic EL element.

[0246] As a member on the cathode side, for example, a cathode made of aluminum or the like is formed on a support (for example, a glass substrate) by vacuum deposition or the like, and an electron transport material layer is applied thereon or by evaporation or the like. Form.

[0247] On the other hand, as a member on the anode side, for example, a hole transport layer and a light emitting layer are sequentially formed by coating or vapor deposition on a glass substrate formed with a thin film such as ITO as an anode.

[0248] An organic EL device is obtained by adhering these two members on the cathode side and the anode side to each other with the organic layers (the electron transport layer and the light-emitting layer), and in the present invention. It is characterized in that the peel strength of the bonded surface of the two organic layers to be bonded is a specific value lONZm or more.

[0249] This solves the problem that the bonded surface does not function as a light emitting element as soon as it is peeled off, and the carrier movement is not smooth due to weak adhesion at the molecular level on the shell-occupying surface. In addition, the present invention provides a method for manufacturing an organic EL device having high emission efficiency and improved emission lifetime.

[0250] The invention (D) according to claims 32 to 40 includes a first electrode substrate having at least n (n≥0) organic layers, and at least m layers (m≥0). In an organic EL device formed by bonding a second electrode substrate having a plurality of organic layers, at least one of the organic layers (m + n≥l) contains a phosphorescent light-emitting compound and bonded. It is an organic EL device characterized by a surface peel strength of lONZm or higher.

[0251] The bonding surface may be any layer of each functional layer of the organic EL element. An organic layer is preferred. Bonding between organic layers is preferred because it is easy to bond and adhere and is difficult to peel off after bonding.

[0252] In addition, light emission unevenness due to nonuniformity in the plane of carrier movement due to defects in the bonding surface is caused by phosphorescence emission method having a light emitting region inside the light emitting layer rather than fluorescence emission method emitting light at the organic layer interface. It is relatively less likely to appear, especially when the relative film thickness ratio of the entire organic layer of the light emitting layer is increased or when the thickness of the light emitting layer is increased, or when the light emitting layers are joined together. Since the phosphorescent light-emitting method containing a phosphorescent light-emitting compound, such as when forming a layer, can reduce unevenness in light emission, the manufacturing method by bonding of the present invention is suitable for the phosphorescent light-emitting method.

[0253] The peel hardness of the bonded surface can be measured by various measuring methods. For example, the SAICAS trowel or SAICAS NN-04 model manufactured by Winples is used. can do. The SAICAS method uses a sharp cutting edge (single crystal diamond, sintered alloy) to measure the horizontal load required to move at a constant speed in the horizontal direction while keeping the vertical load in a constant direction. This is a technique, and the peel strength of the thin film can be measured.

[0254] In the invention (D) according to claims 32 to 40, each organic layer of the organic EL element is formed on the first electrode substrate and on the second electrode substrate. The organic layer is formed as a member on the cathode side and a member for the anode, respectively. However, the method for forming the organic layer for forming each functional layer of these organic EL elements is not particularly limited.

[0255] Most of the organic EL devices currently being promoted are V-type vapor deposition methods, in which low molecular weight materials are vapor-deposited, but these vapor deposition methods and polymer materials are also used. The method of manufacturing a relatively commonly used organic compound layer by spin coating, ink jet, printing, spray coating and any other application (wet) process may be misaligned! /.

[0256] It can be manufactured under atmospheric pressure and can be manufactured at a low cost, and at the same time, the necessary materials (polymer material and Z or low molecular material) are prepared into a solution to form a thin film. Because it is coated, it is possible to precisely mix a plurality of organic materials (for example, it is difficult to prepare dopants for the light emitting host material, etc.), and light emission unevenness is difficult even if the device has a large area. And a wet process is preferred. In addition, if a film substrate with a counter electrode formed in advance is prepared, roll-to-roll continuous production is possible. Wet process is preferred because of its ability to easily bond organic layers.

[0257] When forming an electrode made of metal or metal oxide in the process of manufacturing an organic EL element, force is required to apply high energy in order to make a film with good performance. In the method, since the electrode layer is formed last, there is a concern about the damage of the organic thin film, and the force that can only be formed by vacuum deposition or sputtering under mild conditions. In the legal method, after the electrode layer is formed in advance, each organic layer is laminated, so that the organic layer that has already been formed is damaged compared to the sequential method in which the organic layer is sequentially formed. This is preferable because the electrode film is not given (the emission characteristics and lifetime of the organic EL element are greatly deteriorated), and a high-performance electrode film can be formed.

[0258] At the time of bonding, actinic rays or the like can also be used. Examples of actinic rays include electron beams and ultraviolet rays, and examples of ultraviolet light sources include ultraviolet lamps (for example, low pressure, medium pressure, and high pressure mercury lamps having an operating pressure of 0.5 kPa to lMPa), xenon lamps, tungsten lamps, A halogen lamp or the like is used, and ultraviolet rays having an intensity of about 5000 to 8000 μWZcm ² are preferably irradiated. The amount of energy required for curing ranges from 0.02 to ²⁰ kjZcm2.

In a preferred embodiment of the invention (D) according to claims 32 to 40, the bonded surfaces are bonded to each other after bonding in order to bring them into close contact at the molecular level. We have found that forming a bond is a very effective means.

[0260] A technique for covalently connecting the layers of organic EL is disclosed in Japanese Patent Application Laid-Open No. 2004-103401. In the present invention, this technique is applied as means for interfacial adhesion in the bonding method.

That is, an organic compound having a reactive substituent is contained in both organic layers on the bonding surface. Such a substituent improves the adhesion at the molecular level between the bonded organic layers by causing a chemical change due to the active species generated inside the element and the heat at the time of bonding, and forming a covalent bond.

[0262] In addition, when an organic compound having these reactive substituents is contained, the driving Joule Since the reaction (chemical change) between the compounds proceeds due to heat (that is, when current flows in the device), as a result, adhesion at the molecular level is improved, and luminous performance and luminous lifetime are improved. I also discovered the phenomenon.

[0263] The light-emitting layer of an organic EL element usually uses phosphorescent light emission. In so-called "phosphorescent elements", a phosphorescent material (phosphorescent dopant) is used in a mass ratio of 1 to 20 with respect to the light-emitting host. It is said that mixing in the order of about% is effective from the viewpoint of luminous efficiency. In the case of using phosphorescent light emission in the present invention, it is preferable to use a luminescent host together. Utilizing a chemical reaction between the luminescent host material and a phosphorescent material (phosphorescent dopant) that is reactive to the luminescent host material.

[0264] For example, when the light emitting layers are bonded to each other, or when the light emitting layer is composed of a light dopant and a light emitting host, the chemical change of the phosphorescent light emitting material (phosphorescent dopant) changes with the light emitting host. When using a chemical reaction with a luminescent host that may utilize a reaction (condensation or polymerization, etc.), it emits a reactive substituent that can react with a specific reactive group substituted on the phosphorescent material. Preferred to introduce to the host.

[0265] For example, when a phosphorescent material is substituted with a hydroxyl group (one OH), a material having an isocyanate group (-NCO) or an isothiocyanate group (-NCS) introduced is selected as the light-emitting host. Alternatively, when a bur group is substituted in the phosphor luminescent material, a luminescent host in which a vinyl group capable of radical polymerization is introduced is selected.

[0266] Further, in the invention (D) according to claims 32 to 40, the most preferable aspect is that in the embodiment, a material in which a vinyl group is substituted on both the phosphorescent light emitting material and the light emitting host is used. At least one type is present in the same layer, and when the light-emitting element is energized, a chain or network polymer is formed by using a photo-on radical or a cation radical generated in the light-emitting layer as a polymerization initiator. It is to let you.

[0267] Even when the surface layer of the cathode side member is an electron transport layer and the surface layer of the anode side member is a light emitting layer, for example, an electron transport layer having a reactive substituent such as a vinyl group, and -By laminating members each having a light-emitting host or a light-emitting layer containing a dopant material having a reactive substituent such as a ruthel group, polymerization is performed between the layers, and adhesion between the bonded organic layers is improved. improves. The outermost layer of the cathode side substrate is a light emitting layer, and the anode side substrate Similarly, when the outermost layer is a hole transport layer, a hole transport layer containing a hole transport material having a reactive group may be used.

Accordingly, it is preferable that at least one of the organic layers to be bonded contains an organic compound having a reactive substituent, and the organic compound having a reactive substituent in at least one of the two organic layers to be bonded If a material having a group that reacts with the other is contained, the adhesion can be strengthened by reacting with each other, peeling of the joint surface can be eliminated, and carrier movement can be facilitated. .

[0269] In addition, it is preferable that both of the organic layers to be bonded have a material having a reactive substituent because the adhesion of the laminated surface can be further enhanced.

[0270] Further, in the preferred embodiment of the invention (D) according to claims 32 to 40, the phosphorescent compound, the light emitting host, the hole transport material, and the electron transport material are used. When at least one material substituted with a bur group is present in each organic layer to be bonded, etc., polymerization of the light-on radical or cation radical generated in the light-emitting layer is started by energizing the light-emitting element. It can be used as an agent to form a chain or network polymer, and polymerization within the layer makes the light-emitting element more robust than the initial state, and is energized (driven) In the meantime, it is also possible to realize a light-emitting element that gradually increases in durability.

[0271] Examples of the reactive species generated inside the device and the reactive substituents that cause a chemical change by Joule heat during driving include the following groups including the above-described groups.

[0272] [Chemical 8]

[0273] When a crosslinking reaction with a reactive substituent is used during or after bonding, heat and activity Light rays can be used. In the case of heating, it is 1 second to 5 hours in the range of 60 to 200 ° C, and if it is an actinic ray, for example, the above ultraviolet light source can also be used, and an ultraviolet ray having an intensity of about 5000 to 8000 WZcm ² Should be irradiated. The amount of energy required for the reaction range from 0. 02~20kj / cm ² is used.

[0274] A similar conventional technique has not been seen so far, but as a close technique, there is the following known literature that increases the molecular weight after film formation, and the crosslinking reaction is as follows. It can be used in the present invention.

[0275] For example, Japanese Patent Application Laid-Open No. 5-271166 describes a bifunctional triphenylamine derivative having two vinyl groups in the molecule. It is disclosed that a crosslinked polymer is formed. Also, JP-A-2001-297882 has disclosed a technique for adding a material having two or more vinyl groups to a plurality of layers, and in this case, the polymerization reaction is performed before the cathode is laminated. At the time of layer formation, UV and heat irradiation is used. In JP 2003-73666, AIBN, a radical generator, is added to a mixture of comonomers having a bur group in the same manner as a material having a vinyl group at the end of a phosphorescent dornonto, and a polymerization reaction proceeds during film formation. The manufacturing method to be used is disclosed. Furthermore, JP-A-2003-86371 describes a production method in which a Diels-Alder reaction is caused between two molecules in the same layer to crosslink.

[0276] <Structure layers of organic EL elements>

The constituent layers of the organic EL device of the present invention will be described. In the present invention, preferred specific examples of the layer structure of the organic EL element are shown below, but the present invention is not limited thereto.

[0277] (i) Anode Z light emitting layer Z electron transport layer Z cathode

(ii) Anode Z hole transport layer Z light emitting layer Z electron transport layer Z cathode

(iii) Anode Z hole transport layer Z light emitting layer Z hole blocking layer Z electron transport layer Z cathode

(iv) Anode Z hole transport layer Z light emitting layer Z hole blocking layer Z electron transport layer Z cathode buffer layer Z cathode

(v) Anode Z anode buffer layer Z hole transport layer Z light emitting layer Z hole blocking layer Z electron transport layer Z cathode buffer layer Z cathode

In the organic EL device of the present invention, the emission maximum wavelength of the blue light emitting layer is 430 to 480 nm. The green light-emitting layer that is preferred is a monochromatic light-emitting layer that has a maximum emission wavelength of 510 to 550 nm, and the red light-emitting layer that has a maximum emission wavelength of 600 to 640 nm. An apparatus is preferred. Further, a white light emitting layer may be formed by laminating at least three of these light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and an illumination device using these is preferable.

[0278] Each layer constituting the organic EL device of the present invention will be described.

[0279] <Light emitting layer>

The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from an electrode, an electron transport layer, or a hole transport layer, and the light emitting portion is within the layer of the light emitting layer. It may be the interface between the light emitting layer and the adjacent layer.

[0280] The total film thickness of the light emitting layer is not particularly limited, but it is possible to prevent the application of a high voltage unnecessary for the film homogeneity and light emission, and to improve the stability of the emission color with respect to the driving current. Therefore, it is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 10 to 20 nm.

[0281] For the production of the light-emitting layer, a light-emitting dopant or a host compound described later is formed by a known thin film method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an inkjet method. Can be formed.

[0282] The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (phosphorescent light emitting compound or fluorescent dopant).

[0283] (Host compound (also called light-emitting host))

The host compound used in the present invention will be described.

[0284] Here, in the present invention, the host compound is a compound having a mass ratio of 20% or more in the light-emitting layer and a phosphorous compound at room temperature (25 ° C). Photoluminescence phosphorescence Defined as a compound with a quantum yield of less than 0.1. Preferably, the phosphorescence quantum yield is less than 0.01. Further, among the compounds contained in the light emitting layer, the mass ratio in the layer is preferably 20% or more.

[0285] As the host compound, a known host compound may be used alone or in combination of two or more kinds. May be used. By using multiple types of host compounds, it is possible to adjust the movement of electric charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of types of light emitting dopants described later, it becomes possible to mix different light emission, and thus any light emission color can be obtained. As the host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.

[0286] Specific examples of host compounds that can be preferably used include, for example, force rubazole derivatives, triarylamine derivatives, aromatic borane derivatives (triarylborane derivatives), nitrogen-containing heterocyclic compounds, thiophene derivatives, Those having a basic skeleton such as a furan derivative, an oligoarylene compound, or a carboline (azacarbazole) derivative or diaza-powered rubazole derivative (here, diaza-powered rubazole derivative is a force of a carboline derivative.

Represents a hydrocarbon ring in which at least one carbon atom is substituted with a nitrogen atom. Etc.) and the compounds described in the following documents.

[0287] JP 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860 No., 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579 Gazette, 2002-10544-5, 2002-343568, 2002-141173, 2002-352 957, 2002-203683, 2002-363227, 2002-2 31453, 2003-3165, 2002-234888, 2003-2 7048, 2002-255934, 2002-260861, 2002-280183, 2002- No. 299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, etc.

[0288] The light-emitting host used in the present invention may be a conventionally known low-molecular compound or a high-molecular compound having a repeating unit, and a low-molecular compound having a polymerizable group such as a vinyl group or an epoxy group. (Vapor deposition polymerizable light-emitting host). [0289] In addition, as described above, in order to enhance the adhesion of the laminated surface after bonding and to improve the durability in the layer, a reactive substituent (hydroxyl group, isocyanate group, isothiocyanate group or A host compound introduced with a beryl group or the like) can be used.

[0290] Typical examples of host compounds into which reactive substituents are introduced include the following.

[0291] [Chemical 9]

[0292] [Chemical 10]

[0293] [Chemical 11]

[0294] [Chemical 12]

[0295] [Chemical 13] 1 -24

The light-emitting host used in the invention (B) described in claims 13 to 22 will be described. The light-emitting host used in the invention (B) according to claims 13 to 22 can be a conventionally known low molecular compound or a polymer compound having a repeating unit. Such a low molecular compound having a polymerizable group (evaporation polymerizable light-emitting host) may be used. [0297] Known host compounds that may be used in combination have a hole transporting ability and an electron transporting ability, prevent emission of longer wavelengths, and have a high Tg (glass transition temperature). Compounds are preferred.

[0298] Specific examples of known host compound compounds include compounds described in the following documents, as described above.

[0299] JP 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860 No., 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579 Gazette, 2002-10544-5, 2002-343568, 2002-141173, 2002-352 957, 2002-203683, 2002-363227, 2002-2 31453, 2003-3165, 2002-234888, 2003-2 7048, 2002-255934, 2002-260861, 2002-280183, 2002- No. 299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, etc.

[0300] Specific examples of compounds preferably used as the host compound in the light emitting layer of the organic EL device according to the invention (B) described in claims 13 to 22 are given below. It is not limited.

[0301] [Chemical 14]

15]

In the invention (B) described in claims 13 to 22, the following reactive host compounds are preferably used for forming the light emitting layer, but the present invention is not limited to these. Not.

[0304] [Chemical 16]

MO -20 MO— 21 MO -22

[0305] [Chemical 17] MO— 30 O -31 MO— 32

[0306] [Chemical 18]

MO—35 MO—36 MO—37 MO—38

[0307] As the reactive host compound, a compound having a reactive group shown below in a conventionally known host compound is also preferably used.

[0308] [Chemical 19] To -NH ₂ -OH — SH

[0309] (Luminescent dopant)

The light-emitting dopant according to the present invention will be described.

[0310] As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent light-emitting compound can be used. From the viewpoint of obtaining an organic EL device with higher luminous efficiency. As a light emitting dopant (also referred to simply as a light emitting material) used in the light emitting layer or light emitting unit of the organic EL device of the present invention, the phosphorescent light emitting compound is contained at the same time containing the above-mentioned host compound. It is preferable to contain.

[0311] (Phosphorescent compound)

The phosphorescent light-emitting compound according to the present invention will be described.

[0312] The phosphorescent light-emitting compound according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C). Photoquantum yield force A force defined as a compound of 0.01 or more at 25 ° C. A preferable phosphorescence quantum yield is 0.1 or more.

[0313] The phosphorescent quantum yield can be measured by the method described in the fourth edition of Experimental Chemistry Course 7, Spectroscopy II, page 398 (1992 edition, Maruzen). The phosphorescence quantum yield in a solution can be measured using various solvents, but the phosphorescent light-emitting compound according to the present invention can be measured with any of the above-mentioned phosphorescence quantum yields (0.01 or more). ) Will be achieved!

[0314] There are two types of light emission of phosphorescent light-emitting compounds in principle. One is the recombination of carriers on the host compound to which carriers are transported, and the excited state of the host compound is generated. The energy transfer type is to transfer the energy to the phosphorescent light emitting compound to obtain the light emission of the phosphorescent light emitting compound power. In this case, the energy of the excited state of the phosphorescent light-emitting compound is such that carrier recombination occurs on the phosphorescent light-emitting compound and light is emitted from the phosphorescent light-emitting compound. Is required to be lower than the excited state energy of the host compound.

[0315] The phosphorescent light-emitting compound can be appropriately selected from known materials used for the light-emitting layer of the organic EL device. The phosphorescent light emitting compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex system). Compounds), rare earth complexes, and most preferred are iridium compounds.

[0316] Specific examples of the compound used as the phosphorescent light emitting compound are shown below, but the present invention is not limited thereto. These compounds can be synthesized, for example, by the method described in Inorg. Chem. 40 卷, 1704 to 1711.

[0317] [Chemical 20]

[0318] [Chemical 21]

[0319] [Chemical 22]

[0320] [Chemical 23]

[0321] [Chemical 24]

[0322] [Chemical 25]

Pd-1 Pd-2 Pd 3

[0323] [Chemical 26]

Rh-1 Rh-2 Rh-3

[0324] Typical examples of phosphorescent light-emitting compounds that are preferably used in the present invention and in which a crosslinkable reactive group is introduced into a complex compound are shown below. It is not limited to these.

[0325] [Chemical 27]

[0326] [Chemical 28]

[0327] [Chemical 29]

[0329] [Chemical 31]

[0330] Specific examples of the phosphorescent light-emitting compound (phosphorescent dopant) suitably used in the invention (B) according to claims 13 to 22 are shown, but the invention is not limited thereto. For example, it can be synthesized by the method described in Inorg. Chem. 40 卷, 1704-1711.

[0331] [Chemical 32]

PD-1 PD-2 PD-3

3]

[0333] In addition, the reactive phosphorescent dopant shown below is preferably used for forming the light emitting layer. In the invention (B) according to claims 13 to 22, the invention is not limited to these. .

[0334] [Chemical 34]

[0335] [Chemical 35]

[0336] Further, as the reactive phosphorescent dopant, a compound obtained by substituting a reactive group that may be possessed by the above-mentioned reactive host compound in a conventionally known phosphorescent compound is also preferably used. .

[0337] As the phosphorescent dopant (also referred to as phosphorescent compound, phosphorescent light-emitting compound, etc.) according to the invention (B) of claims 13 to 22, light emission from an excited triplet is possible. The blue light-emitting ortho metal complex shown below as a blue light-emitting dopant, which is blue. Is preferably used.

[0338] Dendrimer-type phosphorescent organometallic complex

In addition, as the phosphorescent dopant according to the invention (B) described in claims 13 to 22, a dendrimer-type phosphorescent organometallic complex represented by the following general formula (D1) may be used. it can.

[0339] General formula (D1)

P— [(Dendron) m] n

In the general formula (D1), dendron represents a tree-like molecule represented by the following general formula (E), n represents an integer greater than 0, m is greater than 0 and less than n Represents an integer. P represents a phosphorescent organometallic complex that becomes a core.

[0340] General formula (E)

[0341] [Chemical 36] General formula (E)

In the general formula (E), Ar represents a trivalent group derived from an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Represents an aromatic heterocycle, and X represents a single bond or a divalent linking group that binds to the phosphorescent organometallic complex P, which serves as the core. n represents the number of branches (also called a generation number).

[0343] In the general formula (E), the aromatic hydrocarbon ring represented by Ar includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a chrysene. Ring, naphthacene ring, triphenylene ring, o-terfel ring, m-terfel ring, p-terfel ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring Perylene ring, pentaphen ring, picene ring, pyrene ring, bianthrene ring, anthraanthrene ring, and the like. In addition, these rings may further have a substituent represented by R in the general formula (A).

[0344] In the general formula (E), examples of the aromatic heterocycle represented by Ar include a furan ring and a thio group. Ophene ring, oxazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, indazole ring, Benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, force rubazole ring, carboline ring, diaza force rubazole ring (carboline) A ring in which one of the carbon atoms of the hydrocarbon ring constituting the ring is further substituted with a nitrogen atom).

In addition, these rings may further have an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, as a substituent which may have a substituent. Hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.) ), Alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, furyl group, naphthyl group, etc.), aromatic heterocyclic group (eg, furyl group, chenyl group, pyridyl group, pyridazinyl group, Pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolyl, carbazolyl, carbolinyl Group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolyl group is replaced by a nitrogen atom), phthaladyl group, etc.), heterocyclic group (for example, pyrrolidyl Group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, , Cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) Group, dodecylthio group, etc.), cycloalkyl Thio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, etc.) , Butoxycarbonyl group, octyl Oxycarbonyl groups, dodecyloxycarbonyl groups, etc.), aryloxycarbonyl groups (eg, phenylcarboxyl groups, naphthyloxycarbox groups, etc.), sulfamoyl groups (eg, aminosulfo groups) -Methyl group, methylaminosulfol group, dimethylaminosulfol group, butylaminosulfol group, hexylaminosulfol group, cyclohexylaminosulfol group, octylaminosulfol group, Dodecylaminosulfol group, phenolaminosulfol group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), isyl group (eg, acetyl group, ethylcarbol group, propylcarbol group, Pentyl carbonate group, cyclohexyl carboxyl group, octyl carboxyl group, 2-ethyl hexyl carbonate group, dodecyl carbonate group, phenol Group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbo-loxy group, dodecylcarbo-loxy group, Phenyl carbonate, etc.), amide groups (for example, methyl carbolumino group, ethyl carbolumino group, dimethyl carbolumino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl carbolumino group) 2-ethylhexylcarbolamino group, octylcarbolamino group, dodecylcarbolamino group, phenylcarbolamino group, naphthylcarbonylamino group, etc.), strong rubamoyl group (for example, aminocarbol group, methylaminocarbol group) Group, dimethylaminocarbol group, propylene Ruaminocarbol group, pentylamino group, cyclohexylaminocarbol group, octylaminocarbol group, 2-ethylhexylaminocarbol group, dodecylaminocarbole group Group, phenolaminocarbol group, naphthylaminocarbole group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, Octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfier group (for example, methylsulfuryl group, ethylsulfuryl group, butylsulfuryl group, cyclohexylsulfuryl group, 2 — Ethylhexylsulfyl group, dodecylsulfyl group, phenylsulfyl group, Butyl sulfiel group, 2-pyridyl sulfiel group, etc.), alkyl sulfol group (for example, methyl sulfol group, ethyl sulfol group, butyl sulfol group, cyclohexyl group) Arylsulfol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.), arylsulfol group or heteroarylsulfol group (eg, phenylsulfol group, naphthylsulfonyl group) 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, arlino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, penta Fluorophenol group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, And triisopropylpropylsilyl group, triphenylsilyl group, phenyljetylsilyl group, etc.). These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

[0346] The divalent linking group represented by! /, X in the general formula (E) includes hydrocarbon groups such as an alkylene group, an alkylene group, an alkylene group, and an arylene group. In the alkylene group, the alkene group, the alkynylene group, and the arylene group, each of them may contain a hetero atom (for example, a nitrogen atom, a sulfur atom, a silicon atom, etc.). Even a divalent linking group derived from a compound having an aromatic heterocycle (also called a heteroaromatic compound) such as a —2, 5-diyl group or a pyrazine-2,3-diyl group. It may be a chalcogen atom such as oxygen or sulfur. In addition, it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilane diyl group, or a diarylgermandyl group.

[0347] Specific examples of the dendrimer represented by the general formula (D1) are shown below.

However, the invention (B) described in Item 22 is not limited thereto.

[0348] [Chemical 37]

D- 1

[0349] <Cyclodextrin derivative>

The invention described in claims 13 to 22 (B) can be a cyclodextrin derivative represented by the following general formula (D). The cyclodextrin derivative is a general term for compounds having a structure in which a plurality of D-darcoviranose groups are cyclized by 1, 4 glycosidic bonds. The primary and secondary hydroxyl groups present in the molecule may be substituted with substituents.

[0350] [Chemical 38]

[0351] In the general formula (D), R represents a substituent, and Z represents a residue of a phosphorescent compound.

[0352] In the general formula (D), the substituent represented by R in the general formula (E) may be a substituent that the aromatic hydrocarbon ring represented by Ar may have. Synonymous with group. [0353] In the general formula (D), as the phosphorescent compound used as the residue of the phosphorescent compound represented by Z, the phosphorescent compound (also called a phosphorescent dopant) is used. , U) can be used.

[0354] Preferred examples of the cyclodextrin derivatives used in the invention (B) according to claims 13 to 22 are shown below, but not limited thereto.

[0355] [Chemical 39]

CD— 1 CD— 2

[0356] In CD-1 and CD2, Ac represents a acetyl group.

[0357] 《Calixarene derivative》

The invention (B) described in claims 13 to 22 will be described as a calixarene derivative used as a kind of such phosphorescent dopant.

[0358] The calixarene derivative used in the invention (B) according to claims 13 to 22 is an alkylene group or a phenol derivative as represented by the following general formula (A). This is a general term for compounds having a cyclic structure bonded by an oxyalkylene group, and the phenolic hydroxyl group in the molecule may be substituted with a substituent.

[0359] [Chemical 40] —General formula (A)

[0360] In the general formula (A), the divalent linking groups represented by A and L, respectively, include the divalent linking group represented by X in the general formula (E). It is synonymous.

[0361] Furthermore, examples of the divalent linking group represented by A and L include, for example, a force rubazole ring, a carboline ring, a diaza force rubazole ring (also referred to as a monoazacarboline ring, and carbon atoms constituting the carboline ring). One of these is replaced with a nitrogen atom), triazole ring, pyrrole ring, pyridine ring, pyrazine ring, quinoxaline ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring, indole ring, etc. Aromatic heterocycle group force such as Aromatic heterocycle force selected A divalent group or the like derived can be used.

[0362] Further, in the general formula (E), the aromatic hydrocarbon ring represented by Ar may have a substituent.

[0363] The ability to list specific examples of calixarene derivatives used in the invention (B) according to claims 13 to 22 below is not limited to these.

[0364] [Chemical 41]

[0365] In CA-1, A represents CH or N, R represents a hydrogen atom, a methyl group or an acetyl group, and n represents an integer of 1 to 6.

[0366] <Crown ether derivative>

The invention according to claims 13 to 22 (B), a crown ether derivative used as a kind of phosphorescent dopant, will be described.

[0367] The crown ether derivative used in the invention (B) according to claims 13 to 22 is represented by the following general formula (B) or general formula (C), respectively: Cyclic polyether, which is a generic name for compounds that have polydentate ligands with the entire ring as a multidentate ligand, and have a function of inclusion with metal ions or organic ions, and part or all of them are nitrogen, instead of oxygen atoms, It may be substituted with sulfur.

[0368] [Chemical Formula 42] General Formula (B) — General Formula (C)

[0369] In each of the general formulas (B) and (C), L represents a single bond or a divalent linking group.

Ch represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 9, n represents an integer of 1 to 3, and Z represents a residue of a fluorescent compound or a phosphorescent compound.

[0370] In each of the general formulas (B) and (C), the divalent linking group represented by L is a divalent group represented by A and L in the general formula (A). It is synonymous with the linking group.

[0371] In each of the general formulas (B) and (C), the phosphorescent compound used as the residue of the phosphorescent compound represented by Z is the phosphorous described later. Examples thereof include compounds described in Photochemical Compounds (also referred to as phosphorescent dopants).

[0372] Further, the crown ether derivatives represented by the above general formulas (B) and (C) each have a substituent R which the calixarene derivative represented by the above general formula (A) has, and Moyo! /

[0373] Specific examples of the crown ether derivative used in the invention (B) according to claims 13 to 22 are listed below, but the invention is not limited thereto.

[0374] [Chemical 43]

[0375] In each of the above specific examples, CE-1 and CE-2, A represents CH or N

, N represents an integer of 1-9.

[0376] The phosphorescent compound used in the invention (B) according to claims 13 to 22 is: For example, Organic Letter, vol3, No. 16, p2579-2581 (2001), Inorganic Chemistry, No. 30, No. 8, pp. 1685-1687 (1991), Am. Chem. So c., 123 卷, 4304 Page (2001), Inorganic Chemistry, No. 40, No. 7, 1 704-1711 (2001), Inorganic Chemistry, No. 41, No. 12, 3055-3066 (2002), New Journal of Chemistry., Vol. 26, page 1171 (2002), and further by applying methods such as references described in these documents.

[0377] This time, too, if f row, J. Am. Chem. Soc. 123-4304-412 (2001), International Publication No. 00Z70655 pamphlet, 02Z15645 Pamphlet K JP 200

1-247859, 2001-345183, 2002-117978, 2002-170684, 2002-203678, 2002-235076, 2002-302671, No. 2002-324679, No. 2002-332291, No. 2002-332292, No. 2002-338588, etc. Open 200

Examples include iridium complexes represented by the formula (IV) described in 2-8860.

[0378] (Fluorescent dopant (also fluorescent compounds!))

Examples of fluorescent dopants (fluorescent compounds) used in the present invention include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, Examples thereof include rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

[0379] The fluorescent dopant that can be suitably used in the invention (B) according to claims 13 to 22 includes cyclodextrin derivatives represented by the above general formula (D)! Thus, there are those having a fluorescent compound residue in place of the residue of the phosphorescent compound represented by Z.

[0380] Examples of the fluorescent dopant that can be used in the invention (B) according to claims 13 to 22 include the above general formula (B) and general formula (C). In the crown ether derivative represented by each, instead of the phosphorescent compound residue represented by Z, fluorescence A compound is mentioned using the residue of a chemical compound.

[0381] Here, as the fluorescent compound, specific examples of the dye, the fluorescent compound or the fluorescent dopant described in the fluorescent dopant (also referred to as fluorescent compound) are described. Is mentioned.

Next, an injection layer, a blocking layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.

[0383] <Injection layer: electron injection layer, hole injection layer>

The injection layer is provided as necessary, and includes an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or hole transport layer and between the cathode and the light emitting layer or electron transport layer. Hey.

[0384] The injection layer is a layer provided between the electrode and the organic layer in order to reduce the drive voltage and improve the luminance of the light emission. (Published by ES Co., Ltd.) ”, Chapter 2“ Chapter 2 Electrode Materials ”(pages 123-166) in detail, the hole injection layer (anode buffer layer) and electron injection layer (cathode buffer layer) There is.

[0385] The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9260062, JP-A-8-288069 and the like. A phthalocyanine buffer layer represented by phthalocyanine, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyarene (emeraldine) or polythiophene. Etc.

[0386] The details of the cathode buffer layer (electron injection layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Metal buffer layer typified by aluminum or titanium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, acid typified by acid aluminum One thing buffer. The buffer layer (injection layer) is preferably a very thin film, although the film thickness is preferably in the range of 0.1 nm to 5 m, although it depends on the desired material.

[0387] <Blocking layer: hole blocking layer, electron blocking layer>

The blocking layer is provided as necessary in addition to the basic component layer of the organic compound thin film as described above. It is what For example, it is described in JP-A-11 204258, 11-204359, and “Organic EL device and the forefront of its industrialization” (published by NTS Corporation on November 30, 1998). There is a hole blocking layer.

[0388] In a broad sense, the hole blocking layer has the function of an electron transporting layer, and has the function of transporting electrons while having the capability of transporting holes, and is a hole blocking material force that transports electrons. By blocking holes, the recombination probability of electrons and holes can be improved. Further, the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary.

[0389] The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

[0390] The hole blocking layer preferably contains the azacarbazole derivative mentioned as the above-mentioned host compound.

[0391] Further, in the present invention, when a plurality of light emitting layers having different emission colors are provided, it is preferable that the light emitting layer having the longest emission maximum wavelength is closest to the anode among all the light emitting layers. In such a case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more with respect to the host compound of the shortest wave emitting layer. Better!/,.

[0392] The ionic potential is defined by the energy required to release an electron at the HOMO (highest occupied molecular orbital) level of a compound to the vacuum level, and can be obtained by, for example, the following method .

[0393] (1) Gaussian98 (Gaussian98, Revision A. 丄 1.4, MJ Frisch, et al, Lraussian, Inc., Pittsburg h PA, 2002.) The ionization potential can be calculated by rounding off the second decimal place of the value (eV unit converted value) calculated by structural optimization using B3LYPZ6-31G * as a keyword. The reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value.

[0394] (2) The ion potential can also be obtained by direct measurement with photoelectron spectroscopy. it can. For example, a method known as ultraviolet photoelectron spectroscopy using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd. can be suitably used.

[0395] On the other hand, the electron blocking layer has the function of a hole transport layer in a broad sense, and has a function of transporting holes while having a material force that is extremely small to transport electrons, and transports holes. However, by blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thicknesses of the hole blocking layer and the electron transport layer according to the present invention are preferably 3 to LOONm, and more preferably 5 to 30 nm.

[0396] << Hole Transport Layer >>

The hole transport layer is a hole transport material having a function of transporting holes. In a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

[0397] The hole transport material has either injection / transport of holes, electron barrier properties! /, Or deviation, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, violazoline derivatives and pyrazolone derivatives, fluorenedamine derivatives, arylene amine derivatives, amino substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

[0398] The ability to use the above-mentioned materials as the hole transport material [0398] The use of borfilin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds. preferable.

[0399] Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-1,4'-daminophenol; N, N' —Diphenol N, N '— Bis (3-methylphenol) 1 [1, 1' — Biphenyl] 1, 4, 4 '— Diamine (TPD); 2, 2-bis (4-dione p-tolylaminophenol) propane; 1, 1-bis (4-di-p-tri) N, N, N ′, N ′ —tetra-l-tolyl-l, 4,4′-diaminobiphenyl; 1,1-bis (4-di-l-tol-aminol-phenyl) 4-phenyl Hexane; Bis (4-dimethylamino-2-methylphenol) phenylmethane; Bis (4-di-ρ-tolylaminophenol) phenolmethane; Ν, N '— Diphenyl 一, N' — Di (4-methoxyphenol) 4,4'-diaminobiphenyl; Ν, Ν, Ν ', N' —tetraphenyl —4,4'-diaminodiphenyl ether; 4,4 ′ bis (diphenylamino) quadryl; —, Ν, トリ Tri (ρ-triyl) amine; 4— (Di-ρ-triylamino) — 4 ′ — [4 -— (Di—ρ-triylamino) styryl] stilbene; 4-— Ν, Ν Diphenylamine (2-Diphenyl) Ruby) benzene; 3-methoxy 1 4 '— Ν, Ν diphenylaminostilbenzene; Phenolcarbazole and, further, those having two condensed aromatic rings described in US Pat. No. 5,061,569, for example, 4, 4 ′ bis [Ν- (1- Naphtil) [Feramino] Bifurle (NPD), three triamine units described in JP-A-4 308688 are connected in a starburst type 4, 4 ', Α "— Tris [? ^-(3-methylphenol) Νphenolamino] triphenylamine (MTDΑΤΑ) and the like.

[0400] Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Also, inorganic compounds such as vertical-type Si and p-type SiC can be used as the hole injection material and the hole transport material.

[0401] Also, so-called p-type hole transport as described in JP-A-11-251067 and J. Huang et. Al. (Applied Physics Letters 80 (2002), p. 139). Materials can also be used. In the present invention, it is preferable to use these materials because a light emitting element with higher efficiency can be obtained!

[0402] The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. Can be formed. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, about 5-5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure having one or more of the above materials.

[0403] Also, a p-type high hole transport layer doped with impurities can be used. As an example JP-A-4-297076, JP-A-2000-196140, 2001-1021.

No. 75, J. Appl. Phys., 95, 5773 (2004), etc.

[0404] In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

[0405] Even if it is connected to the hole transport layer, it is possible to use a material in which a reactive substituent is introduced into the hole transport material molecule, and a particularly preferable hole transport material having a reactive substituent. Examples include the following.

[0406] [Chemical 44]

[f ^ [LOW]

[0408] [Chem 46]

-13

]

[0410] Specific examples of the compounds preferably used for forming the hole transport layer of the organic EL device according to the invention (B) described in claims 13 to 22 are given below. However, it is not limited to these.

[0411] [Chemical 48]

[0412] For forming the hole transport layer, the following reactive hole transport materials are also preferably used, but in the invention (B) according to claims 13 to 22, these materials can be used. It is not limited to.

[0413] [Chemical 49]

[0414] [Chemical 50]

[0415] [Chemical 51] MO— 13 MO— 14

[0416] 《Electron transport layer》

In the present invention, the electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

[0417] Conventionally, in the case of a single electron transport layer and multiple layers, it is adjacent to the light emitting layer on the cathode side As an electron transport material (also serving as a hole blocking material) used for the electron transport layer in contact with the electron transport layer, any material known in the art may be used as long as it has a function of transmitting electrons injected from the negative electrode to the light emitting layer. Any one of the compounds can be selected and used, such as -to-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, rubodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and Anthrone derivatives, oxadiazole derivatives and the like can be mentioned. Furthermore, thiadiazole derivatives in which the oxygen atom of the oxaziazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

[0418] Also, metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5, 7-dive mouth) 8 quinolinol) aluminum, tris (2methyl 8quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Metal complexes replacing Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials. In addition, metal free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylvirazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type Si and n-type SiC Can also be used as an electron transporting material.

[0419] The electron transport layer is obtained by thin-filming the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can be formed. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may be a single layer structure having one or more of the above materials.

[0420] An n-type high electron transport layer doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140. No. 1, 2001-102175, Appl. Phys., 95, 5773 (2004) and the like.

[0421] In the present invention, it is preferable to use an electron transport layer having such a high η property because a device with lower power consumption can be produced.

[0422] Examples of the electron transporting material having a reactive substituent include the following.

[0423] [Chemical 52]

[0424] [Chemical 53]

[0425] [Chemical 54]

[0426] [Chemical 55] 3-17

[0427] Further, specific examples of the compounds preferably used for forming the electron transport layer of the organic EL device according to the invention (B) described in claims 13 to 22 are listed below. It is not limited to.

[0428] [Chemical 56]

[0429] [Chemical 57]

[0430] In the invention (B) described in claims 13 to 22, the following electron transporting materials are preferably used for forming the electron transporting layer, but the invention is not limited thereto. No.

[0431] [Chemical 58]

O -51 MO— 52

[0432] [Chemical 59]

[0433] Further, as the reactive electron transport material, a compound obtained by substituting a reactive group that may be possessed by the above-described reactive host compound in a conventionally known electron transport material is also preferably used.

[0434] Condensation polymer

In the method of manufacturing an organic EL element according to the invention (B) according to claims 13 to 22, in addition to the constituent material of the organic layer of the organic EL element, the following condensation polymer Can be used as appropriate.

[0435] Hereinafter, examples of the condensation polymer used in the invention (B) according to claims 13 to 22 include, but are not limited to, compounds represented by the following general formula (1).

[0436] [Chemical 60]

[0437] In the general formula (1), [Ar] n represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring having n substitutable sites. Z represents a fluorescent compound residue or a phosphorescent compound residue, and m of n replaceable sites of Ar are linked via K. K represents a divalent linking group or a single bond. n represents a number from 1 to 3, and m represents a number from l to n. Here, when there are a plurality of Z and K, each may be independently the same or different. L is a divalent linking group selected from the linking group group 1 described below.

In the general formula (1), the aromatic hydrocarbon ring represented by Ar is a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene. Ring, triphenylene ring, o-terfel ring, m-terfel ring, p-terfel ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring , Pentaphen ring, picene ring, pyrene ring, bianthrene ring, anthraanthrene ring and the like. In addition, these rings may further have a substituent represented by R in the general formula (A).

[0439] In the general formula (1), examples of the aromatic heterocycle represented by Ar include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, Cinnoline ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, force rubazole ring, carboline ring, diaza force rubazole ring (one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom) Etc.) It is done.

[0440] Note that these rings may further have an aromatic hydrocarbon ring represented by Ar in the general formula (E), or may have a substituent! /, .

[0441] In the general formula (1), the divalent linking group represented by K has the same meaning as the divalent linking group represented by A in the general formula (1).

[0442] In the general formula (1), the residue of the fluorescent compound represented by Z and the phosphorescent compound residue are the fluorescent compound represented by Z in the general formula (1), respectively. Residue and phosphorescent compound residue are synonymous with each other.

[0443] In the general formula (1), the divalent linking group represented by L is selected from the following linking group group 1.

[0444] [Chemical 61]

[0445] In the linking group group 1 above, R to R

14 each represents an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0446] In the linking group group 1, the alkyl groups represented by R to R include, for example,

14

Examples include til, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like. These may further have a substituent represented by R in the general formula (A).

[0447] In the linking group group 1 above, R to R

Examples of the aromatic hydrocarbon group represented by 14 include a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthyl group, Examples thereof include a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group, and the like.

[0448] These groups may further have a substituent represented by R in the general formula (A). [0449] Examples of the aromatic heterocyclic group represented by R to R in the above linking group group 1 include:

14

Lysyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazyl group, triazolyl group (for example, 1, 2, 4 triazole-1-yl group, 1, 2, 3 triazole— 1— Oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, chenyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzochel group, dibenzochel group , Indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbo group is replaced by a nitrogen atom), quinoxalinyl group, pyridazyl group , Triazinyl group, quinazolinyl group, phthalazinyl group and the like.

[0450] In the above general formula (E), these groups may further have an aromatic hydrocarbon ring represented by Ar, or may have a substituent.

[0451] Specific examples of the condensation polymer represented by the general formula (1) are shown below.

However, the invention (B) described in Item 22 is not limited thereto.

[0452] [Chemical 62]

[0453] [Chemical 63]

R = 2—Ethylhexyl group 64]

Other

[0455] 《Anode》

In the present invention, for example, as the anode formed on the first electrode substrate, a material having a large work function (4 eV or more) metal, alloy, electrically conductive compound and a mixture thereof is preferably used. It is done. Specific examples of such electrode materials include metals such as Au, conductive transparent materials such as Cul, indium tinoxide (ITO), SnO, and ZnO.

2

I can get lost. In addition, IDIXO (ln O-ZnO) and other amorphous materials that can produce transparent conductive films are also available.

twenty three

It may be used. For the anode, these electrode materials can be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern of the desired shape can be formed by a single photolithography method. The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Alternatively, when a material that can be applied, such as an organic conductive compound, is used, a wet film forming method such as a printing method or a coating method can also be used. In the case where light emission is extracted from this anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω or less. Further, the film thickness is a force depending on the material. Usually, 10 to: L000 nm, preferably 10 to 200 nm is selected.

[0456] 《Cathode》

On the other hand, for example, as a cathode formed on the first electrode substrate, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are used as an electrode material. What to do is used. Specific examples of such electrode materials include sodium, sodium monopotassium alloy, magnesium, lithium, magnesium Z copper mixture, magnesium Z silver mixture, magnesium Z aluminum mixture, magnesium Z aluminum mixture, aluminum Z acid aluminum (Al 2 O 3) mixture, indium, lithium

twenty three

Examples include aluminum mixtures and rare earth metals. Among these, from the viewpoint of electron injectability and durability against oxidation, etc., a mixture of an electron injectable metal and a second metal, which is a stable metal having a larger work function value than this, for example, magnesium Z silver Mixture, Magnesium Z Aluminum mixture, Magnesium Z Indium mixture, Aluminum Z Oxide Aluminum (Al 2 O 3) mixture, Lithium Z Aluminum mixture, Aluminum etc. are suitable

twenty three

It is. [0457] The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / mouth or less. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

[0458] In addition, after the metal is formed to a thickness of 1 to 20 nm on the cathode, the transparent conductive material described in the description of the anode is formed thereon, whereby a transparent or translucent cathode is manufactured. Togashi.

[0459] In the present invention, since these electrode layers are first formed on the substrate and then the organic layer is formed, for example, it is possible to form an electrode that does not require the last cathode formation as in a normal case. Sometimes the organic layer (film) is less damaged. In addition, since the restrictions on the film formation conditions are small, it is easy to form electrodes.

[0460] 《Support base》

The support substrate (hereinafter also referred to as a substrate, a substrate, a substrate, or a support) according to the organic EL device of the present invention is not particularly limited in the type of glass, plastic, and the like, and is transparent or opaque. May be. When taking out the support substrate side force light, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. Particularly preferably, the support substrate is a resin film that can give the organic EL element flexible and can be formed by roll-to-roll.

[0461] Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellose diacetate, senorelose triacetate, sanolose acetate butyrate, senore mouth. Cellulose esters such as Sacetate Propionate (CAP), Cellulose Acetate Phthalate (TAC), Cellulose Nitrate or their derivatives, Polysalt vinylidene, Polybulal alcohol, Polyethylenebutal alcohol, Syndiotactic polystyrene , Polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfone , Polyetherimide, polyetherketoneimide, polyamide, fluorine resin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (JSR) or Abel (Mitsui Chemicals) t And the like.

[0462] The water vapor permeability measured by a method in accordance with JIS K 7129-1992, in which an inorganic film, an organic film, or both of them are coated on the surface of the resin film, is acceptable. It is more preferable that the film is a non-reactive film with a temperature of 25 ± 0.5 ° C and a relative humidity (90 ± 2)% RH of 0.01 g / (m ² '24h) or less. compliant measured oxygen permeability in a way that 10 111 ³ 7 (111 ² '2411' ^ 111) or less, the water vapor permeability of 10 ³ g / (m ² · 24h) or less of a high Roh rear film in Is preferred to be.

[0463] As a material for forming a barrier film formed on the surface of the resin film in order to obtain a high-nore film, any material that has a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the element may be used. For example, silicon oxide, silicon dioxide, silicon nitride or the like can be used.

Furthermore, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers that have organic material strength. There is no particular limitation on the order of lamination of the inorganic layer and the organic layer, but it is preferable to alternately laminate the layers a plurality of times.

[0464] The method of forming the barrier film is not particularly limited, for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure Power capable of using a plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, etc. A method using an atmospheric pressure plasma polymerization method as described in JP-A No. 2004-68143 is particularly preferable. .

[0465] Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, non-transparent resin substrates, ceramic substrates, and the like.

[0466] The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted outside the organic EL element Z the number of electrons flown through the organic EL element X 100 [0467] In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λ max of light emission of the organic EL element is preferably 480 nm or less.

[0468] <Sealing>

Examples of the sealing means used for sealing the organic EL element of the present invention include a method of bonding a sealing member, an electrode, and a support base with an adhesive. The sealing member may be in the form of a concave plate or a flat plate as long as it is arranged so as to cover the display area of the organic EL element. Moreover, transparency and electrical insulation are not particularly limited. Specific examples include a glass plate, a polymer plate 'film, a metal plate' film, and the like. Examples of the glass plate include soda lime glass, norlium strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, norium borosilicate glass, and quartz.

[0469] Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include one having at least one metal or alloy power selected from a group force consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. In the present invention, a polymer film and a metal film can be preferably used because the element can be made into a thin film.

[0470] Furthermore, the polymer film, water vapor as measured by JIS K 7126- 1987 oxygen permeability ^{^{10- 4 «11 3 7 (111}} 2 '24h'atm) below, in compliance with JIS K 7129- 1992 method permeability force ^{^{SlO- 3 gZ (m 2 - 24h}} ) or less, in particular ^{^{10- 5 gZ (m 2 - 24h}} )ヽis preferably be of less. Further, it is more preferable oxygen permeability even ^{^{^{10- 6 cm 3 / (m 2}}} '24h'atm) or less. Sand blasting and chemical etching are used to process the sealing member into a concave shape.

[0471] Specific examples of adhesives include photo-curing and thermosetting adhesives having a reactive vinyl group of acrylic acid-based oligomers and methacrylic acid-based oligomers, and moisture-curing adhesives such as 2 cyanoacrylates. Can be mentioned. In addition, heat- and chemical-curing types (two-component mixing) such as epoxy type can be mentioned. Also, hot-melt type polyamide, polyester And polyolefin. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned. In addition, since the organic EL element may be deteriorated by heat treatment, it is preferable that the adhesive can be cured from room temperature to 80 ° C. In addition, a desiccant may be dispersed in the adhesive. The adhesive can be applied to the sealing part using a commercially available dispenser or printing like screen printing.

[0472] Alternatively, the electrode and the organic layer may be coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer may be formed in contact with the support substrate to form a sealing film. It can be preferred. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of the element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, etc. Can be used. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and organic material layers.

[0473] There are no particular restrictions on the method of forming these films, for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, An atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

[0474] In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon or an inert liquid such as fluorinated hydrocarbon or silicon oil is used in the gas phase and the liquid phase. It is preferable to inject. A vacuum can also be used. Also, a hygroscopic compound can be enclosed inside. Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, and acid medium), sulfuric acid, and the like. Salts (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.), metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, (Norium iodide, magnesium iodide, etc.), perchloric acids (for example, barium perchlorate, magnesium perchlorate, etc.) and the like, and anhydrous salts are preferred for sulfates, metal halides, and perchloric acids. Used for.

[0475] 《Protective film, protective plate》

The sealing film on the side facing the support substrate with the organic layer interposed therebetween, or the sealing film In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided outside. In particular, when sealing is performed with the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate 'film, metal plate' film, etc. that are used for the sealing can be used. It is preferable to use a polymer film.

[0476] <Method for manufacturing organic EL element>

A method for producing the organic EL element of the present invention will be described.

[0477] A desired electrode material, for example, a thin film having a material force for an anode, is formed on a suitable support substrate by a method such as vapor deposition or sputtering so that the film thickness is 1 μm or less, preferably 10 to 200 nm. Then, an anode is produced and used as an anode substrate. Next, organic layers such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed as an organic material thin film in this order. Any of these layers may be formed on the anode substrate side. For example, the anode side member is produced by forming the hole transport layer. As a method for forming this organic compound thin film, there are a vapor deposition method and a wet process (spin coating method, casting method, ink jet method, printing method) as described above. From the viewpoint of difficulty in forming holes, the vacuum deposition method, spin coating method, inkjet method, and printing method are particularly preferable. Different film forming methods may be applied for each layer.

[0478] Further, another thin film having a cathode material force is also formed on the second supporting substrate by the same method: vapor deposition, sputtering or the like so as to have a film thickness of Lm or less, preferably 10 to 200 nm. A cathode substrate is prepared.

[0479] Next, each layer to be formed on the subsequent cathode side of the hole transport layer formed on the anode substrate thereon in the order reverse to the above, for example, an electron transport layer, a hole blocking layer, A cathode side member is fabricated by sequentially forming a light emitting layer. As a method for forming each layer of the organic layer formed on the cathode substrate, any of the vapor deposition method and the wet process (spin coating method, casting method, ink jet method, printing method) may be used as described above.

[0480] In the case of employing an evaporation method as a film forming method, the deposition conditions may differ force generally boat temperature 50 to 450 ° C by the species and the like of the compound used, the degree of vacuum 10- ⁶ to ^10-2 Pa Steamed It is desirable to select a deposition rate of 0.01 to 50 nm Z seconds, substrate temperature—50 to 300 ° C., film thickness of 0.1 to 5 μm, and preferably 5 to 200 nm! /.

[0481] In the invention C according to claims 23 to 31, the surface layer formed on the anode side substrate and the cathode side substrate has a surface roughness (Ra), It is adjusted as described in claim 23. For example, surface roughness (Ra) = 0. Lnm is passed through a metal roller (linear pressure: 500 NZcm, temperature: 60 ° C) to give the same surface roughness as the metal roll surface.

[0482] Next, the hole transport layer (anode-side member) and the light-emitting layer (cathode-side member), the surface roughness of which has been adjusted in step 1, are opposed to each other and adhered and bonded using a joining jig.

[0483] In the bonding, the anode-side substrate on which the organic layer is formed in this way, and the hole transport layer (anode-side member) and the light-emitting layer (cathode-side member) of the cathode-side substrate are opposed to each other. Adhere and bond with a jig.

[0484] The joining jig may be a stamper-like jig that can be pressed with a uniform pressure with both substrates facing each other, and a base, and the pressure can be set by, for example, a vacuum laminator. used to crimp a pressing force 0. IMPa under vacuum environment l X 10- ² Pa, tight adhesion both organic layer and fixed lamination.

[0485] In the facing layer, for example, a luminescent host or phosphorescent light-emitting compound, or a hole transport material in the hole transport layer (layers to be bonded, functional materials contained in the layer) are chemically treated. When the reaction is used to crosslink by forming a covalent bond to improve adhesion, an active light such as ultraviolet light may be used.

[0486] In the above, the positive hole transport layer is provided on the anode substrate, and the light emitting layer and subsequent layers are provided on the cathode substrate. However, other combinations are also possible. For example, the light emitting layer is provided on both sides, and the light emitting layers are in close contact (or crosslinked). ). Other combinations are acceptable.

[0487] In such an organic EL device, when a DC voltage is applied, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as one polarity. An AC voltage may be applied. The alternating current waveform to be applied may be arbitrary.

[0488] 《Light extraction》

The organic EL element emits light inside the layer, which has a higher refractive index than air (refractive index is about 1.7 to 2.1). It is said that only 15% to 20% of the generated light can be extracted. This is because light incident on the interface (interface between the transparent substrate and air) at an angle Θ greater than the critical angle causes total reflection, so that light is totally reflected between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the element.

[0489] As a technique for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435) ), A method for improving the efficiency by giving the substrate light condensing (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on the side surface of the element (Japanese Patent Laid-Open No. 1-2220394) ), A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the substrate and the light emitter (Japanese Patent Laid-Open No. Sho 62-172691), and lower than the substrate between the substrate and the light emitter. A method of introducing a flat layer having a refractive index (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer and the light-emitting layer (including between the substrate and the outside world) (Kaihei 11-283751).

[0490] In the present invention, these methods can be used in combination with the organic EL device of the present invention. In particular, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a diffraction grating between the substrate, the transparent electrode layer, and the light emitting layer (including between the substrate and the outside world). The method of forming can be used suitably.

[0491] In addition, a medium having a low refractive index, for example, a layer of air mouth gel, porous silica, magnesium fluoride, fluorine-based polymer, or the like having a thickness longer than the wavelength of light is interposed between the transparent electrode and the transparent substrate. When formed, the light extracted from the transparent electrode has a higher extraction efficiency as the refractive index of the medium is lower. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

[0492] The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.

[0493] A method of introducing a diffraction grating into an interface or any medium that causes total reflection is based on light. There is a feature that the effect of improving the extraction efficiency is high. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Of these, light that cannot be emitted due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (in the transparent substrate or transparent electrode). They are trying to take it out.

[0494] It is desirable that the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so a general one-dimensional diffraction grating having a periodic refractive index distribution only in one direction diffracts only light traveling in a specific direction. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, the light traveling in all directions is diffracted, and the light extraction efficiency increases.

[0495] As described above, the position where the diffraction grating is introduced may be in any one of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. .

[0496] At this time, the period of the diffraction grating is preferably about 1Z2 to about 3 times the wavelength of light in the medium.

[0497] The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

[0498] 《Condenser sheet》

In addition, the organic EL device of the present invention is processed so as to provide a microlens array structure on the light extraction side of the substrate, or is combined with a so-called condensing sheet, for example, in a specific direction, for example, the front surface of the device light emitting surface. Luminance can be increased by focusing in the direction.

[0499] As an example of a microlens array, a quadrangular pyramid with a side of 30 μm and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate. One side is preferably 10: LOO m. If it is smaller than this, the effect of diffraction is generated, and if it is too large, the thickness becomes too thick, which is not preferable.

[0500] As the light condensing sheet, for example, a sheet that has been put to practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, manufactured by Sumitomo 3EM A brightness enhancement film (BEF) or the like can be used. As the shape of the prism sheet, for example, the base material may be formed with stripes having a vertex angle of 90 degrees and a pitch of 50 111, a shape with rounded vertex angles, and a random pitch. It may be a changed shape or other shapes.

[0501] In order to control the light emission angle from the light emitting element, a light diffusing plate 'film may be used in combination with the light collecting sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

[0502] << Application >>

The organic EL element of the present invention can be used as a display device and various light sources. For example, home lighting, interior lighting, backlights for watches and liquid crystals, signboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sensors However, the present invention is not limited to this, and it can be effectively used as a knock light for a liquid crystal display device combined with a color filter, or as a light source for illumination.

[0503] In the organic EL device of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or in the production of an element that may be patterned on the entire layer, a conventionally known method Method can be used.

[0504] The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in Fig. 4.16 on page 108 of "New Color Science Nord Book" (edited by the Japan Society for Color Science, University of Tokyo Press, 1985). Therefore, it is determined by the color when the result measured with the spectral radiance meter CS-1000 (manufactured by Co-Force Minolta Sensing) is applied to the C IE chromaticity coordinates.

[0505] When the organic EL device of the present invention is a white device, white means chromaticity in the CIE1931 color system at lOOOCdZm ² when the 2 ° viewing angle front luminance is measured by the above method. It is in the region of force ¾ = 0.33 ± 0.07, Y = 0.33 ± 0.1.

[0506] 《Display device》

The display device of the present invention will be described. The display device of the present invention is multicolor or white Used for color display devices. In the case of a multicolor or white display device, a shadow mask is provided only when the light emitting layer is formed. In the case of patterning the light emitting layer, the method is not limited, but the vapor deposition method, the ink jet method, and the printing method are preferable. When using the vapor deposition method, patterning using a shadow mask is preferable. When a DC voltage is applied to the thus obtained multicolor or white display device, light emission can be observed by applying a voltage of about 2V to 40V with the anode as + and the cathode as one polarity. In addition, even if a voltage is applied with the opposite polarity, no current flows and no light is emitted. In addition, when an AC voltage is applied, light is emitted only when the anode is + and the cathode is in a single state. The applied AC waveform may be arbitrary.

[0507] 《Lighting device》

The lighting device of the present invention will be described. The organic EL device of the present invention may be used as a kind of lamp for illumination or exposure light source, or a projection device for projecting an image, or directly viewing a still image or a moving image. It may be used as a knocklight for a type of display device (display). When used as a knocklight for a liquid crystal display device, the driving method of the liquid crystal may be either a simple matrix (passive matrix) method or an active matrix method. If it is a backlight in a liquid crystal display device, the light emitting material used for the light emitting layer is not particularly limited, and any light emitting material is selected from the light emitting materials so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. Or in combination with the light extraction and Z or condensing sheet or the like.

[0508] As described above, the organic EL element of the present invention is combined with a CF (color filter) and arranged in accordance with the CF (color filter) pattern to arrange the element and the driving transistor circuit, thereby extracting the organic EL element power. Blue light (having an emission maximum in the range of 430 to 480 nm), green light (having an emission maximum in the wavelength range of 510 to 550 nm) through the blue filter, green filter and red filter. ) And red light (having a light emission maximum in the wavelength range of 600 to 640 nm), it is possible to produce a full-color organic-electric-luminescence display with a low driving voltage and a long life.

[0509] In addition to these displays, various light-emitting light sources and lighting devices such as household lighting, interior lighting, and a kind of lamp such as an exposure light source, backlights for liquid crystal display devices, etc. It is also useful for display devices. In addition, backlights such as watches, signboard advertisements, traffic lights, light sources such as optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processing machines, light sources for optical sensors, etc. There are a wide range of uses such as household appliances. Example

[0510] Hereinafter, the present invention will be described by way of examples, but the embodiments of the present invention are not limited thereto.

[0511] The invention (A) described in claims 1 to 12 will be specifically described below with reference to Examples 1 to 14.

[0512] Example 1

<< Preparation of Comparative Example Sample 1 >>

100 mm X 100 mm X I. 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, and then a glass substrate (NA Tetanoglas NA45) was commercially available. Attached to a spin coater, spin-coated (film thickness 4045nm) at 1000rpm for 30 seconds using a solution of Exemplified Compound 4-8 (50mg) dissolved in 10ml of 1,2 dichloroethane, and vacuum dried at 25 ° C for 1 hour Then, an organic layer 1 containing exemplary compound 48, which is an organic compound having a reactive substituent, was produced on a glass substrate.

[0513] Similarly to the above, an organic layer 2 containing Exemplified Compound 48 was produced on a glass substrate.

[0514] The organic layer 1 and the organic layer 2 on each glass substrate obtained in this manner were overlapped with each other and fixed with a joining jig to produce Comparative Example Sample 1.

[0515] <Preparation of Example Sample 1>

Next, the sample 1 of Comparative Example obtained above was irradiated with ultraviolet light for 120 seconds to produce Example Sample 1.

[0516] << Analysis of residual amount of Exemplified Compound 48 in organic layer >>

The residual amount of Exemplified Compound 48 in the organic phase was determined by a method of measuring the residual amount of the bur group of Exemplified Compound 48. The distribution of the double bond of the vinyl group was determined by the following means. [0517] The IR spectrum of each sample was measured with a Fourier transform infrared spectrometer (FTIR-8300, manufactured by Shimadzu Corporation), and the peak intensity derived from C = C stretching vibration detected at 1626 cm " ¹ was compared.

[0518] [Table 1]

[0519] From the measurement results, it was confirmed from the peak strength derived from C = C stretching vibration of Comparative Sample 1 and Example Sample 1 that almost all vinyl groups of Exemplified Compound 48 were reacted. It was.

[0520] Example 2

<< Preparation of Comparative Example Sample 2 >>

A 100 mm x 100 mm x 100 μm polyethylene terephthalate film substrate 1 is attached to a commercially available spin coater, and a solution in which the exemplified compound 48 (50 mg), which is an organic compound having a reactive substituent, is dissolved in 10 ml of 1,2 dichloroethane is used. Then, spin coating (film thickness: about 40 nm) was performed under conditions of 1000 rpm and 30 seconds, and vacuum drying was performed at 25 ° C. for 1 hour to produce an organic layer 1 containing Exemplified Compound 4-8 on the film substrate 1.

[0521] Similarly to the above, on the polyethylene terephthalate film substrate 2 having a thickness of 100 m, an organic layer 2 containing the exemplified compound 48 was produced.

[0522] The organic layer 1 and the organic layer 2 on each polyethylene terephthalate film substrate thus obtained were overlapped and fixed with a joining jig to produce Comparative Sample 2.

[0523] <Preparation of Example Sample 2>

Next, the sample 2 of Comparative Example obtained above was irradiated with ultraviolet light from the polyethylene terephthalate film substrate 1 side for 120 seconds to prepare Example Sample 2.

[0524] << Analysis of residual amount of Exemplified Compound 48 in organic layer >>

The unreacted exemplified compound 48 in the thin film was determined by a method of measuring the distribution of vinyl groups in the exemplified compound 48. The presence of the double bond of the bur group Can be sought.

[0525] In order to secure the analysis area, oblique cutting was performed with a die-brush CYTUS NN04 type manufactured by Wintes. Cutting was performed with an enlargement ratio of 500 times, and an analysis area of 20 m width was obtained. Next, the double bond remaining in the thin film was labeled on the cut surface by the bromine addition method. For the sample after labeling, the elemental composition distribution on the cutting surface was measured using an X-ray photoelectron spectrometer, QuanteraSX M manufactured by ULVAC-FAI, and the elemental composition distribution on the cutting surface was obtained. The measurement results are shown below.

[0526] [Table 2]

[0527] From the measurement results, it was confirmed that almost all of the vinyl groups of Exemplified Compound 48 had reacted regardless of the depth direction of the layer.

[0528] Example 3

<< Preparation of Comparative Sample 3 >>

100mm X 100mm XI. 1mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, then attached to a commercially available spin coater, and exemplified compound 1-ll (50mg) Using a solution in which 10 ml of 1,2 dichloroethane is dissolved, spin-coat (film thickness of about 40 nm) under conditions of 1000 rpm for 30 seconds, and vacuum-dried at 25 ° C for 1 hour to have reactive substituents Organic layer 1 containing exemplary compound 111, which is an organic compound, was produced on a glass substrate.

[0529] Similarly to the above, an organic layer 2 containing the exemplified compound 411 was produced on a glass substrate.

[0530] The organic layer 1 and the organic layer 2 on each glass substrate obtained in this manner were overlapped with each other and fixed with a joining jig to produce Comparative Example Sample 3.

[0531] <Preparation of Example Sample 3> Next, Comparative Example Sample 3 obtained above was heated at 150 ° C. for 1 hour to produce Example Sample 3.

[0532] 《Study on reactivity at bonding interface》

The produced Comparative Example Sample 3 and Example Sample 3 were immersed in 50 ml of tetrahydrofuran, and after sufficiently stirring, the glass substrate was removed, and the solvent of the resulting solution force was distilled off. When the residue was analyzed with a time-of-flight secondary ion mass spectrometer (TOF-SIMS), Compound 1 11 and Compound 4 11 reacted only from the residue of the solution in which Example Sample 3 was immersed. A peak with a molecular weight of 1248 corresponding to the molecular weight of reactant A was detected.

[0533] From the above, it was confirmed that the reaction proceeded at the bonded interface.

[0534] [Chemical 65]

Example 4

100mm X 100mm X I. As an anode, put a pattern on a substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45) made of ITO (Indium Toxide) on a 1mm glass substrate. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

[0536] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving the following compound BCP (60 mg) in 10 ml of toluene was spin-coated (film thickness: about 40 nm) under conditions of 1000 rpm and 30 seconds to obtain an organic layer 1 The anode side part which has a layer was produced.

[0537] <Preparation of cathode region>

Attach the UV ozone-cleaned substrate used for the preparation of the anode part to a commercially available spin coater and use a solution of the following compound CBP (60 mg) dissolved in 10 ml of toluene, spin coating (film) under the condition of lOOOr pm for 30 seconds. A cathode portion having a thickness of about 40 nm and having one organic layer was produced.

[0538] The organic layer of the anode side part and the cathode part obtained in this way were placed facing each other, fixed with a joining jig, and heat-treated at 100 ° C for 1 hour to produce an organic EL element 11 did

[0539] Organic EL element 11 was prepared in the same manner as organic EL element 1-1, except that the compounds used in the organic layer of the anode side portion and the cathode portion were replaced with the compounds shown in Table 3. E

L elements 1-2 to 1-3 were produced.

[0540] (Measurement of peel strength)

The peel strength of the organic EL element was measured by the SAICAS method using a SAICAS NN-04 model manufactured by Daibra-Wintes. The SAICAS method uses a sharp cutting edge (single crystal diamond, sintered alloy) to measure the horizontal load required to move at a constant speed in the horizontal direction while maintaining a constant vertical load. Thus, the peel strength of the thin film can be measured. The measurement conditions are as follows.

[0541] Psycho measurement conditions

Equipment: Daipla · Wintes Cycus NN-04 type

Measurement conditions: A diamond lmm wide blade is used. Shear angle is 45 °

The pressing load 2 N, and the balance weight 1 _mu New, vertical speed InmZ sec, horizontal velocity lOOnm

Cutting was performed in Z seconds, and horizontal and vertical forces were recorded. The sampling step is 0.2 second Zpoint. [0542] [Chem 66]

CBP BCP

[0543] [Table 3]

[0544] While the peel strength of the bonding surface of the organic layer formed of low molecular weight compounds is low, an organic compound having a reactive substituent in the molecular structure in at least one organic layer. It can be seen that those subjected to heat treatment or ultraviolet irradiation using a product exhibit a high peel strength at the joint surface.

[0545] Example 5

<< Production of organic EL elements 2-1 to 2-3 >>

100mm X 100mm X I. A 1mm glass substrate is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, and then fixed to a substrate holder of a commercially available vacuum deposition device. Aluminum (thickness: about lOnm) and lithium fluoride (thickness: about 0.5 nm) were applied.

[0546] This substrate was attached to a commercially available spin coater, and a solution in which BCP (20 mg) was dissolved in 10 ml of toluene was used. Spin coating (film thickness about lOnm) at 60 ° C for 1 hour under conditions of 1000 rpm and 30 seconds It vacuum-dried, provided the electron carrying layer, and produced the cathode side site | part.

[0547] <Production of anode side part>

ITO (indium tin oxide) on a glass substrate of 100mm X 100mm X I. 1mm as the anode After putting a lOOnm film substrate (NH Techno Glass NA45) on the substrate, this transparent support substrate with ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol and dried with dry nitrogen gas. UV ozone cleaning was performed for 5 minutes.

[0548] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 41 (60 mg) in 10 ml of toluene was spin-coated (film thickness of about 40 nm) and ultraviolet light under conditions of 1000 rpm and 30 seconds. After irradiation for 30 seconds, vacuum drying was performed at 60 ° C. for 1 hour to form a hole transport layer.

[0549] Next !, using a solution of CBP (60mg) and Ir-1 (3. Omg) dissolved in 6ml of toluene, spin-coated under the condition of 1 OOOrpm for 30 seconds (film thickness about 60nm) Then, it was vacuum-dried at 60 ° C. for 1 hour to form a light emitting layer, and an anode side portion was produced.

[0550] <Bonding>

Thus superimposed to face the light-emitting layer electron-transporting layer and the anode side portion of the resulting cathode site, pressure 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa using a bonding jig Crimping, sticking, and fixing at 100 ° C for 1 hour was performed, and the resulting device was sealed (using an epoxy adhesive) to produce an organic EL device 2-1.

[0551] In the production of the organic EL device 2-1, the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 4, and the organic EL device 2-1. Organic EL devices 2-2 and 2-3 were fabricated using the same method.

[0552] <Evaluation of organic EL elements 2-1 to 2-3>

The organic EL devices 2-1 to 2-3 produced as follows were evaluated, and the results are shown in Table 4.

[0553] (External quantum efficiency)

With respect to the produced organic EL device, the external extraction quantum efficiency (%) was measured when a constant current of ^2.5 mA / cm ² was applied in a dry nitrogen gas atmosphere at 23 ° C. For measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used in the same manner.

[0554] (Life)

2. When driving at a constant current of 5 mAZcm ² , measure the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance), and this is the half-life time (τ 0.5). And used as an index of life. For measurement, the spectral radiance meter CS-1000 (Co-Caminoolta Made).

[0555] The measurement results of external extraction quantum efficiency and lifetime in Table 4 are expressed as relative values when the organic EL element 2-1 is 100.

[0556] [Table 4]

[0557] From Table 4, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and had a long lifetime!

[0558] Example 6

《Preparation of organic EL element 3-1 to 3-3》

[0559] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 3-2 (20 mg) in 10 ml of toluene was spin-coated (film thickness: about 10 nm), ultraviolet light under conditions of 1000 rpm and 30 seconds. After being irradiated for 30 seconds, it was vacuum dried at 60 ° C. for 1 hour to provide an electron transport layer.

[0560] Next, spin-coat using a solution of Ji 8? (60111 ₈ ) and 11: -12 (3. Omg) dissolved in 12ml of toluene at 1000rpm for 30 seconds (approx. Film thickness approx. 30 nm) at 60 ° C. for 1 hour in vacuum to form a light emitting layer, and a cathode side portion was prepared.

As a positive electrode, a ITO substrate (100 mm X 100 mm X I. 1 mm thick ITO (indium tin oxide) filmed on lOOnm substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45)) was put on this ITO transparent electrode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. [0562] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness of about 40 nm) and ultraviolet light under conditions of 1000 rpm and 30 seconds. After irradiation for 30 seconds, vacuum drying was performed at 60 ° C. for 1 hour to form a hole transport layer.

[0563] Next, a solution obtained by dissolving CBP (60 mg) and Ir 1 (3. Omg) in 12 ml of toluene was spin-coated under a condition of 1000 rpm for 30 seconds (film thickness of about 30 nm) at 60 ° C. It vacuum-dried for 1 hour, it was set as the light emitting layer, and the anode side site | part was produced.

[0564] <Joint>

Thus it is opposed to the light-emitting layer and the light emitting layer on the anode side portion of the resulting cathode site overlay, using a bonding jig, the pressing force 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa It is pressed, adhered, fixed, and the anode side force is irradiated with ultraviolet light (lOOmWZcm ² ) for 90 seconds, and the resulting device is sealed (the glass substrates are bonded to each other using an epoxy adhesive) Organic EL element 3-1 was fabricated.

[0565] Organic EL device 3-1, except that the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 5 in the production of organic EL device 3-1. Organic EL devices 3-2 and 3-3 were fabricated using the same method.

[0566] 《Evaluation of organic EL device 3-1 to 3-3》

In the same manner as in Example 5, the external extraction quantum efficiency and lifetime were evaluated.

[0567] [Table 5]

[0568] From Table 5, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and achieved a long life!

[0569] Example 7

100mm X 100mm X I. Ultrasonic cleaning of 1mm glass substrate with isopropyl alcohol It was cleaned, dried with dry nitrogen gas, and washed with UV ozone for 5 minutes. This substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, 200 mg of aluminum is put into one of the resistance heating boats made of molybdenum, 200 mg of lithium fluoride is put into another resistance heating boat made of molybdenum, and Put another 200 mg BCP in a resistance heating boat made of molybdenum, put 200 mg CBP as a host compound in another resistance heating boat made of molybdenum, put lOO mg of Ir 9 in another resistance heating boat made of molybdenum, and put it in a vacuum evaporation system Attached.

[0570] in the following, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing the aluminum, aluminum was vapor-deposited (thickness of about l lOnm), followed by A thermal boat containing lithium fluoride was energized and heated to deposit lithium fluoride (film thickness of about 0.5 nm).

[0571] Next, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0. InmZ seconds to provide an electron transport layer having a thickness of about lOnm. Further, the heating boat containing CBP and Ir-9 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nmZ seconds and 0.012 nmZ seconds, respectively, A light emitting layer was provided, and a cathode side portion was prepared.

The ITO transparent electrode was provided after patterning was performed on a substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45) obtained by depositing ITO (indium tin oxide) on a 100 mm X 100 mm XI .1 mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, and a resistance heating boat made of molybdenum a N

200 mg of PD was placed and attached to a vacuum evaporation system.

[0573] After pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing a-NPD, it was deposited on the transparent supporting substrate at a deposition rate of 0. InmZ sec, film thickness 40nm The positive hole transport layer was provided, and the anode side part was produced.

[0574] <Join>

Thus overlay are opposed to the hole-transporting layer of a light-emitting layer and the anode side portion of the resulting cathode site, using a bonding time of ingredients, the pressing force under a reduced pressure environment of l X 10- ² Pa 0. IMPa The resulting device was sealed as it was, and the resulting device was sealed (glass substrates were bonded together using an epoxy adhesive) to produce an organic EL device 4-1.

[0575] Same as organic EL device 4-1, except that the compounds used in the electron transport layer, light emitting layer, and hole transport layer were replaced with the compounds shown in Table 6 in the preparation of organic EL device 41. The organic EL devices 4-2 and 4-3 were fabricated by this method.

[0576] Further, each of the organic EL devices 4-1 to 4-3 is a device after applying 5.0 mAZcm ² constant current for 100 hours at 23 ° C in a dry nitrogen gas atmosphere. — 6

[0577] <Evaluation of organic EL elements 4 1 to 4 6>

[0578] [Chemical 67] — PD

[0579] [Table 6]

[0580] From Table 6, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and achieved a long life!

[0581] Example 8

(Blue light emitting organic EL device) As the blue light-emitting organic EL element, the organic EL element 3-3 produced in Example 6 was used, and a blue light-emitting organic EL element 5-1B (blue) was obtained.

[0582] (Green light-emitting organic EL device)

A green light-emitting organic EL element 5-1G (green) was prepared in the same manner as in the production of the organic EL element 3-3 of Example 6 except that 2-7 was changed to 2-1.

[0583] (Red light-emitting organic EL device)

A red light emitting organic EL element 5-1R (red) was produced in the same manner as in the production of the organic EL element 3-3 of Example 6 except that 2-7 was changed to 2-5.

[0584] The above red, green and blue light emitting organic EL elements are juxtaposed on the same substrate to produce an active matrix type full color display device having the configuration shown in Fig. 1, and Fig. 2 shows the produced display. Only a schematic diagram of the display A of the apparatus is shown. That is, a wiring section including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (emission color is a pixel in a red region, a pixel in a green region, a pixel in a blue region, etc.) The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material force, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions ( Details are not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was fabricated by juxtaposing the red, green, and blue pixels appropriately.

[0585] It was confirmed that by driving the full-color display device, a full-color moving image display with a high luminous efficiency and a long luminous lifetime was obtained.

[0586] Example 9

In the same manner as in Example 6 except that the organic EL device 3-3 was changed to a mixture of 2-7, 2-1, and 2-5, and the white light emitting organic EL device 6 — 1W (white) was produced.

[0587] In evaluating the obtained organic EL element 6-1W, the non-light-emitting surface was covered with a glass case to obtain a lighting device. The lighting device emits white light with high luminous efficiency and long emission life It could be used as a thin lighting device.

[0588] Example 10

<< Production of organic EL elements 3e- l to 3e-3 >>

[0589] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving (t—Bu) PBD (20 mg) in 80 ml of toluene was spin-coated at 1000 rpm for 30 seconds, and vacuumed at 60 ° C for 1 hour. It dried and provided the electron carrying layer and produced the cathode side site | part.

[0590] <Production of anode side part>

As a positive electrode, a ITO substrate (100 mm X 100 mm X I. 1 mm thick ITO (indium tin oxide) filmed on lOOnm substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45)) was put on this ITO transparent electrode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

[0591] This substrate was attached to a commercially available spin coater, and poly (3,4 ethylene dioxythiophene) -polystyrene sulfonate (PEDOT / PSS ゝ Bayer, Baytron P A1 40 83) was made up to 70% with pure water. The diluted solution was formed into a film by spin coating at 3000 rpm for 30 seconds, and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

[0592] This substrate was transferred to a nitrogen atmosphere, and a solution obtained by dissolving Exemplified Compound 4 14 (50 mg) in 10 ml of toluene on the first hole transport layer was spin-coated under conditions of 1000 rpm and 30 seconds. After irradiation with ultraviolet light for 30 seconds, vacuum drying was performed at 60 ° C. for 1 hour to form a second hole transport layer.

[0593] Next! Was spin-coated using a solution of Comparative Compound 1 (60 mg) and Ir-1 (6. Omg) in 6 ml of toluene at 1000 rpm for 30 seconds (film thickness of about 60 nm). ), Vacuum-dried at 60 ° C. for 1 hour to form a light-emitting layer, and an anode side portion was prepared.

[0594] [Chemical 68]

[0595] <Bonding>

Thus superimposed to face the light-emitting layer electron-transporting layer and the anode side portion of the resulting cathode site, pressure 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa using a bonding jig The resulting device was subjected to heat treatment at 100 ° C for 1 hour, and the resulting device was sealed (using an epoxy adhesive) to produce an organic EL device 3e-1.

[0596] Organic EL device 3e-1 was prepared except that the compounds used in the electron transport layer, the light emitting layer, and the second hole transport layer were replaced with the compounds shown in Table 7 in the production of organic EL device 3e-1. Organic EL devices 3e-2 and 3e-3 were fabricated using the same method as l.

[0597] << Evaluation of organic EL elements 3e-1 to 3e-3 >>

[0598] [Table 7]

[0599] From Table 7, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and achieved a long life!

[0600] Example 11

100mm X 100mm X I. Ultrasonic cleaning of 1mm glass substrate with isopropyl alcohol After cleaning with dry nitrogen gas and UV ozone cleaning for 5 minutes, it is fixed to the substrate holder of a commercially available vacuum deposition apparatus, and aluminum (thickness: approx. LOnm), lithium fluoride (thickness: approx. 0) Wearing 5nm).

[0601] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 3-2 (20 mg) in 10 ml of toluene was spin-coated (film thickness about lOnm), ultraviolet light under conditions of 1000 rpm and 30 seconds. After being irradiated for 30 seconds, it was vacuum dried at 60 ° C. for 1 hour to provide an electron transport layer.

[0602] Next, using a solution of Ji 8? (60111 ₈ ) and 11: -12 (3. Omg) dissolved in 12 ml of toluene, spin-coated at 1000 rpm for 30 seconds (film thickness approx. 30 nm) at 60 ° C. for 1 hour in vacuum to form a light emitting layer, and a cathode side portion was prepared.

[0603] <Fabrication of anode side part>

[0604] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness of about 40 nm) and ultraviolet light under conditions of 1000 rpm and 30 seconds. After irradiation for 30 seconds, vacuum drying was performed at 60 ° C. for 1 hour to form a hole transport layer.

[0605] Next, a solution obtained by dissolving CBP (60 mg) and Ir 1 (3. Omg) in 12 ml of toluene was spin-coated at 1000 rpm for 30 seconds (film thickness of about 30 nm) at 60 ° C. It vacuum-dried for 1 hour, it was set as the light emitting layer, and the anode side site | part was produced.

[0606] <Joint>

Thus it is opposed to the light-emitting layer and the light emitting layer on the anode side portion of the resulting cathode site overlay, using a bonding jig, the pressing force 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa It is pressed, adhered, fixed, and the anode side force is irradiated with ultraviolet light (lOOmWZcm ² ) for 90 seconds, and the resulting device is sealed (the glass substrates are bonded to each other using an epoxy adhesive) An organic EL element 4e-1 was fabricated.

[0607] The same method as for organic EL element 4e-1, except that the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 8 in the preparation of organic EL element 4e-1. Organic EL devices 4e-2 and 4e-3 were fabricated by the above method.

[0608] << Evaluation of organic EL elements 4e- l to 4e-3 >>

[0609] [Table 8]

[0610] From Table 8, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and achieved a long life!

[0611] Example 12

<< Production of organic EL elements 5e- l to 5e-5 >>

100 mm X 100 mm X I. A 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaned for 5 minutes. This substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, 200 mg of aluminum is put into one of the resistance heating boats made of molybdenum, 200 mg of lithium fluoride is put into another resistance heating boat made of molybdenum, and Put 200 mg of BCP in a separate resistance heating boat made of molybdenum, put 200 mg of CBP as a host compound in another resistance heating boat made of molybdenum, put Ir 9 mg in another molybdenum resistance heating boat, and put it in a vacuum evaporation system. Attached.

[0612] in the following, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing the aluminum, aluminum was vapor-deposited (thickness of about l lOnm), followed by A thermal boat containing lithium fluoride was energized and heated to deposit lithium fluoride (film thickness of about 0.5 nm).

[0613] Next, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0. InmZ seconds to provide an electron transport layer having a thickness of about lOnm. Further, the heating boat containing CBP and Ir-9 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nmZ seconds and 0.012 nmZ seconds, respectively, Emissive layer is provided, cathode A side site was created.

[0614] <Fabrication of anode side part>

The ITO transparent electrode was provided after patterning was performed on a substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45) obtained by depositing ITO (indium tin oxide) on a 100 mm X 100 mm XI .1 mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, 200 mg of molybdenum resistance heating boat cocoon a-NPD was added, and it was attached to the vacuum vapor deposition apparatus.

[0615] After pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing a-NPD, it was deposited on the transparent supporting substrate at a deposition rate of 0. InmZ sec, film thickness 40nm The positive hole transport layer was provided, and the anode side part was produced.

[0616] <Bonding>

Thus overlay are opposed to the hole-transporting layer of a light-emitting layer and the anode side portion of the resulting cathode site, using a bonding time of ingredients, the pressing force under a reduced pressure environment of l X 10- ² Pa 0. Crimping, adhering, and fixing with IMPa, the resulting device was sealed as it was (glass substrates were bonded together using an epoxy adhesive) to produce organic EL device 5e-1.

[0617] In the production of the organic EL element 5e-1, the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 9, and the organic EL element 5e-1 Organic EL devices 5e-2 and 5e-3 were fabricated using the same method.

[0618] Further, each of the organic EL elements 5e-l to 5e-3 is 23 ° C under a dry nitrogen gas atmosphere 5.

The elements after applying OmAZcm ² constant current for 100 hours were designated as organic EL elements 5e-4 to 5e-6.

[0619] << Evaluation of organic EL elements 5e- l to 5e-6 >>

[0620] [Chem 69] α-NPD

[0621] [Table 9]

[0622] From Table 9, it was found that the organic EL device of the present invention was excellent in external extraction quantum efficiency and had a long lifetime!

[0623] Example 13

(Blue light emitting organic EL device)

As the blue light emitting organic EL element, the organic EL element 4e-3 prepared in Example 11 was used, and a blue light emitting organic EL element 6e-IB (blue) was obtained.

[0624] (Green light-emitting organic EL device)

A green light-emitting organic EL element 6e-1G (green) was produced in the same manner as in the production of the organic EL element 4e-3 of Example 11 except that 2-7 was changed to 2-1.

[0625] (Red light-emitting organic EL device)

A red light-emitting organic EL element 6e-1R (red) was produced in the same manner as in the production of the organic EL element 4e-3 of Example 11 except that 2-7 was changed to 2-5.

[0626] The above red, green, and blue light emitting organic EL elements are juxtaposed on the same substrate to fabricate an active matrix type full color display device having the configuration shown in FIG. 1, and FIG. Only the schematic diagram of the display part A of the manufactured display device is shown. That is, a wiring section including a plurality of scanning lines 5 and data lines 6 on the same substrate, and a plurality of juxtaposed pixels 3 (emission color is a pixel in a red region, a pixel in a green region, a pixel in a blue region, etc.) The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material force, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions ( Details are not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was fabricated by juxtaposing the red, green, and blue pixels appropriately.

[0627] It was confirmed that by driving the full-color display device, a full-color moving image display with a high light emission efficiency and a long light emission lifetime was obtained.

[0628] Example 14

In the same manner as in Example 11 organic EL device 4e-3, except that 2-7 was changed to a mixture of 2-7, 2-1, and 2-5, white light emitting organic EL device 7e-1W (white) was Produced.

[0629] In evaluating the obtained organic EL device 7e-1W, the non-light-emitting surface was covered with a glass case to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

[0630] Next, the invention (B) described in claims 13 to 22 will be specifically described below with reference to Examples 15 to 18.

[0631] The structures of the compounds used in Examples 15 to 18 are shown below.

[0632] [Chemical 70]

CBP NPD

[0633] Example 15

<< Preparation of organic-elect mouth luminescence element lb-1 (1) >>: Vapor deposition + bonding

The anode side substrate lb— 1—A and the cathode side substrate lb—1—B were prepared as follows, and then the anode side substrate lb—1—A and the cathode side substrate lb—1—B. The organic electoluminescence device lb-1 (1) was fabricated by pasting together.

[0634] <Preparation of anode side substrate lb-1A>

The ITO transparent electrode was provided after patterning was performed on a substrate (NH Techno Glass, NA45) on which ITO (Indium Toxide) was deposited on a 100 mm X 100 mm XI .1 mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

[0635] On this transparent support substrate, a solution obtained by diluting poly (3,4 ethylenedioxythiophene) polystyrene sulfonate (PEDOTZPSS ゝ Bayer, Baytron P A1 4083) to 70% with pure water, 3000rpm, After forming a film by spin coating in 30 seconds, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

[0636] The transparent support substrate provided with the first hole transport layer is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and on the other hand, as a material for forming the second hole transport layer on a resistance heating boat made of molybdenum, 4, 4'-Bis [N- (1-naphthyl) -N-phenolamino] biphenyl (OC-2: a-NPD) 200mg is put in a separate molybdenum resistance heating boat as a host compound. Add 200 mg of 4-di (n-power rubazole) biphenyl (OC 6), put 50 mg of tris (2 phenolic lysine) iridium (PD-1) into another molybdenum resistance heating boat, and put it in a vacuum evaporation system. Installed.

[0637] Next, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing OC- 2, at a deposition rate of 0. InmZ seconds, the first hole transport layer A second hole transport layer having a thickness of 30 nm was provided.

[0638] Further, the heating boat containing OC-6 and PD-1 was heated by energization, and co-deposited on the hole transport layer at a deposition rate of 0.2 nmZ seconds and 0.012 nmZ seconds, respectively. A light-emitting layer with a thickness of 25 nm was provided, and an anode side substrate lb-1A was produced. The substrate temperature during vapor deposition was room temperature. [0639] 《Preparation of cathode substrate lb— 1-B》

100 mm X 100 mm X I. A 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Add 200 mg of bis (2-methyl-8quinolinolato)-(p-phenolphenolato) aluminum (OC-28) as a material for forming an electron transport layer in a resistance heating boat made of molybdenum. boat and OC- 6 placed 200mg as Hosutoi匕合was a PD- 1 in a third resistive heating molybdenum boat charged 50mg, attached to a vacuum deposition apparatus, pressure in the vacuum tank was reduced to ⁴ X 10- 4 Pa.

[0640] On the substrate, aluminum lOnm and then lithium fluoride 0.5nm were vapor-deposited to form a cathode, and then the heating boat containing OC-28 was energized and heated, with a vapor deposition rate of 0.1nm. Vapor deposition was performed at a rate of 50 nm per second to provide an electron transport layer having a thickness of 50 nm.

[0641] Further, the heating boat containing OC-6 and PD-1 was heated by energization, and co-deposited on the electron transport layer at a deposition rate of 0.2 nmZ second and 0.012 nm / second, respectively. A light-emitting layer with a thickness of 25 nm was provided, and a cathode side substrate lb-1-B was produced. The substrate temperature during vapor deposition is room temperature.

[0642] << Preparation of organic EL element lb-1 (1) by bonding >>

The obtained glove box in a nitrogen atmosphere without contacting the anode side substrate lb-1—A and the cathode side substrate lb—1—B to the atmosphere (atmosphere of high purity nitrogen gas with a purity of 99.999% or more). in囲気under), and pressed at a pressing force 0. IMPa under vacuum environment lb-1-a 1 superposed and ^{lb- 1-B X 10- 2 Pa} , adhesion, and fixing, the organic EL element lb-1 (1) was produced.

[0643] <Production of organic EL device lb— 1 (2) to (5)>

Organic EL elements lb-1 (1) were manufactured in the same manner except that the manufacturing method was different, and organic EL elements lb 1 (2) to lb-1 (5) were respectively manufactured.

[0644] << Organic EL element lb 2 ~: Preparation of Lb 14 >>

In the production of the organic EL device lb-1, the thickness of each light emitting layer of the anode side substrate lb-1 A and the cathode side substrate lb-1 B was changed to the thickness shown in Table 10 at all. In the same manner, the elements lb-2 to Lb-14 were produced.

[0645] In Table 10, organic EL elements lb— 2 (1) to: Lb— 2 (5), lb— 5 (1) and lb— 5 ( 2), lb-6 (1), lb-6 (2), lb-7 (1), and lb-7 (2) each representing a different sample.

[0646] <Evaluation of organic EL device lb— 1 to lb— 14>

For each of the obtained organic EL devices lb-1 to Lb-14, color unevenness and driving voltage (also simply referred to as voltage) were measured and evaluated by the methods described below.

[0647] When evaluating the obtained organic EL devices lb-1 to Lb-14, the non-light-emitting surface of each organic EL device after fabrication was covered with a glass case, and a glass substrate having a thickness of 300 m was sealed. An epoxy-based photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material around the substrate as a sealing substrate, and this is overlaid on the cathode to be in close contact with the transparent support substrate. The substrate side cover was irradiated with UV light, cured and sealed, and an illumination device as shown in FIGS. 4 and 5 was formed and evaluated.

FIG. 4 shows a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102. Note that the glass cover was sealed with a glove box in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere (in a high purity nitrogen gas atmosphere with a purity of 99.999% or more). FIG. 5 shows a cross-sectional view of the lighting device. In FIG. 5, 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

[0649] <Measurement of drive voltage>

The voltage at the start of light emission was measured at a temperature of 23 ° C. in a dry nitrogen gas atmosphere. The voltage at the start of light emission was measured when the luminance was 50 cd / m ² or more. A spectral radiance meter CS-1000 (manufactured by Koryo Minolta Sensing) was used for the luminance measurement.

[0650] <Measurement of non-light emitting point and color unevenness>

About the produced organic EL element, the non-light-emitting point and the color unevenness of the light-emitting surface when the luminance reached 300 cdZm ² or more were measured visually at 23 ° C. in a dry nitrogen gas atmosphere.

[0651] Table 10 shows the obtained results.

[0652] Regarding the evaluation, the following rank evaluation was performed.

[0653] ○: No non-light-emitting point and color unevenness were observed,

X: Non-light emitting point and color unevenness were observed, The driving voltage is expressed as a relative value when the value of the organic EL element lb-1 (1) is 100.

[Table 10]

From Table 10, it can be seen that the organic EL element power of the present invention shows good characteristics for both the non-emission point and the color unevenness. In addition, when the thickness of the light emitting layer is 40 nm or less, non- It is clear that the emission point and emission unevenness occur, and that if the emission layer thickness exceeds lOOnm, the emission start voltage increases and the organic EL device cannot perform sufficiently.

[0656] Example 16

<Production of organic EL element 2b-1>: Production by coating and bonding

The anode side substrate 2b—1—A and the cathode side substrate 2b—1—B were respectively prepared as follows, and then the anode side substrate 2b—1—A and the cathode side substrate 2b—1—B. The organic electoluminescence device 2b-1 was produced by pasting together.

[0657] <Preparation of anode-side substrate 2b-1-A>

The ITO transparent electrode was provided after patterning was performed on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) on which ITO (indium oxide) was deposited on a 100 mm X 100 mm X I. 1 mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

[0658] On this transparent support substrate, a solution of poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOTZPSS P Bayer, Baytron P A1 4083) diluted to 70% with pure water at 3000 rpm After forming a film by spin coating in 30 seconds, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

[0659] On the first hole transport layer, a solution of 30 mg of MO-10 in 3 ml of toluene was formed by spin coating at 1000 rpm for 30 seconds, and the temperature was adjusted to 150 ° C under nitrogen. The mixture was heated for 1 hour to polymerize the reactive groups in the MO-10 molecule, and an insoluble soot treatment was performed.

[0660] As a result, a second hole transport layer having a film thickness of 30 nm composed of a polymer film of MO-10 was provided by heat treatment. Furthermore, a solution of 30 mg OC-6 and 1.5 mg PD-1 dissolved in 3 ml of toluene was formed on the second hole transport layer by spin coating under conditions of 1500 rpm and 30 seconds. 15 The substrate was dried at 0 ° C. for 1 hour, provided with a light emitting layer having a thickness of 25 nm, and an anode side substrate 2b-1-A was produced.

[0661] << Preparation of cathode side substrate 2b-1-B >>

100 mm X 100 mm X I. A 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Attached to the vacuum evaporation system and the vacuum chamber is 4 X 10— ⁴ The pressure was reduced to Pa. An aluminum-magnesium alloy lOnm was deposited on the substrate to form a negative electrode.

[0662] Separately, a solution of 30 mg of MO-52 polymer (number average molecular weight 71,000), prepared by radical polymerization of MO-52 using peroxybenzoyl as an initiator, was dissolved in 3 ml of dichroic benzene. On the cathode, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds, and dried at 150 ° C. for 1 hour to provide an electron transport layer having a thickness of 50 nm.

[0663] Further, on the electron transport layer, a solution of 30 mg OC-6 and 1.5 mg PD-1 dissolved in 3 ml of toluene was formed by spin coating at 1500 rpm for 30 seconds. The substrate was dried at 150 ° C. for 1 hour, a light emitting layer having a film thickness of 25 nm was provided, and a cathode side substrate 2b-1-B was produced. The substrate temperature during vapor deposition was room temperature.

[0664] << Preparation of organic EL element 2b-1 by bonding >>

Organic EL device lb-1 in Example 15 1 As in the production of (1), the anode side substrate 2b— 1—A and the cathode side substrate 2b—1—B were bonded together, and the organic EL device 2b—1 Was made.

[0665] << Preparation of organic EL device 2b-2 >>: Comparative example (Sequential deposition deposition)

[0666] A solution obtained by diluting poly (3,4 ethylenedioxythiophene) -polystyrene sulfonate (PEDOTZPSS Bayer, Baytron P Al 4083) to 70% with pure water on this transparent support substrate at 3000 rpm, After forming a film by spin coating in 30 seconds, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

[0667] The transparent support substrate provided with the first hole transport layer is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and on the other hand, as a material for forming the second hole transport layer on a resistance heating boat made of molybdenum, 200 mg of OC-1 is put into another resistance heating boat made of molybdenum, 200 mg of OC 6 as a host compound, 50 mg of PD-1 is put into an additional IJ molybdenum resistance heating hot water bath, and 200 mg of OC-18 is put into vacuum. Attached to the vapor deposition equipment.

[0668] Next, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, the heating boat containing OC- 1 The second hole transport layer having a film thickness of 30 nm was provided by heating by energization and depositing on the first hole transport layer at a deposition rate of 0. InmZ seconds.

[0669] Further, the heating boat containing OC-6 and PD-1 was heated by energization, and co-evaporated on the second hole transport layer at a deposition rate of 0.2 nmZ second and 0.012 nm / second, respectively. Then, a light emitting layer with a thickness of 50 nm was provided, and then heated by energizing the heating boat containing OC-18, and deposited on the light emitting layer at a deposition rate of 0. InmZ seconds. An electron transport layer was provided. Finally, lithium fluoride 0.5 nm and then aluminum lOnm were vapor-deposited to form a cathode, and an organic EL device 2b-2 was produced.

[0670] << Evaluation of organic EL element lb-1 (1), 2b-1, 1, 2b-2 >>

For each of the obtained organic EL devices lb-1 (1), 2b-1, and 2b-2, the external extraction quantum efficiency, emission lifetime, and driving voltage (also simply referred to as voltage) The light emission point and color unevenness were measured and evaluated. Measurements of drive voltage, non-light emission point, and color unevenness were performed in exactly the same manner as in Example 15.

[0671] The external extraction quantum efficiency, the light emission lifetime, and the driving voltage are expressed as relative values when the organic EL element lb-1 (1) is 100.

[0672] <Measurement of external extraction quantum efficiency>

With respect to the produced organic EL device, the external extraction quantum efficiency (%) was measured when a constant current of ^2.5 mA / cm ² was applied in a dry nitrogen gas atmosphere at 23 ° C. The measurement was performed using a spectral radiation luminance meter CS-1000 (manufactured by Coforce Minolta Sensing).

[0673] <Measurement of luminous lifetime>

When driving at a constant current of 2.5 mAZcm ^{2 in} a dry nitrogen gas atmosphere at a temperature of 23 ° C, the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured. Was used as an index of life as a half-life time (τ 0.5). For the measurement, a spectral radiance meter CS-1000 (manufactured by Coforce Minolta Sensing Co., Ltd.) was used.

[0674] Organic EL devices lb— 1 (1) (invention), 2b-2 (invention) and 2b-3 (comparative example) external extraction quantum efficiency, emission lifetime, drive voltage, non-emission point and Table 11 shows the measurement results of color unevenness. Each measured value is expressed as a relative value when the organic EL element lb-1 (1) is 100. [0675] [Table 11]

[0676] From Table 11, the basic performance of the organic EL elements such as external extraction quantum efficiency, emission lifetime, drive voltage, non-emission point, and color unevenness are the same as those using the conventional vapor deposition lamination process. Is shown. In particular, even when the coating method, which has been said to be inferior to the deposition system so far, was used, it showed almost the same performance. It has been found that by using the manufacturing method of the present invention, an innovative organic EL device manufacturing process can be provided without degrading various performances as an organic EL device.

[0677] Example 17

(Blue light emitting organic EL device)

A blue light-emitting organic EL device 2b-1B (blue) was prepared in the same manner as in the production of the organic EL device 2b-1 of Example 16, except that PD-1 was changed to PD-12.

[0678] (Green light-emitting organic EL device)

As the green light-emitting organic EL element, the organic EL element 2b-1 produced in Example 16 was used.

[0679] (Red light-emitting organic EL device)

A red light-emitting organic EL device 2b-1R (red) was produced in the same manner as in the organic EL device 2b-1 of Example 16, except that PD-1 was changed to PD-6.

[0680] The red, green, and blue light-emitting organic EL elements described above are juxtaposed on the same substrate to produce an active matrix full-color display device having the form shown in FIG. 1, and FIG. Only a schematic diagram of the display unit A of the display device is shown. That is, a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 arranged in parallel on the same substrate (light emitting color is a pixel in a red region, a pixel in a green region, a pixel in a blue region, etc.) The scanning line 5 and the plurality of data lines 6 in the wiring part are each made of a conductive material, and the scanning line 5 and the data line 6 are orthogonal to each other in a lattice shape. Thus, the pixel 3 is connected at the orthogonal position (details are not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is received from a scanning line 5. When applied, it receives an image data signal from the data line 6 and emits light according to the received image data. In this way, a full-color display device was produced by appropriately juxtaposing the red, green, and blue pixels.

[0681] It was confirmed that by driving the full-color display device, it was possible to obtain a full-color moving image display with high luminous efficiency and long emission life.

[0682] Example 18

(a) In the organic EL device 2b-1 of Example 16, the PD-1 used for the anode side substrate 2b-1A and the cathode side substrate 2b-1 B is PD-1, PD-6, A white light-emitting organic EL device 2b-1W (white) was produced in the same manner except that PD-12 was used.

[0683] (b) In the organic EL element 2b-1 of Example 16, PD-1 used for the anode side substrate 2b-1A was PD-13, and further, for preparing the cathode side substrate 2b-1B A white light-emitting organic EL device 3b-1W (white) was produced in the same manner except that the PD-1 used was changed to PD-10.

[0684] When the obtained organic EL elements 2b-1W and 3b-1W were evaluated, the non-light emitting surface was covered with a glass case in the same manner as in Example 15 to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

[0685] The invention described in claims 23 to 31 will be specifically described below with reference to Examples 19 to 24.

[0686] Example 19

100 mm X 100 mm X I. 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, attached to a commercially available spin coater, and α-NPD (60 mg) was added. Using a solution dissolved in 10 ml of toluene, a sample a was obtained by spin coating (film thickness: about 40 nm) under conditions of 1000 rpm and 30 sec.

[0687] [Chemical 71]

[0688] On the α-NPD side of this sample a, press it onto a metal roller with Ra = lOOnm at a surface temperature of the metal roller of 60 ° C, linear pressure of 500 NZcm, 1. OmZsec. Obtained. Similarly, Sample 1 was treated with a metal roller with Ra = 0.lnm to obtain Sample 2c-2.

[0689] Next, a 100mm X 100mm X 1.1mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, and then a substrate for a commercial vacuum deposition apparatus. Fixed to a holder, 200 mg of a-NPD was placed in a molybdenum resistance heating boat and attached to a vacuum evaporation system. After pressure in the vacuum tank was reduced to ^{4 X 10- 4 Pa, a- NP} D of containing and heated by supplying an electric current to the boat, deposited on a transparent supporting substrate at a deposition rate of 0. InmZsec (thickness 40 nm), a sample got b.

[0690] Sample lc-3 was obtained by pressing the sample b on the α-NPD side against a metal roller with Ra = 80 nm (linear pressure 500 NZ cm, temperature 60 ° C, speed 1. OmZsec). Similarly, Sample 1 was treated with a metal roller with Ra = 0.lnm to obtain Sample lc-4.

[0691] The surface roughness (Ra) of samples lc—l to lc—4 obtained in this way was measured using AFM (atomic force microscope; Seiko Instruments Inc. SPI3800N probe station and SPA400 multifunctional type. Unit), and the results shown in Table 12 were obtained.

[0692] [Table 12]

[0693] In both the coating layer and the organic thin film obtained by vapor deposition, the specified surface roughness (Ra It is clear that an organic thin film (layer) with a corresponding surface roughness can be obtained by a metal roller with).

[0694] Example 20

Production of cathode side member

[0695] This substrate was attached to a commercially available spin coater, and a solution in which BCP (20 mg) was dissolved in 10 ml of toluene was used. Spin coating (film thickness: about 10 nm) at 60 ° C for 1 hour under conditions of 1000 rpm and 30 sec. It dried and provided the electron carrying layer, and produced the cathode side member.

[0696] Fabrication of anode side member

[0697] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness: about 40 nm) and ultraviolet light was used under conditions of 1000 rpm and 30 sec. After irradiation for 2 seconds, it was vacuum-dried at 60 ° C for 1 hour to form a hole transport layer.

[0698] Next !, using a solution of CBP (60 mg) and the exemplified compound Ir 1 (3. Omg) dissolved in 6 ml of toluene, spin-coated at 1000 rpm for 30 sec (film thickness: about 60 nm) Then, it was vacuum dried at 60 ° C. for 1 hour to form a light emitting layer, and an anode side member was produced.

[0699] Surface treatment with metal roller

The prepared cathode-side member and anode-side member were each pressed with a metal roller having a specific surface roughness under the conditions of Example 19 to obtain members having a surface roughness (Ra) shown in Table 13.

[0700] Joining

The electron transport layer of the cathode-side member and the light-emitting layer of the anode-side member obtained in this way are respectively provided. Overlay Re are opposed, with a joining jig and pressed by the pressing force 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa, adhesion, fixing, for 1 hour heat treatment at 100 ° C, the finished The device was sealed (using an epoxy adhesive) to produce an organic EL device 2c-1.

[0701] In the production of the organic EL device 2c-1, the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 13, and the metal roller on the surface of the organic layer was replaced. 2c-The same method as for organic EL elements 2c-1 except that the surface roughness of each layer was changed as shown in Table 13 by changing the type (surface roughness) of the metal roller during the crimping surface treatment. -2 to 2c-6 were prepared. The structure of the compound used above is shown below.

[0702] [Chemical 72]

CBP BCP

[0703] [Table 13]

CO 1

CM CM

Element Element Element Element Two Element Element Element Two Element 22221

CO 03

Inventor Inventor Inventor Inventor Comparer Comparer Ratio Ratio 1

Layer transport

ΙΩ Light emitting layer

1

CM transport hole

ΟΓ οεOToοοτα πΐ mu ιπιι

1 \ 1 layer) (Trans-Transfer Ol Rnm a.

CO <M oOTou r

Light (layer) Ol Ol 20 R Olnmnmnranm a ...

1 inch

O

1

1 ^

<0704] <Evaluation of organic EL devices 2c— l to 2c— 6>

Evaluation of organic EL devices 2c— :! to 2c—4 produced as follows was performed, and the results are shown in Table 14.

[0705] (External extraction quantum efficiency) The fabricated organic EL device was measured for external extraction quantum efficiency (%) when a 2.5 mA / cm ′ constant current was applied at 23 ° C. in a dry nitrogen gas atmosphere. For measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used in the same manner.

[0706] The measurement results of the external extraction quantum efficiency in Table 14 are expressed as relative values when the measured value of the organic EL element 2c-1 is 100.

[0707] (Life)

2. When driving at a constant current of 5 mAZcm ² , measure the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance), and this is the half-life time (τ 0.5). And used as an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used.

[0708] The lifetime measurement results in Table 14 are expressed as relative values when the organic EL element 2c-1 is 100.

[0709] [Table 14]

[0710] From Table 14, it was found that the organic EL device of the present invention achieved a longer life than the comparison. In particular, a material having a reactive substituent (bule group) is included in each of the two layers to be bonded by heat treatment (an electron transport material having a vinyl group is present in the electron transport layer of the cathode side member). In addition, the lifetime of the elements 2c-5 and 2c-6 is further improved. The light emitting layer of the anode side member also contains a host material and a dopant material having a bull group.

[0711] Example 21

Production of cathode side member

[0712] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 3-2 (20 mg) in 10 ml of toluene was spin-coated (film thickness about lOnm) and ultraviolet light under conditions of 1000 rpm and 30 sec. After irradiation for 30 seconds, vacuum drying was performed at 60 ° C for 1 hour to provide an electron transport layer.

[0713] Next, a solution obtained by dissolving CBP (60 mg) and the exemplified compound Ir-12 (3. Omg) in 12 ml of toluene was spin-coated under a condition of 1000 rpm and 30 sec (film thickness of about 30 nm). A cathode side member was produced by vacuum drying at ° C for 1 hour to form a light emitting layer (light emitting layer 1).

[0714] Fabrication of anode side member

[0715] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness of about 40 nm) and ultraviolet light was used under conditions of 1000 rpm and 30 sec. After irradiation for 2 seconds, it was vacuum-dried at 60 ° C for 1 hour to form a hole transport layer.

[0716] Next, a solution obtained by dissolving CBP (60 mg) and the exemplified compound Ir-12 (3. Omg) in 12 ml of toluene was spin-coated under a condition of 1000 rpm and 30 sec (film thickness of about 30 nm). Vacuum drying was performed at ° C for 1 hour to form a light emitting layer (light emitting layer 2), and an anode side member was produced.

[0717] Surface treatment with metal roller

The prepared cathode-side member and anode-side member (the surfaces (the surfaces of the light-emitting layer 1 and the light-emitting layer 2)) were pressure-bonded in the same manner as in Example 19 with metal rollers having inherent surface roughness, The members having the surface roughness (Ra) shown in Table 15 were obtained.

[0718] Joining

Thus it is opposed to the light emitting layer of the light-emitting layer and the anode-side member of the resulting cathode side member overlay, using a bonding jig, the pressing force 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa Pressed, adhered and fixed, and the anode side force was irradiated with ultraviolet light (lOOmWZcm ² ) for 90 seconds. The device was sealed (glass substrates were bonded together using an epoxy adhesive) to produce an organic EL device 3c-1.

[0719] In the production of the organic EL device 3c-1, the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 15, and the surface of the metallic roller during the surface treatment (compression treatment) was changed. Organic EL element 3c except that the type was changed and the surface roughness was changed as shown in Table 15.

-3c-2 to 3c-4 were prepared in the same way as 1.

[0720] [Table 15]

[0721] <Evaluation of organic EL devices 3c— l to 3c— 4>

The organic EL devices 3c-1 to 3c-4 produced as follows were evaluated and the results are shown in Table 16.

[0722] (External extraction quantum efficiency)

[0723] The measurement results of the external extraction quantum efficiency in Table 16 are expressed as relative values when the measured value of the organic EL element 3c-1 is 100.

[0724] (Life)

2. When driving at a constant current of 5 mAZcm ² , measure the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance), and this is the half-life time (τ 0.5). And used as an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used. [0725] The lifetime measurement results in Table 16 are expressed as relative values when the organic EL element 3c-1 is 100.

[0726] [Table 16]

[0727] From Table 16, it was found that the organic EL device of the present invention had a long lifetime.

In addition, a device having a reactive substituent (vinyl group) reacted by UV irradiation and bonded to device 3c-4 (both the light-emitting layers 1 and 2 contain a host material and a dopant material having a vinyl group). The life is further improved.

[0728] Example 22

Production of cathode side member

100 mm X 100 mm X I. A 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaned for 5 minutes. This substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, 200 mg of aluminum is put in one of the resistance heating boats made of molybdenum, and 200 mg of lithium fluoride is put in another resistance heating boat made of molybdenum. 200 mg of BCP is put into a resistance heating boat made of molybdenum, 200 mg of CBP as a host compound is put into another resistance heating boat made of molybdenum, and lOOmg of the exemplified compound Ir 9 is put into another resistance heating boat made of molybdenum and attached to a vacuum evaporation system. It was.

[0729] in the following, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing the aluminum, aluminum was vapor-deposited (thickness of about l lOnm), followed by Then, electricity was supplied to a heat boat containing lithium fluoride and heated to deposit lithium fluoride (film thickness: about 0.5 nm).

[0730] Next, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0. InmZsec to provide an electron transport layer having a thickness of about lOnm.

[0731] Further, the heating boat containing CBP and the exemplified compound Ir 9 was energized and heated, and co-evaporated on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.012 nm / sec, respectively. do it, A light emitting layer having a thickness of 40 nm was provided to produce a cathode side member.

[0732] Fabrication of anode side member

The ITO transparent electrode was provided after patterning was performed on a substrate (ΝΗ Techno Glass Co., Ltd. ΝΑ45) obtained by depositing ITO (indium tin oxide) on a 100 mm X 100 mm XI .1 mm glass substrate as an anode. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. This transparent support substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, and a molybdenum resistance heating boat is used.

— 200 mg of NPD was added and attached to the vacuum evaporation system.

[0733] After pressure in the vacuum tank was reduced to ⁴ X 10- 4 Pa, and heated by supplying an electric current to the boat containing a-NPD, it was deposited on the transparent supporting substrate at a deposition rate of 0. InmZsec, the film thickness 40nm A positive hole transport layer was provided to produce an anode side member.

[0734] Surface treatment with metal roller

The prepared cathode-side member and anode-side member were each pressed with a metal roller having a specific surface roughness in the same manner as in Example 19, peeled, and peeled to the surface roughness (Ra) members shown in Table 17. Got.

[0735] Joining

Thus it is opposed to the light emitting layer of the light-emitting layer and the anode-side member of the resulting cathode side member overlay, using a bonding jig, the pressing force 0. IMPa under a reduced pressure environment of 1 X 10- ² Pa The organic EL device 4c-1 was produced by sealing, bonding, and fixing the resulting device as it was (glass substrates were bonded together using an epoxy adhesive).

[0736] In the production of the organic EL device 4c 1, the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 17 in the same manner as the organic EL device 4c 1. 2-4c-4 were produced.

[0737] Further, each of the organic EL elements 4c-l to 4c-4 was subjected to an OmAZcm ² constant current for 100 hours at 23 ° C in a dry nitrogen gas atmosphere. -4c-8.

[0738] [Table 17] Element 4 c-1 Element 4 c -2 Element 4 c One 3 Element 4 c -4 Element 4 c One 5 Element 4 c One 6 Element 4 c -7 Element 4 c One 8 Comparison Comparison The present invention Electron transport Layer BCP BCP BCP 3- 2

CBP / lr- 9 CBP / lr-9 CBP / lr-9 1 1 2/2 5 Hole transport layer a-NPD a -NPD a-NPD 4-1

R a (light emitting layer) 100 lOOnm O.lnm O.lnm

R a (hole transport layer) lOOnm O.lnm O.lnm O.lnm

[0739] <Evaluation of organic EL devices 4c l to 4c 8>

Evaluation of organic EL devices 4c-1 to 4c-8 produced as follows was performed, and the results are shown in Table 18.

[0740] (External quantum efficiency)

[0741] The measurement results of the external extraction quantum efficiency in Table 18 are expressed as relative values when the measured value of the organic EL element 4c 1 is 100.

[0742] (Life)

When driving at a constant current of 2.5 mAZcm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) is measured, and this is used as the half-life time (τ 0.5). It was used as an index. For the measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used.

[0743] The measurement results of lifetime in Table 18 are expressed as relative values when the organic EL element 4c-1 is 100.

[0744] [Table 18] External quantum efficiency 卩 Remarks

Element 4 c-1 100 100 Comparison

Element 4 c 1 2 81 91 Comparison

Element 4 c-3 112 123 Present invention

Element 4 c to 4 119 250 The present invention

Element 4 c 1 5 88 84 Comparison (energization)

Element 4 c 1 6 72 66 Comparison (energization)

Element 4 c-7 108 182 Present invention (energized)

Element 4 c-8 116 381 Present invention (energized)

[0745] From Table 18, it was found that the organic EL device of the present invention had a long lifetime.

It can be seen that materials using a polymerizable vinyl group (host material, hole transport material, etc.) in the two bonded layers have a longer lifetime, and organic EL elements 4c— l to 4c— 4 Of the organic EL elements 4c-5 to 4c-8, each of which is driven at a constant current for 100 hours, the lifetimes of the elements 4c-7 and 4c-8 of the present invention are further improved.

[0746] Example 23

(Blue light emitting organic EL device)

As the blue light emitting organic EL element, the organic EL element 3c-4 prepared in Example 21 was used, and a blue light emitting organic EL element 5c-1B (blue) was obtained.

[0747] (Green light-emitting organic EL device)

Green light-emitting organic EL element 5c-1G (green) was produced in the same manner as in the production of organic EL element 3c-4 of Example 21, except that 2-7 was changed to 2-1.

[0748] (Red light-emitting organic EL device)

A red light emitting organic EL element 5c-1R (red) was produced in the same manner as in the production of the organic EL element 3c-4 of Example 21, except that 2-7 was changed to 2-5.

[0749] The above red, green, and blue light emitting organic EL elements are juxtaposed on the same substrate to produce an active matrix type full-color display device having the form shown in FIG. 1, and FIG. Only a schematic diagram of the display unit A of the display device is shown. That is, a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 arranged in parallel on the same substrate (light emission color is a pixel in a red region, a pixel in a green region, a pixel in a blue region, etc.) Scanning lines 5 and multiple Each of the data lines 6 has a conductive material force, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are not shown). The plurality of pixels 3 (a schematic diagram of the drive circuit of each pixel is shown in FIG. 3) is an organic EL element corresponding to each emission color, a switching transistor 11 and an drive transistor 12 which are active elements, respectively. When the scanning signal is applied from the scanning line 5, an image data signal is received from the data line 6, and light is emitted according to the received image data. 7 is a power line, 10 is an organic EL element, and 13 is a capacitor.

[0750] In this way, a full-color display device was produced by appropriately juxtaposing the red, green, and blue pixels.

[0751] It was confirmed that by driving the full-color display device, a full-color moving image display with a high luminous efficiency and a long luminous lifetime was obtained.

[0752] Example 24

In the same manner as in Example 21 organic EL device 3c-4, except that 2-7 was changed to a mixture of 2-7, 2-1, and 2-5, white light emitting organic EL device 6c-1W (white) was Produced.

[0753] When the obtained organic EL element 6c-1W was evaluated, the non-light-emitting surface was covered with a glass case to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

[0754] Hereinafter, the inventions described in claims 32 to 40 will be specifically described by Examples 25 to 30.

[0755] Example 25

[0756] This substrate was attached to a commercially available spin coater, and the following compound BCP (60 mg) was added to toluene 10 Using a solution dissolved in ml, spin coating (film thickness of about 40 nm) under conditions of 1000 rpm and 30 sec

Then, a first electrode substrate having one organic layer was produced.

[0757] <Production of second electrode substrate>

Attach the UV ozone-cleaned substrate used in the preparation of the first electrode substrate to a commercially available spin coater, and use a solution of the following compound CBP (60 mg) dissolved in 10 ml of toluene.

Spin coat (film thickness about 40nm) under the condition of 1000rpm, 30sec, and the first organic layer

Two electrode substrates were prepared.

[0758] The organic layers of the first electrode substrate and the second electrode substrate obtained as described above were overlapped with each other, fixed with a joining jig, and heat-treated at 100 ° C for 1 hour to obtain an element. Id-1 was produced.

[0759] Element Id-1 was prepared except that the compounds used in the organic layers of the first electrode substrate and the second electrode substrate and the post-treatment method were replaced with the methods shown in Table 19 in the preparation of element Id-1. The devices Id-2 and Id-3 were fabricated by the same method.

[0760] The structures of the compounds used above are shown below.

[0761] [Chemical 73]

CBP BCP

[0762] [Measurement of peel strength]

The peel strength of the element was measured by the SAICAS method using a SAICAS NN-04 model manufactured by Daipura Wintes. The SAICAS method uses a sharp cutting edge (single crystal diamond, burned-bonded gold) to measure the horizontal load required to move at a constant speed in the horizontal direction while maintaining a constant vertical load. Thus, the peel strength of the thin film can be measured.

[0763] The measurement conditions are as follows.

[0764] Psycho measurement conditions Equipment: Daipla · Wintes Cycus NN-04 type

Measurement condition;

A diamond lmm wide blade is used. Shear angle is 45 °

The pressing load 2 mu New, and balance weight 1 _mu New, vertical speed LnmZsec, perform cutting in a horizontal velocity 100η mZsec, were recorded horizontal and vertical forces. The sampling step is 0.2 sec / point.

[Table 19]

[0766] It can be seen that the peel strength between layers can be measured by the above measurement method.

Example 26

100mm X 100mm X I. lmm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, UV ozone cleaned for 5 minutes, then fixed to a commercially available vacuum evaporation system substrate holder, Aluminum (thickness: about lOnm) and lithium fluoride (thickness: about 0.5 nm) were applied.

[0767] This substrate was attached to a commercially available spin coater, and a solution of BCP (20 mg) dissolved in 10 ml of toluene was used. Spin coating (film thickness: about 10 nm) at 60 ° C for 1 hour under conditions of 1000 rpm and 30 sec. After drying, an organic layer (electron transport layer) was provided, and a first electrode substrate (cathode side) was produced.

[0768] <Production of second electrode substrate>

As a positive electrode, a ITO substrate (100 mm X 100 mm X I. lmm) on which ITO (indium tin oxide) is deposited on lOOnm (Pure 45 made by Techno Glass Co., Ltd.) was patterned, and then this ITO transparent electrode was provided. A transparent support substrate with isopropyl alcohol Washed, dried with dry nitrogen gas, and UV ozone washed for 5 minutes.

[0769] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness: about 40 nm) and ultraviolet light was used under conditions of 1000 rpm and 30 sec. After irradiation for 2 seconds, it was vacuum dried at 60 ° C for 1 hour to form an organic layer (hole transport layer).

[0770] Next, spin-coat using a solution of CBP (60 mg) and the exemplified compound Ir 1 (3. Omg) dissolved in 6 ml of toluene at 1000 rpm for 30 sec (film thickness of about 60 nm) Then, it was vacuum-dried at 60 ° C. for 1 hour to form a light emitting layer. In this way, a second electrode substrate (anode side) having a hole transport layer and a light emitting layer as an organic layer was produced.

[0771] The organic layers of the first electrode substrate (cathode side) and the second electrode substrate (anode side) obtained in this way were placed facing each other, fixed with a joining jig, and 1 ° C at 100 ° C. Overtime heat treatment was performed, and the resulting device was sealed to produce an organic EL device 2d-1.

[0772] Same as organic EL device 2d-1, except that the compounds used in the electron transport layer, light emitting layer, and hole transport layer were replaced with the compounds shown in Table 20 in the preparation of organic EL device 2d-1. Organic EL devices 2d-2 and 2d-3 were fabricated by this method.

[0773] [Table 20]

<0774] <Evaluation of organic EL elements 2d-l to 2d-3>

Evaluation of organic EL devices 2d-1 to 2d-3 produced as follows was performed and the results are shown in Table 21.

[0775] (External extraction quantum efficiency)

[0776] The measurement results of external extraction quantum efficiency in Table 21 are the measured values of organic EL element 2d-1 100. It was expressed as a relative value.

[0777] (Life)

[0778] The lifetime measurement results in Table 21 are expressed as relative values when the organic EL element 2d-1 is 100.

[0779] The peel strength at the joint surface was measured in the same manner as in Example 25, and the results are shown in Table 21.

[0780] [Table 21]

[0781] From Table 21, it was found that the organic EL device of the present invention had a long lifetime.

[0782] Example 27

[0783] This substrate was attached to a commercially available spin coater, and a solution of Exemplified Compound 3-2 (20 mg) dissolved in 10 ml of toluene was used. Spin coating (film thickness: about 10 nm) and ultraviolet light were performed at 1000 rpm for 30 sec. After irradiation for 30 seconds, vacuum drying was performed at 60 ° C for 1 hour, and an electron transport layer was provided as an organic layer. [0784] Next, a solution obtained by dissolving CBP (60 mg) and the following compound Ir-12 (3. Omg) in 12 ml of toluene was spin-coated under a condition of 1000 rpm and 30 sec (film thickness: about 30 nm). A light emitting layer was formed by vacuum drying at ° C for 1 hour. In this way, a first electrode substrate (cathode side) having an electron transport layer and a light emitting layer as an organic layer was produced.

[0785] <Production of second electrode substrate>

[0786] This substrate was attached to a commercially available spin coater, and a solution obtained by dissolving Exemplified Compound 4 1 (60 mg) in 10 ml of toluene was spin-coated (film thickness: about 40 nm) and ultraviolet light was used under conditions of 1000 rpm and 30 sec. After irradiation for 2 seconds, vacuum drying was performed at 60 ° C. for 1 hour to form a hole transport layer as an organic layer.

[0787] Next, a solution obtained by dissolving Compound CBP (60 mg) and Compound Ir 1 (3. Omg) in 12 ml of toluene was spin-coated under conditions of 1000 rpm and 30 seconds (film thickness of about 30 nm), and 60 ° A light emitting layer was formed as an organic layer by vacuum drying with C for 1 hour. In this way, a second electrode substrate (anode side) having a hole transport layer and a light emitting layer as an organic layer was produced.

[0788] The light emitting layers of the first electrode substrate (cathode side) and the second electrode substrate (anode side) obtained in this way are overlapped and fixed with a bonding jig, and the anode side force is also UV light. Was irradiated for 90 seconds, and the resulting device was sealed to produce an organic EL device 3d-1.

[0789] Same as organic EL element 3d-1, except that the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 22 in the preparation of organic EL element 3d-1. 3d-2 and 3d-3 were prepared by this method.

[0790] [Table 22] Device No. Electron transport layer Fluorescent layer Hole transport layer Remarks

3 d-1 3-2 C B P / l r-12 4-1 Comparison

3 d-2 3-2 1 1 2 / I r— 12 4 1 1

3 d— 3 3-2 1 1 2 / 2— 7 4-1 The present invention [0791] <Evaluation of organic EL device 3d- l 3d-3>

Evaluation of the organic EL devices 3d-l 3d-3 produced as follows was performed, and the results are shown in Table 23.

[0792] (External extraction quantum efficiency)

[0793] The measurement results of the external extraction quantum efficiency in Table 23 are expressed as relative values when the measured value of the organic EL element 3d-1 is 100.

[0794] (Life)

[0795] Lifetime measurement results in Table 23 are expressed as relative values when the organic EL element 3d-1 is assumed to be 100.

[0796] The peel strength at the joint surface was measured in the same manner as in Example 25. The results are shown in Table 23.

[0797] [Table 23]

[0798] From Table 23, it was found that the organic EL device of the present invention had a long lifetime.

[0799] Example 28

<Production of first electrode substrate> 100 mm X 100 mm XI. A 1 mm glass substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaned for 5 minutes. This substrate is fixed to the substrate holder of a commercially available vacuum evaporation system, 200 mg of aluminum is put in one of the resistance heating boats made of molybdenum, and 200 mg of lithium fluoride is put in another resistance heating boat made of molybdenum. 200 mg of BCP was put in a molybdenum resistance heating boat, and 200 mg of CBP as a host compound was put in another resistance heating boat made of molybdenum.

[0800] in the following, after pressure in the vacuum tank was reduced to 4 X 10- ⁴ Pa, and heated by supplying an electric current to the boat containing the aluminum, aluminum was vapor-deposited (thickness of about l lOnm), followed by Then, electricity was supplied to a heat boat containing lithium fluoride and heated to deposit lithium fluoride (film thickness: about 0.5 nm).

[0801] Next, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0. InmZsec to provide an electron transport layer having a thickness of about lOnm.

[0802] Further, the heating boat containing CBP and Ir-9 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.012 nm Zsec, respectively. A 40 nm light-emitting layer was provided to fabricate a first electrode substrate (cathode side).

[0803] <Production of second electrode substrate>

[0804] After pressure in the vacuum tank was reduced to ⁴ X 10- 4 Pa, and heated by supplying an electric current to the boat containing a-NPD, it was deposited on the transparent supporting substrate at a deposition rate of 0. InmZsec, the film thickness 40nm A hole transport layer was provided to prepare the anode side part.

[0805] The light emitting layer at the cathode side portion and the hole transport layer at the anode side portion thus obtained were overlapped and fixed with a bonding tool, and the resulting device was sealed and treated organically. An EL device 4d-1 was fabricated. [0806] Same as organic EL element 4d-1, except that the compounds used in the electron transport layer, the light emitting layer, and the hole transport layer were replaced with the compounds shown in Table 24 in the preparation of organic EL element 4d-1. 4d-2 and 4d-3 were prepared by this method.

[0807] Further, each of the organic EL elements 4d-l to 4d-3 was placed at 23 ° C in a dry nitrogen gas atmosphere.

5. The devices after applying a 0 mAZcm ² constant current for 100 hours were designated as organic EL devices 4d-4 to 4d-6.

[0808] [Chemical 74] NPD

[0809] [Table 24]

[0810] <Evaluation of organic EL elements 4d-1 to 4d-6>

The organic EL devices 4d-1 to 4d-6 fabricated as follows were evaluated and the results are shown in Table 25.

[0811] (External extraction quantum efficiency)

[0812] The measurement results of the external extraction quantum efficiency in Table 25 are expressed as relative values when the measured value of the organic EL element 4d-1 is 100.

[0813] (Life) 2. When driving at a constant current of 5 mAZcm ² , measure the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance), and this is the half-life time (τ 0.5). And used as an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Ko-Force Minolta) was used.

[0814] Lifetime measurement results in Table 25 are expressed as relative values when the organic EL element 4d-l is 100.

[0815] The peel strength at the joint surface was measured in the same manner as in Example 25. The results are shown in Table 25.

[0816] [Table 25]

[0817] From Table 25, it was found that the organic EL device of the present invention had a long lifetime.

[0818] Example 29

(Blue light emitting organic EL device)

As the blue light-emitting organic EL element, the organic EL element 3d-3 prepared in Example 27 was used, and a blue light-emitting organic EL element 5d-IB (blue) was obtained.

[0819] (Green light-emitting organic EL device)

A green light-emitting organic EL element 5d-1G (green) was produced in the same manner as in the production of the organic EL element 3d-3 of Example 27, except that 2-7 was changed to 2-1.

[0820] (Red light emitting organic EL device)

A red light-emitting organic EL element 5d-1R (red) was produced in the same manner as in the production of the organic EL element 3d-3 of Example 27 except that 2-7 was changed to 2-5.

[0821] The above red, green, and blue light-emitting organic EL devices are juxtaposed on the same substrate and shown in Fig. 1. An active matrix type full-color display device having the above-described form was manufactured, and FIG. 2 shows only a schematic diagram of the display portion A of the manufactured display device. That is, a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 arranged in parallel on the same substrate (light emission color is a pixel in a red region, a pixel in a green region, a pixel in a blue region, etc.) The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material force, and the scanning line 5 and the data line 6 are orthogonal to each other in a grid pattern and are connected to the pixel 3 at the orthogonal position. (Details not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is received from a scanning line 5. When applied, it receives an image data signal from the data line 6 and emits light according to the received image data. In this way, a full-color display device was produced by appropriately juxtaposing the red, green, and blue pixels.

[0822] It was confirmed that by driving the full-color display device, a full-color moving image display with a high luminous efficiency and a long luminous lifetime was obtained.

[0823] Example 30

In the same manner as in Example 27 organic EL device 3d-3, except that 2-7 was changed to a mixture of 2-7, 2-1, and 2-5, white light emitting organic EL device 6d-1W (white) was Produced.

[0824] In evaluating the obtained organic EL element 6d-1W, the non-light-emitting surface was covered with a glass case to obtain a lighting device. The illuminating device could be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

Claims

The scope of the claims

[1] An organic electoluminescence device having a plurality of organic layers between an anode and a cathode, and at least one first organic layer containing an organic compound having a reactive substituent on one electrode An organic elect mouth characterized in that it is formed by forming at least one second organic layer on the other electrode, and bonding the first organic layer and the second organic layer so as to face each other. Luminescence element.

[2] The organic electroluminescent device according to [1], wherein the second organic layer contains an organic compound having a reactive substituent.

[3] The organic electroluminescent device according to [1] or [2], wherein at least one of the plurality of organic layers contains a phosphorescent light emitting compound.

[4] The organic electoluminescence according to any one of claims 1 to 3, wherein the reactive substituent is a reactive substituent selected from the following substituent group: element.

[Chemical 1]

^^ CH ₂ ~ = CH — NH ₂ —OH — SH

(In the reactive substituent, A is a linking group having at least one selected from the following general formula (a), -O- and -S-powered linking groups, or a plurality of combinations of the linking groups) Represents a divalent linking group represented by a combination, and B represents a hydrogen atom or a substituent.

[Chemical 2] —General formula (a)

(In the formula, R and R ′ each represent a hydrogen atom or a substituent, and n represents an integer of 1 or more.)

[5] The first and second organic layers, wherein the first organic layer and the second organic layer are bonded to each other so as to form a bond between the organic compounds having a reactive substituent. 4. The organic electroluminescence device according to item 4, wherein any force of item 4.

[6] The organic elect according to any one of claims 1 to 5, wherein the bond is formed at an interface between the first organic layer and the second organic layer. Mouth luminescence element.

[7] The organic electroluminescent device according to [5] or [6], wherein the bond is a covalent bond.

[8] The first organic layer and the second organic layer have the same composition, and the bond is formed below the glass transition temperature (Tg) of the first organic layer and the second organic layer. The organic electoluminescence device according to any one of claims 5 to 7, wherein:

[9] The organic electroluminescent device according to any one of [1] to [8], wherein at least one of the organic layers is formed by a wet method.

[10] The method for producing an organic electoluminescence device according to any one of claims 1 to 9, which has a plurality of organic layers between an anode and a cathode, on one electrode Forming at least one first organic layer, forming at least one second organic layer on the other electrode, and allowing the first and second organic layers to face each other. And a method for producing an organic electoluminescence device, comprising: a step of bonding

[11] An illuminating device using the organic electoluminescence element according to any one of claims 1 to 9.

[12] The organic electroluminescent device according to any one of claims 1 to 9 A display device characterized by using a child.

[13] In the method of manufacturing an organic electroluminescent device having at least an anode and a cathode on a support substrate, and having an organic layer including at least one light emitting layer between the anode and the cathode, the total film of the light emitting layer The thickness T (EM) (nm) satisfies the following relational expression (1), at least one of the light emitting layers has a phosphorescent light emitting material, and at least one of the organic layers is composed of layer A and layer B. The manufacturing method of an organic electoluminescence element characterized by having the process formed by bonding with.

Relational expression (1)

40nm <T (EM) ≤ lOOnm

14. The method for producing an organic electroluminescent device according to claim 13, wherein the organic layer has three or more layers.

[15] The organic elect mouth according to claim 13 or 14, wherein each of the layer A and the layer B contains a compound having the same structure as a main component! A method for manufacturing a luminescence element.

[16] The organic electoluminescence device according to any one of claims 13 to 15, wherein a shift of the layer A or the layer B includes a phosphorescent material. Production method.

[17] The method for producing an organic electroluminescent device according to any one of claims 13 to 15, wherein each of the layer A and the layer B contains a phosphorescent material. .

[18] The method for producing an organic electoluminescence device according to item 17, wherein the layer A and the layer B are layers containing the same phosphorescent material.

[19] The method for producing an organic electoluminescence device according to any one of [13] to [18], wherein the phosphorescent material is an iridium complex or a platinum complex.

[20] An organic electoluminescence device produced by the method for producing an organic electroluminescence device according to any one of claims 13 to 19

[21] An illuminating device comprising the organic electoluminescence element according to claim 20.

[22] A display device comprising the organic electoluminescence element according to claim 20.

[23] A first electrode substrate having at least n (n≥0) organic layers and a second electrode substrate having at least m (m + n≥1) organic layers are bonded to each other. In the organic electoluminescence device, at least one of the organic layers contains a phosphorescent light-emitting compound, and the surface roughness (Ra) of two opposing laminated surfaces is in the range of 0.05 to LOnm, An organic electoluminescence device characterized in that the surface roughness ratio of the two laminated surfaces is within a range of 0.5 to 2.0.

[24] The organic electroluminescent device according to item 23, wherein the two laminated surfaces to be bonded together are organic layers.

[25] The organic electroluminescent element according to item 23 or 24, which contains an organic compound having a reactive substituent on at least one of the two laminated surfaces to be bonded.

[26] The organic electoluminescence device according to any one of claims 23 to 25, which contains an organic compound having a reactive substituent on both of the laminated surfaces to be bonded. .

[27] The organic electroluminescent device according to item 25 or 26, wherein the reactive substituent is represented by the following general formula.

[Chemical 3]

= — NH ₂ —OH — SH

[28] The method according to claim 23, wherein the organic layer is laminated by a wet method. The organic electoluminescence device according to item 1 above.

[29] A first electrode substrate having at least n (n≥0) organic layers and a second electrode substrate having at least m (m + n≥1) organic layers are bonded to face each other. A method for producing an organic electroluminescence device, wherein at least one of the organic layers contains a phosphorescent light-emitting compound, and the surface roughness (Ra) of two opposing laminated surfaces is 0.05 to: LOnm A method for producing an organic electoluminescence device, wherein the ratio of the surface roughness of the two laminated surfaces is within the range of 0.5 to 2.0.

[30] An illuminating device comprising the organic electoluminescence element according to any one of items 23 to 28.

[31] A display device comprising the organic electoluminescence device according to any one of items 23 to 28.

[32] An organic elect formed by bonding together a first electrode substrate having at least n (n≥0) organic layers and a second electrode substrate having at least m (m≥0) organic layers In the mouth luminescence device, the organic electroluminescence is characterized in that at least one of the organic layers (m + n≥1) contains a phosphorescent light emitting compound, and the peel strength of the bonded surface is lONZm or more. Luminescence element.

[33] The organic electoluminescence device according to item 32, wherein the surfaces to be bonded are organic layers.

[34] The organic electroluminescent device according to claim 32 or 33, which contains an organic compound having a reactive substituent on at least one of the surfaces to be bonded.

[35] The organic electroluminescent device according to any one of claims 32 to 34, which contains an organic compound having a reactive substituent on both surfaces to be bonded.

[36] The organic electroluminescent device according to [34] or [35], wherein the reactive substituent is represented by the following general formula (1).

[Chemical 4]

[37] The organic electroluminescent device according to any one of [32] to [36], wherein the organic layer is formed by a wet method.

[38] In the method for producing an organic electoluminescence device for producing an organic electroluminescence device according to any one of claims 32 to 37, at least one of the organic layers is provided. And a phosphorescent light-emitting compound, and the peel strength of the bonded surface is lONZm or more.

[39] An illuminating device comprising the organic electoluminescence element according to any one of claims 32 to 37.

[40] A display device comprising the organic electroluminescent device according to any one of claims 32 to 37.