WO2015001922A1

WO2015001922A1 - Method for manufacturing organic electroluminescence element, organic electroluminescence element, and organic electroluminescence module

Info

Publication number: WO2015001922A1
Application number: PCT/JP2014/065303
Authority: WO
Inventors: 小島　茂
Original assignee: コニカミノルタ株式会社
Priority date: 2013-07-05
Filing date: 2014-06-10
Publication date: 2015-01-08
Also published as: JP6337897B2; JPWO2015001922A1

Abstract

　The present invention addresses the problem of providing a method for manufacturing an organic EL element, etc., in which a light-emitting display pattern has an excellent shape accuracy (sharpness), the light emission brightness is high, the light emission pattern can be switched, and different images can be displayed simultaneously or individually on the same display region. This method for manufacturing an organic EL element which has, on a transparent substrate, a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, a third transparent electrode, and a transparent sealing member is characterized in that the first organic functional layer unit and the second organic functional layer unit can be electrically driven to emit light individually or simultaneously, light is emitted at different patterns from the transparent substrate side and the transparent sealing member side, and different display images constituted by a region in which the light-emitting function is modulated and a region in which the light-emitting function is not modulated are formed in the first organic functional layer unit and the second organic functional layer unit.

Description

Organic electroluminescence device manufacturing method, organic electroluminescence device, and organic electroluminescence module

The present invention relates to a method for producing an organic electroluminescence element, an organic electroluminescence element produced thereby, and an organic electroluminescence module including the same. More specifically, the present invention relates to a method of manufacturing an organic electroluminescence element that has no emission unevenness, has a high definition of a display image shape, and can switch a light emission pattern.

In recent years, light emitting diodes using a light guide plate (Light Emitting Diode, abbreviated as LED) and organic light emitting diodes (Organic Light Emitting Diode, abbreviated as OLED, hereinafter also referred to as an organic electroluminescent element) are used as planar light sources. Attention has been paid. The light guide plate LED has been used not only for general illumination but also for various scenes and applications such as a backlight for a liquid crystal display (Liquid Crystal Display, abbreviated as LCD) (for example, see Patent Document 1). .)

In particular, since around 2008, the production of smart devices (for example, smartphones, tablets, etc.) has increased greatly as portable terminals, and light guide plate LEDs are widely used there.

Although it is mainly used as a backlight for a main display (for example, LCD), a light guide plate LED is often incorporated as a backlight for a common function key button at the lower part of the device as another use. Yes.

The common function key buttons are mainly used in three types: home (displayed with a square mark), back (displayed with an arrow mark, etc.), and search (displayed with a magnifying glass mark, etc.).

In the method described in Patent Document 1 described above, these common function key buttons print a pattern of a mark to be displayed on the cover glass, install the light guide plate LED as described above inside the cover glass, The LED emits light according to the required scene, the light is guided through the light guide plate (film), and the light is extracted to the display side through the dot-shaped diffusion member printed on the pattern portion.

However, the method disclosed in Patent Document 1 cannot display images having different shapes at the same position on the display screen.

On the other hand, at the time of manufacturing the organic electroluminescence element, at least one layer of the organic functional layer or the constituent electrode layer is irradiated with ultraviolet light through a photomask to deactivate the light emitting function, thereby changing the light emitting function of a predetermined pattern region. An organic light emitting device having a specific light emission pattern has been proposed (see, for example, Patent Document 2).

However, even with the method disclosed in Patent Document 2, it is possible to form different patterns in different regions on the same plane, but two different patterns can be formed in the same region. The above pattern cannot be formed.

In addition, it is possible to pattern the shape corresponding to the key display with a mask at the time of manufacturing the organic electroluminescence element, but this method also switches an arbitrary mark shape to the same place according to the scene display. It was impossible to display a plurality of light emission patterns.

Furthermore, the patterning method using a mask during film formation has a problem that the resolution of the display pattern image is low.

US Pat. No. 8,330,724 JP 2012-28335 A

The present invention has been made in view of the above-described problems and situations, and the problem to be solved is that the display image of the light emission display pattern is excellent in shape accuracy (sharpness), has high light emission luminance, and the light emission pattern is switched. And a method of manufacturing an organic electroluminescent element capable of displaying a plurality of different images individually or simultaneously in the same display region, an organic electroluminescent element obtained by the method, and further comprising the organic electroluminescent element An organic electroluminescence module is provided.

As a result of intensive studies to solve the above problems, the present inventor has at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, Having a third transparent electrode and a transparent sealing member, the two organic functional layer units can emit light by electrical drive individually or simultaneously, and individually irradiate light from the transparent substrate side and the transparent sealing member side, Each organic functional layer unit forms a different display image composed of a region in which the light emitting function is modulated and a region in which the light emitting function is not modulated. Excellent pattern shape accuracy (sharpness), high emission brightness, switchable emission patterns, and display different images individually or simultaneously in the same display area It found that it is possible to produce machine electroluminescent device, leading to the present invention.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. An organic electroluminescence device having at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, a third transparent electrode, and a transparent sealing member in this order on a transparent substrate. A method for producing an organic electroluminescence element to be produced, comprising:
The first organic functional layer unit and the second organic functional layer unit are independently capable of emitting light by electrical driving individually or simultaneously,
Light irradiation is performed in different patterns from the transparent substrate side and the transparent sealing member side, respectively, and the first organic functional layer unit and the second organic functional layer unit are modulated with regions where the light emitting function is modulated. A method for producing an organic electroluminescence element, comprising forming different display images composed of regions that are not formed.

2. 2. The organic electro according to claim 1, wherein the patterning method by light irradiation is a method of patterning different display images from the transparent substrate side and the transparent sealing member side using ultraviolet rays as an irradiation light source. Manufacturing method of luminescence element.

3. 3. The organic electroluminescence device according to claim 1, wherein at least one electrode selected from the first transparent electrode, the second transparent electrode, and the third transparent electrode is formed of a thin film metal. Method.

4. 3. The method for producing an organic electroluminescent element according to claim 1, wherein all of the first transparent electrode, the second transparent electrode, and the third transparent electrode are formed of a thin film metal.

5. The first transparent electrode, the second transparent electrode, or the third transparent electrode, wherein the thickness of the second transparent electrode is set to be the thickest. The manufacturing method of the organic electroluminescent element of description.

6. The method for producing an organic electroluminescent element according to any one of items 3 to 5, wherein the electrode formed of the thin film metal is a thin silver electrode.

7. 7. The method for producing an organic electroluminescent element according to claim 6, wherein a base layer containing an organic compound having at least one atom selected from nitrogen and sulfur is provided below the thin silver electrode.

8. The method for producing an organic electroluminescent element according to any one of claims 1 to 7, wherein the first transparent electrode and the third transparent electrode are formed as anodes.

9. The method for producing an organic electroluminescent element according to any one of items 1 to 7, wherein the first transparent electrode and the third transparent electrode are formed as cathodes.

10. An organic electroluminescence device manufactured by the method for manufacturing an organic electroluminescence device according to any one of items 1 to 9,
On the transparent substrate, at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, a third transparent electrode and a transparent sealing member are provided in this order, and the first An organic electroluminescent element, wherein the organic functional layer unit and the second organic functional layer unit have a function of displaying different images formed by light irradiation.

11. An organic electroluminescence module comprising the organic electroluminescence element according to item 10.

12. 12. The organic electroluminescence module according to item 11, comprising a polarizing member, a half mirror member, or a black filter on the light emitting surface side of the transparent substrate constituting the organic electroluminescence element.

By the above means of the present invention, the shape display accuracy (sharpness) of the light emission display pattern image is excellent, the light emission luminance is high, the light emission pattern can be switched, and different images are displayed individually or simultaneously in the same display area. An organic electroluminescence element production method for producing an organic electroluminescence element that can be produced, an organic electroluminescence element obtained thereby, and an organic electroluminescence module equipped with the organic electroluminescence element can be provided.

The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

As a result of studying a method capable of displaying different images in the same region, the present inventor has at least a first transparent electrode, a first organic functional layer unit, a first organic electroluminescence element as a configuration. 2 transparent electrodes, a second organic functional layer unit, a third transparent electrode, and a transparent sealing member. The light irradiation is performed in different patterns from the transparent substrate side and the transparent sealing member side, and the first In the organic functional layer unit and the second organic functional layer unit, different display images composed of a region where the light emitting function is modulated and a region where the light emitting function is not modulated are formed, and the first organic functional layer unit and the second organic functional layer unit By making each organic functional layer unit emit light independently or simultaneously by electrical drive, different image information with high definition can be obtained within the same area. Optionally, and it has been found a method of manufacturing an organic electroluminescent device can be displayed instantaneously.

In the present invention, the first to third transparent electrodes are all composed of transparent electrodes, so that even if the displayed images are observed from different angles, the color change hardly occurs, and it is excellent. Visibility can be expressed.

Schematic sectional view showing an example of the configuration of an organic electroluminescence element The schematic diagram which shows one example of two different display images formed in a 1st organic functional layer unit and a 2nd organic functional layer unit The schematic diagram which shows the other example of the two different display images formed in a 1st organic functional layer unit and a 2nd organic functional layer unit Schematic diagram illustrating an example of a method for displaying two different images The schematic diagram which shows an example of two different display images formed in a 1st organic functional layer unit and a 2nd organic functional layer unit The schematic diagram which shows another example of two different display images formed in a 1st organic functional layer unit and a 2nd organic functional layer unit. The schematic diagram which shows another example of two different display images formed in a 1st organic functional layer unit and a 2nd organic functional layer unit. Schematic diagram showing an example of two different display images and their combined display images formed on the first organic functional layer unit and the second organic functional layer unit Schematic sectional view showing an example of the configuration of an organic electroluminescence module provided with an organic electroluminescence element Schematic sectional view showing the configuration A of the organic EL element 101 produced in the example Schematic sectional view showing the configuration B of the organic EL element 103 produced in the example Schematic sectional view showing the configuration C of the organic EL element 104 produced in the example Schematic sectional view showing the configuration D of the organic EL element 105 produced in the example Schematic sectional view showing the configuration E of the organic EL element 106 produced in the example Schematic sectional view showing the configuration F of the organic EL element 107 produced in the example

The manufacturing method of the organic electroluminescent element (hereinafter abbreviated as an organic EL element) of the present invention includes at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, and a second organic material on a transparent substrate. A method for manufacturing an organic electroluminescent element, which includes a functional layer unit, a third transparent electrode, and a transparent sealing member in this order, the first organic functional layer unit and the second organic functional layer unit Are capable of independently or simultaneously emitting light individually or simultaneously, irradiating light in different patterns from the transparent substrate side and the transparent sealing member side, respectively, the first organic functional layer unit and the first 2 For the organic functional layer unit, different areas composed of a region where the light emitting function is modulated and a region which is not modulated And forming a display image. This feature is a technical feature common to the inventions according to claims 1 to 12.

In the manufacturing method of the organic EL element of the present invention, the patterning method by light irradiation according to the present invention further uses different ultraviolet light as an irradiation light source to display different display images from the transparent substrate side and the transparent sealing member side. The patterning method is a preferable aspect from the viewpoint that a sharp display image with higher definition can be formed.

Further, at least one electrode selected from the first transparent electrode, the second transparent electrode, and the third transparent electrode is formed of a thin film metal, and further, the first transparent electrode, the second transparent electrode, and the third transparent electrode It is preferable that all of the electrodes are formed of a thin film metal from the viewpoint that the hue of the display image does not change when observed from different angles and the visibility of the display image can be improved.

Further, among the first transparent electrode, the second transparent electrode, and the third transparent electrode, setting the thickness of the second transparent electrode to be the thickest is specific to the organic functional layer unit from one surface side. It is preferable from the viewpoint of preventing the influence of light irradiation on the organic functional layer unit disposed on the other surface side when the pattern is irradiated with light.

In addition, it is preferable that the electrode formed of the thin film metal is a thin silver electrode from the viewpoint of obtaining higher transparency.

In addition, a base layer containing an organic compound having at least one atom selected from nitrogen and sulfur is provided below the thin silver electrode, and the uniformity of the thin silver electrode formed thereon can be improved. To preferred.

In addition, it is easy to design the drive circuit by forming the first transparent electrode and the third transparent electrode as anodes, or forming the first transparent electrode and the third transparent electrode as cathodes. preferable.

Moreover, the organic EL element of the present invention can be suitably provided in an organic EL module.

As a configuration of the organic EL module of the present invention, having a polarizing member, a half mirror member or a black filter on the light emitting surface side of the support substrate constituting the organic EL element displays a clear black image when no light is emitted. It is preferable because it can be used.

Hereinafter, details of the present invention, its components, and modes and modes for carrying out the present invention will be described. In the present invention, “˜” representing a numerical range is used in the sense that numerical values described before and after it are included as a lower limit value and an upper limit value.

<< Configuration of organic EL element >>
(Overview of overall configuration of organic EL element)
The structure of the organic EL element manufactured by the method for manufacturing the organic EL element of the present invention includes at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit on a transparent substrate. The third transparent electrode and the transparent sealing member are configured in this order, and the first organic functional layer unit and the second organic functional layer unit can independently and simultaneously emit light individually or simultaneously, Light irradiation is performed in a different pattern from each of the transparent substrate side and the transparent sealing member side, and the first organic functional layer unit and the second organic functional layer unit have a region in which a light emitting function is modulated by light irradiation, In this case, different display images composed of unmodulated regions are formed.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the organic electroluminescence element of the present invention.

As shown in FIG. 1, the organic EL element EL includes a first transparent electrode A, a first organic functional layer unit U1, a second transparent electrode B, a second organic functional layer unit U2, and a third transparent substrate on a transparent substrate 1. It consists of an electrode C and a transparent sealing member D.

Different display images are formed on the first organic functional layer unit U1 and the second organic functional layer unit U2. As a method for forming a display image, as shown in FIG. 1, in the process of manufacturing an organic EL element, after producing an organic EL element (EL), light irradiation L1 is performed through a mask member from the transparent substrate 1 side. In the first organic functional layer unit U1, a region where the light emission function is modulated by the light irradiation L1 and a region where the light emission function is not modulated are formed to form a specific display image. Similarly, light irradiation L2 is performed from the transparent sealing member D side, and a region where the light emitting function is modulated and a region where the light emitting function is not modulated are formed in the second organic functional layer unit U2, and the first organic functional layer is formed. A specific display image different from the image formed in the unit U1 is formed. A detailed manufacturing method will be described in a method for manufacturing an organic EL element described later.

The first transparent electrode A and the second transparent electrode B are wired with a lead wire 20A, and a voltage within a range of 2 to 40 V from the drive power source V1 is applied to each connection terminal, thereby providing the first organic function. The layer unit U1 is caused to emit light independently. Similarly, the second transparent electrode B and the third transparent electrode C are also wired with a lead wire 20B, and a voltage within a range of 2 to 40 V from the drive power supply V2 is applied to each connection terminal, whereby the second organic The functional layer unit U2 emits light independently with an image different from that of the first organic functional layer unit U1.

In the organic EL element having the above-described configuration, different images are displayed at the time of light emission, but the formed pattern does not appear at all at the time of non-light emission.

(Image display of organic EL elements)
Next, different images displayed by the organic EL element of the present invention will be described.

As described above, in the organic EL element of the present invention, the first organic functional layer unit U1 and the second organic functional layer unit U2 display different images.

2A and 2B are schematic views showing examples of two different display images formed by the first organic functional layer unit U1 and the second organic functional layer unit U2.

For example, the drive power source V1 is applied between the first transparent electrode A and the second transparent electrode B, and an upward arrow image 22A as shown in FIG. 2A is displayed. At this time, the background 21 is a region where the light emitting function formed by light irradiation is modulated, that is, a non-light emitting region where the light emitting function is deactivated by light irradiation. The upward arrow image 22A is formed in an unmodulated area where no light irradiation is performed, that is, a light emitting area maintaining the light emitting function, and displays the upward arrow image 22A as a display image.

Similarly, the drive power source V2 is applied between the second transparent electrode B and the third transparent electrode C, and the downward arrow image 22B shown in FIG. 2B is displayed. At this time, the background 21 is a region where the light emitting function formed by light irradiation is modulated, that is, a non-light emitting region. The downward arrow image 22B is formed as an unmodulated area where no light irradiation is performed, that is, a light emitting area, and displays the downward arrow image 22B as a display image.

FIG. 3 is a schematic diagram for explaining an example of a method for displaying two different images.

A method for independently displaying an upward arrow image and a downward arrow image as shown in FIG. 2 will be further described.

In FIG. 3, an image E is a light emission pattern (upward arrow image 22 </ b> A in FIG. 2) of the first organic functional layer unit U <b> 1 sandwiched between the first transparent electrode A and the second transparent electrode B, and the image F is It is the light emission pattern (downward arrow image 22B in 9 in FIG. 2) of the 2nd organic functional layer unit U2 pinched | interposed into the 2nd transparent electrode B and the 3rd transparent electrode C. FIG.

In FIG. 3, the image E and the image F are displayed in a state where they do not overlap each other, but a method of displaying images while overlapping each other may be used.

FIG. 4 is a schematic diagram illustrating another example of two different display images formed on the organic functional layer unit U1 and the organic functional layer unit U2.
In FIGS. 2A, 2B, and 3, the upward and downward arrow images are described as examples of display images. However, in the organic EL element of the present invention, the display image shown in FIG. “○”, “×” display as shown, display of different types of traffic signs as shown in FIG. 4B, signal display at pedestrian crossings etc. as shown in FIG. 4C (“advance” and “stop”) In addition to individually displaying each of the different geometric figures as shown in FIG. 4D, a method of simultaneously displaying (combining patterns) combining them can also be cited. In addition, in the organic EL element of the present invention, in addition to changing the display image shape as exemplified above, a method of changing the emission color between the organic functional layer unit U1 and the organic functional layer unit U2, for example, In the configuration as shown in FIG. 4C, the “advance” display can be displayed in blue, and the “stop” display can be displayed in red.

<< Method for producing organic EL element having different light emission patterns >>
In the present invention, the organic EL device having different light emission patterns of the present invention has a structure in which at least two organic functional layer units are laminated between at least a pair of transparent electrodes, and the light emission patterns differ depending on the state. It is possible to switch between and display.

Here, the “light emission pattern” is displayed by an organic EL element, for example, a design (pattern or pattern in the figure), characters, and images as illustrated in FIGS. 2A, 2B, and 4A to 4D. Image shape information such as the above, and in addition, color information for emitting light with different emission colors between the organic functional layer unit U1 and the organic functional layer unit U2.

Here, as an example, a method for manufacturing the organic EL element (EL) shown in FIG. 1 will be described.

(1) Laminating Step The organic EL element (EL) of the present invention has a first transparent electrode A, a first organic functional layer unit U1, a second transparent electrode B, a second organic functional layer unit U2, The 3rd transparent electrode C and the transparent sealing member D can be manufactured by the process (lamination process) which laminates | stacks in this order.

First, a transparent substrate 1 is prepared, and a thin film made of a material for forming a first transparent electrode, for example, a material for an anode, is formed on the transparent substrate 1 so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm. In addition, the first transparent electrode A is formed by a method such as vapor deposition or sputtering.

Next, on the first transparent electrode A, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like are sequentially laminated to form a first organic functional layer unit U1.

As a method of forming each of these layers, there are a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but from the point that a homogeneous layer is easily obtained and pinholes are difficult to generate. Vacuum deposition or spin coating is particularly preferred. Further, different formation methods may be applied for each layer. When a vapor deposition method is employed for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C. and the degree of vacuum is 1 × 10 ⁻⁶ to Within a range of 1 × 10 ⁻² Pa, a deposition rate within a range of 0.01 to 50 nm / second, a substrate temperature within a range of −50 to 300 ° C., and a layer thickness within a range of 0.1 to 5 μm. Therefore, it is desirable to appropriately select each condition.

After forming these layers, the second transparent electrode B is formed thereon.

Next, each layer of the second organic functional layer unit U2 is formed in the same manner as the formation of the first organic functional layer unit U1.

After forming the second organic functional layer unit U2 as described above, the third transparent electrode C is formed thereon by a film forming method such as a vapor deposition method or a sputtering method.

(2) Sealing process After the said lamination process, the process (sealing process) which seals an organic EL element (EL) is performed.

That is, a transparent sealing member D for blocking at least the first organic functional layer unit U1 and the second organic functional layer unit U2 from the outside air is provided on the transparent substrate 1.

(3) Light irradiation process In this invention, after forming and sealing the 1st organic functional layer unit U1 and the 2nd organic functional layer unit U2, it differs from the transparent substrate 1 side and the transparent sealing member D side, respectively. An organic EL element using a patterning method in which light irradiations L1 and L2 are performed in a pattern to form two different display images (light emission patterns) that are divided into a region where the light emission function is modulated and a region where the light emission function is not modulated It is characterized by manufacturing.

Here, modulating the light emitting function by light irradiation means deactivating or lowering the light emitting function of the material constituting the light emitting unit by light irradiation. In the present invention, in particular, a hole transporting material, etc. A method of changing the light emitting function of the light emitting unit by changing the function is preferable.

As a light irradiating method in the light irradiating step, a predetermined pattern region of the first organic functional layer unit U1 and the second organic functional layer unit U2 is irradiated with a predetermined light to make the irradiated part a light emitting region whose luminance has changed. Any method can be used as long as it is possible, and the method is not limited to a specific method.

In the present invention, the light irradiated in the light irradiation step may have ultraviolet light, visible light, or infrared light, but light irradiation including ultraviolet light is particularly preferable.

Here, the term “ultraviolet rays” as used in the present invention refers to electromagnetic waves having a wavelength longer than that of X-rays and shorter than the shortest wavelength of visible light, and specifically, light having a wavelength in the range of 1 to 400 nm.

The ultraviolet ray generating means and the irradiating means are not particularly limited as long as the ultraviolet ray is generated and irradiated by a conventionally known apparatus or the like. Specific examples of the light source include a high-pressure mercury lamp, a low-pressure mercury lamp, a hydrogen (deuterium) lamp, a rare gas (xenon, argon, helium, neon, etc.) discharge lamp, a nitrogen laser, and an excimer laser (XeCl, XeF, KrF, KrCl). Etc.), hydrogen laser, halogen laser, various harmonics of visible (LD) -infrared laser (THG (Third Harmonic Generation) light of YAG laser) and the like.

Such a light irradiation step is preferably performed after the sealing step.

As described above, an organic EL element (EL) having two different light emission patterns can be manufactured. In the manufacture of such an organic EL element (EL), it is preferable that the first transparent electrode D to the third transparent electrode C are manufactured consistently by a single evacuation. May be taken out and subjected to different forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

In addition, when applying a DC voltage to the organic EL element (EL) thus obtained, the first transparent electrode A is an anode, the second transparent electrode B is a cathode and an anode, and the third transparent electrode C is a cathode. The first transparent electrode A may be configured as a cathode, the second transparent electrode B may be configured as an anode and a cathode, and the third transparent electrode C may be configured as an anode. In the present invention, the drive system in which the first transparent electrode A and the third transparent electrode C act as anodes and the second transparent electrode B acts as a cathode, or the first transparent electrode A, for ease of design of the drive circuit. A driving method in which the third transparent electrode C acts as a cathode and the second transparent electrode B acts as an anode is more preferable.

<< Method of forming light emission pattern of organic EL element >>
When the organic EL element having the two first organic functional layer units U1 and the second organic functional layer unit U2 is irradiated with light to change or reduce the emission luminance, one surface side of the organic EL element after the sealing process is finished As a matter of course, it is impossible to display different symbols and symbols for each light emitting unit.

The present invention is characterized in that light irradiation is performed from the transparent substrate side and the transparent sealing member side as described above, and different display images are patterned.

In this light irradiation, in the light irradiation process, for example, when the light emission pattern of the first organic functional layer unit U1 is formed, the irradiated light passes through the second transparent electrode B and affects the second organic functional layer unit U2. The conditions are set so that the irradiated light passes through the second transparent electrode B and does not affect the first organic functional layer unit U1 when the light emitting pattern of the second organic functional layer unit U2 is formed. This is important in forming a sharp light emission pattern (display image) with high accuracy and excellent sharpness.

As a method for preventing the unnecessary light irradiation (light leakage) as described above, the film thickness of the second transparent electrode is set to be the thickest among the first transparent electrode, the second transparent electrode, and the third transparent electrode. , A method for preventing the passage of unnecessary light, a method for controlling the amount of light to be irradiated to an optimum condition, for example, when irradiating ultraviolet rays from the transparent substrate side, the first transparent electrode A or the first first through which the ultraviolet rays pass. Since it is absorbed stepwise by the constituent layers of the organic functional layer unit U1, it is preferable to set the light amount so as not to finally reach or pass through the second transparent electrode B.

Further, by appropriately adjusting the light intensity or the irradiation time and controlling the light irradiation amount, it is possible to change the light emission luminance of the light irradiation portion according to the light irradiation amount. The greater the light irradiation amount, the lower the emission luminance, and the smaller the light irradiation amount, the smaller the emission luminance attenuation rate. Therefore, when the light irradiation amount is 0, that is, when no light is irradiated, the light emission luminance is maximum. Further, in the case of light irradiation, for example, ultraviolet irradiation, the ultraviolet light irradiated from the surface side is absorbed and attenuated as it passes through the organic functional layer as described above, and therefore when reaching the second transparent electrode. The amount of light decreases considerably, and the probability of passing through the second transparent electrode and affecting the other organic functional layer unit is low.

In the present invention, the light absorptance of each organic layer, which is a measure of the light attenuation rate when passing through each organic layer, is, for example, the optical constant (refractive index n, extinction coefficient k) of each organic layer. It can be obtained by performing a simulation based on this measured value.

Also, the light passing through the second transparent electrode can be kept low by adjusting the film thickness of the organic layer and the intermediate electrode.

Hereinafter, the organic EL element 1 shown in FIG. 1 will be described in more detail with reference to the drawings.

In the manufacturing method of the organic EL element of the present invention, after forming each component of the organic EL element and sealing with the transparent sealing member D, different display images from the transparent substrate 1 side and the transparent sealing member D side, respectively. Are patterned by light irradiation.

In the light irradiation step, for example, in order to obtain a light emission shape as shown in FIG. 2A, a non-transparent processed mask plate so that the non-irradiation region 22A (non-modulated region, light emission region) of FIG. Prepare. Next, as a first step, the mask plate is fixed by aligning the light emission position of FIG. 2A and the mask plate from the transparent substrate 1 side. After the alignment is completed, a light irradiation process is performed to change the brightness of the arrow-shaped peripheral part (irradiation region 21). As a second step, the mask plate is fixed by aligning the light emission position of FIG. 2B and the mask plate from the transparent sealing substrate D side. After the alignment is completed, a light irradiation process is performed to change the brightness of the arrow-shaped peripheral part (irradiation region 21).

In the organic EL element (EL) thus manufactured, when only the first organic functional layer unit U1 is driven, an upward arrow-shaped light emission pattern 22A as shown in FIG. 2A is observed, and the second organic functional layer is observed. If only the unit U2 is driven, a light emission pattern 22B having a downward arrow shape shown in FIG. 2B is observed.

The electrical driving of the first organic functional layer unit U1 and the second organic functional layer unit U2 by the driving voltages V1 and V2 is controlled by a driver IC (Integrated Circuit) based on information from a position sensor or the like.

In addition, in the said light emission pattern, the luminescent color of the 1st organic functional layer unit U1 and the 2nd organic functional layer unit U2 is arbitrary, and may be the same or different.

<< Constituent materials for organic EL elements >>
Subsequently, the detail of each component which comprises an organic EL element is demonstrated.

[Transparent substrate]
Examples of the transparent substrate 1 applicable to the organic EL element of the present invention include transparent materials such as glass and plastic. Examples of the transparent substrate 1 that is preferably used include glass, quartz, and a resin film. The “transparent substrate” in the present invention is a substrate having a light transmittance of 50% or more at a light wavelength of 550 nm, preferably. The base material is 70% or more, and more preferably 80% or more.

Examples of the glass material include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass. On the surface of these glass materials, from the viewpoint of adhesion with adjacent layers, durability, and smoothness, a physical treatment such as polishing, a coating made of an inorganic material or an organic material, or these coatings, if necessary. A combined hybrid coating can be formed.

Examples of the constituent material of the resin film include polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), and cellulose acetate. Cellulose esters such as butyrate, cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate and their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene Abbreviations: resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone (abbreviation: PE ), Polyphenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic and polyarylates, Arton (trade name, manufactured by JSR) and Appel (trade name, Mitsui Chemicals) And other cycloolefin resins (abbreviation: COP).

The surface of the transparent substrate 1 is preferably made hydrophilic by a surface activation treatment. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

In the organic EL element of the present invention, the transparent substrate 1 described above may have a configuration in which a gas barrier layer is provided as necessary.

The transparent substrate 1 on which the gas barrier layer is formed has a water vapor transmission rate of 1 × 10 ⁻³ g at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% measured by a method according to JIS K 7129-1992. is preferably / ^m 2 · 24h or less, more, oxygen permeability measured by the method based on JIS K 7126-1987 ^{^{is, 1 × 10 -3 ml / m}} 2 · 24h · atm (1atm is 1.01325 × 10 ⁵ Pa) or less, and the water vapor permeability at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% is 1 × 10 ⁻³ g / m ² · 24 h or less. Is preferred.

As a material for forming the gas barrier layer, any material may be used as long as it has a function of suppressing intrusion into the system, although it causes deterioration of the organic EL element such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride An inorganic layer made of an inorganic material such as Furthermore, in order to improve the fragility of the gas barrier layer, a laminated structure of these inorganic layers and an organic layer made of an organic material is more preferable. Although there is no restriction | limiting in particular about the lamination order of an inorganic layer and an organic layer, It is preferable that it is the structure which laminates | stacks both alternately several times.

[Transparent electrode]
All of the first to third transparent electrodes according to the present invention are transparent electrodes. Here, “transparent” means that the light transmittance at a light wavelength of 550 nm is 50% or more.

As a group of materials that can be used for the first transparent electrode to the third transparent electrode, all metal materials that can be used for forming electrodes of organic EL elements can be used. Specifically, aluminum, silver, magnesium, lithium, magnesium / same mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO (indium tin oxide ( Indium Tin Oxide (ITO)), ZnO, TiO ₂ , SnO _{2 and} other oxide semiconductors.

In the present invention, in the first transparent electrode to the third transparent electrode, at least one electrode is preferably formed of a thin film metal, more preferably all of the first transparent electrode, the second transparent electrode, and the third transparent electrode. The electrode is formed of a thin film metal.

In the present invention, when the first transparent electrode to the third transparent electrode are made of a thin film metal, the electrode film thickness is preferably in the range of 5 to 30 nm, more preferably 5 to 20 nm.

Moreover, in this invention, it is preferable to set the film thickness of a 2nd transparent electrode among the 1st transparent electrode, a 2nd transparent electrode, and a 3rd transparent electrode, and it is preferable to set as a film thickness a 1st transparent electrode and The film thickness of the second transparent electrode is preferably 1.1 to 2.0 times that of the second transparent electrode, and more preferably 1.2 to 1.6 times.

In the present invention, the electrode formed of a thin film metal is preferably a thin silver electrode composed of silver or an alloy containing silver as a main component, and has a thickness in the range of 5 to 30 nm. The thickness is preferably 5 to 20 nm. The alloy having silver as a main component in the present invention means that the proportion of silver in the metal constituting the alloy is 60% by mass or more, preferably 80% by mass or more.

[Underlayer]
When the first transparent electrode to the third transparent electrode are thin silver electrodes composed of silver or an alloy containing silver as a main component, at least one selected from nitrogen atoms and sulfur atoms is provided below the first transparent electrodes. It is preferable to have a base layer containing an organic compound having the above atoms, and in particular, it is preferable to provide a base layer having the structure between the transparent substrate and the first transparent electrode formed of a thin silver electrode.

The material constituting the underlayer is not particularly limited as long as it can suppress aggregation of silver when forming a thin silver electrode made of silver or an alloy containing silver as a main component, For example, the organic compound etc. which have at least 1 sort (s) of atom selected from a nitrogen atom and a sulfur atom are mentioned.

The organic compound may be one kind or a mixture of two or more kinds. In addition, it is allowed to mix a compound having no nitrogen atom and sulfur atom within a range that does not impair the effect of the underlayer.

The upper limit of the thickness of the underlayer is preferably less than 50 nm, more preferably less than 30 nm, still more preferably less than 10 nm, and particularly preferably less than 5 nm. By making the layer thickness less than 50 nm, optical loss can be minimized. On the other hand, the lower limit of the layer thickness is preferably 0.05 nm or more, more preferably 0.1 nm or more, and particularly preferably 0.3 nm or more. By setting the layer thickness to 0.05 nm or more, the underlayer can be uniformly formed, the above effect as the underlayer (inhibition of silver aggregation) can be exhibited, and the thin silver electrode layer can be made uniform.

The method for forming the underlayer is not particularly limited. For example, a method using a wet process such as an inkjet method, a coating method, or a dip method, a vapor deposition method (for example, resistance heating, EB method, etc.), a sputtering method, Examples include a method using a dry process such as a CVD method. Among these, the vapor deposition method is preferably applied.

Hereinafter, an organic compound having at least one atom selected from a nitrogen atom and a sulfur atom that can be applied to the formation of the underlayer will be described.

(Organic compounds having nitrogen atoms)
The organic compound having a nitrogen atom is preferably a compound having a melting point of 80 ° C. or higher and a molecular weight Mw in the range of 150 to 1200, and having a large interaction with silver or a silver alloy, Examples thereof include nitrogen-containing heterocyclic compounds and phenyl group-substituted amine compounds.

The organic compound having a nitrogen atom has an effective unshared electron pair content [n / M] (a ratio of the number n of effective unshared electron pairs to the molecular weight M of the organic compound having a nitrogen atom) of 2.0. Preferably, the compound is selected so as to be × 10 ⁻³ or more, and more preferably 3.9 × 10 ⁻³ or more.

Here, the effective unshared electron pair is an unshared electron pair that is not involved in aromaticity among the unshared electron pairs of the nitrogen atoms constituting the compound.

The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel rule”, and is included in the π electron system on the ring. Is 4n + 2 (n is an integer of 0 or more).

The effective unshared electron pair as described above is such that the unshared electron pair possessed by the nitrogen atom is aromatic regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a heteroatom constituting the aromatic ring. It is selected based on whether or not it is involved in the family. For example, even if a nitrogen atom is a heteroatom constituting an aromatic ring, if the nitrogen atom has an unshared electron pair that does not participate in aromaticity, the unshared electron pair is an effective unshared electron pair. Counted as one of

In contrast, even if a nitrogen atom is not a heteroatom that constitutes an aromatic ring, if all of the non-shared electron pairs of the nitrogen atom are involved in aromaticity, the nitrogen atom is not shared. An electron pair is not counted as a valid unshared electron pair.

In each compound, the number n of effective unshared electron pairs coincides with the number of nitrogen atoms having effective unshared electron pairs.

When the underlayer is composed of an organic compound having a plurality of nitrogen atoms, the effective unshared electron pair content [n / M] is based on the mixing ratio of each compound and the effective molecular weight M of the mixed compound. The number n of unshared electron pairs is calculated, and the ratio of the number n of effective unshared electron pairs to the molecular weight M is defined as the effective unshared electron pair content [n / M], and this value is within the predetermined range described above. It is preferable that

Hereinafter, as the low molecular weight organic compound having a nitrogen atom constituting the underlayer, the above-described exemplary compound No. 1 having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more is used. 1 to 45 are shown, but the present invention is not particularly limited thereto. In addition, Exemplified Compound No. In 31 copper phthalocyanine, among the unshared electron pairs of nitrogen atoms, the unshared electron pairs of nitrogen atoms not coordinated to copper are counted as effective unshared electron pairs.

The above exemplified compound No. Table 1 shows the number n of effective unshared electron pairs, the molecular weight M, and the effective unshared electron pair content [n / M] for 1 to 45.

(Polymer having nitrogen atom)
In the present invention, a polymer can also be used as the organic compound having a nitrogen atom.

The polymer having a nitrogen atom preferably has a weight average molecular weight in the range of 1,000 to 1,000,000.

The polymer having a nitrogen atom is preferably a polymer having a partial structure represented by the following general formula (P1) or a partial structure represented by the following general formula (P2).

In General Formula (P1), A ¹ represents a divalent nitrogen atom-containing group. Y ¹ represents a divalent organic group or a bond. n1 represents the number of repetitions with a weight average molecular weight in the range of 1,000 to 1,000,000.

In General Formula (P2), A ² represents a monovalent nitrogen atom-containing group. n2 represents an integer of 1 or more. n2 is preferably an integer in the range of 1 to 3 from the viewpoint of interaction with silver, and more preferably 1 or 2 from the viewpoint of ease of synthesis. When n2 is 2 or more, the plurality of A ² may be the same or different. A ³ and A ⁴ each represent a divalent nitrogen atom-containing group. A ³ and A ⁴ may be the same or different. n3 and n4 each independently represents 0 or 1. Y ² represents an (n2 + 2) valent organic group. n1 represents the number of repetitions with a weight average molecular weight in the range of 1,000 to 1,000,000.

The polymer having the partial structure represented by the general formula (P1) or (P2) is a homopolymer composed of only a single structural unit derived from the general formula (P1) or (P2). It may be a copolymer (copolymer) composed of only two or more structural units derived from the above general formula (P1) or (P2).

Further, in addition to the structural unit represented by the general formula (P1) or (P2), the copolymer may be formed by further having another structural unit having no nitrogen atom-containing group.

When the polymer having a nitrogen atom has another structural unit not having a nitrogen atom-containing group, the content of the monomer derived from the other structural unit has the effect of the polymer having a nitrogen atom according to the present invention. Although it is not particularly limited as long as it is not impaired, it is preferably in the range of 10 to 75 mol%, more preferably in the range of 20 to 50 mol% in the monomers derived from all structural units.

The terminal of the polymer having the partial structure represented by the general formula (P1) or (P2) is not particularly limited and is appropriately defined depending on the type of raw material (monomer) used. is there.

In the general formula (P2), the monovalent nitrogen atom-containing group represented by A ² is not particularly limited as long as it is an organic group having a nitrogen atom. Examples of such nitrogen atom-containing groups include amino groups, dithiocarbamate groups, thioamide groups, cyano groups (—CN), isonitrile groups (—N ⁺ ≡C ⁻ ), isocyanate groups (—N═C═O). ), A thioisocyanate group (—N═C═S), or a group containing a substituted or unsubstituted nitrogen-containing aromatic ring.

Hereinafter, specific examples (PN1 to 41) of monomers constituting the polymer having a nitrogen atom according to the present invention are shown, but the invention is not particularly limited thereto. The polymer having a nitrogen atom is composed of a monomer shown below with a repeating number n1 in a range where the weight average molecular weight is in the range of 1,000 to 1,000,000.

In the present invention, the low molecular weight organic compound and polymer having a nitrogen atom can be synthesized by a known and well-known method.

(Organic compounds having sulfur atoms)
The organic compound having a sulfur atom applicable to the present invention preferably has a sulfide bond, a disulfide bond, a mercapto group, a sulfone group, a thiocarbonyl bond or the like in the molecule. Among these, it is more preferable to have a sulfide bond or a mercapto group. These organic compounds having a sulfur atom are described in, for example, JP-A No. 2009-163177.

The organic compound and polymer having a sulfur atom used in the present invention can be synthesized by a known and well-known method.

[Organic functional layer unit]
Next, each layer constituting the organic functional layer unit will be described in the order of a charge injection layer, a light emitting layer, a hole transport layer, an electron transport layer, and a blocking layer.

The organic EL element of the present invention is characterized by having at least two organic functional layer units (the first organic functional layer unit U1 and the second organic functional layer unit U2 shown in FIG. 1). The organic functional layer unit may have the same constituent material and the same layer order, or the same constituent material, but the layer order may be reversed, or the constituent material or the layer order may be completely different.

(Charge injection layer)
In the present invention, the charge injection layer is a layer provided between an electrode and a light emitting layer in order to lower drive voltage or improve light emission luminance. “Organic EL element and its industrialization front line (November 30, 1998) The details are described in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Nippon TS Co., Ltd.”, and there are a hole injection layer and an electron injection layer.

In general, the charge injection layer is present between the anode and the light emitting layer or the hole transport layer in the case of a hole injection layer, and between the cathode and the light emitting layer or the electron transport layer in the case of an electron injection layer. However, in the present invention, it is a preferable aspect to dispose the charge injection layer adjacent to the transparent electrode.

The hole injection layer according to the present invention is a layer disposed adjacent to the anode, which is a transparent electrode, in order to lower the drive voltage and improve the light emission luminance. The details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Month 30th, NTS Corporation”.

The specific structure of the hole injection layer is described in detail, for example, in JP-A-9-45479, JP-A-9-260062, and JP-A-8-288069, and is used for the hole injection layer. Examples of materials that can be used include porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triaryls. Amine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinyl carbazole, aromatic amine main chain Is a polymer material or oligomer introduced into the side chain, polysilane, conductive polymer or oligomer (for example, PEDOT (polyethylenedioxythiophene): PSS (polystyrenesulfonic acid), aniline copolymer, polyaniline, polythiophene, etc.) Can be mentioned.

Examples of the triarylamine derivative include benzidine type represented by α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), and MTDATA (4,4 ′, 4 ″). Examples include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine), a compound having fluorene or anthracene in the triarylamine-linked core.

Also, hexaazatriphenylene derivatives such as those described in JP-T-2003-519432 and JP-A-2006-135145 can be used as the hole transport material.

The electron injection layer is a layer provided between the cathode and the light emitting layer for lowering the driving voltage and improving the light emission luminance. When the cathode is composed of the transparent electrode according to the present invention, Chapter 2 “Electrode materials” (pages 123 to 166) of the second edition of “Organic EL devices and their industrialization front line (issued by NTS, November 30, 1998)” ) Is described in detail.

The specific structure of the electron injection layer is described in detail in, for example, JP-A-6-325871, JP-A-9-17574, and JP-A-10-74586, and is preferably used for the electron injection layer. Specific examples of such metals include metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metals typified by magnesium fluoride, calcium fluoride, etc. Examples include halide layers, alkaline earth metal compound layers typified by magnesium fluoride, metal oxides typified by molybdenum oxide and aluminum oxide, and metal complexes typified by lithium 8-hydroxyquinolate (Liq). It is done.

The electron injection layer is preferably a very thin film, and depending on the constituent materials, the layer thickness is preferably in the range of 0.1 to 10 μm.

(Light emitting layer)
The light emitting layer constituting the organic functional layer unit of the organic EL device of the present invention preferably has a structure containing a phosphorescent light emitting compound or a fluorescent light emitting compound as a light emitting material.

The light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting region is within the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

Such a light emitting layer is not particularly limited in its configuration as long as the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, the light emitting layers are preferably separated by a non-light emitting intermediate layer.

The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between light emitting layers.

In the present invention, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably within a range of 1 to 20 nm.

The light-emitting layer having the above-described structure is prepared by using a light-emitting material or a host compound described below, for example, a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir-Blodget, Langmuir Brodgett method), and an inkjet method. It can form by well-known methods, such as.

In the light-emitting layer, a plurality of light-emitting materials may be mixed, and a phosphorescent light-emitting material (also referred to as a phosphorescent dopant or a phosphorescent compound) and a fluorescent light-emitting material (also referred to as a fluorescent dopant or a fluorescent compound) are the same. You may mix and use in a light emitting layer. The structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound) and emits light from the light-emitting material.

<Host compound>
As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

As the host compound, a known host compound may be used alone, or a plurality of types of host compounds may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

The host compound used in the light emitting layer 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 (evaporation polymerizable light emitting host). )

As the known host compound, a compound that has a hole transporting ability or an electron transporting ability, prevents emission light from being increased in wavelength, and has a high Tg (glass transition point) is preferable. The glass transition point (Tg) here is a value determined by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

Examples of host compounds applicable to the present invention include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002 -75645, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002 36 No. 227, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183. No. 2002, No. 2002-299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, US Patent Publication No. 2003/0175553, US Patent Publication No. 2006/0280965, United States Patent Publication No. 2005/0112407, United States Patent Publication No. 2009/0017330, United States Patent Publication No. 2009/0030202, United States Patent Publication No. 2005/2389. No. 9, International Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007 / No. 063796, International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898 And compounds described in International Publication No. 2012/023947, JP 2008-074939 A, JP 2007-254297 A, European Patent No. 2034538, and the like.

<Light emitting material>
Examples of the light-emitting material that can be used in the present invention include phosphorescent compounds and fluorescent compounds.

<Phosphorescent compound>
A phosphorescent compound 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.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7. The phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

There are two methods for the light emission principle of the phosphorescent compound. One method is to generate an excited state of the host compound by recombination of the carrier on the host compound to which the carrier is transported, and transfer this energy to the phosphorescent compound. It is an energy transfer type that obtains light emission from. Another method is a carrier trap type in which a phosphorescent compound serves as a carrier trap, carrier recombination occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

The phosphorescent compound can be appropriately selected from known compounds used for the light-emitting layer of a general organic EL device, but preferably contains a group 8 to 10 metal in the periodic table of elements. More preferred are iridium compounds, more preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds) or rare earth complexes, and most preferred are iridium compounds.

In the present invention, at least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.

Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents or patents.

Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Publication No. 2006/835469, US Patent Publication No. 2006/020202194. The compounds described in the specification, US Patent Publication No. 2007/0087321, US Patent Publication No. 2005/0244673, and the like can be mentioned.

Also, Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Publication No. 2002/0034656, US Pat. No. 7,332,232, US Patent Publication No. 2009/0108737, US Patent Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Publication No. 2007/0190359, US Patent Publication No. 2006 No./0008670, U.S. Patent Publication No. 2009/0165846, U.S. Patent Publication No. 2008/0015355, U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598, U.S. Patent Publication No. 2006 / 026363 Pat, U.S. Patent Publication No. 2003/0138657, U.S. Patent Publication No. 2003/0152802, may be mentioned compounds described in U.S. Patent No. 7,090,928 Pat like.

Also, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics 23, 3745 (2004), Appl. Phys. Lett. 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Publication No. 2006/0251923, US Publication No. 2005/0260441, US Pat. No. 7,393,599. U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Publication No. 2007/0190359, U.S. Patent Publication No. 2008/0297033, U.S. Pat. No. 7,338,722, U.S. Pat. No. 2002 0134984 Pat, U.S. Pat. No. 7279704, U.S. Patent Publication No. 2006/098120, compounds described in U.S. Patent Publication No. 2006/103874 Pat like can be mentioned.

Furthermore, International Publication No. 2005/076380, International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339. No., International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, JP2012-069737, JP2009-114086, JP2003-81988, JP2002-302671, JP2002-363552, and the like.

In the present invention, preferred phosphorescent dopants include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

The phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and the methods described in references in these documents should be applied. Can be synthesized.

<Fluorescent compound>
Fluorescent compounds include, for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

(Hole transport layer)
The hole transport layer is composed of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer and the electron blocking layer also have a function as a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

The hole transport material has characteristics of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, and thiophene oligomers.

As the hole transport material, those described above can be used. Specifically, porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary compounds. It is preferable to use an amine compound.

Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) Quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N -Diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like.

Further, those having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino ] Biphenyl (abbreviation: NPD), 4,4 ′, 4 ″ -tris [N- (3-methyl) in which triphenylamine units described in JP-A-4-308688 are linked in a three star burst type Phenyl) -N-phenylamino] triphenylamine (abbreviation: MTDATA) and the like.

Furthermore, a polymer material in which these hole transport materials are introduced into a polymer chain or these hole transport materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

Also, JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials from the viewpoint of obtaining a light emitting element with higher luminous efficiency.

For the hole transport layer, the hole transport material may be formed 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, and an LB method (Langmuir Brodget, Langmuir Brodgett method). Thus, it can be formed by thinning. The layer thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 to 200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

Also, the p property can be increased by doping impurities into the material of the hole transport layer. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.

Thus, it is preferable to increase the p property of the hole transport layer because an element with lower power consumption can be manufactured.

(Electron transport layer)
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 structure or a laminated structure including a plurality of layers.

In the electron transport layer having a single-layer structure and the electron transport layer having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc. and the central metal of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as a material for the electron transport layer.

In addition, metal-free or metal phthalocyanine or those having a terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer. Further, distyrylpyrazine derivatives exemplified as the material for the light emitting layer can also be used as the material for the electron transport layer, and n-type-Si, n-type-SiC, etc. as well as the hole injection layer and the hole transport layer. These inorganic semiconductors can also be used as a material for the electron transport layer.

The electron transport layer can be formed by thinning the above 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, and an LB method. The thickness of the electron transport layer is not particularly limited, but is usually about 5 nm to 5 μm, preferably 5 to 200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

Also, impurities can be doped in the electron transport layer to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, it is preferable to contain potassium, a potassium compound, etc. in an electron carrying layer. As the potassium compound, for example, potassium fluoride can be used. Thus, by increasing the n property of the electron transport layer, an organic EL element with lower power consumption can be obtained.

Further, as the material for the electron transport layer (electron transport compound), the same material as that for the intermediate layer described above may be used. This is the same for the electron transport layer that also serves as the electron injection layer, and the same material as that for the intermediate layer described above may be used.

(Blocking layer)
Examples of the blocking layer include a hole blocking layer and an electron blocking layer. In addition to the layers constituting the organic functional layer unit described above, these layers are provided as necessary. For example, JP-A-11-204258 No. 11-204359, and “Organic EL devices and their forefront of industrialization” (issued on November 30, 1998 by NTS), page 237, etc. ) Layer.

The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons and has a very small ability to transport holes. By blocking holes while transporting electrons, The recombination probability can be improved. Moreover, the structure of an electron carrying layer can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons. By blocking electrons while transporting holes, the electron recombination probability is reduced. Can be improved. Moreover, the structure of a positive hole transport layer can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

(Transparent sealing member)
As a sealing means used for sealing the organic EL element of this invention, the method of adhere | attaching a transparent sealing member, a 2nd transparent electrode, and a transparent substrate with an adhesive agent can be mentioned, for example.

The transparent sealing member may be disposed so as to cover the display area of the organic EL element, and may be a concave plate shape or a flat plate shape. Moreover, electrical insulation is not particularly limited. Moreover, you may use the transparent substrate demonstrated above as a transparent sealing member.

Examples of the transparent sealing member applicable to the present invention include a glass plate, a polymer plate, and a film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

As the transparent sealing member, a polymer film can be preferably used from the viewpoint of reducing the thickness of the organic EL element. Furthermore, the polymer film has a water vapor transmission rate of 1 × 10 ⁻³ g / m ² · 24 h at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% measured by a method according to JIS K 7129-1992. The oxygen permeability measured by a method according to JIS K 7126-1987 is preferably 1 × 10 ⁻³ ml / m ² · 24 h · atm (1 atm is 1.01325 × 10 ⁵ Pa amount of) or less, the temperature 25 ± 0.5 ° C., water vapor permeability at a relative humidity of 90 ± 2% is preferably not more than ^{^{1 × 10 -3 g / m 2}} · 24h.

The sand sealing process or the chemical etching process is used to process the transparent sealing member into a concave shape. Specific examples of the adhesive include a photo-curing adhesive having a reactive vinyl group such as an acrylic acid oligomer and a methacrylic acid oligomer, a thermosetting adhesive, or a moisture curable adhesive such as 2-cyanoacrylate. And the like. Moreover, the thermosetting type | molds, such as an epoxy type, and a chemical curing type | mold (two-component mixing) can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. 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, an adhesive that can be adhesively cured from room temperature to 80 ° C. is preferable. Further, a desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing member may use commercially available dispenser, and may print like screen printing.

In addition, the third transparent electrode and the second organic functional layer unit are covered outside the third transparent electrode on the side facing the transparent substrate, and an inorganic or organic layer is formed in contact with the transparent substrate and sealed. A film can also be suitably used. In this case, the material for forming the sealing film may be a transparent material having a function of suppressing intrusion of moisture, oxygen, or the like that degrades the organic EL element. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. Can be used. Furthermore, in order to improve the brittleness of the sealing film, it is preferable to have a laminated structure of these inorganic layers and organic layers made of organic materials. The method for forming these films 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 plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

In the gap between the sealing member and the display area of the organic EL element, it is preferable to inject an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil in the gas phase and the liquid phase. . Further, the gap between the sealing member and the display area of the organic EL element can be evacuated, or a hygroscopic compound can be sealed in the gap. Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide or aluminum oxide), sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate or cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide or magnesium iodide) and perchloric acids (eg perchloric acid) Barium or magnesium perchlorate) and the like, and anhydrides are preferably used in sulfates, metal halides and perchloric acids.

<< Organic EL module >>
The organic EL element of the present invention is provided in an organic EL module.

[Configuration of organic EL module]
In the present invention, the organic EL module is an independent function in which the anode and the cathode of at least one organic EL element are connected to a conductive material (connection terminal) and further connected to a wiring board or the like. This means a mounting body having

FIG. 5 is a schematic cross-sectional view showing an example of an organic EL module including the organic EL element of the present invention.

As shown in FIG. 5, the organic EL module 30 mainly includes an organic EL element (EL), an anisotropic conductive film (Anisotropic Conductive Film, abbreviated as ACF) 32, and a flexible printed circuit board (abbreviated as FPC). 34).

The organic EL element (EL) has a laminate 14 including a transparent electrode and an organic functional layer unit on the transparent substrate 1. At the side end of the transparent substrate 1 on which the laminate 14 is not laminated, a first transparent electrode is drawn to form a takeout electrode A2, and the takeout electrode A2 and the flexible printed circuit board (FPC) 34 are anisotropic. Are electrically connected through an electrically conductive film (ACF) 32.

The flexible printed circuit board (FPC) 34 is bonded onto the organic EL element (EL) (laminated body 14) via an adhesive 36. The flexible printed circuit board (FPC) 34 is connected to a driver IC (not shown) or a printed circuit board.

In the present invention, the polarizing member 38 may be provided on the light emitting surface side of the transparent substrate 1. Instead of the polarizing member 38, a half mirror or a black filter may be used. Thereby, the organic EL module 30 of the present invention can express black that cannot be expressed by the light guide dots in the LED used in the conventional method.

<Anisotropic conductive film>
The anisotropic conductive film 32 constituting the organic EL module of the present invention is obtained by dispersing conductive particles, for example, a metal core itself such as gold, nickel, silver, or a resin core gold-plated in a binder.

As the binder, a thermoplastic resin or a thermosetting resin is used, and among them, a thermosetting resin is preferable, and an epoxy resin is more preferable.

An anisotropic conductive film in which nickel fiber (fibrous) is oriented as a filler can also be suitably used.

In the present invention, a fluid material such as a conductive paste, such as a silver paste, may be used instead of the anisotropic conductive film.

<Polarizing member>
Examples of the polarizing member 38 constituting the organic EL module of the present invention include a commercially available polarizing plate or a circularly polarizing plate.

A polarizing film, which is a main component of a polarizing plate, is an element that transmits only light having a polarization plane in a certain direction, and a typical example is a polyvinyl alcohol polarizing film. This mainly includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. A polarizing film having a polarizing film thickness in the range of 5 to 30 μm, preferably in the range of 8 to 15 μm is preferably used. In the present invention, such a polarizing film is also preferably used. it can.

It is also preferable to use a commercially available polarizing plate protective film, specifically, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR -2, KC8UE, KC4UE (manufactured by Konica Minolta Co., Ltd.) and the like.

The pressure-sensitive adhesive used for bonding the polarizing member and the support substrate is preferably optically transparent and exhibits moderate viscoelasticity and adhesive properties.

Specific examples include acrylic copolymers, epoxy resins, polyurethane, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers. Among these, an acrylic copolymer can be preferably used because it is most easy to control the adhesive physical properties and is excellent in transparency, weather resistance, durability, and the like.

These pressure-sensitive adhesives can be cured after being formed on a substrate by forming a film by a drying method, a chemical curing method, a thermal curing method, a thermal melting method, a photocuring method, or the like.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<< Production of organic EL element >>
[Production of Organic EL Element 101]
According to the following method, the organic EL element 101 having the configuration shown as configuration A in FIG. 6A was produced.

(Preparation of transparent substrate 1)
As the transparent substrate 1, a 125 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, Ltd., ultra-high transparency PET Type K) was prepared.

On the transparent substrate 1, the following polysilazane-containing liquid is applied with a wireless bar so that the average film thickness after drying is 300 nm, and heat-treated for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. And dried. Subsequently, it was kept in an atmosphere of a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) for 10 minutes to perform a dehumidification treatment, thereby forming a polysilazane-containing layer (polysilazane precursor layer).

Next, the transparent substrate 1 on which the polysilazane-containing layer is formed is fixed on the operation stage of an excimer irradiation apparatus MECL-M-1-200 (manufactured by M.D. Com) and under the following reforming treatment condition 1 A modification treatment was performed to form a 300-nm-thick polysilazane modified layer (however, not shown in FIG. 6A), and a transparent substrate 1 was obtained.

<Polysilazane-containing liquid>
As the polysilazane-containing liquid, a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was prepared.

<Reforming treatment condition 1>
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 0.5%
Excimer lamp irradiation time: 5 seconds (Formation of the first transparent electrode 2-1)
A first transparent electrode 2-1 (ITO) was formed on the transparent substrate 1 by using a commercially available sputtering apparatus to deposit ITO (indium tin oxide) with a thickness of 150 nm. Further patterning was performed to form an electrode pattern having a light emitting area of 30 × 30 mm.

(Formation of first organic functional unit U1: hole injection transport layer 3A to electron transport layer 6A)
The transparent substrate 1 having the first transparent electrode 2-1 made of ITO is ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. It fixed to the substrate holder of the vacuum evaporation system.

Each of the deposition crucibles in the vacuum deposition apparatus was filled with the constituent material of each layer in an amount optimal for device fabrication. The evaporation crucible used was made of a resistance heating material made of molybdenum or tungsten.

<Formation of hole injection transport layer 3A>
After reducing the vacuum degree of the vacuum deposition apparatus to 1 × 10 ⁻⁴ Pa, the deposition crucible containing the following compound M-2 was heated by energization, and the first transparent electrode of the transparent substrate 1 was deposited at a deposition rate of 0.1 nm / second. Vapor deposition was performed on 2-1 to form a hole injection transport layer 3A having a thickness of 40 nm.

<Formation of fluorescent light emitting layer 4A>
Next, using the following compound BD-1 and compound H-1, co-evaporation was performed at a deposition rate of 0.1 nm / second so that the compound BD-1 had a concentration of 5% and the compound H-1 had a concentration of 95%. A fluorescent light emitting layer 4A having a film thickness of 15 nm and emitting blue light was formed.

<Formation of phosphorescent layer 5A>
Then, using the following compound GD-1, compound RD-1 and compound H-2, compound GD-1 was 17% in concentration, RD-1 was 0.8% in concentration, and compound H-2 was 82.2% The phosphorescent light emitting layer 5A having a film thickness of 15 nm and having a yellow color was formed by co-evaporation at a deposition rate of 0.1 nm / second so as to achieve a concentration of 5 nm.

<Formation of Electron Transport Layer 6A>
Thereafter, the following compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer 6A having a thickness of 30 nm.

(Formation of LiF layer 7A)
Furthermore, LiF was vapor-deposited to a film thickness of 1.5 nm to form a LiF layer 7A as a buffer layer. When forming the LiF layer 7A, an upward arrow pattern as shown in FIG. 2A was formed using a vapor deposition mask so that the lithium fluoride layer was formed only on the upward arrow portion 22A.

(Formation of Al layer 8A)
Further, an aluminum film was deposited with a thickness of 10 nm by an evaporation method to form an Al layer 8A.

(Formation of third transparent electrode 9-1)
Next, using a commercially available sputtering apparatus, ITO was deposited to a thickness of 150 nm to form a third transparent electrode 9-1.

(Preparation of transparent sealing substrate 10)
As with the transparent substrate 1, a polysilazane-containing liquid similar to that described above is applied onto a 125 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, Ltd., PET Type K), and treated with an excimer lamp. Thus, a gas barrier layer was formed to obtain a transparent sealing substrate 10 with a gas barrier layer.

(Sealing of organic EL element 101)
Adhesion of the transparent sealing substrate 10 uses an epoxy thermosetting adhesive (Elephan CS manufactured by Yodogawa Paper Co., Ltd.) as an adhesive, and is carried out at 80 ° C. and 0 ° C. in a glove box having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less. The gas barrier layer of the transparent sealing member 10 is directed to the organic EL element 101 under the condition of 0.04 MPa load under reduced pressure (1 × 10 ⁻³ MPa or less) suction for 20 seconds and pressing for 20 seconds. It vacuum-pressed so that it might become an element side.

Thereafter, in the glove box, the adhesive layer was thermally cured by heating on a hot plate at 110 ° C. for 30 minutes to obtain an organic EL element 101. The structure of the produced organic EL element 101 is referred to as structure A, and a schematic cross-sectional view thereof is shown in FIG. 6A.

When the organic EL element 101 having one set of the prepared organic functional layer unit was caused to emit light, light was emitted in the upward arrow pattern shown in FIG. 2A in the same manner as the mask used when lithium fluoride was deposited by vacuum deposition. .

In the system having one set of organic functional layer units for producing the organic EL element 101, it was possible to shine one shape, but naturally, two or more different shapes are displayed individually or in combination. I couldn't.

[Production of Organic EL Element 102]
Similar to the production of the organic EL element 101, the first organic functional layer unit 1 from the hole injection transport layer 3A to the electron transport layer 6A and the LiF layer 7A were formed on the transparent substrate 1. At this time, the upward arrow pattern 22A as shown in FIG. 2A was formed at the time of forming the LiF layer 7A in the same manner as the fabrication of the organic EL element 101.

Next, aluminum was formed into a film with a thickness of 2 nm by a vacuum evaporation method to form an Al layer 8A.

Next, using a commercially available sputtering apparatus, ITO was deposited to a thickness of 150 nm to form the second transparent electrode 11-1.

Subsequently, in the same manner as the formation of the first organic functional layer unit U1 (hole injection transport layer 3A to electron transport layer 6A) used for the manufacture of the organic EL element 101, the hole injection transport layer 3B to the electron transport layer 6B. The 2nd organic functional layer unit U2 was formed.

Next, lithium fluoride was formed in the same manner as the LiF layer 7A, and the LiF layer 7B was formed in the same manner except that the electrode pattern was changed to the downward arrow pattern 22B as shown in FIG. 2B. .

Further, similarly to the formation of the Al layer 8A in the organic EL element 101, Al was vapor-deposited with a thickness of 10 nm to form the Al layer 8B, and the third transparent electrode 9-1 was formed thereon.

Then, the transparent sealing member 10 was sealed in the same manner as the organic EL element 101 to obtain an organic EL element 102. The layer configuration of the organic EL 102 is the same as the configuration B described in FIG. 6B shown as the layer configuration of the organic EL element 103 described later.

In the organic element 102, when the first transparent electrode 2-1 was used as an anode and the second transparent electrode 11-1 was used as a cathode, when the drive power supply V1 was used, light was emitted in an upward arrow pattern 22A as shown in FIG. 2A. Further, when the second transparent electrode 11-1 is used as an anode and the third transparent electrode 9-1 is used as a cathode, when the drive power supply V2 is energized, light is emitted in a downward arrow pattern 22B as shown in FIG. 2B. did.

[Production of Organic EL Element 103]
In the same manner as in the production of the organic EL element 102, an organic EL element 103 having a layer configuration shown in the configuration B illustrated in FIG. 6B was produced.

However, the LiF layers 7A and 7B were formed as uniform LiF films having no image pattern without using a mask. The film thickness of the second transparent electrode 11-2 was changed to 200 nm.

Next, on the transparent substrate 1 surface side of the organic EL element 103 provided up to the transparent sealing member 10, a pattern mask and an ultraviolet absorption filter (manufactured by Isuzu Seiko Glass Co., Ltd.) as shown in FIG. Using a UV tester (manufactured by Iwasaki Electric Co., Ltd., SUV-W151: 100 mW / cm ² ), ultraviolet rays were irradiated from the transparent substrate 1 side for 1 hour to form an arrow image on the organic functional layer unit U1. As an arrow image, a mask was prepared so that the region 21 shown in FIG. 2A is a region where the light emitting function is modulated, and the region 22A is a region not modulated, so that only the region 22A emits light.

In addition, the ultraviolet absorption filter used the thing with the light transmittance of the wavelength component of 320 nm or less 50% or less (cut wavelength: 320 nm).

Next, similarly, from the transparent sealing member 10 side, a pattern mask as shown in FIG. 2B is arranged and adhered, and a UV tester (SUV-W151: 100 mW / cm ² , manufactured by Iwasaki Electric Co., Ltd.) is used. Then, ultraviolet rays were irradiated from the transparent sealing member 10 side for 1 hour to form an arrow image on the organic functional layer unit U2. As an arrow image, a mask was prepared so that the region 21 shown in FIG. 2B is a region where the light emitting function is modulated, and the region 22B is a region not modulated, so that only the region 22B emits light.

When the organic EL element 103 produced as described above is energized by the driving power source V1 with the first transparent electrode 2-1 as an anode and the second transparent electrode 11-1 as a cathode, an upward arrow pattern 22A as shown in FIG. 2A is formed. Emitted light. Further, when the second transparent electrode 11-1 is used as an anode and the third transparent electrode 9-1 is used as a cathode, when the drive power supply V2 is energized, light is emitted in a downward arrow pattern 22B as shown in FIG. 2B. did.

[Production of Organic EL Element 104]
In the production of the organic EL element 103, instead of the second transparent electrode 11-1 (ITO), silver was deposited to a thickness of 15 nm by vapor deposition to form a second transparent electrode 11-2 (thin silver electrode). Similarly, instead of the third transparent electrode 9-1 (ITO), silver is formed into a third transparent electrode 9-2 (thin silver electrode) by vapor deposition to form a third transparent electrode 9-2 (thin silver electrode). 2 and the transparent sealing member 10, an organic EL element 104 was produced in the same manner except that a hole injection / transport layer 3C having the same composition as the hole injection / transport layer 3A was formed to a thickness of 50 nm. did. The configuration of the organic EL element 104 is shown as configuration C in FIG.

About the produced organic EL element 104, it patterned by the ultraviolet irradiation from the transparent substrate side and the transparent sealing member side similarly to the pattern formation of the said organic EL element 103, and formed the display image shown to FIG. 2A and FIG. 2B. .

When the organic EL element 104 produced as described above is energized by the driving power source V1 with the first transparent electrode 2-1 as an anode and the second transparent electrode 11-2 as a cathode, an upward arrow pattern 22A as shown in FIG. 2A is formed. Emitted light. When the second transparent electrode 11-2 is used as an anode and the third transparent electrode 9-2 is used as a cathode, when a drive power supply V2 is energized, light is emitted in a downward arrow pattern 22B as shown in FIG. 2B. did.

[Production of Organic EL Element 105]
In the production of the organic EL element 104, the first transparent electrode 2-1 (ITO) is changed to the first transparent electrode 2-2 (thin silver electrode) shown below, and the transparent substrate 1 and the first transparent electrode are further changed. The undercoat layer 12 described below was provided between the 2-2 and 2-2.

(Formation of underlayer 12)
On the transparent substrate 1 which is a 125 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd., ultra-high transparency PET Type K), the following compound (R-1) is deposited at a thickness of 25 nm by a known vapor deposition method. The underlayer 12 was formed by vapor deposition.

(First transparent electrode 2-2: thin silver electrode)
Next, silver was vapor-deposited with a thickness of 10 nm on the underlayer 12 by vapor deposition to form a first transparent electrode 2-2 (thin silver electrode).

Other than that, the organic EL element 105 was produced in the same manner as the production of the organic EL element 104. The configuration of the organic EL element 105 manufactured as described above is shown as configuration D in FIG.

When the organic EL element 105 produced as described above is energized by the driving power source V1 with the first transparent electrode 2-2 as an anode and the second transparent electrode 11-2 as a cathode, an upward arrow pattern 22A as shown in FIG. 2A is formed. Emitted light. When the second transparent electrode 11-2 is used as an anode and the third transparent electrode 9-2 is used as a cathode, when a drive power supply V2 is energized, light is emitted in a downward arrow pattern 22B as shown in FIG. 2B. did.

[Production of Organic EL Element 106]
In the production of the organic EL element 105, as shown in the configuration E shown in FIG. 7B, the arrangement of the second organic functional layer unit U2, the LiF layer 7B, and the Al layer 8B is the same except that the configuration is reversed. An organic EL element 106 was produced.

Specifically, as in the configuration E shown as a cross-sectional view in FIG. 7B, the Al layer 8B, the LiF layer 7B, the electron transport layer 6B, the phosphorescent light emitting layer 5B, the fluorescent light emission, on the second transparent electrode 11-2. The layer 4B and the hole injecting and transporting layer 3B were stacked in this order.

In the produced organic EL element 106, the first transparent electrode 2-2 and the third transparent electrode 9-2 were used as anodes, and the second transparent electrode 11-2 was used as cathodes. When the first transparent electrode 2-2 was used as the anode and the second transparent electrode 11-2 was used as the cathode, when the drive power supply V1 was used, light was emitted in the pattern of the upward arrow 22A as shown in FIG. 2A. In addition, when the second transparent electrode 11-2 is used as a cathode and the third transparent electrode 9-2 is used as an anode, when a drive power supply V2 is energized, light is emitted in a pattern of a downward arrow 22B as shown in FIG. did.

In the organic EL element 106, since the second transparent electrode 11-2 is always operated as a cathode, switching of lighting becomes easy. Moreover, it was easy to emit light by overlapping arrows.

[Production of Organic EL Element 107]
In the production of the organic EL element 105, as shown in the configuration F shown in FIG. 7C, the configuration of the first organic functional layer unit U1, the LiF layer 7A, and the Al layer 8A is the same except that the configuration is reversed. An organic EL element 107 was produced.

Specifically, as shown in Configuration F in FIG. 7C, on the first transparent electrode 2-2, an Al layer 8A, a LiF layer 7A, an electron transport layer 6A, a phosphorescent light emitting layer 5A, and a fluorescent light emitting layer 4A. The hole injection transport layer 3A was formed in this order.

In the produced organic EL element 107, the first transparent electrode 2-2 and the third transparent electrode 9-2 were used as cathodes, and the second transparent electrode 11-2 was used as anodes. When the first transparent electrode 2-2 was used as a cathode and the second transparent electrode 11-2 was used as an anode, when the drive power supply V1 was used, light was emitted in the pattern of the upward arrow 22A as shown in FIG. 2A. When the second transparent electrode 11-2 is used as an anode and the third transparent electrode 9-2 is used as a cathode, when the drive power supply V2 is energized, light is emitted in a pattern of a downward arrow 22B as shown in FIG. did.

In the organic EL element 107, since the second transparent electrode 11-2 is always operated as an anode, switching of lighting becomes easy. Moreover, it was easy to emit light by overlapping arrows.

<< Evaluation of organic EL elements >>
[Evaluation of sharpness of display pattern]
A current of 5 mA / cm ² was passed through each of the drive power supply V1 and the drive power supply V2 (however, the organic EL element 101 was only the drive power supply V1) to display the respective image patterns. Next, at the interface between the displayed arrow image and the non-light emitting portion (region 21 in FIG. 2), the blur width at the boundary portion is observed visually and with a commercially available microscope, and the sharpness of the display pattern is evaluated according to the following criteria: did.

A: The blur width at the boundary is less than 0.4 mm, and the image is clear. B: The blur width at the boundary is not less than 0.4 mm and less than 0.8 mm, and the image is almost clear. C: The blur width at the boundary is 0.8 mm or more, and the image is unclear [Measurement of display pattern luminance]
An image pattern (22A in FIG. 2A and 22B in FIG. 2B) was displayed by applying a current of 5 mA / cm ^{2 to} each of the drive power supply V1 and the drive power supply V2 (however, the organic EL element 101 is only the drive power supply V1). . Next, the luminance of the first organic functional layer unit U1 provided on the transparent substrate side and the second organic functional layer unit U2 provided on the transparent sealing member side is measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta). And measured from the transparent substrate 1 side.

The relative luminance of each organic EL element was determined with the luminance of the first organic functional layer unit U1 of the organic EL element 101 as 100.

Table 2 shows the results obtained as described above.

As is clear from the results shown in Table 2, in the organic EL elements 103 to 107 of the present invention in which the display image was formed by ultraviolet patterning, the blur in the boundary region of the display image was small and excellent in clarity, and transparent. It can be seen that the brightness is increased by using a thin film electrode, specifically, a thin silver electrode as the electrode. Furthermore, it can be seen that the use of thin silver electrodes for all the transparent electrodes reduces the luminance difference between the first organic functional layer unit U1 and the second organic functional layer unit U2.

Moreover, in the organic EL elements 106 and 107, the first transparent electrode and the third transparent electrode are configured to have the same polarity, so that switching of lighting is easy.

Moreover, a polarizing member, a half mirror member, or a black filter is provided on the light emitting surface side of the transparent substrate 1 of each of the organic EL elements of the present invention produced above via an adhesive, and the organic EL as shown in FIG. As a result of producing a module and evaluating its function, it was confirmed that the organic EL module of the present invention including the organic EL element of the present invention can exhibit good display performance.

The manufacturing method of the organic electroluminescence element of the present invention is excellent in the shape display accuracy (sharpness) of the light emission display pattern image, has high light emission luminance, can switch the light emission pattern, and displays different images in the same display area. An organic electroluminescent element that can be displayed individually or simultaneously can be manufactured, and the organic electroluminescent element can easily switch a light emission pattern, and is suitable for smart devices such as smartphones and tablets that are portable terminals. Available.

1 Transparent substrate 2-1 First transparent electrode (ITO)
2-2 First transparent electrode (thin silver electrode)
3A, 3B Hole

injection transport layer

4A, 4B Fluorescent

light emitting layer

5A, 5B Phosphorescent

light emitting layer

6A, 6B

Electron transport layer

7A,

7B LiF layer

8A, 8B Al layer 9-1 Second transparent electrode (ITO)
9-2 Second transparent electrode (thin silver electrode)
10, D Transparent sealing member 11-1 Third transparent electrode (ITO)
11-2 Third transparent electrode (thin silver electrode)
12 Underlayer 14

Laminate

20A, 20B Lead wire 21 Background (area where light emitting function is modulated)
22A, 22B Arrow image (area where the light emission function is not modulated)
30 Organic EL Module 32 Anisotropic Conductive Film 34 Flexible Printed Circuit Board 36 Adhesive 38 Polarizing Member A First Transparent Electrode A2 Extraction Electrode B Second Transparent Electrode C Third Transparent Electrode E, F Image EL Organic EL Element L1, L2 Light Irradiation U1 First organic functional layer unit U2 Second organic functional layer unit

Claims

An organic electroluminescence device having at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, a third transparent electrode, and a transparent sealing member in this order on a transparent substrate is manufactured. A method for producing an organic electroluminescent device comprising:
The first organic functional layer unit and the second organic functional layer unit are independently capable of emitting light by electrical driving individually or simultaneously,
Light irradiation is performed in different patterns from the transparent substrate side and the transparent sealing member side, respectively, and the first organic functional layer unit and the second organic functional layer unit are modulated with regions where the light emitting function is modulated. A method for producing an organic electroluminescence element, comprising forming different display images composed of regions that are not formed.
2. The organic electro according to claim 1, wherein the patterning method by light irradiation is a method of patterning different display images from the transparent substrate side and the transparent sealing member side by using ultraviolet rays as an irradiation light source. Manufacturing method of luminescence element.
3. The organic electroluminescence device according to claim 1, wherein at least one electrode selected from the first transparent electrode, the second transparent electrode, and the third transparent electrode is formed of a thin film metal. Method.
3. The method of manufacturing an organic electroluminescent element according to claim 1, wherein all of the first transparent electrode, the second transparent electrode, and the third transparent electrode are formed of a thin film metal.
5. The film thickness of the second transparent electrode is set to be the thickest among the first transparent electrode, the second transparent electrode, and the third transparent electrode. 6. The manufacturing method of the organic electroluminescent element of description.
The method for producing an organic electroluminescent element according to any one of claims 3 to 5, wherein the electrode formed of the thin film metal is a thin silver electrode.
The method for producing an organic electroluminescent element according to claim 6, wherein a base layer containing an organic compound having at least one atom selected from nitrogen and sulfur is provided below the thin silver electrode.
The method for producing an organic electroluminescent element according to any one of claims 1 to 7, wherein the first transparent electrode and the third transparent electrode are formed as anodes.
The method for producing an organic electroluminescent element according to any one of claims 1 to 7, wherein the first transparent electrode and the third transparent electrode are formed as cathodes.
An organic electroluminescent element manufactured by the method for manufacturing an organic electroluminescent element according to any one of claims 1 to 9,
On the transparent substrate, at least a first transparent electrode, a first organic functional layer unit, a second transparent electrode, a second organic functional layer unit, a third transparent electrode and a transparent sealing member are provided in this order, and the first An organic electroluminescent element, wherein the organic functional layer unit and the second organic functional layer unit have a function of displaying different images formed by light irradiation.
An organic electroluminescence module comprising the organic electroluminescence element according to claim 10.
The organic electroluminescence module according to claim 11, further comprising a polarizing member, a half mirror member, or a black filter on a light emitting surface side of the transparent substrate constituting the organic electroluminescence element.