JP2019106332A - Organic electroluminescent device and method for manufacturing the same, and display device - Google Patents

Abstract

To provide an inexpensive organic electroluminescent device capable of reproducing tone and gradation through control of light emitting areas of organic electroluminescent elements individually emitting red light, green light and blue light by a light shielding portion and thereby capable of forming a still image with a simple structure, a method for manufacturing the organic electroluminescent device, and a display device.SOLUTION: An organic electroluminescent device of the present invention includes two or more organic electroluminescent elements having luminescent colors different from each other. In the organic electroluminescent device, the organic electroluminescent elements having luminescent colors different from each other are arranged in the same plane, and a light shielding part is provided on a surface of a light extraction side of the organic electroluminescent elements, the light shielding part having light transmittance in a visible light region which gradually changes or is uniform.SELECTED DRAWING: Figure 8

Description

  The present invention relates to an organic electroluminescent device, a method of manufacturing the same, and a display device, and more specifically, the color tone is controlled by controlling the light emission area of each of the organic electroluminescent elements emitting red, green and blue. And an inexpensive organic electroluminescent device capable of reproducing gradations and forming a still image with a simple structure.

  In recent years, organic electroluminescent devices using electroluminescence (ElectroLuminescence) of an organic material are rapidly spreading, and this organic electroluminescent device is a thin film type capable of emitting light at a low voltage of several volts to several tens of volts. It is a completely solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness and light weight. For this reason, as a surface light emitter such as a display device, a display, an illumination light source, etc., examination of the application field is energetically made.

  Furthermore, as a display device, there is an increasing demand for a display device using a still image intended for a poster or the like, not a moving image display.

  In organic electroluminescent devices, when expressing the image to be displayed in multiple colors, when a constant voltage is applied due to the difference in emission start voltage of each pixel, red is most likely to emit light, then green emission and blue emission In order to obtain uniform white light emission, for example, it is necessary to control the voltage applied to each organic electroluminescent element. Therefore, in the case of a display application, a method of adjusting the voltage of each pixel with a thin film transistor: TFT (Thin Film Transistor) and emitting light with an arbitrary luminance is adopted.

  However, in the case of a device for a still image application such as a poster, TFTization requiring a photolithographic process is not suitable for so-called on-demand, in which the device is simply manufactured according to the user's request. In addition, there is a problem that a TFT is required to have a driver for driving, and it becomes complicated as the configuration of the organic electroluminescent device and becomes expensive as a device.

  Furthermore, when signage or the like by irradiation of the entire surface of a signboard is manufactured using the TFT-formed organic electroluminescent device, a huge amount of power consumption is required at night, and the power distribution facility cost becomes high.

  On the other hand, organic electroluminescent elements that emit red, green and blue light without adjusting the device to TFTs are respectively adjusted in voltage and made to emit white light, and display is made by appropriately combining red, green and blue color filters Methods for expressing images in multiple colors are known (see, for example, Patent Documents 1 to 3). However, in this method, since it is necessary to control the color tone and gradation via the color filter for each pixel, the process of producing and arranging the color filter is complicated, and the on-demand property is lacking. There is a problem that luminance and color purity are likely to be low because of the filter, and an immediate response is required.

JP, 2006-73219, A JP, 2011-181590, A JP, 2013-211147, A

  The present invention has been made in view of the above problems and circumstances, and the problem to be solved is to control the light emission area of each of the organic electroluminescent elements emitting red, green and blue by means of the light shielding portion to obtain a color tone. And an inexpensive organic electroluminescent device capable of reproducing gradations and forming a still image with a simple structure, a method of manufacturing the same, and a display device equipped with the same.

  In the process of examining the cause of the above problems by the present inventor in order to solve the above problems, two or more organic electroluminescent elements having different emission colors are respectively disposed in the same plane, and An organic electroluminescent device that emits red, green and blue light by an organic electroluminescent device having a light shielding portion in which the light transmittance of the visible light region changes stepwise or is uniform on the light extraction side of the organic electroluminescent device The inventors have found that it is possible to obtain an inexpensive organic electroluminescent device capable of reproducing a color tone and a gradation and forming a still image with a simple structure by controlling the light emitting area of each of the luminescent elements.

  That is, the above-mentioned subject concerning the present invention is solved by the following means.

1. An organic electroluminescent device comprising two or more organic electroluminescent devices different in luminescent color, comprising
The organic electroluminescent elements having different luminescent colors are disposed in the same plane, and
The surface of the light extraction side of the said organic electroluminescent element WHEREIN: The light shielding part which the light transmittance of a visible light area | region changes stepwise or is uniform is characterized by the above-mentioned.

  2. The organic electroluminescent device according to claim 1, wherein the light shielding portion contains a light absorbing material or a light reflecting material.

  3. The organic electroluminescent device according to claim 1 or 2, wherein the light shielding portion has gradation in which the light transmittance changes stepwise.

  4. 3. The organic electroluminescent device according to item 1 or 2, wherein the light transmittance of the light shielding portion in the visible light region is uniformly 5% or less and does not have gradation.

  5. The organic electroluminescent device according to any one of Items 1 to 4, wherein the shape of the light shielding portion is a concave shape from the peripheral portion to the central portion.

  6. 6. The organic electroluminescent device according to any one of items 1 to 5, wherein the light shielding part contains carbon black, silver nanoparticles or titanium oxide particles.

  7. The organic electroluminescent device according to any one of claims 1 to 5, wherein the light shielding portion contains a red, green or blue coloring material.

8. The two or more organic electroluminescent elements having different emission colors constitute a pixel unit in which three pixels emitting red, green or blue are combined as one set.
Among the pixels included in the pixel unit, the light shielding portion is provided to the light shielding pixel, and the light shielding portion contains a red, green or blue color material of the same color as the light emitted from the pixel transmitting the light. The organic electroluminescent device according to claim 7, characterized in that:

  9. With respect to the three pixels included in the pixel unit, the light shielding portion is a color complementary to the light emitting color in which each light emission color and the reflected light color of the light shielding portion are mixed under the illumination environment. The organic electroluminescent device according to claim 7, containing a coloring material to be visually recognized as a related color.

  10. 9. The organic electroluminescent element having different luminescent color is disposed in parallel in the same plane and in two or more lines of different luminescent color, one of the items 1 to 9 The organic electroluminescent device as described in.

  11. A tenth aspect of the invention is characterized in that the organic electroluminescent elements arranged in parallel in the form of two or more lines of different emission colors in the same plane are connected to a power source by conductive members having different resistance values. The organic electroluminescent device as described in a term.

  12. The two or more organic electroluminescent elements having different luminescent colors are disposed in one pixel, and the anode of the organic electroluminescent element emitting one luminescent color emits the other adjacent luminescent color. The organic electroluminescent device according to any one of claims 1 to 11, which is electrically connected in series to the cathode of the element.

13. 13. A method of manufacturing an organic electroluminescent device, which manufactures the organic electroluminescent device according to any one of the items 1 to 12;
The method of manufacturing an organic electroluminescent device, wherein the light shielding portion is formed by an ink jet printing method using an ink liquid containing a light absorbing material or a light reflecting material.

14. 13. A method of manufacturing an organic electroluminescent device, which manufactures the organic electroluminescent device according to any one of the items 1 to 12;
A method of manufacturing an organic electroluminescent device, comprising: bonding a sheet containing a light absorbing material or a light reflecting material as the light shielding portion on a light extraction surface of the organic electroluminescent element.

  15. A display comprising the organic electroluminescent device according to any one of items 1 to 12.

  By controlling the emission area of each of the organic electroluminescent elements emitting red, green and blue by the above means of the present invention, it is possible to reproduce color tone and gradation and to form a still image with a simple structure. An electroluminescent device, a method of manufacturing the same, and a display device can be provided.

  The expression mechanism or action mechanism of the effects of the present invention is presumed as follows.

  In the configuration of the organic electroluminescent device of the present invention, two or more organic electroluminescent devices having different emission colors are disposed in the same plane, and visible light is emitted to the surface on the light extraction side of the organic electroluminescent device. It has a light shielding portion in which the light transmittance of the region changes stepwise or is uniform. According to the configuration, by controlling the light emitting area of each of the organic electroluminescent elements emitting red, green and blue, color tone and gradation can be reproduced, and a still image can be formed with a simple structure. It is an organic electroluminescent device.

  1A and 1B are schematic views showing the mechanism of light control of the organic electroluminescent device of the present invention.

FIG. 1A is a plan view of the organic electroluminescent device of the present invention. Organic electroluminescent devices emitting red light (EL _R ), green light (EL _G ) and blue light (EL _B ) are arranged in a line in the same plane to form an organic electroluminescent device (OLED), The light emission part L is shielded by the light shielding part 9 about a part of the said organic electroluminescent element, and other elements are embodiment from which the emission light L is taken out as it is.

FIG. 1B is a cross-sectional view taken along line AA 'of FIG. 1A. Luminescent light L from the organic electroluminescent device emitting a plurality of red light (EL _R ), green light (EL _G ) and blue light (EL _B ) is partially emitted on the light extraction side of the organic electroluminescent device It is a schematic diagram which shows that it is shielded by shielding part 9 and luminescence light L is taken out other than that as it is. By blocking the emitted light L by the light shielding portion 9, it is possible to arbitrarily reproduce the color tone or the gradation that indicates the pattern such as a pattern, and a plurality of red light emission (EL _R ), green light emission (EL _G ) and It is possible to form a full-color still image by an organic electroluminescent device that emits blue light (EL _B ).

Therefore, as in the conventional device, red light emission (EL _R ), green light emission (EL _G ), and blue light emission (EL _B ) are mixed to be white light, and the combination of the white light and the color filter causes color tone and gradation. This method is not a method for reproducing the image data, so that a still image having excellent image quality can be formed without a drop in luminance or color purity due to the color filter.

In addition, the organic electroluminescent device of the present invention incorporates a TFT into each of the organic electroluminescent devices that emit red light (EL _R ), green light (EL _G ) and blue light (EL _B ), and individually produces color tone and gradation. Since it does not have a complicated and expensive mechanism to control the reproduction of the device, it can be said that the device has a simple and inexpensive structure and is excellent in on-demand characteristics.

  Further, in the organic electroluminescent device of the present invention, the light shielding portion preferably contains a red, green or blue coloring material, and the two or more organic electroluminescent elements having different emission colors are red or green. Alternatively, a pixel unit is configured to be a set of three pixels that emit blue light, and among the pixels included in the pixel unit, the pixels that are provided with the light shielding portion for light shielding pixels and transmit light It is also preferable to contain a red, green or blue coloring material of the same color as that of the light emitted from the light shielding portion.

  Furthermore, with respect to the three pixels included in the pixel unit, the light shielding portion mixes the light emission color of the light shielding portion with the light emission color of the light shielding portion under the illumination environment, and It is also preferable to contain a colorant that is visually recognized as a complementary color.

  In the case of such an embodiment, for example, effects other than the effect of uniformly shielding light by a black light shielding part by carbon black, Ag nano ink, or the like can be expected.

  That is, when a pixel emitting red, green or blue is one pixel unit, for example, for a pixel unit for which green light is to be extracted, green having low light transmittance of red and blue with respect to pixels emitting red and blue By shielding with a light shielding part containing a coloring material, the appearance when the organic electroluminescent device emits no light matches the appearance when light is emitted, and in the daytime, a still image by subtractive color method (reflection of illumination light In the nighttime, it is possible to switch a still image (image by light emission) by the addition method. In a bright environment, it is also possible to add an image by light emission to the image by reflected light, and it is possible to obtain a still image with higher visibility.

  In addition, with respect to the pixels emitting light in red, green or blue, the light shielding portion mixes the respective emission colors and the reflected light color of the light shielding portion under the illumination environment, and the light emission color By containing the coloring material to be visually recognized as the complementary color, it is possible to obtain a still image using the subtractive color method for color reproduction under the illumination environment. Furthermore, it is also possible to add a still image using subtractive color reproduction to the same screen of a still image using additive color reproduction by light emission, and obtain a still image capable of expressing more widely. be able to.

The top view which shows the mechanism of the light control of the organic electroluminescent device of this invention Sectional drawing which shows the mechanism of light control of the organic electroluminescent device of this invention Sectional drawing which shows the basic composition of the organic electroluminescent element applicable to this invention Another cross-sectional view showing the basic configuration of the organic electroluminescent device applicable to the present invention A schematic view of a light shielding part without gradation A schematic view of a light shield having gradation Schematic which shows the relationship which concerns on the magnitude | size of the light-shielding part which concerns on this invention, and a pixel A schematic view when forming a light shielding part by the ink jet printing method A schematic view showing an example of a method of applying a light shielding part using an inkjet printing method Schematic perspective view showing an example of an inkjet head An example showing the outline of the circuit diagram of the organic EL device of the present invention An example showing an outline of another circuit diagram of the organic EL device of the present invention Schematic diagram showing an example of the configuration of the organic EL device of the present invention provided with two or more organic EL elements having different luminescent colors (Embodiment 1) Enlarged schematic view of the pixel portion of the configuration of the organic EL device (first embodiment) A schematic cross-sectional view showing a configuration represented by a cross section A-A 'of the pixel unit Schematic cross-sectional view showing a configuration represented by the cross section B-B 'of the pixel unit Schematic diagram of the manufacturing method using the inkjet printing method of Embodiment 1. Schematic diagram of the second half of the manufacturing method using the ink jet printing method of Embodiment 1. Schematic diagram showing another example of the configuration of the organic EL device of the present invention provided with two or more organic EL elements having different luminescent colors (Embodiment 2) Sectional view of an organic EL element unit when an anode and a cathode are electrically connected in series The schematic diagram which shows the manufacture example of an organic EL element unit when an anode and a cathode are electrically connected in series Schematic drawing showing the emission spectrum of blue light Schematic diagram showing the emission spectrum of green light Schematic drawing showing the emission spectrum of red light A schematic view showing a mechanism of light control by a light shielding portion containing a blue, green or red coloring material A schematic view showing the reflection spectrum of yellow (Y) to be visually recognized A schematic view showing the reflection spectrum of magenta (M) to be visually recognized A schematic view showing the reflection spectrum of cyan (C) to be visually recognized

  The organic electroluminescent device of the present invention is an organic electroluminescent device provided with two or more organic electroluminescent elements different in emission color, and the organic electroluminescent elements different in emission color are arranged in the same plane, respectively. And a light shielding portion in which the light transmittance of the visible light region changes stepwise or is uniform on the surface on the light extraction side of the organic electroluminescent element. This feature is a technical feature common to the following embodiments.

  As an embodiment of the present invention, from the viewpoint of being able to further express the intended effect of the present invention. It is preferable that the light shielding portion contains a light absorbing material or a light reflecting material from the viewpoint of easily exhibiting the function as the light shielding portion.

  It is preferable that the light shielding portion has gradation in which light transmittance changes stepwise, and by having gradation, the color tone and gradation can be finely controlled, and a high-quality still image is obtained. Can be formed.

  In addition, the light transmittance of the light shielding portion in the visible light region is uniformly 5% or less and does not have gradation, and it is possible to easily exhibit the effect of light shielding to reproduce color tone and gradation. From this, it is a preferred form.

  The shape of the light shielding portion is preferably a concave shape from the peripheral portion to the central portion, and the film thickness of the peripheral portion is thicker than that in the central portion, so that scattered light from the organic electroluminescent element as a pixel is effective. It is possible to provide a so-called still image with a sharp edge.

  As an embodiment of the present invention, the light shielding portion containing carbon black, silver nanoparticles or titanium oxide particles effectively realizes the control of the light transmittance and obtains the excellent effect of the present invention. This is a preferred embodiment from the viewpoint.

  Further, as an embodiment of the present invention, it is also preferable that the light shielding portion contains a coloring material of red, green or blue. By using a light shielding portion containing such a coloring material, it can be expected to obtain the following effects.

  That is, the two or more organic electroluminescent elements having different emission colors constitute a pixel unit in which three pixels emitting red, green or blue are combined to form a pixel unit, and the pixels included in the pixel unit Among them, the organic electroluminescent device emits light when the light shielding portion is provided to the light shielding pixel and the light shielding portion contains a red, green or blue coloring material of the same color as the light emitted from the pixel transmitting light. While matching the appearance when not emitting light and when emitting light, the still image (image to be recognized by the reflection of the illumination light) by the subtractive method in the daytime, the still image (image by the light emission) by night method at the nighttime Switching is possible. In a bright environment, it is also possible to add an image by light emission to the image by reflected light, and it is possible to obtain a still image with higher visibility.

  Furthermore, with respect to the three pixels included in the pixel unit, the light shielding portion mixes the light emission color of the light shielding portion with the light emission color of the light shielding portion under the illumination environment, and It is also preferable to contain a coloring material to be visually recognized as a complementary color, and for example, it is possible to obtain a still image by the subtractive color method or to obtain a still image mixed with the subtractive color method and the color addition method.

  Further, as the organic electroluminescent elements having different emission colors are arranged in parallel in the same plane in two or more lines of different emission colors, it is possible to efficiently make light transmitting pixels and non-light transmitting pixels. This is a preferable form from the viewpoint of obtaining stable light emission characteristics by efficiently forming a wide area. Here, “line-like” means that the organic electroluminescent elements are arranged linearly and in parallel so as to be represented by stripes (striped patterns).

  It is preferable that the organic electroluminescent elements arranged in parallel in the form of two or more lines of different emission colors in the same plane are connected to the application power supply unit by conductive members having different resistance values, respectively. Thus, when white light is emitted as one pixel unit, the light emission control of the organic electroluminescent element emitting red light, green light and blue light can be performed in a well-balanced manner.

  Further, two or more organic electroluminescent devices having different luminescent colors are disposed in one pixel, and the anode of the organic electroluminescent device emitting one luminescent color emits the other adjacent luminescent color. It is preferable from the viewpoint of obtaining uniform light emission that the voltage drop in the case of a large-area organic electroluminescent device can be reduced by electrically connecting in series with the cathode of the electroluminescent element.

  The method of manufacturing an organic electroluminescent device of the present invention is characterized in that the light shielding portion is formed by an ink jet printing method using an ink liquid containing a light absorbing material or a light reflecting material. I assume. By employing the ink jet printing method, large-sized equipment is not necessary as a manufacturing means, a light shielding portion can be disposed at an arbitrary position and in any size, and on-demand performance is further improved.

  In the method of manufacturing an organic electroluminescent device according to the present invention, a sheet containing a light absorbing material or a light reflecting material is attached to the light extraction surface of the organic electroluminescent element as the light shielding portion. It is also preferable to be a combined aspect, which is simple and inexpensive, and the on-demand property is further improved.

  The organic electroluminescent device of the present invention can be preferably applied to a display device for still images such as outdoor advertisements (digital signage) and posters.

  Hereinafter, the components of the present invention and the embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, in this application, "-" showing a numerical range is used by the meaning included as a lower limit and an upper limit with the numerical value described before and behind that. In addition, in description of each figure, the number described in the parenthesis at the end of a component represents the code | symbol in each figure.

[1] Overview of the Organic Electroluminescent Device of the Present Invention The organic electroluminescent device of the present invention is an organic electroluminescent device comprising two or more organic electroluminescent elements having different luminescent colors, and the organic luminescent devices having different luminescent colors. A light shielding portion in which electroluminescent elements are respectively arranged in the same plane, and the light transmittance in the visible light region changes stepwise or is uniform on the light extraction side of the organic electroluminescent element It is characterized by having.

  Here, in the present application, the organic electroluminescent device is hereinafter referred to as "organic EL device", and the organic electroluminescent element is hereinafter referred to as "organic EL element". The "organic EL device" of the present invention is a device in which a plurality of organic EL elements constituting a plurality of divided light emitting areas are arranged in the same plane as pixels to constitute a large area light emitter. In the drawings, the symbol "OLED" is indicated.

  Moreover, the form which arrange | positioned several organic EL elements which comprise the light emission area divided into the said some in the same planar form may be called a "pixel unit", and it abbreviates it as "ELU."

  The "organic EL element" in the present invention is a light emitting element constituting a divided light emitting area, and on a base material, at least one of a pair of opposing electrodes has a light transmitting electrode (anode and cathode), and the electrode In between, an organic functional layer unit (hereinafter sometimes simply referred to as “U”) composed mainly of an organic functional layer that controls transport of electrons or holes and a light emitting layer, and further having an upper part thereof sealed It says the composition which provided the stop member. However, for convenience of description, the description and the description of the sealing member may be omitted. Moreover, in the present invention, the description of the control circuit that controls the light emission of the organic EL element and the wiring associated therewith may be omitted.

  The “organic functional layer unit” in the present invention will be described with reference to FIG. 2 described later, and as one example, organic functional layer group 1 (for example, hole injection layer, hole transport layer, etc.) on a substrate And a light emitting layer containing a phosphorescent compound and the like, and an organic functional layer group 2 (for example, a hole blocking layer, an electron transporting layer, an electron injecting layer, etc.) are stacked and arranged.

  The "light emitting area" in the present invention refers to a region in which all of the anode, the organic functional layer unit and the cathode are present in the layer thickness direction.

  The "anode" in the present invention is an electrode to which (+) is applied as a voltage, and may be referred to as "anode" or "first electrode or first electrode". Moreover, a "cathode" is an electrode which applies (-) as a voltage, and may be called "cathode" or "2nd electrode or 2nd electrode."

  Further, the "light transmitting property" in the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more, preferably 60% or more, and more preferably 70% or more.

  Hereinafter, the components of the present invention and the embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, in this application, "-" showing a numerical range is used by the meaning included as a lower limit and an upper limit with the numerical value described before and behind that. In the description of each drawing, the alphanumeric characters described in parentheses at the end of the component represent the reference numerals in each drawing.

[2] Basic Configuration of Organic EL Element The details of the configuration will be described later, but first, the configuration of the organic EL element applicable to the present invention will be described. However, the description is an example and is not limited thereto.

  FIG. 2A is a schematic cross-sectional view showing a basic configuration including an organic functional layer unit of an organic EL element applicable to the present invention.

  The organic EL device according to the present invention shown in FIG. 2A has a structure in which an organic functional layer unit including a light emitting layer is laminated on a light transmitting substrate (1), for example, a glass substrate or a flexible resin substrate. Is shown.

  In FIG. 2A, a light transmitting anode (2) is formed as a first electrode on a light transmitting substrate (1), and, for example, from a hole injection layer, a hole transport layer, etc. Organic functional layer group 1 (3), light emitting layer (4), and organic functional layer group 2 (5) composed of, for example, an electron transport layer, an electron injection layer, etc. (U) is composed. Furthermore, a cathode (6) is provided above the functional layer unit (U) as a second electrode acting as a light reflecting electrode. And in the structure which covers the whole above-mentioned layered product, the adhesion layer (7) for closure and the sealing member (8) are provided, and also the light shielding part (9) concerning the present invention is a substrate (1) The organic functional layer unit is disposed on the side opposite to the side where the organic functional layer unit is present, and constitutes the organic EL element (OLED) according to the present invention. In this case, the emitted light (L) from the light emitting layer (4) is extracted from the side of the base material (1) and is shielded by the light shielding part (9).

  FIG. 2B is a schematic cross-sectional view showing another configuration of the organic EL element according to the present invention.

  In this configuration, the anode (2) as the first electrode is a light reflecting electrode, the cathode (6) as the second electrode is a light transmitting electrode, and the sealing adhesive layer (7) and the sealing This is the case where the member (8) is light transmissive, and the emitted light (L) from the light emitting layer (4) is extracted from the sealing member (8) side. In this case, the light shielding portion (9) according to the present invention is disposed on the surface of the sealing member (8) opposite to the surface having the organic functional layer unit (U), and light emitted from the light emitting layer (4) (L) is shielded by the light shielding part (9).

[3] Light Shielding Section The organic EL device of the present invention is provided with the light shielding section according to the present invention, so that the light shielding section appropriately shields the emitted light from the organic EL element, whereby the color tone of the entire device is obtained. And reproduce the gradation to form a still image.

  That is, the light shielding portion according to the present invention is disposed on the surface on the light extraction side of the organic EL element, and light control (light shielding) such that the light transmittance of the visible light region changes stepwise or blocks uniformly. Have the ability to

  The light shielding portion according to the present invention, as one embodiment, is for uniformly shielding light of wavelengths in the visible light region, and is a light control filter that absorbs light of a specific wavelength like a color filter. It is different. Here, the "visible light region" refers to a region with a light wavelength of 380 to 780 nm. The "uniformly blocking" means not uniformly controlling the transmittance of light of a specific wavelength as in a color filter, but uniformly blocking the entire transmitted light in the visible light region. That is, for example, by using a light absorbing material having a black color such as carbon black, one that uniformly blocks light in the visible light region can be mentioned as an example.

  The light shielding portion may contain either a light absorbing material or a light reflecting material. Generally, it is preferable to contain a light absorbing material from the viewpoint of reducing scattered light in the organic EL element.

  That is, by using a light absorbing material, it is possible not only to shield the light emitted from the organic EL element but also to absorb the scattered light and the reflected light inside the organic EL element to enhance the contrast.

  The light transmittance of the light shielding portion in the case of using a light absorbing material is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less of incident light in the light wavelength region of 380 to 780 nm. % Or less. The light transmittance can be measured by a commercially available spectrophotometer. For example, the integrating sphere can be mounted on a Hitachi spectrophotometer U-4100 manufactured by Hitachi or a UV-3101 spectrophotometer manufactured by Shimadzu Corporation. The light transmittance can be controlled by the amount of the light absorbing material applied and the thickness of the light shielding portion.

  The light absorbing material used for the light shielding part according to the present invention is not particularly limited, and black materials such as carbon black, silver paste containing carbon particles, silver nanoparticles, aluminum-tungsten, and aluminum-molybdenum are used. It is preferable to use, and it is preferable to use carbon black or silver nanoparticles among others. Examples of carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black.

  The formation of the light shielding portion according to the present invention can be carried out, for example, by spin coating a photoresist material containing carbon black or ink jet printing on the surface of the substrate (1) opposite to the organic functional layer unit (U). The light shielding portion of the carbon black-containing thin film can be formed by coating at a desired position at a desired position by a coating method such as a method and baking the film. It is preferable to adopt an inkjet printing method from the viewpoint of ease of coating. That is, it is preferable that the light shielding part according to the present invention adopt a manufacturing method formed by an ink jet printing method described later using an ink liquid containing a light absorbing material as a light shielding material or a light reflecting material.

  FIG. 3A is a schematic view showing an example of the light shielding unit according to the present invention.

  This light shielding portion is a member that does not have gradation, and shields the light in the visible light region uniformly over the entire surface. Here, "uniformly" means that when the light transmittance of any five parts of the light shielding portion is measured, the variation of the light transmittance is within ± 2% in the visible light region. To say that

  FIG. 3B is a schematic view showing another example of the light shielding portion according to the present invention.

  This light shielding portion has gradation, and is, for example, a light shielding portion in which the light transmittance changes preferably in a range of 5 to 50% in one member. The change may be continuous or may be stepwise changed discontinuously. The term "stepwise change" in the present invention is synonymous with "continuously or discontinuously changing with gradation". A light shielding portion having such gradation can be produced, for example, by controlling the amount of carbon black applied, or by controlling the density of ink dots when using an ink jet printing method. From the viewpoint of the simplicity of the manufacturing method, it is preferable to perform control of the amount of attached ink and control of the density of ink dots by the inkjet printing method.

  FIG. 4A is a schematic view showing the relationship between the area of the light shielding portion and the pixel (here, the organic functional layer unit) according to the present invention.

  In FIG. 4A, pixel: width of organic functional layer unit (U) is x, thickness of base material (1) is y, width of light shielding portion 9 is z, emitted light is oriented from organic functional layer unit (U) When light is emitted at an angle θ, the following equation (1) holds.

Equation (1) Width of light shielding portion z = 2y × tan θ + x
Therefore, when the light distribution angle is 45 °, the width of the pixel + the thickness of the base material × 2 is the minimum required width to block the light. Since the light shielding portion has an area, a rectangular member having the width z of the light shielding portion on the long side and the short side obtained by the above calculation based on the widths of the long side and the short side of the pixel It may be produced. Of course, the size of the light shielding portion may be larger or smaller because it is a size necessary to shield the emitted light efficiently. For example, when adjacent pixels are in proximity, forming a light shielding portion of the size calculated in the above calculation may block light emitted from pixels that you do not want to block by the light shielding portion. In such a case, it is preferable to adjust the size of the light shielding portion appropriately.

  FIG. 4B is a schematic view when manufacturing the shielding portion by the inkjet printing method. An ink liquid containing, for example, carbon black and a solvent from the inkjet nozzle 30 on the surface opposite to the organic functional layer unit (U) with respect to the substrate (1) is used as ink droplets on the substrate (1) The light shielding portion (9) is formed by injecting the light. After formation, the light shielding portion is fixed by baking at a temperature in the range of 50 to 200 ° C.

  The thickness of the light shielding portion can be arbitrarily set, but is preferably in the range of 0.1 to 100 μm. If it is 0.1 μm or more, the light transmittance can be controlled to an extent that the effect of the present invention can be obtained, and if it is 100 μm or less, various printability can be satisfied.

  More preferably, the thickness is in the range of 1 to 50 μm, and the thickness in the above range can be controlled by adjusting the application amount of the ink.

  In addition, it is preferable that the shape of the light shielding portion according to the present invention is a concave shape from the peripheral portion to the central portion, and the thick film in the peripheral portion effectively shields the scattered light from the pixels. It is possible to provide a so-called still image with an edge.

  In order to make the light shielding part concave from the peripheral part to the central part, it is effective to use the ink jet printing method, and the solvent in the ink volatilizes in the drying process, resulting in the concave shape toward the central part Since it is easy, it is possible to realize the film thickness deviation of the above-mentioned light shielding part.

  A contact-type film thickness meter DekTakXT (made by Bruker) can be used as an example for the measurement of the thickness shape of a light shielding part. Specifically, the stylus is operated so as to cross ink dots printed on the substrate, and the film thickness is determined from the height difference with the substrate.

  On the other hand, the light reflecting material used for the light shielding portion according to the present invention preferably reflects 95% or more of the light incident in the light wavelength region of 380 to 780 nm, more preferably 99% or more, still more preferably It is 99.9% or more.

  As a material having such light reflectance, it is preferable to use white pigment such as titanium oxide, or metal such as silver, aluminum, etc. Among them, titanium oxide or the like which has small light wavelength dependency and is capable of uniform light reflection It is preferable to form a film using a white pigment of the above or silver, and it is particularly preferable to use silver.

  In the case of film formation using silver, the film can be appropriately formed at a desired location by vapor deposition using a photomask or the like. In addition, it can be formed using screen printing or the above-mentioned ink jet printing method using silver paste or silver ink.

  Moreover, it is preferable that the light shielding part which concerns on this invention bonds the sheet | seat containing the said light absorption material or light reflection material on the light extraction surface of the said organic EL element. For example, it is possible to use a black sheet or a light reflecting sheet produced by coating or the like on a substrate using carbon black, silver nanoparticles, titanium oxide particles or the like. Moreover, a commercially available ND filter etc. can also be used and Fujifilm Co., Ltd. product ND filter (for example, ND = 4.0) etc. are suitable. An adhesive layer can be provided on one side of the sheet or the ND filter, and it can be used as a light shielding portion by bonding to a base material.

  Further, as another embodiment of the light shielding portion according to the present invention, it is also preferable that the light shielding portion contains a coloring material of red, green or blue, and as described above, two or more light emitting parts having different emission colors. The organic electroluminescent element constitutes a pixel unit in which three pixels emitting red, green or blue are combined as one set, and the pixel for light shielding among the pixels included in the pixel unit is the above-mentioned It is also preferable to include a light shielding portion, and include in the light shielding portion a red, green or blue coloring material of the same color as the light emitted from the pixel that transmits light. In that case, the appearance when the organic EL device emits no light and the appearance when the organic EL device emits light can be matched.

  Furthermore, with respect to the three pixels included in the pixel unit, the light shielding portion mixes the light emission color of the light shielding portion with the light emission color of the light shielding portion under the illumination environment, and It is also preferable to contain a colorant that is visually recognized as a complementary color. For example, by emitting light from the pixels in the daytime or indoors, the light emission color and the reflected light color of the light shielding portion can be simultaneously perceived, so that color light complementary to the light emission color is obtained and a still image is formed by the subtractive method. It becomes possible.

  Therefore, in the daytime, it is possible to switch between a still image (image recognized by reflection of illumination light) by the subtractive color method, and in the nighttime, a still image (image by light emission) can be switched. Since the light emission image can be simultaneously perceived in the image, it is possible to form a still image with higher visibility.

  The red, green and blue colorants used may be pigment pigments or pigment dyes commonly used in ink jet printing.

  The red color material is a color material having an absorption maximum value in the range of 600 to 700 nm as a light wavelength. Similarly, the green colorant is in the range of 500 to 600 nm, and the blue colorant is a colorant having an absorption maximum in the range of 400 to 500 nm. The absorption maximum wavelength of the color material is preferably selected from inks to be described later according to the emission maximum wavelength of the organic EL element emitting red, green and blue.

  The ink contains a coloring material, and the coloring material may be a pigment or a dye, but is preferably a pigment because it has good dispersibility with respect to the constituent components of the ink and is excellent in weather resistance. The pigment is not particularly limited, and for example, organic pigments of the following numbers described in Color Index can be used alone or in combination.

  Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red, soluble azo pigments such as lithole red, helio Bordeaux, pigment scarlet and permanent red 2B; alizarin, indanthrone, Derivatives from vat dyes such as thioindigo maroon; Phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green; Quinacridone-based organic pigments such as quinacridone red and quinacridone magenta; perylene-based organic pigments such as perylene red and perylene scarlet; Isoindolinone-based organic pigments such as linon yellow and isoindolinone orange; pyranthrone-based organic pigments such as pyranthrone red and pyranthrone orange; thioin Organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; other pigments such as flavanthrone yellow, acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonil red, dioxazine violet and the like.

  The organic pigments are exemplified below by color index (CI) numbers.

C. I. Pigment yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185,
C. I. Pigment orange 16, 36, 43, 51, 55, 59, 61,
C. I. Pigment red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240,
C. I. Pigment violet 19, 23, 29, 30, 37, 40, 50,
C. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64,
C. I. Pigment green 7, 36,
C. I. Pigment brown 23, 25, 26,
Among the above pigments, quinacridone pigments, phthalocyanine pigments, benzimidazolone pigments, isoindolinone pigments, condensation azo pigments, quinophthalone pigments, isoindoline pigments, and the like are preferable because of their excellent light resistance.

  The organic pigment preferably has an average particle size in the ink of 10 nm to 150 nm as measured by laser scattering. When the average particle size of the pigment is less than 10 nm, the reduction of the particle size may cause a decrease in light resistance. When it exceeds 150 nm, minute mists called satellites are easily generated, and liquid droplets are generated due to the adhesion of the mists, and discharge defects due to the liquid droplets are easily generated.

  Further, it is preferable to remove coarse particles by sufficient dispersion or filtration so that the maximum particle size of the pigment in the inkjet ink does not exceed 3.0 μm.

  The light shielding portion according to the present invention containing the coloring material is formed by applying a light shielding portion containing the coloring material corresponding to the light transmitting pixel portion to the light shielding pixel portion by increasing the applied film thickness. , Can be light shielded.

  In the light shielding portion of the present invention, a color material in which each light emission color and the reflected light color of the light shielding portion are mixed in an illumination environment, and the color material is visually recognized as a color complementary to the light emission color. In the case where the light shielding portion is coated by reducing the coating thickness of the light shielding portion, it is possible to obtain color light which is visually recognized as a complementary color to the light emitting color under the illumination environment.

  It is preferable to perform adjustment of the said application film thickness using the inkjet printing method mentioned later.

[4] Ink Jet Printing Method It is preferable to use an ink jet printing method for forming the organic EL device of the present invention, the organic EL element of the present invention, and the light shielding portion of the present invention.

[4.1] Ink Jet Printing Method The ink jet printing method will be described below, but in the present invention, a known ink jet printing method and ink jet apparatus can be applied as appropriate.

  FIG. 5 is a schematic view showing an example of a method for applying a light shielding part on the surface of a substrate (1) using a coating apparatus using an inkjet head. The inkjet printing method according to the present invention includes organic EL elements (for example, an anode, an organic functional layer unit, a cathode, an adhesive for sealing agent, a sealing member, other functional layers, etc.), bus lines, insulating layers, etc. It can also be suitably used to divide and apply a certain area.

  As shown in FIG. 5, the substrate is continuously moved, and the side opposite to the surface on which the organic functional layer unit of the substrate on which the organic EL device (OLED) is formed by the inkjet head (30) is formed. Form a light shield on the face of the

  There is no particular limitation on the ink jet head (30), and a shear mode type (for example, having a diaphragm provided with a piezoelectric element in the ink pressure chamber and discharging the ejection liquid by pressure change of the ink pressure chamber by this diaphragm The head may be a piezo type head or may be a thermal type head having a heat generating element and discharging the ejection liquid from the nozzle by a rapid volume change due to film boiling of the ink liquid by heat energy from the heat generating element It is also good.

  A mechanism or the like for supplying an ejection liquid is connected to the inkjet head (30). Supply of the injection liquid is performed by the tank (38A). In this example, the tank level is made constant so as to keep the injection liquid pressure in the ink jet head (30) always constant. To that end, the tank (38A) overflows and the injection liquid is returned to the tank (38B) by gravity flow. Supply of the injection liquid from the tank (38B) to the tank (38A) is performed by the pump (31), and the operating conditions are such that the liquid level of the tank (38A) becomes stable stably in accordance with the injection conditions. It is set.

  When the injection liquid is returned from the pump (31) to the tank (38A), it is carried out through the filter (32). Thus, it is preferable that the ejection liquid passes through the filter medium having absolute filtration accuracy or quasi-absolute filtration accuracy of 0.05 to 50 μm at least once before being supplied to the inkjet head (30).

  Also, the injection liquid is forced from the tank (36) and the washing solvent from the tank (37) to the ink jet head (30) by the pump (39) in order to carry out the washing operation and liquid filling operation of the ink jet head (30). It is possible to supply Such tank pumps may be divided into a plurality of parts with respect to the ink jet head (30), a branch of piping may be used, or a combination thereof may be used. In FIG. 5, the pipe branch (33) is used. Furthermore, in order to remove air in the ink jet head (30) sufficiently, the injection liquid is forcedly sent from the tank (36) to the ink jet (30) by the pump (39) while being ejected from the air vent piping described below The liquid may be withdrawn and sent to a waste tank (34).

  Furthermore, a heat exchanger may be provided between the tank (38A) and the inkjet head (30) in order to keep the temperature of the ejected liquid in the inkjet head (30) constant, or the heat in the inkjet head (30) An injection liquid temperature control mechanism such as an exchanger may be provided.

  It is preferable that the light absorbing material and the light reflecting material used for inkjet printing be used as an ink liquid by dissolving or dispersing a desired amount in a solvent. For example, the solvent used for the inkjet ink liquid is not particularly limited as long as it can disperse a desired amount of the above-mentioned material and can eject droplets from the inkjet nozzle. It is preferable to select suitably according to a kind etc. Specifically, water, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, hexanol, heptanol, octanol, decanol, cyclohexanol, terpineol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene Hydrocarbon compounds such as xylene, cymene, dulene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane Ether compounds such as bis (2-methoxyethyl) ether and p-dioxane, glycol ether ester compounds such as ethylene glycol monomethyl ether acetate, glycol oligomer ether esters such as diethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate, acetic acid Aliphatic or aromatic esters such as ethyl, propyl benzoate, dicarboxylic acid diesters such as diethyl carbonate, alkoxy 3-carboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl acetoacetate Ketocarboxylic acid esters, further propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl ether Polar compounds such as chill sulfoxide, cyclohexanone and the like can be exemplified.

  In the method of manufacturing an organic EL device according to the present invention, the respective constituent materials described above are used in the respective ink liquids used for forming the insulating layer, the organic EL element, the lead electrode for the first electrode, the connecting portion of the bus line and the bus line. In addition to the method of using it as an ink liquid as it is, in order to obtain an ink liquid suitable for the inkjet printing method, the constituent material is dissolved in an ink solvent or the like to prepare an ink liquid, and various functional additives are included. it can.

  For example, according to the purpose of ejection stability, print head compatibility, storage stability, image storability, and other performance improvement, various known additives such as solvents, viscosity modifiers, surface tension modifiers, ratios A resistance regulator, a film-forming agent, a dispersant, a surfactant, an ultraviolet light absorber, an antioxidant, an anti-fading agent, an anti-mold agent, an anti-rust agent and the like can be appropriately selected and used.

  The application procedure is shown below.

  First, in the procedure for filling the ejection head with the inkjet head (30), the ejection head is forcedly ejected from the tank (36) by the pump (39) at the standby position of the inkjet head (30). Pour into). The ejection liquid discharged at this time is received by a catch pan not shown. By this operation, the ink jet head (30) is filled with the injection liquid, and after the inside of the head is evacuated, cleaning of the nozzle surface (injection surface) is performed.

  Next, the injection liquid is sent from the tank (38B) to the tank (38A) at a predetermined flow rate, and circulation is started by the overflow. By closing the valve between the pump (39) and the inkjet head (30) and opening the valve between the pump (38) and the inkjet head (30), it is possible to eject the ink from the inkjet head (30). The substrate (1) is transported at a predetermined speed, and the jet head (30) ready for injection is brought close to a predetermined distance of the substrate (1), and injection of the injection liquid is started under predetermined injection conditions. Since the liquid level of the tank (38A) is held constant by overflowing, the injection amount becomes stable.

  The type of the ink jet head (30) is arbitrary, but in the present invention, it is preferable to select a condition that the droplet volume of one droplet is several 10 pL and the ejection frequency can be stably ejected at several hundreds to several tens of thousands Hz. Also, if the speed is arbitrary and fast, it leads to the improvement of productivity. The frequency is adjusted and injected so that the target wet film thickness is obtained with respect to the speed.

[4.2] Ink Jet Head An example of the ink jet head (30) is shown in FIG.

  FIG. 6 (a) is a schematic perspective view showing an inkjet head (100) applicable to the present invention, and FIG. 6 (b) is a bottom view of the inkjet head (100).

  An inkjet head (100) applicable to the present invention is mounted on an inkjet printer (not shown), and includes a head chip for discharging ink from a nozzle, a wiring substrate on which the head chip is disposed, and the head chip. A drive circuit board connected via a wiring board and a flexible board, a manifold for introducing ink into a channel of a head chip via a filter, a case (56) in which the manifold is housed, and the case ( 56) a cap receiving plate (57) attached to close the bottom opening, first and second joints (81a, 81b) attached to the first ink port and the second ink port of the manifold, and the manifold A third joint (82) attached to the third ink port and a cover attached to the housing (56) And a member (59). Further, mounting holes (68) for mounting the housing (56) to the printer main body side are respectively formed.

  Further, the cap receiving plate (57) shown in (b) of FIG. 6 is formed as a substantially rectangular plate whose outer shape is elongated in the left-right direction corresponding to the shape of the cap receiving plate mounting portion (62) In order to expose a nozzle plate (61) in which a plurality of nozzles are disposed substantially at the center, a nozzle opening (71) elongated in the left-right direction is provided. Moreover, regarding the specific structure inside the inkjet head shown by (a) of FIG. 6, it can refer, for example to FIG. 2 etc. which are described in Unexamined-Japanese-Patent No. 2012-140017.

  Although the representative example of the inkjet head was shown in FIG. 6, in addition to that, for example, Unexamined-Japanese-Patent 2012-140017, Unexamined-Japanese-Patent 2013-010227, 2014-058171, 2014-097644 is shown. JP, 2015-142979, 2015-142980, 2016-002675, 2016-002682, 2016-107401, 2017-109476, The inkjet head which consists of a structure described in Unexamined-Japanese-Patent No. 2017-177626 etc. can be selected suitably, and can be applied.

  It is preferable to heat after printing a predetermined pattern by the inkjet printing method. Thereby, for example, the fusion of metal fine particles used for an electrode or the like proceeds, and the electrode becomes highly conductive, which is particularly preferable.

  The heating temperature is preferably 100 ° C. or more and 500 ° C. or less. The time depends on the temperature and the material used, but is preferably 10 seconds to 30 minutes, and from the viewpoint of productivity, preferably 10 seconds to 15 minutes, and 10 seconds to 5 minutes. Is more preferred.

  When using a resin substrate or a resin film for a base material, it is preferable to heat at the temperature which does not damage a base material in the temperature range of 100 degreeC or more and 250 degrees C or less.

  The heat treatment method is not particularly limited, and a known treatment method can be used.

  For example, as the heat treatment mode, heating using a heater or an IR heater, drying under reduced pressure, and the like can be mentioned, but it is not limited thereto.

[5] Components of Organic EL Element The details of the main components of the organic EL element constituting the organic EL device of the present invention will be described.

  In the organic EL element according to the present invention, as described in FIG. 2A, the first electrode (anode (2)), and then, for example, the hole injection layer, on the light-transmissive substrate (1), Organic functional layer group 1 (3) composed of hole transport layer etc., light emitting layer (4), for example, organic functional layer group 2 (5) composed of electron transport layer, electron injection layer etc. , Light emitting area. A second electrode (cathode (6)), which is a second electrode, a sealing adhesive layer (7) and a sealing member (8) are provided further on the upper side. As the other layers, an underlayer, a light scattering layer, a planarization layer, a gas barrier layer, a protective layer and the like can be appropriately provided. For example, it is preferable that a base material (1) and a sealing member (8) have a gas barrier layer (11).

  Although the representative example of a structure of an organic EL element is shown below, this invention is not limited to this.

(I) First electrode (2, anode) / light emitting layer (4) / second electrode (6, cathode)
(Ii) First electrode (2, anode) / organic functional layer unit (U) [organic functional layer group 1 (3: hole injecting and transporting layer) / light emitting layer (4) / organic functional layer group 2 (5: electron Injection transport layer)] / second electrode (6, cathode)
(Iii) First electrode (2, anode) / organic functional layer unit (U) [organic functional layer group 1 (3: hole injection layer / hole transport layer) / light emitting layer (4) / organic functional layer group 2 (5: electron injection layer / electron transport layer)] / second electrode (6, cathode)
(Iv) First electrode (2, anode) / organic functional layer unit (U) [organic functional layer group 1 (3: hole injection layer / hole transport layer / electron blocking layer) / light emitting layer (4) / organic Functional layer group 2 (5: hole blocking layer / electron injection layer / electron transport layer)] / second electrode (6, cathode)
About the outline | summary of the organic EL element which can be applied to this invention, the Unexamined-Japanese-Patent 2013-157634, Unexamined-Japanese-Patent 2013-168552, Unexamined-Japanese-Patent 2013-177361, Unexamined-Japanese-Patent 2013-18721, for example is mentioned, for example. 2013-191644, JP-A 2013-191804, JP-A 2013-225678, JP-A 2013-235994, JP-A 2013-243234, JP-A 2013-243236, JP-A 2013- 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-017493 Publication, JP-A-2014-017494 It can be mentioned configurations described in.

  In addition, a tandem type organic EL element can also be used. Specific examples of the tandem type are, for example, US Pat. No. 6,337,492, US Pat. No. 742,0203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6107734, U.S. Pat. No. 6,337,492, International Publication No. 2005/009087, Japanese Patent Application Publication No. 2006-228712, Japanese Patent Application Publication No. 2006-24791, Japanese Patent Application Publication No. 2006-49393, Japanese Patent Application Publication No. 2006-49394, JP-A-2006-49396, JP-A-2011-96679, JP-A-2005-340187, Patent No. 4711424, Patent No. 3496681, Patent No. 3884564, Patent No. 4213169, JP-A JP-A-2010-192719, JP-A The elements described in 009-076929, JP-A-2008-078414, JP-A-2007-059848, JP-A-2003-272860, JP-A-2003-045676, WO 2005/094130, etc. Although a structure, a constituent material, etc. are mentioned, this invention is not limited to these.

  As a method for producing the organic EL device of the present invention, the anode, the functional layer group 1, the light emitting layer, the light emitting layer, the organic functional layer group 2 and the cathode are laminated on a substrate to form a laminate. , Dry process such as sputtering method, magnetron sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD method, coating method, ink jet printing method It is formed by a wet process such as a printing method. Among these, the wet process such as the coating method has a great advantage in the manufacturing process because it does not require a vacuum process as compared with the dry process and it is easy to increase the area. Among them, it is a preferable production method also from the viewpoint of on-demand property to produce by the above-mentioned ink jet printing method.

  Furthermore, each layer which comprises an organic EL element is demonstrated.

〔Base material〕
The substrate (1) applicable to the organic EL device according to the present invention is preferably a substrate having light transmittance, and the material to be used is not particularly limited, and for example, types such as glass and plastic are listed. be able to.

  As a base material (1) which has the light transmittance applicable to this invention, glass, quartz, and a resin base material can be mentioned. More preferably, it is a flexible resin base material from the viewpoint of being able to impart flexibility to the organic EL element.

  Examples of resin materials constituting the resin base material applicable to the present invention include polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose Cellulose esters such as triacetate (abbr .: TAC), cellulose acetate butyrate, cellulose acetate propionate (abbr .: CAP), cellulose acetate phthalate, cellulose nitrate and derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol Syndiotactic polystyrene, polycarbonate (abbreviation: PC), norbornene resin, polymethylpentene, polyether ketone, polyimide, poly Tersulphone (abbreviation: PES), polyphenylene sulfide, polysulphones, polyether imide, polyether ketone imide, polyamide, fluorocarbon resin, nylon, polymethyl methacrylate, acrylic and polyarylates, artone (trade name, manufactured by JSR), and apel Examples thereof include cycloolefin resins such as (trade name, manufactured by Mitsui Chemicals, Inc.) and the like.

  Among these resin substrates, films such as polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), etc. are flexible in terms of cost and availability. It is preferably used as a resin substrate having

  Moreover, the above-mentioned resin base material may be an unstretched film or a stretched film.

  The resin base material applicable to the present invention can be manufactured by a conventionally known general film forming method. For example, a resin as a material is melted by an extruder, and extruded and quenched by an annular die or T-die, whereby a substantially amorphous, non-oriented, unoriented resin substrate can be produced. In addition, the unstretched resin base material is conveyed in the transfer direction of the resin base material by a known method such as uniaxial drawing, tenter type sequential biaxial drawing, tenter type simultaneous biaxial drawing, tubular type simultaneous biaxial drawing, etc. A stretched resin substrate can be produced by stretching in the direction (MD direction) or the direction (horizontal axis direction, TD direction) perpendicular to the transport direction of the resin substrate. Although the draw ratio in this case can be suitably selected according to resin used as the raw material of a resin base material, it is preferable to exist in the range of 2 to 10 time in the vertical axis direction and the horizontal axis direction, respectively.

  The thickness of the resin base is preferably a thin film resin base in the range of 3 to 200 μm, more preferably 10 to 100 μm, still more preferably 20 to 80 μm. In particular, the thickness is preferably in the range of 20 to 50 μm, and by using a thin film, light shielding can be effectively performed without enlarging the light shielding portion. In the embodiment to be described later, a PET film having a thickness of 50 μm was used as the substrate (1).

  In addition, as a glass substrate applicable as the light-transmissive substrate used in the present invention, soda lime glass, barium / strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, Quartz etc. can be mentioned.

[First electrode: anode]
As an anode which comprises an organic EL element, it is an electrode which has light reflectivity or light transmittance, and it is common to have light transmittance. The material used is preferably a metal or alloy of an oxide semiconductor or thin film, for example, a metal such as Ag or Au or an alloy containing a metal as a main component, CuI, or indium tin. And oxide semiconductors such as SnO ₂ and ZnO.

  In the case of an anode having light transparency, it is preferable to be composed of silver as a main component, and the purity of silver is preferably 99% or more. In addition, palladium (Pd), copper (Cu), gold (Au) or the like may be added to secure the stability of silver.

  In the case of the layer in which the light-transmitting anode is composed mainly of silver, specifically, it may be formed of silver alone or may be composed of an alloy containing silver (Ag). . As such an alloy, for example, silver, magnesium (Ag, Mg), silver, copper (Ag, Cu), silver, palladium (Ag, Pd), silver, palladium, copper (Ag, Pd, Cu), silver Indium (Ag · In) and the like.

  Among the constituent materials constituting the anode, as the anode constituting the organic EL element according to the present invention, an anode having a light transmitting property mainly composed of silver and having a thickness in the range of 2 to 20 nm Is preferably, but more preferably, the thickness is in the range of 4 to 12 nm. If the thickness is 20 nm or less, the absorption component and the reflection component of the light transmitting anode are suppressed to a low level, and a high light transmittance is maintained, which is preferable.

  The layer composed of silver as a main component in the present invention means that the content of silver in the light transmitting anode is 60% by mass or more, and preferably the content of silver is 80% by mass. It is the above, More preferably, content of silver is 90 mass% or more, Especially preferably, content of silver is 98 mass% or more. Moreover, the above-mentioned "light transmittance" means that the light transmittance in wavelength 550nm is 50% or more.

  In the light transmitting anode, the layer composed mainly of silver may be divided into a plurality of layers and laminated as necessary.

  In the present invention, in the case where the anode is a light-transmitting anode comprising silver as a main component, the lower part of the light-transmitting anode is formed from the viewpoint of enhancing the uniformity of the silver film. It is preferable to provide an underlayer. The underlayer is not particularly limited, but is preferably a layer containing an organic compound having a nitrogen atom or a sulfur atom, and a method of forming a light transmitting anode on the underlayer is a preferred embodiment. is there. The details of the underlayer applicable to the present invention will be described later.

  In the organic EL device according to the present invention, two or more organic EL elements having different emission colors are disposed in one pixel, and the anode of the organic EL element emitting one emission color is the other emission color adjacent to the other It is preferable from the viewpoint of obtaining uniform light emission that the voltage drop in the case of a large-area organic EL device can be reduced by electrically connecting in series with the cathode of the organic EL element that emits light. Details will be described in a second embodiment described later.

  Further, the lead-out electrode (23) of the first electrode according to the present invention is formed by extending the constituent material of the first electrode from the same material as that of the first electrode.

[Light emitting layer]
The light emitting layer (4) constituting the organic EL element according to the present invention can use a phosphorescent compound or a fluorescent compound as a light emitting material, but in the present invention, in particular, it is phosphorescent as a light emitting material The configuration in which the light emitting compound is contained is preferable.

  This light emitting layer is a layer in which electrons injected from the electrode or the electron transport layer recombine with holes injected from the hole transport layer to emit light, and the light emitting portion is in the layer of the light emitting layer. However, it may be the interface between the light emitting layer and the adjacent layer.

  There is no particular limitation on the configuration of such a light emitting layer as long as the contained light emitting material satisfies the light emitting requirements. In addition, a plurality of layers having the same emission spectrum or emission maximum wavelength may be provided. In this case, it is preferable to have a non-luminescent intermediate layer between each light emitting layer.

  The total thickness of the light emitting layer is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower emission initiation 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 layer, when the non-light-emitting intermediate layer exists between light emitting layers.

  The light emitting layer as described above includes, for example, a vacuum evaporation method, a spin coating method, a casting method, an LB method (Langmuir-Blodgett, Langmuir Blodgett method), an inkjet printing method, and the like of the light emitting material and host compound described later. In the present invention, it can be formed by a method, and is preferably formed by a wet coating method by spin coating method, casting method, cravia coating method, ink jet printing method or the like, and in particular, it is preferable to form by ink jet printing method.

  In the light emitting layer, a plurality of light emitting materials may be mixed, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer. As a configuration of the light emitting layer, a host compound (also referred to as a light emitting host or the like) and a light emitting material (also referred to as a light emitting dopant compound) are contained, and light is preferably emitted from the light emitting material.

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

  As the host compound, a known host compound may be used alone, or a plurality of host compounds may be used. By using a plurality of host compounds, charge transfer can be adjusted, and the efficiency of the organic electroluminescent device can be increased. Further, by using a plurality of light emitting materials to be described later, it is possible to mix different light emissions, and thereby it is possible to obtain any light emission color.

  The host compound used in the light emitting layer may be a conventionally known low molecular weight compound or a high molecular weight compound having a repeating unit, and a low molecular weight compound having a polymerizable group such as a vinyl group or an epoxy group (vapor deposition polymerizable light emitting host ) May be.

  As host compounds applicable to the present invention, for example, JP-A-2001-257076, JP-A-2001-357977, JP-A-2002-8860, JP-A-2002-43056, JP-A-2002-105445, and the like. 2002-352957, 2002-2314453, 2002-234888, 2002-260861, 2002-305083, US Patent Application Publication No. 2005/0112407, US Patent Application Publication WO 2009/0030202, WO 2001/039234, WO 2008/056746, WO 2005/089025, WO 2007/063754, WO 2005/030900, WO 2009 No. 086028, WO 2012/023947, can be mentioned JP 2007-254297, JP-European compounds described in Japanese Patent No. 2034538 Pat like.

<Light emitting material>
As a light emitting material which can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material or a phosphorescent dopant) and a fluorescent compound (also a fluorescent compound or a fluorescent material) In particular, it is preferable to use a phosphorescent compound from the viewpoint of obtaining high luminous efficiency.

<Phosphorescent compound>
The phosphorescent compound is a compound in which light emission from the excitation triplet is observed, and specifically, a compound which emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. Although it is defined as a compound of .01 or more, a preferable phosphorescence quantum yield is 0.1 or more.

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

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

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

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

  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), WO 2009/100991, WO 2008/101842, WO 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 / The compounds described in the specification of U.S. Pat. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application 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), WO 2009/050290, WO 2009/000673, U.S. Patent No. 7332232, U.S. Patent Application Publication No. 2009/0039776, U.S. Patent No. 6687266, United States of America Patent Application Publication No. 2006/0008670, U.S. Patent Application Publication No. 2008/0015355, U.S. Patent No. 7396598, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent No. 7090928 The compound as described in etc. can be mentioned.

  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), WO 2006/056418, WO 2005/123873, WO 2006/082742, U.S. Patent Application Publication No. 2005 / 026,041, U.S. Patent No. 7,534,505. The compounds described in U.S. Patent Application Publication No. 2007/0190359, U.S. Patent No. 7338722, U.S. Patent No. 7279704, U.S. Patent Application Publication No. 2006/103874 and the like can also be mentioned. .

  Furthermore, WO 2005/076380, WO 2008/140115, WO 2011/13401, WO 2010/0806089, WO 2012/020327, WO 2011051404. The compounds described in WO 2011/073149, JP 2009-114086, JP 2003-81988, JP 2002-363552, etc. can also be mentioned.

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

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

<Fluorescent compound>
As a fluorescent compound, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbenes And dyes based on polythiophenes, dyes based on polythiophenes or rare earth complexes.

[Organic functional layer group]
Next, as a representative example of the layers constituting the functional layer group 1 and the organic functional layer group 2, the charge injection layer, the hole transport layer, the electron transport layer and the blocking layer will be described in this order.

(Charge injection layer)
The charge injection layer is a layer provided between the electrode and the light emitting layer for the purpose of lowering the light emission starting voltage and improving the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998 NT) The details are described in the second edition of Chapter 2 "Electrode material" (pages 123 to 166), published by S Inc., and there are a hole injection layer and an electron injection layer.

  As the charge injection layer, in general, if it is a hole injection layer, it is present between the anode and the light emitting layer or the hole transport layer, and if it is an electron injection layer, it is present between the cathode and the light emitting layer or the electron transport layer. However, the present invention is characterized in that the charge injection layer is disposed adjacent to the light transmitting electrode. In addition, when used as an intermediate electrode, at least one of the electron injection layer and the hole injection layer adjacent to each other may satisfy the requirements of the present invention.

  The hole injection layer is a layer disposed adjacent to the anode, which is an electrode having light transmittance, for the purpose of lowering the light emission starting voltage and improving the light emission luminance. 2), “Electrode material” (p. 123 to 166), “No. 30” issued by NTS Co., Ltd.).

  The hole injection layer is described in detail in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. Examples of materials used for the hole injection layer include , Porphyrin derivative, phthalocyanine derivative, oxazole derivative, oxadiazole derivative, triazole derivative, imidazole derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, hydrazone derivative, stilbene derivative, polyarylalkane derivative, triarylamine derivative, carbazole derivative, Indolocarbazole derivative, isoindole derivative, acene derivative such as anthracene or naphthalene, fluorene derivative, fluorenone derivative, polyvinylcarbazole, high molecular weight introduced with aromatic amine in main chain or side chain Material or oligomer, polysilane, a conductive polymer or oligomer (e.g., PEDOT (polyethylene dioxythiophene): PSS (polystyrene sulfonic acid), aniline copolymers, polyaniline, polythiophene, etc.) and the like can be mentioned.

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

  In addition, hexaazatriphenylene derivatives as described in JP-A-2003-519432 and JP-A-2006-135145 can also be used as the hole transport material.

  The electron injection layer is a layer provided between the cathode and the light emitting layer for the purpose of lowering the light emission start voltage and improving the light emission luminance, and the cathode is formed of the light transmitting electrode according to the present invention. In this case, it is provided adjacent to the light-transmissive electrode, and the second chapter of "Organic EL element and its industrialization front line (November 30, 1998 issued by NTS Co., Ltd.)" It is described in detail in "Electrode material" (pages 123-166).

  The details of the electron injection layer are also described in JP-A-6-325871, 9-17574, 10-74586, etc. Specific examples of the material preferably used for the electron injection layer Metals such as strontium and aluminum; alkali metal compounds such as lithium fluoride, sodium fluoride and potassium fluoride; alkali metal halide layers such as magnesium fluoride and calcium fluoride; Examples thereof include alkaline earth metal compound layers represented by magnesium, metal oxides represented by molybdenum oxide and aluminum oxide, and metal complexes represented by lithium 8-hydroxyquinolate (Liq) and the like. When the light-transmitting electrode in the present invention is a cathode, an organic material such as a metal complex is particularly preferably used. It is desirable that the electron injection layer is a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 μm depending on the constituent material.

(Hole transport layer)
The hole transport layer is made 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 the function of the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has either hole injection or transport or 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, styryl anthracene 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, but porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amine compounds should be used. preferable.

  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, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) Odriphenyl, 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 can be mentioned.

  The hole transport layer may be any of the above-mentioned hole transport materials, for example, vacuum deposition, spin coating, casting, printing including inkjet printing, LB (Langmuir Blodgett, Langmuir Blodgett), etc. It can be formed by thinning the film by a method. The layer thickness of the hole transport layer is not particularly limited, but is usually in the range of 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.

  In addition, the p-type can be enhanced by doping the material of the hole transport layer with an impurity. As examples thereof, JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, and J.-A. Appl. Phys. , 95, 5773 (2004) and the like.

  As described above, it is preferable to increase the p property of the hole transport layer because a device 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, the electron injection layer and the hole blocking layer are also included in the electron transport layer. The electron transporting layer can be provided as a single layer structure or a multilayer structure of a plurality of layers.

  An electron transporting material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer in the electron transporting layer having a single layer structure and the electron transporting layer having a laminated structure includes electrons injected from the cathode in the light emitting layer It is sufficient if it has a function to transmit. As such a material, any material can be selected and used from conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethanes, anthrone derivatives, oxadiazole derivatives and the like can be mentioned. Furthermore, in the above-mentioned oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted by a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as a material of the electron transport layer. it can. Furthermore, it is also possible to use a polymer material in which these materials are introduced into a polymer chain or a polymer material in which these materials are used as a polymer main chain.

In addition, metal complexes of 8-quinolinol derivatives, for example, 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 central metals of these metal complexes A metal complex replaced with In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as a material of the electron transport layer.

  The electron transporting layer can be formed by thinning the above-described material by a known method such as a vacuum evaporation method, a spin coating method, a casting method, a printing method including an inkjet printing method, and an LB method. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

(Blocking layer)
The blocking layer may be a hole blocking layer or an electron blocking layer, and may be a layer provided as necessary in addition to the constituent layers of the organic functional layer unit described above. For example, they are described in JP-A-11-204258, JP-A-11-204359, and page 237 of "Organic EL element and its forefront of industrialization (issued on November 30, 1998)". Hole blocking (hole block) layer etc. can be mentioned.

  The hole blocking layer generally has a function of an electron transport layer. The hole blocking layer is made of a hole blocking material having an extremely small ability to transport holes while having the function of transporting electrons, and the electron-hole recombination by stopping the holes while transporting the electrons. The probability can be improved. In addition, the configuration of the electron transport layer can be used as a hole blocking layer, if necessary. 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 has a function of transporting holes and is made of a material having a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. It can be done. In addition, the configuration of the hole transport layer can be used as an electron blocking layer as required. 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.

[Second electrode: cathode]
The cathode according to the present invention is an electrode that functions to supply holes to the organic functional layer group and the light emitting layer, and is an electrode having light reflectivity or light transparency. As materials to be used, metals, alloys, organic or inorganic conductive compounds or mixtures thereof, for example, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, Magnesium / indium mixtures, indium, lithium / aluminum mixtures, rare earth metals, oxide semiconductors such as ITO, ZnO, TiO ₂ and SnO ₂ etc. may be mentioned, among which at least a thin film metal or alloy Is a preferred configuration.

  Examples of silver or a silver-based alloy suitable as a light-transmitting cathode can include the same materials as those described in the description of the above-mentioned anode, and specifically, silver may be formed alone Or an alloy containing silver (Ag). As such an alloy, for example, silver, magnesium (Ag, Mg), silver, copper (Ag, Cu), silver, palladium (Ag, Pd), silver, palladium, copper (Ag, Pd, Cu), silver Indium (Ag · In) and the like.

  The cathode can be produced by forming a thin film of such a conductive material by a method such as vapor deposition or sputtering, but is preferably produced by an inkjet printing method. In addition, the sheet resistance as the second electrode is several hundreds Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In addition, what is necessary is just to select and comprise a cathode with favorable light transmittance, when an organic EL element takes out light emission L from the cathode side.

[Sealing member]
The sealing member may be disposed so as to cover the display region (light emitting region) of the organic EL element, and may be a concave plate shape or a flat plate shape. Moreover, transparency and electrical insulation are not particularly limited.

  Specifically, a glass substrate with flexibility, a resin substrate, a film, a metal film (metal foil) and the like can be mentioned. Examples of the glass substrate include soda lime glass, glass containing barium and strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. Further, as the resin substrate, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like can be mentioned.

  As a sealing adhesive, an adhesive of polyurethane type, polyester type, epoxy type, acrylic type or the like can be used. If necessary, a curing agent may be used in combination. Although a hot melt lamination method, an extrusion lamination method and a coextrusion lamination method can also be used, a dry lamination method is preferred.

In the present invention, as the sealing member, a resin substrate and a glass substrate can be preferably used from the viewpoint of being able to thin the organic EL element. Furthermore, the resin substrate had a water vapor transmission rate of 1 × 10 ^-3 g / m ² · at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% RH, which was measured by a method according to JIS K 7129-1992. The oxygen permeability is preferably 24 h or less, and further, the oxygen permeability measured by the method according to JIS K 7126-1987 is 1 × 10 ⁻³ mL / m ² · 24 h · atm (1 atm is 1.01325 × 10 ⁵ a Pa) equal to or lower than a temperature of 25 ± 0.5 ° C., water vapor permeability at a relative humidity of 90 ± 2% RH is preferably not more than ^{1 × 10 -3 g / m 2} · 24h. In order to satisfy this condition, it is preferable to provide a gas barrier layer described later.

  In the gas phase and liquid phase, an inert gas such as nitrogen or argon or an inert liquid such as fluorohydrocarbon or silicone oil is injected into the gap between the sealing member and the display area (light emitting area) of the organic EL element You can also In addition, the gap between the sealing member and the display region of the organic EL element can be vacuum, or a hygroscopic compound can be sealed in the gap.

  Further, light is completely covered with the organic functional layer unit in the organic EL element, and the terminal portions of the anode (2) which is the first electrode and the cathode (6) which is the second electrode in the organic EL element are exposed. A sealing film can also be provided on a transparent substrate.

[Gas barrier layer]
A light-transmissive gas barrier layer is formed on one side or both sides of the substrate (1), or on the entire surface on which at least the anode (first electrode) is formed. It is possible to suppress the entry of substances that cause deterioration to the constituent materials. The same applies to the case where a resin substrate is used as the sealing member.

The gas barrier layer may be not only an inorganic material film, but also a film made of a composite material with an organic material, or a hybrid film formed by laminating these films. As the performance of the gas barrier layer, the water vapor transmission rate (environmental conditions: 25 ± 0.5 ° C., relative humidity (90 ± 2)%) is approximately 0. 6 according to JIS (Japanese Industrial Standard) -K7129 (2008). 01 g / m ² · 24 h or less, oxygen permeability according to JIS-K 7126 (2006) is about 0.01 mL / m ² · 24 h · atm or less, resistivity is 1 × 10 ¹² Ω · cm or more, light transmission It is preferable that the insulating film has a gas-barrier light-transmitting property such that the rate is about 80% or more in the visible light region.

  As a material for forming the gas barrier layer, any material can be used as long as it is a material that can suppress deterioration of the organic EL element, for example, entry of gas such as water or oxygen into the organic EL element.

  For example, it can be composed of a film made of an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, niobium oxide, molybdenum oxide, Preferably, the main raw material is a silicon compound such as silicon nitride or silicon oxide.

  As a method of forming the gas barrier layer, a conventionally known film forming method can be appropriately selected and used. For example, a vacuum evaporation method, sputtering method, magnetron sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating Coating method, plasma polymerization method, atmospheric pressure plasma polymerization method (refer to JP-A-2004-68143), plasma CVD (Chemical Vapor Deposition) method, laser CVD method, thermal CVD method, ALD (atomic layer deposition) method, A wet coating method using polysilazane or the like can also be applied.

[Underlayer]
The material constituting the above-mentioned underlayer is not particularly limited, and it is possible to suppress the aggregation of silver which is a constituent material of the anode or the cathode formed thereon, and compounds containing nitrogen atoms etc. It can be mentioned.

  The nitrogen atom-containing compound which can be used to form the underlayer is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule, but a compound having a heterocycle having a nitrogen atom as a hetero atom Is preferred. Examples of the hetero ring having a nitrogen atom as a hetero atom include aziridine, azidine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepane, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, Isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and the like.

  Furthermore, the nitrogen atom-containing compound contained in the underlayer is preferably an aromatic heterocyclic compound having a nitrogen atom having a noncovalent electron pair not involved in aromaticity.

  As specific examples of these nitrogen atom-containing compounds, exemplified compound No. 1 described in paragraphs (0097) to (0221) of JP-A-2015-046364. 1 to No. 134 can be mentioned.

[Protective layer]
Preferably, a protective layer is provided to protect the light shielding portion according to the present invention. As the protective layer, a light transmitting plate-like member such as a glass plate or an acrylic plate, a known actinic radiation-curable hard coat layer, or the like can be used.

[6] Basic Configuration of Organic EL Device Next, the details of the basic configuration of the organic EL device of the present invention will be described.

  The organic EL device of the present invention is an organic EL device comprising two or more organic EL elements different in emission color, wherein the organic EL elements different in emission color are arranged in the same plane, and The light extraction side of the organic EL element is characterized by having a light shielding portion in which the light transmittance of the visible light region changes stepwise or is uniform.

  Hereinafter, a basic configuration of the organic EL device of the present invention in which two or more organic EL elements having different luminescent colors are disposed in the same plane will be described.

[6.1] Schematic Circuit Diagram of Organic EL Device FIG. 7 is an example showing a schematic of the circuit diagram of the organic EL device of the present invention, and FIG. 8 is a schematic of another circuit diagram of the organic EL device of the present invention. Is an example showing

In FIG. 7, organic EL elements having different emission colors of a plurality of red light emission (EL _R ), green light emission (EL _G ) and blue light emission (EL _B ) are disposed on the same plane on the base material (1). The organic EL elements of different emission colors are arranged in parallel in the same plane in two or more lines of different emission colors. And some of the organic EL elements having different emission colors of a plurality of red light emission (EL _R ), green light emission (EL _G ) and blue light emission (EL _B ) are indicated by the light shielding portion (9) shown in black. Transmitted light is blocked.

  As shown in FIG. 7, when the organic EL elements are arranged in the same plane in the form of stripes, the number of arrangement of the elements in one line is generally defined according to the size of the substrate and the size of the elements. However, from the viewpoint of obtaining the effects of the present invention, it is preferably in the range of 2 to 20, and more preferably in the range of 2 to 10. Therefore, as an example, in the organic EL device having a substrate width of 10 cm × 10 cm, the size of the light emitting area by the organic EL element is 0.5 cm × 10 cm to 5 cm × 10 cm, preferably Although it is in the range of width 1.0 cm x length 10 cm-width 5 cm x length 10 cm, these light emission area areas can be suitably selected with the size of a base material, and the arrangement | positioning number of organic EL elements.

The anode of each organic EL element is electrically connected by the bus line (21) from the application power supply unit (20). However, in FIG. 7 and FIG. 8, the bus line connected to the cathode of the organic EL element from the application power supply unit (20) is omitted. In the mode shown in this figure, three application power supply units (20) are prepared, and light emission of red light emission (EL _R ), green light emission (EL _G ) and blue light emission (EL _B ) by changing the voltage respectively Control the amount.

  On the other hand, in the embodiment shown in FIG. 8, the organic EL elements arranged in parallel in the form of two or more lines of different luminescent colors in parallel in the same plane have different applied resistances. Connected to the unit (20).

In the mode shown in FIG. 8, one application power supply unit (20) is prepared, and the voltage is changed by the conductive members (22) having different resistance values, respectively, to emit red light (EL _R ) and green light (EL _G ). And the amount of light emission of blue light emission (EL _B ).

  In order to produce the simple organic EL device of the present invention, it is preferable that the organic EL elements have the form shown in FIG. 8 in which they are connected to one applied power source by conductive members having different resistance values. The position where the conductive member is connected may be in the order of an applied power supply unit-conductive member-bus line-organic EL element, or in the order of an applied power supply unit-bus line-conductive member-organic EL element.

  Hereinafter, the configuration shown in FIG. 8 and in which the connection circuit is in the order of an applied power supply unit-bus line-conductive member-organic EL element will be described as a typical configuration of the organic EL device of the present invention. As described in detail.

[6.2] Embodiment 1
First, members used in the first embodiment will be described.

[Bus line (21)]
In the present invention, the bus line is generally a wire for connecting the function of an electronic device, and in the organic EL device of the present invention, a wire for supplying power to each organic EL element from an applied power source. It is. The material used is a metal material having high conductivity, and from the viewpoint of adhesion to a substrate and corrosion prevention, molybdenum clad aluminum (abbreviation: MAM, molybdenum (Mo) / aluminum (Al) / molybdenum (Mo) And molybdenum clad copper (abbreviation: MCM, molybdenum (Mo) / copper (Cu) / molybdenum (Mo)), and the like.

[Extraction electrode (23): plane electrode]
It is preferable to use the same material as the material used in the first electrode for the organic EL element. In particular, it is preferable to use an Ag nanoink.

[Conductive member (22): Resistive material]
The conductive member according to the present invention is made of a conductive material whose resistance value can be adjusted, and is not particularly limited, and known conductive materials can be applied.

  As a conductive material, as an inorganic material, for example, a metal such as gold, silver, copper, aluminum, nickel, or cobalt, or indium tin oxide (ITO), indium zinc oxide (indium tin oxide (ITO)) Examples include metal oxides such as Indium Zinc Oxide (IZO), zinc oxide (Zinc Oxide (ZnO)), or zinc-tin oxide (Zinc Tin Oxide (ZTO)), or antimony-tin oxide (ATO). It is preferable to use a metal nanoink (such as a silver nanoink) containing these metals or metal oxides in the form of particles, since this can impart wet coating suitability. Silver nanoinks can be obtained as commercial products, and SR6000 and SW1020 manufactured by Bando Chemical, colloidal ink JB 0420B manufactured by C-ink Co., Ltd., NBSIJ-MU01 which is a silver nanoink manufactured by Mitsubishi Paper Industries, and NBSIJ -FD02, NBSIJ-KC01 etc. can be mentioned.

  In addition, examples of the organic material include conductive carbon materials such as conductive carbon nanotubes and graphene, and conductive polymers such as polythiophene or polyaniline. Among them, characteristics of excellent flexibility, transparency, and PEDOT / PSS, which is a kind of polythiophene of organic conductive polymer, can be suitably used in that it has a feature of being excellent also in conductivity. PEDOT / PSS is a polymer complex in which PEDOT (polymer of 3,4-ethylenedioxythiophene) and PSS (polymer of styrene sulfonic acid) coexist.

  The thickness of the conductive member is formed to a thickness required to achieve the conductivity, transparency, etc. of the conductive member to be applied, and the resistance required for the conductive member.

[Insulating layer (24)]
Various insulating materials can be used as a material for forming the insulating layer according to the present invention, and in particular, an inorganic oxide film having a high dielectric constant is preferable. As an inorganic oxide, silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, yttrium trioxide, etc. may be mentioned. Among them, preferred are silicon oxide, aluminum oxide, tantalum oxide and titanium oxide. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  The inorganic oxide film can be formed by a dry deposition method such as vacuum evaporation, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, atmospheric pressure plasma, etc. , Spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, coating method such as die coating method, patterning method such as printing method including inkjet printing method, etc. Wet formation methods may be mentioned and can be used depending on the material. Among these, the inkjet printing method is preferred.

  In addition, as the organic compound, polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cationic polymerization photo curable resin, or copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, And cyanoethyl pullulan, polymer bodies, phosphazene compounds including elastomer bodies, and the like can also be used. Moreover, as a commercial item, cells manufactured by Daicel, etc. can be mentioned.

[6.2.1] Configuration of Embodiment 1 As shown in FIGS. 9 and 10, the organic EL device described in Embodiment 1 of the present invention is vertically disposed on a base (not shown). An organic EL element is disposed to form a pixel unit in a region where the bus line V (21 V) and the bus line H (21 H) disposed in the lateral direction intersect in a grid shape. Is preferred.

The image unit is a plurality of organic EL elements different in at least luminescent color, and in FIG. 9 and FIG. 10, the organic EL element emitting red light (EL _R ), the organic EL element emitting green light (EL _G ) and blue light emitting The organic EL elements (EL _B ) are disposed on the same plane.

A conductive member in which the first electrode (2) to the first electrode lead electrode (23) constituting each organic EL element (EL _R , EL _G , EL _B ) are formed, and one end portion has a resistance value It is connected to (22).

Different voltages for obtaining optimal light emission via the bus line H (21H) from a single bus line V (21 V) connected to the application power supply (20) and to which a constant voltage is applied It has a function of applying an optimum voltage to the organic EL elements (EL _R , EL _G , and EL _B ), and each conductive member (22) has an individual resistance value to adjust the applied voltage. . The resistance value of each conductive member varies depending on the characteristics of the organic EL element and the light emitting area, but is in the range of about 1 to 500 Ω, preferably in the range of 2 to 300 Ω, and more preferably in the range of 5 to 150 Ω. It is.

  On the other hand, the bus lines H (21H) arranged in the lateral direction and the conductive members (22) having different resistance values are connected via the bus line connecting portions (26). An applied power supply unit (20) is disposed at an end of the bus line V (21 V) in the vertical direction.

  In the layered insulating layer (24) formed on the substrate (not shown), two open portions (25-1) and (25-2) are formed in each light emitting unit.

One is an area for arranging the organic EL element, and an opening for forming the organic EL element in which each organic EL element (EL _R , EL _G , EL _B ) and the lead-out electrode (23) of the first electrode are arranged. Part (25-1).

  There is another opening, and in the area where the conductive member (22) is disposed, the conductive member, the bus line connecting portion (26), and the conductive portion at which the end of the lead electrode (23) of the first electrode is disposed. It is an opening (25-2) for member formation.

  Although the details of the formation method will be described later, after forming the bus line (21), the bus line connection portion (26), the first electrode (2), the lead electrode (23) and the like on the base material (1), As shown in FIG. 10, an insulating layer (24) having an opening (25-1) for forming an organic EL element and an opening (25-2) for forming a conductive member is formed.

  Using the respective openings (25-1) and (25-2), the respective constituent layers of the organic EL element except the first electrode and the conductive member (22) are formed, for example, using a wet coating method or the like. Do.

  In this method, the respective components do not need to be formed through a mask or the like, and can be formed at predetermined positions with high accuracy and by a simple device.

When forming the organic EL elements (EL _R , EL _G , and EL _B ) having different emission colors shown in FIGS. 9 and 10, the respective formation areas are determined according to the light emission characteristics of the respective organic EL elements. , Can also be adjusted. This is effective for equalizing the rate of decrease in luminance of each organic EL element when the organic EL device is used for a long time, for example, preventing color shift (color tone change) when white light is emitted for a long time Method. Along with this, the area of the opening (25) for forming each organic EL element changes according to the size (light emitting area) of each organic EL element (EL _R , EL _G , EL _B ) installed there Specifically, it is preferable to adjust the area size of (small) EL _G <EL _R <EL _B (large) from the viewpoint of maintaining white light emission over a long period of time.

  As described above, the feature of the first embodiment of the organic EL device according to the present invention is that the pixel unit is disposed in each of the plurality of regions surrounded by the grid-like bus line, and the conductive member having the resistance value is It arrange | positions between the coupling | bond part of a line, and the extraction electrode part of the 1st electrode of an organic EL element. Then, a voltage is applied from a common bus line, and then the light emitting condition of each organic EL element is controlled by conductive members having different resistance values for adjusting the voltage applied to each organic EL element, etc. Light emission can be controlled in a simple manner without the need for complicated light emission control. In the organic EL device of the present invention, light emission in each pixel unit is mainly targeted to display a still image represented by a poster or the like, not a variable light emission method for displaying a moving image or the like. It can be manufactured at low cost because it can be manufactured by a simple control method and a wet coating method that does not require a large-scale facility.

  Next, the specific configuration of the organic EL device described in Embodiment 1 will be described.

  FIG. 11 is a schematic cross-sectional view showing a configuration represented by cut surface AA ′ of the pixel unit shown in FIG. 10, in which one pixel unit is formed on the substrate (1). A configuration example is shown.

  Although a detailed manufacturing flow will be described later, as a flow to be formed, as shown in FIG. 11, two bus lines H (21H) arranged in the lateral direction on one side of the base material (1), A bus line connection portion (26) is formed for the bus line H of FIG. On the other hand, in the organic EL element formation region, the first electrode (2) for the organic EL element and the lead electrode (23) are formed.

  Next, as shown in FIG. 11, the insulating layer is formed in the region excluding the opening (25-1) for forming the organic EL element and the opening (25-2) for forming the conductive member on the base material (1). (24) is formed.

  In the opening (25-1) for forming an organic EL element, an organic functional layer unit including a light emitting layer is formed on the first electrode (2) for the organic EL element. On the other hand, in the form of connecting the end of the first electrode lead-out electrode (23) and the end of the bus line connecting portion (26) to the opening (25-2) for forming the conductive member, desired resistance A conductive member (22) having a value is arranged.

  The upper part of the opening (25-2) for forming the conductive member is provided with an insulating layer (24) for preventing a short circuit between the second electrode (6, cathode) and the conductive member (22) to be formed later. It is done.

  The second electrode (6, the cathode) is formed on the upper part of the opening (25-1) for forming the organic EL element and the opening (25-2) for forming the conductive member, and the whole area is covered. A sealing substrate (8) is provided on the sealing adhesive layer (7) and the outermost surface to constitute an organic EL device (OLED).

  FIG. 12 is a schematic cross-sectional view showing the configuration represented by the cross section B-B 'of the pixel unit shown in FIG. 10, in which three organic EL elements are arranged on the same plane on the substrate (1) An exemplary configuration of the first embodiment is shown.

In FIG. 12, a pair of vertical bus lines V (21 V) covered with an insulating layer (24) and openings (25-1) for forming three organic EL elements are formed on a substrate (1). A red light emitting organic EL element (EL _R ), a green light emitting organic EL element (EL _G ), and a blue light emitting organic EL element (EL _B ) are formed, and an insulating layer (24) is provided between the organic EL elements. To separate the formation regions of the respective organic EL elements.

  A common second electrode (6, a cathode) is formed on the openings (25-1) for forming these organic EL elements, and the whole area is further covered on the upper part thereof, thereby forming an adhesive layer for sealing. (7) The sealing substrate (8) is provided on the outermost surface portion to constitute an organic EL device (OLED).

[6.2.2] Manufacturing Method Generally, for example, the organic EL element is formed by a dry formation method using a chemical vapor deposition method or a vacuum evaporation method, a spin coating method, a casting method, an LB method (Langmuir Bloget, Langmuir It can be formed by applying a known thin film forming method such as wet coating method such as Blodgett method) and inkjet printing method, and among them, as a method of manufacturing the organic EL device of the present invention, at least It is preferable to form a conductive member having a resistance value for adjusting the voltage applied to each of them by a wet coating method. More preferably, at least the insulating layer, the organic EL element, the lead-out electrode portion for the first electrode, the joint portion of the bus line and the bus line are formed by a wet coating method.

  As the wet coating method, it is particularly preferable to apply an inkjet printing method.

  In FIG. 13 and FIG. 14, the manufacturing method of the organic EL device of this invention using the inkjet printing method is demonstrated.

  FIG. 13 and FIG. 14 show the manufacturing steps of the pixel unit on the cross section cut along the line A-A 'described in FIG. 11 in the organic EL device having the configuration shown in FIG.

  FIG. 13 is a diagram showing a first half manufacturing process from formation of a bus line to formation of a conductive member.

<Step 1: Formation of Bus Line and Bus Line Connection>
As shown in (a) of FIG. 13, first, on the base material (1), the bus line H (21H) and the bus line connecting portion (26) at predetermined positions as shown in FIG. 10 and FIG. A forming ink, for example, an ink containing conductive MAM (molybdenum / aluminum / molybdenum) is formed by being ejected from an ink jet head at a predetermined position.

<Step 2: Formation of First Electrode (Anode) and Its Extraction Electrode>
Then, as shown in (b) of FIG. 13, the first electrode (2) and the lead-out electrode (23) are placed at the positions described in FIG. 10 and FIG. 11 from the inkjet head (30). A colloidal ink JB0420B manufactured by C-ink Inc. is discharged and formed.

<Step 3: Application of Insulating Member and Formation of Each Opening>
Next, as shown in FIG. 13C, the bus line H (21H) formed above, a part of the bus line connection part (26) (a region other than the area exposed by the conductive member forming opening), a lead electrode In part (23) (a region other than the area exposed by the opening for forming the organic EL element and the opening for forming the conductive member), an insulating material, for example, a fat which is a transparent sealing agent is used from the inkjet head (30). By discharging an ink containing a cyclic epoxy compound or the like, an opening (25) for forming an organic EL element and an opening (25) for forming a conductive member as shown in FIG. 13 are formed. In the first embodiment, cellus manufactured by Daicel Corporation was used.

<Step 4: Formation of Organic Functional Layer Unit>
Next, as shown in (d) of FIG. 13, on the first electrode (2) formed in the opening (25-1) for forming the organic EL element, each organic The ink containing the functional layer forming material is sequentially discharged to form the organic functional layer unit (U).

<Step 5: Formation of Conductive Member>
Next, as shown in (e) of FIG. 13, the end of the bus line connection portion (26) exposed in the opening (25-2) for forming the conductive member and the end of the lead electrode (23) As a conductive member for resistance adjustment from the ink jet head (30) at the position where it is connected with, for example, a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (PEDOT: PSS) or silver The nanoink is ejected to form the conductive member (22).

  At this time, by changing the discharge amount of the ink and adjusting the layer thickness appropriately, the conductive member (22) having different resistance values can form a conductive member having a desired resistance value.

  FIG. 14 is a diagram showing the second half of the manufacturing process from the formation of the insulating layer for sealing the conductive member to the application of the sealing substrate.

<Step 6: Formation of Insulating Layer for Sealing Conductive Member>
Next, in order to prevent a short circuit between the conductive member (22) formed in the step 5 and the second electrode (6, cathode) formed in the next step 7, the opening (25-1) for forming the conductive member In order to seal the upper part of the above, the insulating layer (24) is formed using the aforementioned insulating member.

<Step 7: Formation of Second Electrode (Cathode)>
Next, a second electrode (6. cathode) is formed on the entire surface of the pixel unit from the ink jet head (30) on the insulating layer (24) and the organic functional layer unit (U). Since the second electrode is a reflective electrode, a magnesium / aluminum mixture was used.

<Steps 8 and 9: Formation of Sealing Adhesive Layer (7) and Sealing Member (8)>
Subsequently, the adhesive layer for sealing (7) and the sealing member (8) are formed by coating or inkjet printing, and the organic EL device before the light shielding portion is provided is manufactured. The sealing adhesive layer and the sealing member were appropriately selected from the above-mentioned materials.

<Step 10: Formation of Light Shielding Portion>
Finally, the fabricated organic EL device is inverted, and a light shielding portion is formed on the surface of the substrate (1) opposite to the organic functional layer unit (U) by inkjet printing as shown in FIG. 4B. The organic EL device of the present invention was produced. In the first embodiment, a light shielding portion is appropriately formed using carbon black (Regal 330R: made by Cabot Corporation) as a light absorbing material. Using a contact film thickness meter DekTakXT (made by Bruker), the stylus was operated so as to cross the ink dots printed on the substrate, and the film thickness was determined from the height difference with the substrate. It was confirmed that the film thickness of the peripheral portion of the shielding portion was thicker than that of the central portion, and was a concave shape from the peripheral portion to the central portion. Moreover, as for the said light-shielding part, the light transmittance of visible region was all 5% or less. As a result of supplying electricity after producing the organic EL device and causing each organic EL element (EL _R , EL _G , EL _B ) to emit light, in the organic EL device of the present invention, the light shielding portion controls the emitted light, color tone and It has been confirmed that the display device can reproduce gradations and can be visually recognized as an excellent still image.

[6.3] Embodiment 2
[6.3.1] Configuration of Embodiment 2 Embodiment 2 of the organic EL device of the present invention will be described with reference to FIGS.

In FIG. 15, the basic configuration is similar to that of the organic EL device shown in Embodiment 1, but red light emitting organic EL element (EL _R ), green light emitting organic EL element (EL _G ), shown by a broken line And the blue light emitting organic EL element (EL _B ) forms a pixel unit (ELU) as one set, and the unit of the other light emitting element adjacent to the anode of the organic EL element emitting light of one emission color It is characterized in that it is electrically connected in series with the cathode of the organic EL element that emits color. Such a connection can reduce the voltage drop in the case of a large-area organic EL device, which is preferable from the viewpoint of obtaining uniform emission light.

  That is, the light emitting unit is divided into a plurality of parts (the number of divisions is N), and the anode forming one light emitting area is electrically connected in series with the cathode forming the other light emitting area. Voltage of the anode or cathode from the feed end to the center of the panel can also be reduced to I / N by reducing the current to I / N, thereby a large area organic EL device with excellent light emission uniformity. Is obtained.

FIG. 16 shows a cross-sectional view of the pixel unit (ELU), in which a plurality of organic EL elements are arranged separately on a light-transmissive substrate (1) having a large area. To form independent light emitting areas and non-light emitting areas. Specifically, a plurality of organic EL elements including the anode (2), the organic functional layer unit (U), the cathode (6) and the like are disposed on the base material (1), and one of the divided light emission The anode (2) constituting the area is electrically connected in series with the cathode (6) constituting the other adjacent light emitting area in the region indicated by the circular broken line (A). With such a configuration, a plurality of organic EL elements can be connected in series. In FIG. 16, the red light emitting organic EL element (EL _R ), the green light emitting organic EL element (EL _G ), and the blue light emitting organic EL element (EL _B ) form a pixel unit (ELU) as one set.

[6.3.2] Manufacturing Method FIG. 17 schematically shows an example of the manufacturing method of the second embodiment. About the part which overlaps with Embodiment 1, it omits.

<Step 1: Preparation of Base Material (1)>
In the second embodiment, the base material (1) has a gas barrier layer (11). The gas barrier layer is formed by a wet coating method using a polysilazane solution, and is reformed by ultraviolet treatment.

<Step 2: Formation of First Electrode (Anode)>
Next, as shown in (b) of FIG. 17, the first electrode (2) is placed at the position of the opening (25-1) for forming an organic EL element described in FIG. 10 and FIG. ), For example, by discharging silver nanoink etc. and forming them separately.

<Step 3: Formation of Organic Functional Layer Unit>
Next, as shown in (c) of FIG. 13, on the first electrode (2) formed in the opening (25-1) for forming an organic EL element, each organic The ink containing the functional layer forming material is sequentially discharged to form the organic functional layer unit (U).

<Step 4: Formation of Second Electrode (Cathode)>
Next, the second electrode (6. cathode) is formed in a predetermined size on the organic functional layer unit (U) from the ink jet head (30). At that time, as shown in FIG. 17, for example, the end of the red light emitting organic EL element (EL _R ) is connected to the end of the anode of the green light emitting organic EL element (EL _G ), and the green light emitting organic EL element ( The organic EL elements are electrically connected in series by connecting the end of the cathode of EL _G ) and the end of the anode of the blue light emitting organic EL element (EL _B ).

  By using the ink jet printing method, it is possible to precisely paint differently even without using a separator (also referred to as a bank) or the like for insulation between cathodes.

  The area from the left end of the cathode (6) to the right end of the anode (2) is the “light emitting area”, and from the right end of the anode (2) to the left end of the cathode (6) of the other adjacent organic EL element It becomes a "non-light emitting area".

<Step 5: Formation of Sealing Adhesive Layer (7) and Sealing Member (8)>
As in the first embodiment, the sealing adhesive layer (7) is applied by coating or inkjet printing, and the sealing member (8) on which the gas barrier layer (11) is provided is adhered and sealed. , The organic EL device before providing a light shielding part is produced. The adhesive layer for sealing and the sealing member were appropriately selected from the aforementioned materials as in the first embodiment.

<Step 6: Formation of Light Shielding Section>
Finally, the produced organic EL device was inverted, and a light shielding portion was formed on the substrate (1) by an inkjet printing method as shown in FIG. 4B to produce the organic EL device (OLED) of the present invention. In Embodiment 2, when a light shielding portion is appropriately formed using silver nanoink (TEC-PA-010: manufactured by Inktec) as a light absorbing material, the light transmittance of the visible light region as the light shielding portion is 5% or less Met. As a result of supplying electricity after producing the organic EL device and causing each organic EL element (EL _R , EL _G , EL _B ) to emit light, in the organic EL device of the present invention, the light shielding portion controls the emitted light, color tone and It has been confirmed that the display device can reproduce gradations and can be visually recognized as an excellent still image.

  Furthermore, the density of the ink dots of the silver nanoink is adjusted so that the light shielding portion has four levels of light transmittance of 5%, 15%, 30% and 50% in the visible light region as shown in FIG. 3B. When it was controlled and formed and used appropriately, it was confirmed that it was a display device capable of visually recognizing a still image with richer gradation.

[6.4] Third Embodiment
[6.4.1] Configuration of Embodiment 3 In Embodiment 1, a configuration in which a sheet containing a light absorbing material or a light reflecting material as a light shielding portion is bonded onto the light extraction surface of the manufactured organic EL element And

[6.4.2] Manufacturing Method A tape obtained by inverting the organic EL device manufactured in the first embodiment and applying carbon black on the substrate (1) so that the light transmittance of visible light is 5% or less Is cut off and appropriately attached to a portion corresponding to the organic EL element (EL _R , EL _G , EL _B ) as a light shielding portion, and in the organic EL device of the present invention, light emission is controlled by the light shielding portion, It has been confirmed that the display device can reproduce tone and gradation and can visually recognize an excellent still image.

[6.5] Embodiment 4
[6.5.1] Configuration of Embodiment 4 Embodiment 4 of the organic EL device of the present invention will be described with reference to FIG. 18, FIG. 19 and FIG.

  The organic EL device according to the fourth embodiment is an embodiment in which the light shielding portion according to the present invention contains a red, green or blue coloring material.

  The light shielding portion forms a pixel unit in which the two or more organic EL elements having different emission colors are combined to form three pixels emitting red, green, or blue, and are included in the pixel unit. The organic EL device is provided with the light shielding portion with respect to the light shielding pixel among the pixels, and contains in the light shielding portion a red, green or blue coloring material of the same color as the light emitted from the pixel transmitting light. It can mention as the said embodiment.

  Furthermore, with respect to the three pixels included in the pixel unit, the light shielding portion mixes the light emission color of the light shielding portion with the light emission color of the light shielding portion under the illumination environment, and An organic EL device containing a coloring material visually recognized as a complementary color can be mentioned as the embodiment.

  FIG. 18 is a schematic view showing emission spectra of blue light, green light and red light.

  Light is reflected corresponding to the emission maximum wavelength of blue light, green light and red light in order to contain the red, green or blue color material of the same color as the light emitted from the pixel to be transmitted in the light shielding part A coloring material having a maximum value is contained. For example, as the red color material, a color material having a light reflection maximum value in the range of 600 to 700 nm as a light wavelength is selected (corresponding to FIG. 18C). Similarly, as the green colorant, a colorant having a light reflection maximum in the range of 500 to 600 nm is selected (corresponding to FIG. 18B), and as the blue colorant, the reflection maximum in the range of 400 to 500 nm The color material is selected (corresponding to FIG. 18A). It is preferable that one or more kinds of coloring materials be selected from the coloring materials described above so as to have a desired light reflection maximum value.

  FIG. 19 is a schematic view showing a mechanism of light control of the organic EL device according to the fourth embodiment.

  Among the pixels included in the pixel unit, which are organic EL elements (pixels) that emit red, green, or blue light, respectively, preparing the ink containing the coloring material, the light shielding portion with respect to the light shielding pixels The light shielding portion contains a red, green or blue coloring material of the same color as the light emitted from the pixel through which light is transmitted. Here, “same color” means that the wavelength showing the maximum value of the reflection spectrum of the color material is equivalent (range of ± 10 nm) corresponding to the wavelength showing the maximum value of the red, green or blue emission spectrum. Say. Further, the wavelength showing the maximum value of the reflection spectrum of the color material is preferably in the range of ± 5 nm.

  From the left side of FIG. 19, when red, green and blue light emitting pixels are one pixel unit, and blue still image is obtained by the pixel unit, red and green light transmitting to red and green light emitting pixels The transmission light is shielded by thickening the coating film thickness of the light shielding portion containing the blue coloring material having a low rate. In this case, only blue emission light is transmitted, so a blue still image is obtained when light is emitted, but when light is not emitted, the blue color material on the adjacent pixel is perceived as blue light of the same color as reflected light. The pixel unit is viewed as a blue still image.

  Similarly, in order to obtain a green still image, the coated film thickness of the light shielding portion containing a green color material having low light transmittance of red and blue light is increased by using red and blue light emitting pixels. , Shield the transmitted light. If it does so, only the green emission light is transmitted, so it becomes a green still image, but if it is not made to emit light, the green color material on the pixels on both sides is perceived as green as reflected light, and the pixel unit is green As a still image of

  In addition, in the case of obtaining a red still image, transmission is performed by thickening the coated film thickness of the light shielding portion containing a red coloring material having low green and blue light transmittances to the pixels emitting green and blue light. Shield the light. Then, when light is emitted, only red emission light is transmitted, resulting in a red still image. However, when light is not emitted, the red coloring material on the adjacent pixel is perceived as reflected light, and the pixel unit is red still. It is visually recognized as an image.

  Furthermore, in the rightmost pixel unit in FIG. 19, the light emission color and the reflected light color are mixed in the illumination environment with respect to the pixels emitting red, green and blue, and the light is viewed as a complementary color. It is a schematic diagram when the light shielding part containing the coloring material to be formed is formed.

  In this case, since the light shielding portion adjusts the coating film thickness relatively thinly, partial light transmission occurs, and a light shielding portion containing a green color material is provided to a pixel that emits red light. As a mixture of red light emission and green reflected light, it is visually recognized as yellow (Y) under the illumination environment. Similarly, by providing a light shielding portion containing a blue coloring material to a pixel which emits green light, it becomes a mixture of green light emission and blue reflected light, and is visually recognized as cyan (C) under the illumination environment. Similarly, by providing a light shielding portion containing a red coloring material to a pixel which emits blue light, it becomes a mixture of blue light emission and red reflected light, and is visually recognized as magenta (M) under the illumination environment.

  Therefore, with the three types of complementary light, it is possible to switch between a picture based on the subtractive method (image visually recognized by reflection of illumination light) and a picture based on light addition (image based on light emission) during the daytime. Furthermore, color reproduction by the subtractive color method can be added to the same screen of a still image using color reproduction by the additive color method. In addition, by adjusting the film thickness of the ink to be placed on the pixel, it is possible to create an image in which various colors of addition and reduction are mixed, and it is possible to obtain a still image which can be expressed more widely. . Each colorant is preferably selected from one or more of the colorants described above.

  FIG. 20 is a schematic view showing reflection spectra of yellow, magenta and cyan which are visually recognized.

[6.5.2] Manufacturing Method Specifically, as the red coloring material, C.I. I. Pigment red 9, and as a color material for green, C.I. I. Pigment green 7, and as a blue coloring material, C.I. I. Pigment Blue 15 can be used respectively, but it is not limited thereto.

  Light shielding pixels of an organic EL element (pixel) emitting red, green or blue light by using an ink in which pigments of respective colors are dissolved in an organic solvent and using an ink different in color material as a light shielding member by ink jet printing Then, the light shielding portion containing the color material corresponding to the light transmitting pixel is formed. The coating film thickness was appropriately determined while monitoring the value of light transmittance.

  When the manufactured organic EL device was made to emit light, a desired emission color was obtained for each pixel unit, and when it was not emitted, a desired reflected light color was visually recognized for each pixel unit. Therefore, the still image can be visually recognized by the reflected light color in the daytime and the transmitted light color in the nighttime. In a bright environment, it is also possible to add an image by light emission to an image by reflected light, and it has become possible to obtain a still image with higher visibility.

  On the other hand, for an organic EL element (pixel) that emits red, green or blue, the light emission color and the reflected light color are mixed under the illumination environment, and a color complementary to the light emission color is visually recognized To form a light shielding portion containing the coloring material. In this case, the coating film thickness needs to be thin enough to allow light emitted from the pixels to be transmitted to the light shielding portion, and was appropriately determined while monitoring the value of the light transmittance.

  When the manufactured organic EL device was made to emit light, under the illumination environment, an image visually recognized as yellow (Y), cyan (C) and magenta (M) which are complementary colors of red, green and blue for each pixel unit was obtained Color reproduction of still images by the subtractive color method.

  Furthermore, as shown in FIG. 19, under the illumination environment, it becomes possible to add a still image using color reproduction by subtractive method to the same screen of a still image using color reproduction by additive light method by light emission, It was possible to obtain a still image that can be expressed more widely.

  In that case, by adjusting the film thickness of the ink to be placed on the pixel, it was possible to create an image in which the colors of the additive method and the subtractive method are variously mixed.

  The organic electroluminescent device of the present invention reproduces color tone and gradation by controlling the light emission area of each of the organic electroluminescent elements emitting red, green and blue, thereby reproducing a still image with a simple structure. It is an inexpensive organic electroluminescent device capable of forming a light emitting diode, and can be suitably used for a display device for displaying a still image such as digital signage (outdoor advertisement) or a poster.

1 substrate 2 first electrode (anode)
3 Organic Functional Group 1
4 light emitting layer 5 organic functional layer group 2
6 Second electrode (cathode)
DESCRIPTION OF SYMBOLS 7 Adhesive layer for sealing 8 Sealing member 9 Light shielding part 11 Gas barrier layer 20 Applied power supply part 21 Bus line 22 Conductive member 23 Extraction electrode 24 Insulating layer 25-1, 25-2 Opening 26 Connection electrode 30, 100 Inkjet Head 31 pump 32 filter 33 piping branch 34 waste liquid tank 35 control section 36 tank 37A tank 38A tank 38B tank 39 pump 30b piezoelectric substrate 30c top plate 30d nozzle plate 30e ink liquid supply pipe 30f piping 56 case 57 cap backing plate 59 cover Member 61 nozzle plate 62 cap receiving plate mounting portion 68 mounting hole 71 nozzle opening 81a 1st joint 81b 2nd joint 82 3rd joint OLED organic EL device U organic functional layer unit L luminescence light ELU pixel unit EL _R , EL _G , EL _B organic EL element

Claims (15)

An organic electroluminescent device comprising two or more organic electroluminescent devices different in luminescent color, comprising
The organic electroluminescent elements having different luminescent colors are disposed in the same plane, and
The surface of the light extraction side of the said organic electroluminescent element WHEREIN: The light shielding part which the light transmittance of a visible light area | region changes stepwise or is uniform is characterized by the above-mentioned.   The organic electroluminescent device according to claim 1, wherein the light shielding portion contains a light absorbing material or a light reflecting material.   The organic electroluminescent device according to claim 1 or 2, wherein the light shielding portion has a gradation in which the light transmittance changes stepwise.   The organic electroluminescent device according to claim 1 or 2, wherein the light transmittance of the visible light region of the light shielding portion is uniformly 5% or less and does not have gradation.   The organic electroluminescent device according to any one of claims 1 to 4, wherein the shape of the light shielding portion is a concave shape from the peripheral portion to the central portion.   The organic electroluminescent device according to any one of claims 1 to 5, wherein the light shielding part contains carbon black, silver nanoparticles or titanium oxide particles.   The organic electroluminescent device according to any one of claims 1 to 5, wherein the light shielding part contains a red, green or blue coloring material. The two or more organic electroluminescent elements having different emission colors constitute a pixel unit in which three pixels emitting red, green or blue are combined as one set.
Among the pixels included in the pixel unit, the light shielding portion is provided to the light shielding pixel, and the light shielding portion contains a red, green or blue color material of the same color as the light emitted from the pixel transmitting the light. The organic electroluminescent device according to claim 7, characterized in that:   With respect to the three pixels included in the pixel unit, the light shielding portion is a color complementary to the light emitting color in which each light emission color and the reflected light color of the light shielding portion are mixed under the illumination environment. The organic electroluminescent device according to claim 7, characterized in that it contains a colorant that is visible in the color of the relationship.   10. The organic electroluminescent element different in luminescent color is arranged in parallel in the same plane and in the form of two or more lines different in luminescent color in any one of claims 1 to 9. The organic electroluminescent device as described in.   The organic electroluminescent elements arranged in parallel in the form of two or more lines of different emission colors in the same plane are connected to a power source by conductive members having different resistance values. The organic electroluminescent device as described in 10.   The two or more organic electroluminescent elements having different luminescent colors are disposed in one pixel, and the anode of the organic electroluminescent element emitting one luminescent color emits the other adjacent luminescent color. The organic electroluminescent device according to any one of claims 1 to 11, which is electrically connected in series to the cathode of the element. A method of manufacturing an organic electroluminescent device for manufacturing the organic electroluminescent device according to any one of claims 1 to 12.
The method of manufacturing an organic electroluminescent device, wherein the light shielding portion is formed by an ink jet printing method using an ink liquid containing a light absorbing material or a light reflecting material. A method of manufacturing an organic electroluminescent device for manufacturing the organic electroluminescent device according to any one of claims 1 to 12.
A method of manufacturing an organic electroluminescent device, comprising: bonding a sheet containing a light absorbing material or a light reflecting material as the light shielding portion on a light extraction surface of the organic electroluminescent element.   A display apparatus comprising the organic electroluminescent device according to any one of claims 1 to 12.

Images