JPWO2019230617A1 - Manufacturing method of surface emitting panel and surface emitting panel - Google Patents

Abstract

An object of the present invention is to manufacture an organic EL device having a simple structure and having improved emission quality and emission brightness difference due to an applied voltage difference, and low cost without requiring large equipment as a manufacturing means. It is an object of the present invention to provide a method for manufacturing an organic EL device capable of producing an organic EL device, and an image display device including the method. The organic EL device of the present invention has a pixel unit including a plurality of organic EL elements, and the organic EL element has at least a first electrode, an organic functional layer including a light emitting layer, and a second on a base material. The pixel unit has an electrode, and the pixel unit has a configuration in which a plurality of the organic EL elements having different emission colors are arranged on the same surface, and a voltage is applied to each first electrode of the plurality of the organic EL elements. It is characterized by having a bus line to be applied, a conductive member having a resistance value for adjusting a voltage applied to each of the organic EL elements, and an applied power supply unit for applying a voltage to the organic EL element.

Description

The present invention relates to a surface-emitting panel provided with a plurality of organic electroluminescence elements and a method for manufacturing the surface-emitting panel. More specifically, the present invention is an organic electroluminescence element having both sealing performance and flexibility and excellent manufacturing ease. The present invention relates to a surface-emitting panel provided with the above, and a method for manufacturing the surface-emitting panel.

In recent years, organic electroluminescence devices (hereinafter abbreviated as "organic EL elements") and the like using electroluminescence (hereinafter abbreviated as "EL") of an organic material have rapidly become widespread. The organic EL element is a thin film type completely solid element capable of emitting light at a relatively low voltage of about several V to several tens of V, and has many excellent features such as high brightness, high emission efficiency, thinness, and light weight. For this reason, the fields of application thereof are being energetically studied as surface emitters for display devices and illumination light sources.

A wet process is attracting attention as a manufacturing method that enables high productivity when forming a layer constituting an organic EL element. The vacuum vapor deposition method that has been applied conventionally has problems that a large vacuum device is required, it takes time for vacuum operation of a substrate and the like, and a vapor deposition process, and the material utilization efficiency is low. In addition, when changing the light emitting shape or size, it is necessary to change the mask to be used, so it takes a long work period and cost in designing and manufacturing the mask, and it is manufactured to support various panels. There was a problem with aptitude. Further, in order to maintain the shape of the mask, there are restrictions on the figures that can be expressed.

On the other hand, one of the features of the organic EL element is that it has a thin film structure, and by applying a flexible base material, the organic EL element can be made flexible, and the flexibility can be achieved. However, since the organic functional layer and the like constituting the organic EL element are easily affected by water and oxygen, it is necessary to protect them with a gas barrier layer and a sealing layer. However, in order to enhance the gas barrier performance and the sealing performance, these gas barrier layers and sealing layers need to be composed of a coating film having high rigidity, for example, a metal oxide, a nitride, an oxynitride, or the like. Therefore, when many of these coating films are subjected to stress such as bending, the coating film is liable to break and the gas barrier property is lowered, so that there is a limit to both gas barrier property and flexibility. there were.

In response to the above problem, a plurality of light emitting units composed of a pixel electrode, a light emitting layer, and a common electrode formed at positions separated from each other are provided on a stretchable base material, and each light emitting unit is individual. A stretchable display member having a structure sealed by a sealing member is disclosed (see, for example, Patent Document 1).

In the display member having a structure as shown in FIG. 1B described later disclosed in Patent Document 1, a gas barrier layer is described on a stretchable base material, and more specifically, light emission formed at positions separated from each other. There is no description of the form of forming an independent gas barrier layer for each unit, so that the gas barrier performance or sealing performance is not sufficient, and there is no clear description about the manufacturing method thereof, but it is a display. Therefore, the manufacturing process is complicated, and there is a concern about ease of manufacturing.

Further, a substrate with a gas barrier layer in which a gas barrier layer is divided and patterned in a plurality of portions on a base material and a display element is formed on each gas barrier layer, and a display element provided with the substrate are disclosed (for example, See Patent Document 2).

The substrate and display element with a gas barrier layer disclosed in Patent Document 2 are only intermediate products, and finally, each unit divided by the gas barrier layer is cut to obtain a display element for mounting. The purpose is to do that. Therefore, there is no wiring for connecting each electrode between the units. Further, the method described in Patent Document 2 is a dry method such as sputtering or vapor deposition except for the organic functional layer, and the equipment used becomes large, the manufacturing process becomes complicated, and there is a problem in manufacturing easiness. There is.

U.S. Patent Publication No. 2016/0211483 JP-A-2009-37798

The present invention has been made in view of the above problems, and the problem to be solved thereof is a surface emitting panel provided with an organic electroluminescent element which has both sealing performance and flexibility and is excellent in manufacturing ease, and a method for manufacturing the same. Is to provide.

As a result of diligent studies in view of the above problems, the present inventor has made a small-area organic EL device in which the gas barrier layer, the first electrode, the organic functional layer group, the second electrode, and the sealing layer are laminated in this order. The gas barrier layer corresponds to each organic EL element, and the plurality of organic EL elements are electrically connected via wiring. It has been found that the panel can realize a surface emitting panel provided with an organic EL element which has both sealing performance and flexibility and is excellent in manufacturing ease, and has reached the present invention.

That is, the above problem of the present invention is solved by the following means.

1. 1. Surface emission having a plurality of organic electroluminescence devices in which at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode, and a sealing layer are laminated in this order on one surface side of the flexible base material. It ’s a panel,
The light emitting area per of the plurality of organic electroluminescent devices is 100 mm ² or less.
The gas barrier layer is independently provided for each organic electroluminescence element, and
A surface emitting panel characterized in that the plurality of organic electroluminescent elements are electrically connected via wiring.

2. The surface emitting panel according to item 1, wherein the sealing layer is independently provided for each organic electroluminescence element.

3. 3. The surface emitting panel according to item (1) or (2), further comprising an adhesive layer adjacent to the sealing layer.

4. The surface emitting panel according to any one of items 1 to 3, wherein an adhesive layer is further provided on the surface of the flexible base material opposite to the surface having the organic electroluminescence element. ..

5. A method for manufacturing a surface emitting panel according to any one of items 1 to 4, wherein the surface emitting panel is manufactured.
The surface light emitting panel has at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode, and a sealing layer laminated on one surface side of a flexible base material by a wet coating method or an inkjet printing method. A method for manufacturing a surface light emitting panel, which is characterized in that the surface light emitting panel is manufactured.

According to the present invention, it is possible to provide a surface emitting panel provided with an organic electroluminescence element which has both sealing performance and flexibility and is excellent in manufacturing ease, and a method for manufacturing the same.

The technical features of the surface light emitting panel having the configuration specified in the present invention and the mechanism for expressing the effect are presumed as follows.

As described above, the organic EL element has a thin film structure and can be made flexible by applying a flexible base material. However, because of the thin film, the resistance to water and oxygen invading from the outside is low, so that the gas It is necessary to protect the organic functional layer and the like from harmful gases such as water and oxygen with a barrier layer and a sealing layer.

As a method of blocking such harmful gas and improving the sealing performance, a method of forming a gas barrier layer or a sealing layer on the entire surface of the flexible base material is known. However, these gas barrier layers and sealing layers are often basically composed of a hard and dense film (for example, a layer composed of metal oxides, nitrides, oxynitrides, etc.). .. A layer made of such a metal oxide, for example, SiO ₂ or the like has high rigidity, and the formed coating film is easily cracked when subjected to bending stress or the like. Therefore, a gas barrier layer having these structures is formed. In the surface light emitting panel to which the sealing layer is applied, the flexibility of the gas barrier layer and the sealing layer does not correspond to the flexible base material, so that cracks and film breakage are likely to occur. There is a problem that leaks and short paths occur from the fractured part and the gas barrier property deteriorates.

In the present invention, as a result of diligent studies on the above problems, a small area ^{having a light emitting area of 100 mm 2} or less having a gas barrier layer independently (separated) corresponding to each organic EL element on a flexible base material. By installing a plurality of organic EL elements and electrically connecting the organic EL elements that are separated from each other via wiring, the stress on the gas barrier layer at the time of bending is dispersed, and surface emission occurs. The flexibility of the entire panel could be improved.

Further, as a method for manufacturing a surface emitting panel of the present invention, at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode and a sealing layer are wet-coated on one surface side of a flexible base material. Alternatively, by applying the method of laminating and manufacturing by the inkjet printing method, a large vacuum device or the like is not required, so that the equipment load is light, the material selection of the flexible base material and the degree of freedom of the light emitting shape are high, and the manufacturing is easy. It is possible to provide an excellent method for manufacturing a surface emitting panel.

Schematic layout showing an example of the configuration of the surface emitting panel of the conventional comparative example. Schematic layout showing another example of the configuration of the surface emitting panel of the conventional comparative example. Schematic layout showing an example of a typical configuration of the surface emitting panel of the present invention (Embodiment 1) Schematic layout showing another example of a typical configuration of the surface emitting panel of the present invention (Embodiment 2) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (first step) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (second step) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (third step) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (fourth step) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (fifth step) Top view showing an example of the manufacturing flow of the surface emitting panel of the present invention (sixth step) FIG. 5C is a cross-sectional view showing a configuration represented by a cut surface AA of the surface emitting panel shown in FIG. 5C (Embodiment 3). FIG. 5C is a cross-sectional view showing a configuration represented by a cut surface BB of the surface emitting panel shown in FIG. 5C (Embodiment 3). Cross-sectional view showing an example of a surface light emitting panel having the configuration shown in FIG. 6 and further incorporating a transparent hygroscopic agent layer (Embodiment 4). Schematic layout drawing showing an example in which an alpette is used as a sealing member in a typical configuration of the surface emitting panel of the present invention (Embodiment 5). Schematic layout showing an example of a surface light emitting panel in which a protective substrate is provided on a sealing layer via an adhesive layer (Embodiment 6). Schematic layout showing another example of a surface light emitting panel in which a protective substrate is provided on a sealing layer via an adhesive layer. Schematic layout showing an example of a surface light emitting panel in which an adhesive layer and a protective substrate are provided on both sides of an organic EL element (Embodiment 7). Schematic layout showing another example of a surface emitting panel in which an adhesive layer and a protective substrate are provided on both sides of an organic EL element. Schematic front view showing an example of the configuration of a vacuum ultraviolet irradiation device applicable to the formation of a gas barrier layer. Schematic diagram showing an example of an inkjet printing method which is an example of a wet coating method Schematic perspective view showing an example of the structure of an inkjet head applicable to the inkjet printing method. Bottom view showing an example of the structure of an inkjet head applicable to the inkjet printing method Schematic flow diagram showing an example of a manufacturing process using the inkjet printing method of the surface emitting panel shown in FIG. 6 (No. 1) Schematic flow diagram showing an example of a manufacturing process using the inkjet printing method of the surface emitting panel shown in FIG. 6 (Part 2).

In the surface emitting panel of the present invention, at least the gas barrier layer, the first electrode, the organic functional layer group, the second electrode, and the sealing layer are laminated in this order on one surface side of the flexible base material. It is a surface light emitting panel having a plurality of luminescence elements, the light emitting area per one of the plurality of organic electroluminescence elements is 100 mm ² or less, and the gas barrier layer is independently for each of the organic electroluminescence elements. It is characterized in that the plurality of organic electroluminescence elements are electrically connected via wiring. This feature is a technical feature common to the inventions according to the following embodiments.

In the embodiment of the present invention, from the viewpoint of further exhibiting the effect intended by the present invention, the sealing layer constituting each organic EL element is also configured to have the same independent gas barrier layer as the gas barrier layer. It is preferable in that the flexibility of the surface emitting panel can be further improved.

Further, by having the adhesive layer adjacent to the sealing layer, the sealing layer can be physically protected without losing the flexibility, and the surface emitting panel can be made of paper, cloth, wall material, or the like. It is preferable because it can be easily attached to another member such as a window glass.

Further, when light is extracted from the flexible base material, the adhesive layer is provided on the surface opposite to the surface having the organic EL element, so that the light is attached to another member and the light is irradiated from the back surface side of the member. It is possible and is preferable in terms of design.

Further, in the method for manufacturing a surface emitting panel, the surface emitting panel has at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode and a sealing layer on one surface side of the flexible base material. It is characterized in that it is manufactured by laminating by a wet coating method or an inkjet printing method.

Hereinafter, the components of the surface emitting panel of the present invention and the embodiment for carrying out the present invention will be described in detail with reference to the drawings. In the present application, "~" representing a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value. In the description of each figure, the numbers described at the end of the components represent the symbols in each figure.

<< Basic configuration of organic EL device >>
In the surface emitting panel of the present invention, the gas barrier layer is formed independently for each organic EL element having a small area, and the plurality of organic EL elements are electrically connected via wiring. It is characterized by.

Prior to the detailed description of the surface emitting panel of the present invention, the configuration of the surface emitting panel which is a conventional comparative example will be described.

1A and 1B are schematic layouts showing an example of the configuration of a surface emitting panel of a conventional comparative example.

FIG. 1A is an example of a conventional surface light emitting panel, in which a common gas barrier layer 2 is formed on the entire surface of the flexible base material F, and the first electrode 4 (anode) is separated from the first electrode 4 (anode). The organic functional layer group 6 including the light emitting layer and the second electrode 7 (cathode) are laminated to form an organic EL element, and the peripheral portion of the laminated body is sealed with the first sealing layer 8 and then the surface light emitting panel. The entire surface of P is covered with a common second sealing layer 9. The first electrodes 4 of each organic EL element are connected by electrode wiring 11 to form a surface light emitting body P.

In such a surface light emitting panel P, the gas barrier layer 2 is formed on the entire surface, and when the base material is made of the flexible base material F, it is common when stress such as bending or tension is applied. Stress is concentrated on the gas barrier layer of the structure, and as a result, cracks (short baths) and film breakage occur in the gas barrier layer, resulting in deterioration of gas barrier performance.

The surface emitting panel P, which is a comparative example of the configuration shown in FIG. 1B, is an organic EL element (the first) in which the second sealing layer 9 is formed so as to be separated from the surface emitting panel P described with reference to FIG. 1A. An example is shown in which the 1 electrode 4, the organic functional layer group 6, and the 2nd electrode 7) are formed independently, but even in this configuration, the gas barrier layer 2 has a common configuration and is subjected to stress. In that case, the same problem as described above occurs.

The configuration shown above is, for example, the configuration described in US Patent Publication No. 2016/0211483, which is Patent Document 1.

Next, the configuration of the surface emitting panel of the present invention will be described with reference to the drawings. The details of each component of the surface emitting panel described below will be described later.

In the surface light emitting panel of the present invention, at least the gas barrier layer, the first electrode, the organic functional layer group, the second electrode and the sealing layer are laminated in this order on one surface side of the flexible base material as described above. The gas barrier layer is formed independently and separately for each organic EL element, and a plurality of organic EL elements having a small area are connected via wiring.

(Embodiment 1)
FIG. 2 is a schematic layout diagram showing the first embodiment, which is an example of a typical configuration of the surface emitting panel of the present invention.

In the surface light emitting panel P of the present invention shown in FIG. 2, a plurality of organic EL elements EL having ^{a light emitting area of 100 mm 2 or less are independently arranged on a flexible base material F.} The light emitting area per organic EL element is more ^{preferably 25 mm 2} or less. The lower limit is not particularly limited, but is preferably ^{4 mm 2 or more.}

Each organic EL element EL has an independent gas barrier layer 2, on which the first electrode 4 (anode), the organic functional layer group 6 including the light emitting layer, and the second electrode 7 (cathode) are laminated. Has been done. The peripheral portion of the laminated body is covered with a common first sealing layer 8 and second sealing layer 9 to form a surface emitting panel P. Further, if necessary, a base layer (not shown) may be provided between the flexible base material F and the gas barrier layer 2 for the purpose of improving the adhesion between the two. Further, in each organic EL element EL, the light emission control of each organic EL element EL is performed by electrically connecting the first electrodes 4 (anodes) with the electrode wiring 11. The electrode wiring 11 between the elements may be installed directly on the flexible base material F, but a base layer (not shown) may be provided and installed on the base layer (not shown). In each organic EL element, the second electrodes 7 (cathodes) are electrically connected by electrode wiring, but the description thereof is omitted in this figure for convenience.

In the surface light emitting panel P shown in FIG. 2, the light transmittance of the material applied to the flexible base material F, the first electrode 4, the second electrode 7, the first sealing layer 8 and the second sealing layer 9 is adjusted or adjusted. By selecting, the light emitting light L is taken out to the upper surface side (sealing layer side) of the surface emitting panel P to be a top emission type TE, or from the lower surface side of the surface emitting panel P (the back surface side of the flexible base material). It can be a bottom emission type BE that extracts the emitted light L.

(Embodiment 2)
FIG. 3 is a schematic layout diagram showing the second embodiment, which is an example of a typical configuration of the surface emitting panel of the present invention.

In the surface emitting panel P according to the second embodiment shown in FIG. 3, the first sealing is further applied to the surface emitting panel (first embodiment) in which only the gas barrier layer 2 shown in FIG. 2 described above has an independent configuration. It shows a form in which the layer 8 and the second sealing layer 9 are formed independently, and is one of the preferable forms in that the bending resistance when subjected to stress such as bending is improved.

(Embodiment 3)
Next, a more detailed configuration (embodiment 3) of the surface emitting panel P including the organic EL element (EL) will be described with reference to FIGS. 4A to 4C, FIGS. 5 to 5C, and FIGS. 6 and 7.

In the surface emitting panel P shown in FIGS. 4A to 4C, 5 to 5C, 6 and 7, the flexible base material F and the gas barrier layer 2 are further compared with the schematic configurations described in FIGS. 2 and 3. A more specific surface emitting panel P in which an insulating layer 5 is provided between the base layer 1, the first electrode 4 (anode), the organic functional layer group 6 including the light emitting layer, and the second electrode 7 (cathode). The configuration of is shown.

4A to 4C and 5 to 5C are manufacturing flow charts (top views) showing the manufacturing steps of the surface emitting panel P having the configurations shown in FIGS. 6 and 7 described later. FIG. 6 is a detailed cross-sectional view showing the configuration represented by the cut surface AA shown in FIG. 5C of the surface emitting panel P manufactured by the above manufacturing flow, and FIG. 7 is a cut surface of the surface emitting panel shown in FIG. 5C. It is a detailed cross-sectional view which shows the structure represented by BB.

First, the manufacturing flow of the surface light emitting panel (Embodiment 3) will be described with reference to FIGS. 4A to 4C and FIGS. 5 to 5C. 4A to 4C and 5 to 5C show a flow for producing a surface light emitting panel P by sequentially laminating each constituent member on the flexible base material F. In the method for manufacturing a surface emitting panel of the present invention, at least the gas barrier layer, the first electrode, the organic functional layer group, the second electrode and the sealing layer described below are laminated by a wet coating method or an inkjet printing method. It is characterized by being manufactured.

In FIG. 4A, a base layer 1 made of, for example, an ultraviolet curable resin is placed on the flexible base material F arranged at the bottom, and then an independent gas barrier corresponding to an organic EL element is placed on the base layer 1. Form layer 2.

Next, a grid-like grid, for example, Ag grid 3, is formed at the position shown in FIG. 4A, and the first electrode 4 (anode) is formed at a predetermined position on the grid, for example, with a conductive polymer or the like.

Next, as shown in FIG. 4B, the surface of the Ag grid 3 in the region excluding the take-out portion, which is the end portion of the first electrode 4, is covered with the insulating layer 5.

Next, as shown in FIG. 4C, a pattern film of the organic functional layer group 6 including the light emitting layer is formed on the first electrode 4, which is an open portion surrounded by the formed insulating layer 5.

Next, the second electrode 7 (cathode) is formed in a grid pattern between the Ag grids 3 on the organic functional layer group 6 at the position shown in FIG. 5A.

Next, as shown in FIG. 5B, the first sealing layer 8 is formed with, for example, polyorganosiloxane, polydimethylsiloxane (abbreviation: PDMS), or the like so as to cover the organic functional layer group 6 and the insulating layer 5.

Finally, as shown in FIG. 5C, the second sealing layer 9 is formed by using, for example, perhydropolysilazane (abbreviation: PHPS) or the like so as to cover the first sealing layer 8, and the surface emitting panel is formed. The organic EL element EL constituting P is manufactured.

At this time, the second sealing layer 9 has a larger area than the first sealing layer 8 because it covers the first sealing layer 8.

FIG. 6 is a cross-sectional view showing a configuration represented by a cut surface AA of the surface light emitting panel shown in FIG. 5C. In the AA line, an organic functional layer group 6 is formed, and a second electrode 7 is formed on the entire surface thereof. Is the area where is formed.

As shown in FIG. 6, an independent gas barrier layer 2 is formed in a part of the flexible base material F via the base layer 1. A first electrode 4 is provided on the lattice-shaped Ag grid 3 so as to cover both ends thereof, and an insulating layer 5 is provided so as to cover both ends of the first electrode 4 to form the insulating layer 5. The organic functional layer group 6 is formed in the non-formed portion (opening), the second electrode 7 is formed over the entire surface thereof, and the first sealing layer 8 and the second sealing are formed in a part of the region above the second electrode 7. The layer 9 is formed to form the surface emitting panel P.

In the configuration represented by the cut surfaces AA, the gas barrier property of the second electrode 7 which is formed on the entire surface and has an exposed portion is also important.

FIG. 7 is a cross-sectional view showing a configuration represented by a cut surface BB of the surface emitting panel shown in FIG. 5C. In the region represented by the BB line, the Ag grid 3 and the insulating layer 5 are formed over the entire surface. Has been done.

The cross-sectional view shown in FIG. 7 has a configuration in which the Ag grid 3 and the insulating layer 5 are formed over the entire width. In such a case, the gas barrier property of the insulating layer 5 is also important.

(Embodiment 4)
FIG. 8 is a cross-sectional view (embodiment 4) showing an example of a surface emitting panel in which a transparent hygroscopic agent layer is further incorporated with respect to the configuration represented by the cut surface AA of the surface emitting panel shown in FIG. 5C.

As shown in FIG. 8, the transparent hygroscopic agent layer 16 may be installed between the first sealing layer 8 and the second sealing layer 9 in the surface emitting panel in order to enhance the sealing performance of the sealing layer. preferable.

Details of the transparent hygroscopic agent layer 16 will be described later.

(Embodiment 5)
FIG. 9 is a schematic layout diagram (Embodiment 5) showing an example in which an alpette is applied as the second sealing layer, which is a typical configuration of the surface emitting panel of the present invention.

In the surface emitting panel P shown in FIG. 9, Alpet AP is applied as the second sealing layer to the surface emitting panel of the first embodiment described with reference to FIG. 2, and at the same time, sealed as the first sealing layer. An example of forming the resin layer 15 is shown.

In the configuration described in the fifth embodiment, since the alpette itself is light opaque, the emitted light L is a bottom emission type that is radiated from the back surface side (lower surface side) of the flexible base material F.

(Embodiment 6)
In the above-described embodiments 2 to 4, the basic configuration of the surface emitting panel has been described, but next, a more practical form as the surface emitting panel will be described.

10A and 10B are schematic layout drawings (Embodiment 6) showing an example of a surface light emitting panel in which a protective substrate is provided on a sealing layer via an adhesive layer.

The surface emitting panel P shown in FIG. 10A has a first adhesive layer 12 and polyethylene terephthalate (PET), polyethylene (PE), etc. on the second sealing layer 9 of the surface emitting panel shown in FIG. 3 described above. The configuration in which the first protective member 13 composed of is laminated is shown. In this structure, a gap V may be formed between the organic EL elements EL, but the gap V is an extremely narrow space, and in particular, a state in which no filler is added, or an adhesive layer is formed if necessary. It is also possible to form a sealing structure by filling with a pressure-sensitive adhesive.

The first protective member 13 also plays a role of protecting the organic EL element EL when the surface light emitting panel P receives an external pressure and a role as a separate film as described in FIG. 10B below.

Further, as shown in FIG. 10B, the surface emitting panel P having the configuration shown in FIG. 10A is exposed by peeling (separating) the first protective member 13 provided on the outermost surface of the surface emitting panel P. A planar lighting device or sign board having excellent flexibility is obtained by attaching to an installation member 14, for example, a member having various shapes such as paper, cloth, a wall surface, or a window glass, via an adhesive layer 12. Can be done.

(Embodiment 7)
11A and 11B are schematic layout views (Embodiment 7) showing an example of a surface light emitting panel in which an adhesive layer and a protective substrate are provided on both sides of the organic EL element.

The surface emitting panel P shown in FIG. 11A according to the seventh embodiment is made of polyethylene via a second adhesive layer 12B on the back surface side of the flexible base material F with respect to the surface emitting panel shown in FIG. 10A described above. A second protective member 13B made of terephthalate (PET), polyethylene (PE), or the like is laminated. Even in the case shown in FIG. 11A, a gap V is formed between the organic EL elements (ELs). This gap V is an extremely narrow space, and a sealing structure can be formed in a state where no filler is added, or, if necessary, a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is filled.

Further, also in the surface emitting panel (P) having the configuration shown in FIG. 11A, as shown in FIG. 11B, the second protective member 13B provided on the back surface of the surface emitting panel P is peeled off (separated) and exposed. A planar lighting device or sign board having excellent flexibility can be attached to an installation member 14, for example, a member having various shapes such as paper, cloth, a wall surface, or a window glass, via a second adhesive layer 12B. Obtainable.

<< Components of organic EL devices >>
Next, the details of the main constituent members of the surface emitting panel of the present invention described with reference to the above figures will be described below.

[Flexible base material F]
The flexible base material F applicable to the surface emitting panel of the present invention may be a base material having flexibility, for example, thin film glass, resin film, metal foil, fabric (for example, fabric, woven fabric, etc.), and the like. Paper, elastomer (rubber cloth) and the like can be applied, and it may be transparent or opaque.

In the case of the bottom emission type BE that extracts the emitted light L from the flexible base material F side as the organic EL element EL, the flexible base material F is preferably light transmissive. The light transmittance means that the total light transmittance in the visible light region is 20% or more, preferably 50% or more, and more preferably 80% or more transparency. preferable. A particularly preferable flexible base material F is a resin film capable of imparting flexibility to the organic EL element.

Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate propionate. CAP), cellulose acetate phthalate, cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol (PVA), polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate (PC), norbornene resin, polymethylpentene. , Polyether ketone, Polyethylene (PI), Polyether sulfone (PES), Polyphenylene sulfide, Polysulfones, Polyetherimide, Polyetherketoneimide, Polyamide, Fluororesin, Nylon, Polymethylmethacrylate (PMMA), Acrylic or Polyallylate Examples thereof include cycloolefin resins such as Arton (trade name: manufactured by JSR) or Apel (trade name: manufactured by Mitsui Kagaku Co., Ltd.).

The fabric may be in any form such as a fabric made of cotton, wool, silk, nylon, linen, rayon, acrylic, polyester, polyurethane or the like, a woven fabric, a knitted fabric, or a non-woven fabric.

Examples of the elastomer include synthetic rubber in addition to natural rubber, such as isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, acrylic rubber, fluororubber, and urethane rubber. Silicone rubber and the like can be mentioned.

The flexible base material can be used alone or in combination of two or more. When the flexible base material has a laminated structure of two or more layers, each base material may be of the same type or of a different type. Further, the structure may be such that the organic EL element can be peeled off and separated after being manufactured.

[Adhesion improvement treatment of flexible base material]
The surface of the flexible base material F may be subjected to a surface activation treatment or may be provided with a base layer in order to enhance the adhesion to the gas barrier layer 2 formed on the flexible base material. Further, a hard coat layer may be provided in order to enhance impact resistance.

Examples of the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.

Examples of the material of the base layer and the hard coat layer include polyester, polyamide, polyurethane, vinyl-based copolymer, butadiene-based copolymer, acrylic-based copolymer, vinylidene-based copolymer, epoxy-based copolymer and the like. Above all, an ultraviolet curable resin can be preferably used. The base layer may be a single layer, but if it has a multi-layer structure, the adhesion is further improved. A commercially available plastic base material on which a hard coat layer is formed in advance may be used, or a base layer or a hard coat layer may be provided by applying and curing only a necessary portion of the flexible base material.

[Gas barrier layer 2]
The gas barrier layer is a layer having a function of preventing harmful components (oxygen, moisture, etc.) from entering the organic EL element from the outside, and in the surface emitting panel of the present invention, each of the plurality of existing organic EL elements has a function. It is characterized by being formed in a corresponding and independent form.

The thickness of the gas barrier layer according to the present invention can be appropriately set depending on the intended purpose, but is generally in the range of 100 nm to 10 μm.

Further, the gas barrier layer according to the present invention is characterized in that it is formed by a wet coating method or an inkjet printing method.

(Silicon-containing polymer)
As a material applicable to the formation of the gas barrier layer according to the present invention, a silicon-containing polymer having a bond of silicon and oxygen (Si—O), silicon and nitrogen (Si—N), etc. is contained in the repeating structure. An example of this configuration can be given.

Specific examples of the silicon-containing polymer include polysiloxane having a Si—O bond (including polysilsesquioxane), polysilazane having a Si—N bond, and Si—O bond and Si—N bond in the repeating structure. Polysilazane and the like containing both can be mentioned. These can be used by mixing two or more kinds. It is also possible to laminate layers of different types of silicon-containing polymers.

<Polysiloxane>
Polysiloxane is a compound containing- _{[RaSiO 1/2} ]-,-[RbSiO]-,-[RcSiO _3/2 ]-,-[SiO _{2]-and the like in the repeating structure.}

Ra, Rb and Rc are independently an alkyl group containing a hydrogen atom and 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) and an aryl group (for example, a phenyl group and an unsaturated alkyl group). ) And other substituents. A preferred example is polyorganosiloxane, polydimethylsiloxane (abbreviation: PDMS). Polysilsesquioxane is a compound among the above polysiloxanes that has the same structure as silsesquioxane in its repeating structure. Silsesquioxane is a compound having a structure represented by the above- [RcSiO _3/2]-.

<Polysilazane>
The structure of polysilazane can be represented by the following general formula (A).

General formula (A)
-[Si (R ₁ ) (R ₂ ) -N (R ₃ )]-
In the above general formula (A), R ₁ , R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. ..

_{Polysilazane in which all of R 1} , R ₂ and R _{3 in} the above general formula (A) are hydrogen atoms is perhydropolysilazane (abbreviation: PHPS). Perhydropolysilazane is preferable because a dense film can be obtained.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 (in terms of polystyrene) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and their states differ depending on the molecular weight.

On the other hand, in the above general formula (A), the polysilane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like is organopolysilazane. Organopolysilazane has improved adhesion to the underlying layer due to alkyl groups such as methyl groups, and can impart toughness to polysilazane, which has hard and brittle properties, so cracks are suppressed even when the film is thickened. There is an advantage that it can be done. Therefore, perhydropolysilazane and organopolysilazane may be appropriately selected depending on the intended use, or both may be mixed and used.

<Polysiloxazan>
Polysiloxazan contains a structure represented by − [(SiH ₂ ) _n (NH) _r ] − and − [(SiH ₂ ) _{m O] − in the repeating structure.} n, m and r independently represent 1-3.

<Other Polysilazane>
As another example of polysilazane that is ceramicized at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane having a main skeleton composed of a unit represented by the above general formula (A) with a silicon alkoxide (for example, JP-A-P). 5-238827 (see JP-A-5238827), glycidol-added polysilazane obtained by reacting glycidol (see, for example, JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (see, for example, JP-A-6-). 240208.), Metal carboxylate-added polysilazane obtained by reacting with a metal carboxylate (see, for example, JP-A-6-299118), and an acetylacetonate complex containing a metal. Examples thereof include polysilazane with an acetylacetonate complex (see, for example, JP-A-6-306329), polysilazane with metal fine particles added by adding metal fine particles (see, for example, JP-A-7-196986), and the like.

(Method of forming a gas barrier layer)
The gas barrier layer according to the present invention is characterized by being formed by a wet coating method or an inkjet printing method. Examples of the forming method include a roll coating method, a flow coating method, a spray coating method, a printing method, a dip coating method, a bar coating method, a cast film forming method, an inkjet printing method, a gravure printing method, and the like, but they are easy to manufacture. When the property is important, the inkjet printing method is preferable.

(Coating liquid for forming gas barrier layer)
As the solvent used for preparing the coating liquid for forming the gas barrier layer, it is preferable to avoid using an alcohol-based organic solvent that easily reacts with polysilazane or an organic solvent containing water. Therefore, examples of the organic solvent that can be used for preparing the coating liquid for forming the gas barrier layer include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, and aliphatic hydrocarbons. Examples thereof include ethers such as ethers and alicyclic ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbesso and terben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to the characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

As the coating liquid for forming the gas barrier layer, a commercially available product in which polysilazane is dissolved in an organic solvent can be used. Examples of commercially available products that can be used include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials.

The coating liquid for forming the gas barrier layer may also contain a catalyst from the viewpoint of accelerating the reforming treatment. As the catalyst, a basic catalyst is preferable, and for example, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N', N'- Amine catalysts such as tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, and Pd compounds such as propionic acid Pd. , Metal catalysts such as Rh compounds such as Rh acetylacetonate, N-heterocyclic compounds and the like.

The content of the silicon-containing polymer in the coating liquid for forming the gas barrier layer varies depending on the thickness of the silicon-containing polymer modifying layer to be formed and the pot life of the coating liquid, but is generally within the range of 0.2 to 35.0% by mass. Is preferable.

The formed gas barrier layer coating film can be dried by heating from the viewpoint of removing the organic solvent in the coating film.

The heating temperature in the drying treatment step can be in the range of 50 to 200 ° C. The heating time is preferably set to a short time in order to prevent deformation of the flexible base material made of a resin film or the like. For example, in the case of a resin film made of polyethylene terephthalate (PET) having a glass transition temperature of 70 ° C. as a flexible base material, the temperature during the drying process is set to 150 ° C. or lower in order to prevent deformation of the resin film. Can be set.

Further, from the viewpoint of removing the moisture in the coating film, the formed coating film of the gas barrier layer can be subjected to a drying treatment for dehumidifying while maintaining a low humidity environment. Since the humidity in a low humidity environment changes with temperature, the relationship between temperature and humidity can be determined by the dew point temperature regulation. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is -8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./25%). Humidity is 1%) or less. It may be dried under reduced pressure to facilitate the removal of moisture. The pressure in vacuum drying can be selected in the range of normal pressure to 0.1 MPa.

(Reform treatment of gas barrier layer)
The gas barrier layer can be formed by forming a coating film using the above-mentioned coating liquid containing a silicon-containing polymer and then subjecting the coating film to a modification treatment. The modified product can be obtained by converting the silicon-containing polymer into silica or the like by the modification treatment, but it is not necessary to modify all of the silicon-containing polymer, and at least a part, for example, the ultraviolet irradiation surface side is It suffices if it is modified.

As a method for modifying the gas barrier layer, a known method with less heat damage to the flexible base material made of a resin film or the like can be applied, and plasma treatment or ozone treatment capable of low temperature treatment can be applied. , Ultraviolet rays, vacuum ultraviolet rays, and the like can be used. Of these, the vacuum ultraviolet irradiation treatment is preferable because the gas barrier property is unlikely to deteriorate due to the influence of the environment between the formation of the modified gas barrier layer of the silicon-containing polymer and the next step.

The vacuum ultraviolet irradiation treatment uses the light energy of vacuum ultraviolet light (Vaccum Ultra Vilet, abbreviated as VUV) in the wavelength range of 100 to 200 nm, which is larger than the atomic bond force constituting the silicon-containing polymer, and photons the bond between atoms. A process called a process, in which a silicon-containing polymer is converted to silica or the like in a relatively low temperature environment of about 200 ° C. or lower by directly cutting by the action of only photons and advancing the oxidation reaction by active oxygen or ozone. Is.

The light source of the vacuum ultraviolet light may be one that generates light having a wavelength in the range of 100 to 200 nm, and a rare gas excimer lamp having an irradiation wavelength of about 172 nm (for example, manufactured by MD.com). Xe excimer lamp MODEL: MECL-M-1-200), low-pressure mercury vapor lamp of about 185 nm, medium-pressure and high-pressure mercury vapor lamp of 200 nm or less, and the like.

The features of excimer lamps are that they emit light of a single wavelength and have extremely high luminous efficiency, that the emitted light has a short wavelength and that the temperature of the object to be irradiated can be kept low, and that it can be turned on and blinked instantly. It is a light source that can be easily applied to a flexible base material made of a resin film that is easily affected by heat. In particular, the short single-wavelength vacuum ultraviolet light of 172 nm emitted by the Xe excimer lamp has a large oxygen absorption coefficient, generates high-concentration active oxygen or ozone from a small amount of oxygen, and has a high ability to dissociate the bonds of organic substances. Therefore, the reforming process can be performed in a short time.

The irradiation conditions of the vacuum ultraviolet rays may be set within a range that does not deteriorate the flexible base material below the gas barrier layer by modifying the silicon-containing polymer. For example, the irradiation time of ultraviolet rays depends on the composition and concentration of the flexible base material, the base layer, the coating liquid for forming the gas barrier layer, etc., but is generally in the range of 0.1 seconds to 10 minutes, 0.5 seconds. It is preferably in the range of ~ 3 minutes. From the viewpoint of uniformly irradiating the ultraviolet rays, it is preferable to irradiate the coating film of the silicon-containing polymer modified layer with the reflected light obtained by reflecting the ultraviolet rays from the light source by the reflector.

The illuminance of the vacuum ultraviolet rays can be in the range of ^{1 mW / cm 2 to} 10 W / cm ^2. When it is 1 mW / cm ² or more, the reforming efficiency is improved, and when it is 10 W / cm ² or less, ablation that may occur in the coating film and damage to the flexible base material and the base layer can be reduced. The irradiation energy amount (irradiation amount) of the vacuum ultraviolet rays can be in the range of ^{0.1 to 10.0 J / cm 2.} Within this range, cracks due to excessive modification, thermal deformation of the flexible base material, and the like can be prevented, and productivity is also improved, which is preferable.

The vacuum ultraviolet irradiation treatment may be a batch treatment or a continuous treatment. In the case of batch processing, the processing can be performed using an ultraviolet firing furnace provided with a light source of vacuum ultraviolet rays (for example, an ultraviolet firing furnace manufactured by Igraphics Co., Ltd.). In the case of continuous processing, the flexible base material may be conveyed and the vacuum ultraviolet rays may be continuously irradiated in the zone provided with the light source of the vacuum ultraviolet rays.

Oxygen is required for the reaction during vacuum ultraviolet irradiation, but since vacuum ultraviolet is absorbed by oxygen and the reforming efficiency tends to decrease, irradiation of vacuum ultraviolet in an atmosphere with as low oxygen concentration and water vapor concentration as possible. Is preferable. For example, the oxygen concentration during vacuum ultraviolet irradiation can be in the range of 10 to 20000 volume ppm (0.001 to 2% by volume). The water vapor concentration is preferably in the range of 1000-4000 volume ppm. For adjusting the atmosphere, it is preferable to use a dry inert gas, particularly a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by adjusting the flow rate ratio of the oxygen gas and the inert gas introduced into the room.

Next, the vacuum ultraviolet irradiation device used for forming the gas barrier layer in the present invention will be described.

FIG. 12 is a schematic front view showing an example of a configuration of a vacuum ultraviolet irradiation device applicable to the formation of a gas barrier layer.

As shown in FIG. 12, the vacuum ultraviolet irradiation device 100 carries a flexible base material F having a silicon-containing polymer-containing film which is a precursor of the base layer 1 and the gas barrier layer on the stage 104 and conveys the inside of the chamber 101. .. Water vapor is removed from the chamber 101 by exhaust gas, and the oxygen concentration is constantly adjusted by introducing an inert gas.

The stage 104 has a built-in heater and can heat the flexible base material F. The inside of the chamber 101 is divided into three zones by a shielding plate 106 in the transport direction V of the flexible base material F, and a plurality of Xe excimer lamps 102 are installed in the central vacuum ultraviolet irradiation zone. The Xe excimer lamp 102 is supported by a holder 103 having a built-in power supply and is controlled to be lit. By passing the flexible base material F on which the silicon-containing polymer-containing film is formed through the vacuum ultraviolet irradiation zone in which the Xe excimer lamp 102 is installed, the flexible base material F is irradiated with vacuum ultraviolet rays to be modified into a gas barrier layer. Can be done.

The silicon-containing polymer modified layer may be a single layer, but may have a laminated structure of two or more layers from the viewpoint of further enhancing the gas barrier property. When the laminated structure is adopted, the laminated structure may have different types of silicon-containing polymers, such as polysiloxane / polysilazane. By changing the type, it is possible to control not only the gas barrier property but also the interlayer adhesion.

[Grid 3]
The grid 3 shown in FIG. 4A is composed of a conductive thin metal wire. The shape of the grid 3 is not limited to a grid shape, and grids having various shapes such as a stripe shape, a honeycomb structure, and a mesh shape can be used. From the viewpoint of obtaining uniform conductivity regardless of the position, the surface emitting panel of the present invention preferably has a lattice shape.

The line width dw of the thin metal wires constituting the grid 3 is preferably in the range of 10 to 2000 μm. When the line width dw is 10 μm or more, sufficient conductivity can be obtained, and when the line width dw is 2000 μm or less, a decrease in transparency can be suppressed.

The height dh of the thin metal wires constituting the grid 3 is preferably in the range of 0.1 to 10.0 μm. If the height dh is 0.1 μm or more, sufficient conductivity can be obtained, and if it is 10.0 μm or less, current leakage can be prevented when used in an electronic device.

The resistivity of the grid 3 is 100 Ω / sq. It is preferably 20Ω / sq. More preferably: The resistivity of the grid 3 can be measured according to JIS K 7194-1994.

The aperture ratio of the grid 3 is preferably 80% or more from the viewpoint of enhancing transparency. The aperture ratio is the ratio of the area occupied by the area where the thin metal wires forming the grid are not arranged in the total area of the surface light emitting portion. For example, the aperture ratio of a grid in which fine metal wires having a line width of 1 mm and a line spacing of 10 mm are formed in a grid pattern is about 90%.

Examples of the conductive metal material that can be used for the fine metal wire of the grid 3 include gold, silver, copper, iron, cobalt, nickel, chromium, and alloys thereof. From the viewpoint of low resistance, silver or copper is preferable, and silver is particularly preferable.

The grid 3 is a coating liquid containing metal nanoparticles, a metal complex, etc. using the above metal material, which is subjected to a letterpress printing method, an intaglio printing method, a stencil printing method, a screen printing method, an inkjet printing method, an inkjet parallel line drawing method, etc. It can be formed by applying it to a desired shape. The inkjet parallel line drawing method utilizes the coffee stain phenomenon in which the coating liquid flows from the center to the end of the line when the coating liquid is applied linearly, and the end is solidified. This is a method of forming two parallel lines from a line. When forming a random mesh shape, as described in Japanese Patent Application Laid-Open No. 2005-530005, a coating liquid containing metal fine particles is applied and then dried to spontaneously form a disordered mesh shape of the metal fine particles. A method of forming is available. Of these, an inkjet printing method in which the shape can be easily controlled or an inkjet parallel line drawing method with high accuracy in forming fine lines is preferable.

The coating liquid containing the metal complex may have the metal forming the complex dispersed or dissolved in the solvent. As the solvent, ketocarboxylic acid, behenic acid, stearic acid and the like can be used. Further, Japanese Patent Application Laid-Open No. 2008-530001 also lists silver complex compounds derived by reacting a silver compound with an ammonium carbonate-based compound. The coating liquid may also contain an amine compound as a reducing agent.

When forming the grid, it is preferable to perform heat treatment within a range that does not damage the flexible base material F. As a result, metal materials such as metal nanoparticles and metal complexes are fused, and the conductivity of the grid is enhanced. For the heat treatment, a general heating method using an oven or a hot plate can be used. Further, local heat treatment may be performed by flash pulse light irradiation treatment, microwave treatment, plasma treatment, dielectric heating treatment, excima light irradiation treatment, ultraviolet treatment, infrared heater treatment, hot air heater treatment, or the like. It may be used in combination with heat treatment using an oven or the like.

As for the smoothness of the surface of the grid 3, the maximum cross-sectional height Rt (p) measured in accordance with JIS B 0601-2013 is preferably 500 nm or less, more preferably 200 nm or less, and 100 nm or less. More preferred. The higher the smoothness, the better the yield and continuous driveability of the organic EL element when used as an electrode.

[First electrode 4]
The first electrode 4 is also referred to as an anode or an anode, and as shown by an example in FIG. 6, the grid 3 is formed on the gas barrier layer 2, and the first electrode 4 is formed so as to cover the grid 3. Has been done. Alternatively, the first electrode 4 may be formed on the gas barrier layer 2, and the grid 3 may be formed on the first electrode 4. It is preferable that the first electrode 4 is mainly composed of a conductive polymer, a carbon material, a metal nanomaterial, or a mixture thereof, and can be formed by a wet coating method or an inkjet printing method.

The thickness of the first electrode layer 4 can be in the range of 30 to 2000 nm. From the viewpoint of increasing conductivity, the thickness is preferably 100 nm or more. From the viewpoint of enhancing the smoothness of the surface, the thickness is preferably 200 nm or more, and from the viewpoint of enhancing the transparency, the thickness is more preferably 1000 nm or less.

(Conductive polymer)
In the present invention, as an example of the conductive polymer applicable to the formation of the first electrode, a π-conjugated conductive polymer containing a polyanion can be mentioned.

Examples of the π-conjugated conductive polymer applicable to the present invention include polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylene vinylenes, and polyazulenes. Examples thereof include polyparaphenylenes, polyparaphenylene sulfides, polyisothianaphenes, polythiazyl and the like. Among them, polythiophenes or polyanilines are preferable, and polyethylenedioxythiophene is more preferable, from the viewpoint of enhancing conductivity, transparency, stability and the like.

The π-conjugated conductive polymer can be easily produced by chemically oxidatively polymerizing a precursor monomer forming the π-conjugated conductive polymer in the presence of an oxidizing agent, an oxidation catalyst and a polyanion. The precursor monomer used for forming a π-conjugated conductive polymer has a π-conjugated system in the molecule, and also has a π-conjugated system in the main chain when polymerized by the action of an oxidizing agent. Examples of such precursor monomers include pyrroles, thiophenes, anilines, and derivatives thereof.

Specific examples of the precursor monomer include pyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-Dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole , 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3 -Butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3 -Cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3 -Heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3-octadecyloxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene , 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene , 3,4-Didodecyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylene dioxythiophene, 3,4-butendioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl- 4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, aniline, 2-methylaniline, 3-isobutylaniline , 2-Aniline sulfonic acid, 3-Aniline Examples include sulfonic acid.

Polyanions are substituted or unsubstituted polyalkylenes, substituted or unsubstituted polyalkenylenes, substituted or unsubstituted polyimides, substituted or unsubstituted polyamides, substituted or unsubstituted polyesters, or copolymers thereof. It is a compound composed of a structural unit having an anionic group and a structural unit having no anionic group. The polyanion solubilizes or disperses the π-conjugated conductive polymer in a solvent, and the anionic group of the polyanion functions as a dopant for the π-conjugated conductive polymer, and the conductivity and heat resistance of the π-conjugated conductive polymer. Improve sex.

The anionic group of the polyanion may be a functional group capable of chemically oxidizing a π-conjugated conductive polymer, but from the viewpoint of facilitating production and improving stability, a monosubstituted sulfate group is used. Substituted phosphate ester groups, phosphate groups, carboxy groups, sulfo groups and the like are preferable. Of these, a sulfo group, a monosubstituted sulfate group or a carboxy group is more preferable from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer.

Specific examples of the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, ethyl acrylate poly acrylate, butyl sulfonic acid poly acrylate, poly-2-acrylamide-2-methyl propane sulfonic acid, and polyisoprene sulfonic acid. Examples thereof include acids, polyvinylcarboxylic acids, polystyrene carboxylic acids, polyallylcarboxylic acids, polyacrylic carboxylic acids, polymethacrylcarboxylic acids, poly-2-acrylamide-2-methylpropanecarboxylic acids, polyisoprenecarboxylic acids, and polyacrylic acids. .. Further, these homopolymers may be used, or two or more kinds of copolymers may be used.

Further, a fluorinated polyanion having a fluorine atom in the molecule can also be used. Specific examples thereof include Nafion (manufactured by DuPont) containing a perfluorosulfonic acid group, Flemion (manufactured by Asahi Glass Co., Ltd.) made of perfluoro vinyl ether containing a carboxylic acid group, and the like. The fluorinated polyanion is preferable when used in combination with the non-fluorinated polyanion because a transparent electrode having a hole injection function can be integrally formed and productivity is increased.

The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of improving the solubility and conductivity in the solvent.

The ratio of the π-conjugated conductive polymer to the polyanion in the conductive polymer, that is, the mass ratio of the π-conjugated conductive polymer: polyanion can be in the range of 1: 1 to 1:20, and the conductivity and From the viewpoint of enhancing dispersibility, the range is preferably in the range of 1: 2 to 1:10.

Commercially available products may be used as the conductive polymer. For example, as a commercially available product of the conductive polymer composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (hereinafter, abbreviated as PEDOT / PSS), Heraeus's Clevios series, Aldrich's PEDOT-PSS 483095, 560596, Nagase Polymer's Denatron series, and the like. Further, as a commercially available product of polyaniline, ORMECON series manufactured by Nissan Chemical Industries, Ltd. or the like can be used.

(Non-conductive polymer)
From the viewpoint of enhancing transparency, the first electrode 4 preferably contains a non-conductive polymer together with the conductive polymer described above, and the non-conductive polymer is at least one of a self-dispersing polymer and a hydroxy group-containing polymer. It is more preferable to contain one. By using a non-conductive polymer, the content of the conductive polymer can be reduced without impairing the conductivity of the first electrode 4, and a transparent electrode having both high conductivity and transparency can be used as the first electrode. Obtainable.

<Autocovariant polymer>
The self-dispersing polymer that can be used in combination with the conductive polymer has a dissociative group, and the colloidal particles formed by the self-dispersing polymer do not aggregate even in the absence of a surfactant or emulsifying agent that assists micelle formation. , A self-dispersing polymer is a non-conductive polymer that can be dispersed in an aqueous medium by itself. When the self-dispersing polymer has high transparency, the transparency of the first electrode 4 can be enhanced, which is preferable.

The amount of the self-dispersing polymer used can be in the range of 50 to 1000% by mass with respect to the conductive polymer.

The main skeleton of the self-dispersing polymer is polyethylene, polyethylene-polyvinyl alcohol, polyethylene-polyvinyl acetate, polyethylene-polyethylene, polybutadiene, polybutadiene-polystyrene, polyamide (nylon), polyvinylidene chloride, polyester, polyacrylate, polyacrylate- Polyester, Polyacrylate-Polyethylene, Polyvinyl Acetate, Polyethylene-Polyester, Polyethylene-Polyether, Polyester-Polyester, Polyester-Polyester, Silicone, Silicone-Polyester, Silicone-Polyacrylate, Vinylidene Polyfluoride-Polyacrylate, Polyfluoroolefin -Polyethylene ether and the like. Further, a copolymer using these skeletons as a base and further using other monomers may be used. Of these, a polyester resin emulsion having an ester skeleton, a polyester-acrylic resin emulsion, an acrylic resin emulsion having an acrylic skeleton, or a polyethylene resin emulsion having an ethylene skeleton is preferable.

Commercially available self-dispersing polymers include, for example, Yodosol AD-176, AD-137 (above, acrylic resin: manufactured by Henkel Japan Ltd.), Byronal MD-1200, MD-1245, MD-1500 (above, polyester resin: above). (Manufactured by Toyo Boseki Co., Ltd.), Plus Coat RZ570, Plus Coat Z561, Plus Coat Z565, Plus Coat Z687, Plus Coat Z690 (all polyester resin: manufactured by Reciprocal Chemical Co., Ltd.) and the like can be used. The self-dispersing polymer dispersion liquid containing a dissociative group that can be dispersed in the aqueous medium can be used alone or in combination of two or more.

<Hydroxy group-containing polymer>
The hydroxy group-containing polymer is a non-conductive polymer having a hydroxy group. The ratio of the conductive polymer to the hydroxy group-containing polymer in the first electrode 4, that is, the mass ratio of the conductive polymer: the hydroxy group-containing polymer is preferably in the range of 100:30 to 100: 900 to prevent current leakage. However, from the viewpoint of enhancing transparency, it is more preferably in the range of 100: 100 to 100: 900.

Examples of the hydroxy group-containing polymer include polymers containing structural units represented by the following general formula (1).

上記一般式（１）において、Ｒは、水素原子又はメチル基を表す。−Ｑ−は、−Ｃ（＝Ｏ）Ｏ−、又は−Ｃ（＝Ｏ）ＮＲｄ−を表し、Ｒｄは、水素原子又はアルキル基を表す。Ａは、置換もしくは無置換のアルキレン基、又は−（ＣＨ_２ＣＨＲｅＯ）_ｘＣＨ_２ＣＨＲｅ−を表し、Ｒｅは、水素原子又はアルキル基を表す。ｘは、平均繰り返しユニット数を表す。

In the above general formula (1), R represents a hydrogen atom or a methyl group. -Q- represents -C (= O) O- or -C (= O) NRd-, and Rd represents a hydrogen atom or an alkyl group. A represents a substituted or unsubstituted alkylene group, _{or-(CH 2} CHReO) _x CH ₂ CHRe-, and Re represents a hydrogen atom or an alkyl group. x represents the average number of repeating units.

The hydroxy group-containing polymer has a wavelength range of 2.5 to 3.0 μm, which is the same as that of infrared rays, because the solvent can be easily removed when infrared rays are used to dry the coating film in the step of forming the first electrode 4. It is preferable to have absorption with an absorbance of 0.1 or more. The absorbance here refers to the absorbance in the coating film having the thickness of the first electrode 4 to be formed.

(Carbon material)
Examples of the carbon material applicable to the formation of the first electrode 4 include graphene, carbon nanotubes, fullerenes and the like. Each of these carbon materials may be used alone, or a plurality of types may be used in combination. Further, the first electrode formed of the carbon material may be a single layer or may have a multi-layer structure composed of a plurality of layers having the same or different carbon materials. The thickness of the first electrode 4 formed of the carbon material can be in the range of 10 nm to 10 μm.

<Graphene>
Graphene is a sheet of carbon atoms bonded in a honeycomb structure, and by transferring this sheet onto, for example, a gas barrier layer, a first electrode composed of carbon can be formed. Examples of the graphene production method include a method of applying graphene oxide described in JP2011-241479 to reduce graphene, a method of using epitaxial growth on a SiC substrate, and thermal CVD using Cu, Ni, or the like as a catalyst metal. It can be produced by applying a known method such as a method for producing graphene or a method for producing graphene on a non-metal substrate such as sapphire.

<carbon nanotube>
Carbon nanotubes are carbon fibers made of hollow graphene. Carbon nanotubes can be produced by catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure to grow in a gas phase. .. As the fullerene, fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes and the like can be used. When carbon nanotubes or fullerenes are used, a first electrode composed of carbon nanotubes can be formed by preparing a coating liquid containing them and coating the coating liquid on the gas barrier layer.

(Metal nanomaterials)
The metal nanomaterial applicable to the formation of the first electrode is a metal material having a size of nanoscale, and is also called a nanotube, nanowire, nanofiber or the like depending on the shape. Examples of the type of metal include silver (Ag), aluminum (Al), copper (Cu), gold (Au), tungsten (W), molybdenum (Mo), alloys thereof and the like. Of these, silver is preferable because it has low resistance, high conductivity, and is easy to process into a desired shape.

When the first electrode is formed of a metal nanomaterial, it can be formed by preparing a coating liquid containing the metal nanomaterial and applying it on the gas barrier layer. The thickness of the first electrode formed of the metal nanomaterial can be in the range of 10 nm to 10 μm.

[First electrode wiring 11]
In the surface light emitting panel of the present invention, a plurality of organic ELs arranged at separated positions are electrically connected via the first electrode wiring 11 as shown in FIGS. 2 and 3. Is one of the features.

The first electrode wiring 11 has a form in which the first electrode 4 is extended to a non-light emitting region, and is electrically connected to each other by connecting to the first electrode of an adjacent organic EL element.

Therefore, the constituent material of the first electrode wiring 11 is the same as the material used for forming the first electrode described above.

[Organic functional group 6]
The following configurations can be mentioned as typical configurations of the organic functional layer group in the organic EL device according to the present invention. In the configuration shown below, the first electrode and the second electrode are described together for convenience in order to show the configuration of the entire organic EL element. The composition of the organic functional group shown below is an example thereof, and the composition of the organic functional group applicable to the present invention is not limited thereto.

(1) (1st electrode) / light emitting layer / (2nd electrode)
(2) (1st electrode) / light emitting layer / electron transport layer / (2nd electrode)
(3) (1st electrode) / hole transport layer / light emitting layer / (2nd electrode)
(4) (1st electrode) / hole transport layer / light emitting layer / electron transport layer / (2nd electrode)
(5) (1st electrode) / hole transport layer / light emitting layer / electron transport layer / electron injection layer / (second electrode)
(6) (1st electrode) / hole injection layer / hole transport layer / light emitting layer / electron transport layer / (second electrode)
(7) (1st electrode) / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / (second electrode)
In each organic functional layer according to the present invention, there is no particular limitation on the specific structure, forming method, etc., and known structures, materials, and forming methods can be applied. For example, paragraph numbers [0014] to [0121] of JP2013-089608, paragraph numbers [0065] to [0262] of JP2014-120334, paragraph numbers of JP2015-201508. The contents described in [0044] to [0118] and the like can be referred to.

[Second electrode 7]
The second electrode 7 is also referred to as a cathode or a cathode, and as the material for forming the second electrode, a conductive polymer, a carbon material, a metal nanomaterial, or a mixture thereof that can be used for forming the first electrode described above is used. Although it can be mentioned, it is particularly preferable to form the second electrode using a metal nanomaterial.

The metal nanomaterial applicable to the formation of the second electrode 7 is a metal material having a size of nanoscale, and is also called nanoparticles, nanotubes, nanowires, nanofibers or the like depending on the shape. Examples of the type of metal include silver (Ag), aluminum (Al), copper (Cu), gold (Au), tungsten (W), molybdenum (Mo), alloys thereof and the like. Of these, silver is preferable because it has low resistance, high conductivity, and is easy to process into a desired shape.

The second electrode can be formed by preparing a coating liquid containing a metal nanomaterial, coating it on the organic functional layer group 6, and drying it. The thickness of the second electrode 7 formed of the metal nanomaterial can be in the range of 10 nm to 10 μm.

When forming the second electrode, it is preferable to perform heat treatment (annealing treatment) within a range that does not damage the organic functional layer group 6 located at the lower part. As a result, the fusion of metal materials such as metal nanoparticles progresses, and the conductivity of the second electrode increases. For the heat treatment, a general heating method using an oven or a hot plate can be used. Further, local heat treatment may be performed by flash pulse light irradiation treatment, microwave treatment, plasma treatment, dielectric heating treatment, excima light irradiation treatment, ultraviolet treatment, infrared heater treatment, hot air heater treatment, or the like. It may be used in combination with heat treatment using an oven or the like.

[Insulation layer 5]
Various insulating materials can be used as the material for forming the insulating layer 5 according to the present invention described in FIG. 4B, but an inorganic oxide film having a high relative permittivity is particularly preferable. Examples of inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium titanate zirate, lead titanate zirate, lead lanthanum titanate, and strontium titanate. , Barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, bismus strontium tantalate, bismuth niobate tantarate, trioxide yttrium, etc., among which the oxidation is preferable. Silicon, aluminum oxide, tantalum oxide, titanium oxide. Inorganic nitrides such as silicon nitride and aluminum nitride can also be preferably used.

Examples of the method for forming the insulating layer composed of the inorganic oxide film include a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and an inkjet printing method. Wet forming methods such as the method by patterning of the above can be mentioned and can be used depending on the material. Of these, the inkjet printing method is preferable.

Further, an organic compound can be mentioned as a material for forming the insulating layer 5 according to the present invention, and examples of the organic compound include photocuring of polyimide, polyamide, polyester, polyacrylate, photoradical polymerization system, and photocationic polymerization system. It is also possible to use a sex resin, a copolymer containing an acrylonitrile component, a polyvinylphenol, a polyvinyl alcohol, a novolak resin, and a phosphazene compound containing a cyanoethylpurrane, a polymer, and an elastomer. Moreover, as a commercial product, selvinus manufactured by Daicel Corporation and the like can be mentioned.

[Encapsulation layer]
In the present invention, a sealing structure is formed by a sealing layer around the peripheral portion of the organic EL unit from the first electrode to the second electrode constituting the organic EL element.

The sealing layer may be configured such that a common sealing layer is formed in a plurality of organic EL elements, or an independent sealing layer is formed for each organic EL element.

As the constituent material and the forming method of the sealing layer, the material such as the silicon-containing polymer described in the above-mentioned formation of the gas barrier layer and the forming method thereof can be similarly applied.

As shown in the related figures, the sealing layer according to the present invention is preferably composed of a first sealing layer 8 and a second sealing layer 9. The first sealing layer 8 and the second sealing layer 9 may be formed of the same material or may be formed of different materials.

For example, a method in which the first sealing layer 8 is formed of polyorganosiloxane, polydimethylsiloxane (abbreviation: PDMS), or the like, and the second sealing layer is formed of perhydropolysilazane (abbreviation: PHPS) can be mentioned as an example. it can.

[Transparent hygroscopic layer]
In order to improve the sealing performance of the sealing layer, the transparent hygroscopic agent layer 16 may be installed.

FIG. 8 shows an example of a schematic cross-sectional view of the surface emitting panel having the configuration shown in FIG. 6 in which a transparent hygroscopic agent layer is further incorporated.

As shown in FIG. 8, when the transparent hygroscopic agent layer 16 is installed in the surface emitting panel, it is preferably installed between the first sealing layer 8 and the second sealing layer 9.

The transparent hygroscopic agent layer 16 is composed of a hygroscopic compound. For example, a configuration consisting of only a hygroscopic compound or a configuration in which particles containing a particulate hygroscopic compound or a hygroscopic compound are dispersed in a binder resin can be mentioned.

The hygroscopic compound can be used without particular limitation as long as it is a compound having a function of adsorbing water. The hygroscopic compound is preferably a compound that can chemically adsorb water and maintains a solid state even after adsorbing water.

Examples of the hygroscopic compound used in the transparent hygroscopic agent layer 16 include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, etc.) and sulfates (for example, lithium sulfate, sodium sulfate, calcium sulfate). , Magnesium sulfate, etc.), metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, etc.), perchlorates (eg, barium perchlorate, magnesium perchlorate, etc.) and the like. Further, a metal alkoxide can also be used. For example, aluminum alkoxide, titanium alkoxide, alkoxysilane and the like can be mentioned.

As the binder resin applied to the formation of the transparent hygroscopic agent layer 16, it is preferable not to inhibit the water adsorption action of the hygroscopic compound, and it is preferable to use a material having high gas permeability. Examples of the binder resin include polymer materials such as polyolefin-based, polyacrylic-based, polyacrylonitrile-based, polyamide-based, polyester-based, epoxy-based, polycarbonate-based, and fluorine-based.

As a method for producing the transparent hygroscopic layer 16, it is preferable to apply a method for producing the transparent hygroscopic layer 16 by a coating method or an inkjet printing method. From the viewpoint of production suitability and moisture absorption performance, a method of synthesizing an organic-inorganic hybrid compound by using a metal alkoxide solution as a raw material, generally called a sol-gel method, by hydrolysis of the metal alkoxide and a subsequent polycondensation reaction to form a film. Is preferable. The method of dissolving the metal alkoxide in the excess fluorinated alcohol is preferable because the sol-gel reaction rate can be relaxed and the stability of the coating liquid can be improved.

Examples of the fluorinated alcohol include 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, and the like. Examples thereof include 2,2,3,3,4,5,5-octafluoropentanol. For example, by adding a very small amount of water to a 3 mass% dehydrated tetrafluoropropanol solution of titanium tetraisopropoxide (Ti (OiPr) ₄ ), a partially advanced sol-gel reaction is applied, and a solvent is applied. A production method that promotes the sol-gel reaction on the surface by irradiating with ultraviolet light after drying and removing is preferable.

The transparent hygroscopic agent layer 16 formed by this method functions as a transparent hygroscopic agent layer because unreacted metal fluorinated alkoxide remains inside. Furthermore, since the fluorinated alcohol generated by reacting with the water molecules that have entered the layer is water repellent, in addition to the original hygroscopicity, a water repellent function is added, and a synergistic effect is exerted on the sealing property. , Has features not found in conventional desiccants.

The film thickness of the transparent hygroscopic layer 16 is in the range of 10 nm to 100 μm in the dry film, more preferably in the range of 0.1 to 1 μm in order to exhibit the effect.

[Alpet AP]
In the present invention, as shown in FIG. 9, an alpette AP can also be applied as a sealing member, for example, a second sealing layer.

Examples of Alpet AP, which is a polyethylene terephthalate film on which aluminum (Al) is vapor-deposited, which can be applied to the present invention, include Alpet 12/34 manufactured by Asia Aluminum Co., Ltd. and 9-100 (aluminum foil: 9 μm) manufactured by Panac Co., Ltd. , PET: 100 μm), 9-125K (aluminum foil: 9 μm, PET: 125 μm), 10-75 (aluminum foil: 10 μm, PET: 75 μm), 12-50 (aluminum foil: 12 μm, PET: 50 μm), 12- 188 (aluminum foil: 12 μm, PET: 188 μm), 20-75 (aluminum foil: 20 μm, PET: 75 μm), 20-100 (aluminum foil: 20 μm, PET: 100 μm), 30-188 (aluminum foil: 30 μm, PET) 188 μm), “Alpet 1N30” manufactured by Tokai Toyo Aluminum Sales Co., Ltd., “Alpet 3025” manufactured by Fukuda Metal Co., Ltd., “ALPET 1025” manufactured by Daido Kako Co., Ltd., and the like.

[Encapsulating resin layer 15]
When Alpet AP is applied as the second sealing layer, it is preferable to provide the sealing resin layer 15 as the first sealing layer. Examples of the material constituting the resin sealing layer 15 include a photocurable or thermosetting resin having a reactive vinyl group of an epoxy-based, acrylic acid-based oligomer, or methacrylic acid-based oligomer, 2-cyanoacrylic acid ester, and the like. Moisture curable resin and the like.

[Adhesive layers 12A and 12B]
Examples of the pressure-sensitive adhesive material applicable to the formation of the pressure-sensitive adhesive layers 12A and 12B according to the present invention include a hydrophilic acrylic polymer-based pressure-sensitive adhesive represented by a polyacrylic acid-based pressure-sensitive adhesive, a polyvinyl acetal-based pressure-sensitive adhesive, and a polyvinyl alcohol-based pressure-sensitive adhesive. Agents, polyvinyl alcohol adhesives, vinyl acetate adhesives, rubber adhesives (eg, natural rubber, synthetic rubber, styrene-isoprene-styrene block copolymer, isoprene rubber, polyisobutylene (PIB), styrene-butadiene- (Styrene block copolymer, styrene-butadiene rubber, polybutene, etc.) can be mentioned.

The thickness of the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive material is not particularly limited, but is preferably selected within the range of 0.1 to 10 μm.

[Protective member 13]
The protective members 13, 13A and 13B shown in FIGS. 10A, 10B and 11A and 11B are not particularly limited, but the thin film glass, the resin film and the metal foil described in the above description of the flexible base material F are used. Fabrics (eg, fabrics, textiles, etc.), paper, elastomers (rubber fabrics, etc.) and the like can be applied in the same manner, and may be transparent or opaque.

Further, like the first protective member 13 shown in FIGS. 10A and 10B and the second protective member 13B shown in FIGS. 11A and 11B, the adhesive layer surface is peeled off, and for example, an installation member such as paper or cloth. When applied to the application of attaching a surface emitting panel to a wall surface, window glass, or the like, it is preferable that these protective members function as a separator (isolation sheet). For example, a base material such as polyester, polyethylene, polypropylene, or paper coated with silicon, a polyalkylene coat, or a fluororesin can be used, but the polyester film is coated with silicon from the viewpoint of dimensional stability, smoothness, and peeling stability. Is preferable.

The thickness of the protective member is preferably in the range of 10 to 200 μm, more preferably 20 to 100 μm.

<< Manufacturing method of surface emitting panel >>
Generally, a surface emitting panel provided with an organic EL element includes, for example, a dry forming method using a chemical vapor deposition method, a vacuum deposition method, or the like, a spin coating method, a casting method, or an LB method (Langmuir Brodgett method). It can be formed by applying a known thin film forming method such as a wet coating method such as an inkjet printing method, but in the method for producing a surface emitting panel of the present invention, it is formed on one surface side of a flexible base material. At least, the gas barrier layer, the first electrode, the organic functional layer group, the second electrode, and the sealing layer are laminated by a wet coating method or an inkjet printing method to produce a surface emitting panel.

[Method of forming surface emitting panel]
The present invention is characterized in that a surface emitting panel is manufactured by a wet coating method or an inkjet printing method.

(Wet coating method)
As wet coating methods other than the inkjet printing method applicable to the present invention, spin coating method, casting method, screen printing method, die coating method, blade coating method, roll coating method, spray coating method, curtain coating method, LB method ( The Langmuir-Bloget method) and the like are mentioned, and the die coating method, the roll coating method, the spray coating method and the like are preferable from the viewpoint of easy to obtain a uniform thin film and high productivity.

(Inkjet printing method)
In the production of the surface emitting panel of the present invention, in particular, it is possible to apply the inkjet printing method to at least the formation of the gas barrier layer, the first electrode, the organic functional layer group, the second electrode and the sealing layer. It is preferable in that a plurality of organic EL elements having a small area can be efficiently formed at an arbitrary position on the panel.

Hereinafter, the manufacturing flow of the inkjet head used in the inkjet printing method, the injection conditions of ink droplets, the inkjet recording method and recording apparatus, and the specific surface emitting panel inkjet printing method will be described with reference to the drawings.

<Inkjet head>
The inkjet head used in the inkjet printing method may be an on-demand method or a continuous method. The discharge method includes an electric-mechanical conversion method (for example, single cavity type, double cavity type, bender type, piston type, shared mode type, shared wall type, etc.) and an electric-heat conversion method (for example, thermal). Specific examples include an inkjet type, a bubble jet (registered trademark) type, etc.), an electrostatic attraction method (for example, an electric field control type, a slit jet type, etc.), and a discharge method (for example, a spark jet type, etc.). However, any discharge method may be used. Further, as the printing method, a serial head method, a line head method, or the like can be used without limitation.

<Ink drop size>
In forming each constituent layer, the volume of ink droplets ejected from the inkjet head is preferably in the range of 0.5 to 100 pL. It is more preferably in the range of 2 to 20 pL from the viewpoint that the coating unevenness of the cambium is small and the printing speed can be increased. The volume of the ink droplet can be appropriately adjusted to a desired condition by adjusting the applied voltage or the like.

<Printing method>
The printing method by the inkjet printing method includes a one-pass printing method and a multi-pass printing method. The one-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged in a predetermined printing area and printing is performed by one head scan. On the other hand, the multi-pass printing method (also referred to as a serial printing method) is a method of printing a predetermined print area by a plurality of head scans.

In the one-pass printing method, it is preferable to use a wide head in which nozzles are arranged side by side over a width equal to or larger than a desired coating pattern width. When forming a plurality of independent coating patterns whose patterns are not continuous with each other on the same substrate, a wide head having at least the width of each coating pattern may be used.

FIG. 13 is a schematic view showing an example of a method for forming an organic EL element using an inkjet printing method of a one-pass printing method.

FIG. 13 shows a gas barrier layer, a first electrode, an organic functional layer group, a second electrode, and a sealing layer constituting an organic EL element on a flexible base material F using an inkjet printer provided with an inkjet head 30. An example of a method of sequentially ejecting ink containing each forming material to form a plurality of independent forms of an organic EL element EL is shown.

As shown in FIG. 13, while continuously transporting the flexible base material F, the ink jet head 30 sequentially ejects ink containing an organic EL element forming material as ink droplets to obtain a desired constituent layer (gas barrier layer). , 1st electrode, organic functional layer group, 2nd electrode and sealing layer) to form an organic EL element EL.

The inkjet head 30 applicable to the method for manufacturing a surface emitting panel of the present invention is not particularly limited. For example, the ink pressure chamber has a diaphragm provided with a piezoelectric element, and the ink pressure chamber using the diaphragm has a diaphragm. It may be a shear mode type (piezo type) head that ejects ink liquid by a pressure change, or it has a heat generating element, and the heat energy from this heat generating element causes a sudden volume change due to the boiling of the ink liquid film from the nozzle. It may be a thermal type head that ejects ink liquid.

An ink jet liquid supply mechanism for ejection is connected to the inkjet head 30. The ink liquid is supplied by the tank 38A. In this example, the tank liquid level is kept constant so that the ink liquid pressure in the inkjet head 30 is always kept constant. As a method, the ink liquid overflows from the tank 38A and is returned to the tank 38B by natural flow. The ink liquid is supplied from the tank 38B to the tank 38A by the pump 31, and the liquid level of the tank 38A is controlled to be stable according to the injection conditions.

The ink liquid is returned from the pump 31 to the tank 38A after passing through the filter 32. As described above, it is preferable that the ink liquid is passed through a filter medium having an absolute filtration accuracy or a quasi-absolute filtration accuracy of 0.05 to 50 μm at least once before being supplied to the inkjet head 30.

Further, in order to perform cleaning work, liquid filling work, and the like of the inkjet head 30, ink liquid can be forcibly supplied from the tank 36 and cleaning solvent from the tank 37 can be forcibly supplied to the inkjet head 30 by the pump 39. Such tank pumps may be divided into a plurality of such tank pumps with respect to the inkjet head 30, a branch of a pipe may be used, or a combination thereof may be used. In FIG. 12, the pipe branch 13 is used. Further, in order to sufficiently remove the air in the inkjet head 30, the ink liquid may be drawn out from the air bleeding pipe and sent to the waste liquid tank 34 while forcibly sending the ink liquid from the tank 36 to the inkjet 30 by the pump 39. ..

14A and 14B are schematic external views showing an example of the structure of the inkjet head applicable to the inkjet printing method.

14A is a schematic perspective view showing the inkjet head 100 applicable to the present invention, and FIG. 14B is a bottom view of the inkjet head 100.

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

Further, the cap receiving plate 57 shown in FIG. 14B is formed as a substantially rectangular plate whose outer shape is long in the left-right direction corresponding to the shape of the cap receiving plate mounting portion 62, and a plurality of nozzles are formed in the substantially central portion thereof. In order to expose the arranged nozzle plate 61, a long nozzle opening 71 is provided in the left-right direction. Further, regarding the specific structure inside the inkjet head shown in FIG. 14A, for example, FIG. 2 and the like described in Japanese Patent Application Laid-Open No. 2012-140017 can be referred to.

Representative examples of the inkjet head are shown in FIGS. 14A and 14B. In addition, for example, JP-A-2012-140017, JP-A-2013-010227, JP-A-2014-058171 and JP-A-2014- 097644, 2015-142979, 2015-142980, 2016-002675, 2016-002682, 2016-107401, 2017-109476 An inkjet head having the configuration described in Japanese Patent Application Laid-Open No. 2017-177626 can be appropriately selected and applied.

[Manufacturing flow of surface emitting panel]
Hereinafter, as an example of a method for manufacturing a surface emitting panel, a process flow for manufacturing the organic EL element EL represented by the cut surface AA shown in FIG. 6 by using an inkjet printing method will be described with reference to the drawings. ..

15 and 16 are schematic flow charts showing an example of a manufacturing process using the inkjet printing method of the organic EL element EL having the structure on the AA cut surface shown in FIG.

<Step 1: Formation of base layer>
By the method shown in FIG. 15a, an ink liquid for forming a base layer containing, for example, an ultraviolet curable resin is inkjet-inked at a position on the flexible base material F shown in FIG. 4A, which is the production flow diagram (top view). After ejecting from the head 30 to form a pattern, it is cured by irradiating with ultraviolet rays to form the base layer 1.

<Step 2: Formation of gas barrier layer>
Next, by the method shown in b of FIG. 15, a gas barrier layer forming ink liquid containing, for example, a silicon-containing polymer or the like is ejected from the inkjet head 30 at the position shown in FIG. 4A (top view) to form a pattern. Then, after the solvent was dried and removed, the modification treatment was performed by irradiating 172 nm vacuum ultraviolet light with an Xe excimer lamp in an environment in which the oxygen concentration and the water vapor concentration were controlled to form the gas barrier layer 2. To do.

<Step 3: Grid formation>
Next, by the method shown in c of FIG. 15, a grid forming ink liquid containing, for example, silver nanoparticles is applied from the inkjet head 30 to a predetermined position on the gas barrier layer 2 shown in FIG. 4A (top view). After discharging and forming a pattern of the grid 3 in a grid pattern, heat treatment is performed within a range that does not damage the flexible base material F to form the grid 3 having improved conductivity.

<Step 4: Formation of the first electrode>
Then, by the method shown in d of FIG. 15, a conductive polymer such as poly (3,4-ethylenedioxythiophene) is placed on the grid 3 at the predetermined light emitting position shown in FIG. 4A (top view). A first electrode forming ink solution containing a composite (PEDOT: PSS) of and polystyrene sulfonic acid is discharged from the inkjet head 30 to form a pattern, and then the solvent is dried and removed to form the first electrode 4. To do.

<Step 5: Formation of insulating layer>
Next, by the method shown in FIG. 15e, as described in FIG. 4A (top view), an ink for forming an insulating layer containing an insulating material is used, and the upper surface of the grid 3 excluding the electrode extraction portion is pressed by the inkjet head 30. After forming the pattern so as to cover it, the solvent is dried and removed, and a curing treatment suitable for the ink for forming the insulating layer is performed to form the insulating layer 5. At this time, as shown in FIG. 4B, a region for forming the organic functional layer group was provided as an opening in the next step.

<Step 6: Formation of organic functional group>
Next, by the method shown in FIG. 16a, as described in FIG. 4C (top view), each organic functional layer is placed on the first electrode 4 of the opening surrounded by the insulating layer 5 from the inkjet head 30. (For example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc.) After sequentially ejecting each organic functional layer group forming ink containing a forming material, the solvent is dried and removed. , Form the organic functional layer group 6.

<Step 7: Formation of the second electrode>
Next, in the method shown in FIG. 16b, as described in FIG. 5A (top view), the second electrode forming ink containing the second electrode forming material was used, and the second electrode was formed in a grid pattern from the inkjet head 30. After forming the electrode 7, the solvent is dried and removed, and heat treatment is performed within a range that does not damage the organic functional layer group 6 to form the second electrode 7. The AA cut surface is formed on the entire surface.

<Step 8: Formation of first sealing layer>
Then, by the method shown in c of FIG. 16, as described in FIG. 5B (top view), the first sealing layer forming material containing the first sealing layer forming material, for example, polydimethylsiloxane (abbreviation: PDMS) is formed. A pattern is formed on the second electrode 7 from the inkjet head 30 using the ink for coating the organic functional layer group 6 and the insulating layer 5, the solvent is dried and removed, and then ultraviolet light is irradiated. The first sealing layer 8 is formed by the modification treatment.

<Step 9: Formation of second sealing layer>
Then, by the method shown in d of FIG. 16, as described in FIG. 5C (top view), a second sealing layer forming material containing, for example, perhydropolysilazane (abbreviation: PHPS) is formed. A pattern is formed from the inkjet head 30 in a form that covers the first sealing layer 8 using the ink for ink jet, the solvent is dried and removed, and then an Xe excimer lamp is used in an environment in which the oxygen concentration and the water vapor concentration are controlled. The modification treatment can be performed by irradiating with vacuum ultraviolet light of 172 nm to form the second sealing layer 9, and a surface emitting panel containing an organic EL element can be formed.

Further, in order to improve the sealing performance of the sealing layer, the transparent hygroscopic agent layer 16 may be installed. When the transparent hygroscopic agent layer 16 is installed, it is preferable to install it between the first sealing layer 8 and the second sealing layer 9, as shown in FIG.

The surface light emitting panel of the present invention can realize a surface light emitting panel having both sealing performance and flexibility and having an organic EL element excellent in manufacturing ease. The surface light emitting panel of the present invention is a display device. , Display, illumination light source, etc. Can be suitably used as a surface emitter.

1 Underlayer 2 Gas barrier layer 3 Grid (Ag grid)
4 First electrode (anode)
5 Insulation layer 6 Organic functional layer group 7 Second electrode (cathode)
8 1st sealing layer 9 2nd sealing layer 10, 30, 100 Jet head 11 1st electrode wiring 12, 12A 1st adhesive layer 12B 2nd adhesive layer 13, 13A 1st protective member 13B 2nd protective member 14 Installation Member 15 Encapsulating resin layer 16 Transparent hygroscopic agent layer 31, 39 Pump 32 Filter 33 Piping branch 34 Waste liquid tank 35 Control unit 36, 37, 38A, 38B Tank 56 Housing 57 Cap receiving plate 59 Cover member 61 Nozzle plate 62 Cap receiving Plate mounting part 68 Mounting hole 71 Nozzle opening 81a 1st join 81b 2nd joint 82 3rd joint 100 Vacuum ultraviolet irradiation device 101 Chamber 102 Xe excimer lamp 104 Stage AP Alpet F Flexible base material L Luminous light LA Luminous area EL Organic EL element P surface light emitting panel V gap

Claims (5)

Surface emission having a plurality of organic electroluminescence devices in which at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode, and a sealing layer are laminated in this order on one surface side of the flexible base material. It ’s a panel,
The light emitting area per of the plurality of organic electroluminescent devices is 100 mm ² or less.
The gas barrier layer is independently provided for each organic electroluminescence element, and
A surface emitting panel characterized in that the plurality of organic electroluminescent elements are electrically connected via wiring. The surface emitting panel according to claim 1, wherein the sealing layer is independently provided for each organic electroluminescence element. The surface emitting panel according to claim 1 or 2, further comprising an adhesive layer adjacent to the sealing layer. The surface emitting panel according to any one of claims 1 to 3, wherein an adhesive layer is further provided on the surface of the flexible base material opposite to the surface having the organic electroluminescence element. .. A method for manufacturing a surface emitting panel according to any one of claims 1 to 4, wherein the surface emitting panel is manufactured.
The surface light emitting panel has at least a gas barrier layer, a first electrode, an organic functional layer group, a second electrode, and a sealing layer laminated on one surface side of a flexible base material by a wet coating method or an inkjet printing method. A method for manufacturing a surface light emitting panel, which is characterized in that the surface light emitting panel is manufactured.

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