JP2011141990A - Organic electroluminescent device and method of manufacturing the same, and organic electroluminescent display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: an organic electroluminescent device having a first optical path length-adjusting layer made of an organic material and a second optical path length-adjusting layer made of an inorganic material, and with durability improved; a method of manufacturing the organic electroluminescent device with its manufacturing process simplified; and an organic electroluminescent display. <P>SOLUTION: The organic electroluminescent device includes a reflecting metal layer, a translucent member, an organic electroluminescent element having at least a light-emitting layer and an optical path length-adjusting layer in at least a pixel area among a plurality of pixel areas corresponding to red, green and blue colors, respectively, and includes a resonant structure for resonating light emission from the organic electroluminescent element. The optical path length-adjusting layer consists of a first optical path length-adjusting layer made of light-transmissive resin, and a second optical path length-adjusting layer made of an inorganic material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention has a first optical path length adjusting layer made of an organic material and a second optical path length adjusting layer made of an inorganic material, an organic electroluminescent device with improved durability, and an organic electric field that simplifies the manufacturing process. The present invention relates to a method for manufacturing a light emitting device and an organic electroluminescent display.

  In recent years, thin and light flat panel displays have been used in a wide range of fields in place of cathode ray tubes (CRT), and their applications have been extended. This is because personal information terminals such as personal computers and network access-compatible mobile phones have been rapidly spread due to the development of information equipment and infrastructure for service networks centered on the Internet. In addition, the market for flat panel displays has been expanding to home TVs, which have traditionally been exclusive to CRTs.

  Among them, there is an organic electroluminescent element as a device that has attracted particular attention in recent years. An organic electroluminescent element is an element configured to emit light in response to an electric signal and to use an organic compound as a luminescent substance. Organic electroluminescent elements inherently have excellent display characteristics such as a wide viewing angle, high contrast, and high-speed response. In addition, since there is a possibility of realizing thin and light and high-quality display devices from small to large, it has been attracting attention as an element replacing CRT and LCD.

  Various full-color display devices using organic electroluminescent elements have been proposed. For example, as means for obtaining three basic colors of red (R), green (G), and blue (B) for full-color expression. There is a method of taking out only light of a specific wavelength to the outside of the organic electroluminescent element by combining multiple interference effects between the white organic electroluminescent element and the light reflecting film. This configuration employs a semi-transparent cathode for the upper electrode and a top emission configuration that achieves high color reproducibility, and a bottom emission configuration that uses a semi-transmissive or transparent lower electrode for the lower electrode and a dielectric multilayer mirror. is assumed. Further, a method of combining a color filter with a multi-interference structure has been studied for this kind of full-color display device.

For example, a first electrode made of a light reflecting material, an organic layer provided with an organic light emitting layer, a light translucent reflecting layer, and a second electrode made of a transparent material are sequentially stacked, and the organic layer becomes a resonance part. In the organic electroluminescent device, an organic electroluminescent device configured to satisfy the following formula is known, where λ is the peak wavelength of the spectrum of light to be extracted.
(2L) / λ + Φ / (2π) = m
Where L is an optical distance (optical path length), λ is a wavelength of light to be extracted, m is an integer, Φ is a phase shift, and the optical distance L is a positive minimum value. Constitute.
In a full-color display device in which a color filter is combined with a white organic electroluminescent display element of this type, the length of the optical path length L for each pixel is changed by changing the thickness of an anode made of an inorganic material such as ITO (Indium Tin Oxide). Are adjusted so that light of each color is extracted (see Patent Documents 1 and 2).

However, when an inorganic material such as ITO is used as the optical path length adjusting layer, there is a problem that the manufacturing process of the organic electroluminescent device becomes complicated, and the production cost is increased and the productivity is lowered.
The interference length adjusting film is laminated for each pixel by an organic material or inorganic material vapor deposition method using a metal mask. However, metal masks are expensive and difficult to deal with in the production of large area displays. By forming a film for adjusting the interference length, which has a different thickness for each RGB pixel, using a resist material by a photolithography process that has been proven in the production of a color filter with a larger area than before, a large area display Fabrication is possible.
On the other hand, when the interference length adjusting film is formed of an organic material, there is a problem that the durability of the organic electroluminescent device is reduced by a substance derived from the organic material. In this case, Patent Document 3 is provided with a passivation layer made of transparent SiO ₂ , but does not have a resonance structure and does not disclose or suggest the purpose of adjusting the interference length.

A process for manufacturing an organic electroluminescent device having an optical path length adjusting layer according to the prior art will be described below.
First, the reflective metal layer 2 is arranged on the substrate 1 corresponding to a plurality of pixels corresponding to red, green, and blue (see FIG. 13).
Next, an ITO film 10 is formed on the substrate on which the reflective metal layer 2 is disposed by sputtering, vapor deposition, or the like (see FIG. 14).
Next, a resist composition made of a curable resin is applied on the ITO film 10 to form a resist layer 20 (see FIG. 15).
In this way, with the reflective metal layer 2, the ITO film 10, and the resist layer 20 disposed on the substrate 1, the substrate 1 is covered with a mask 4 that can be partially shielded, and irradiated with light L, and then on one pixel. The resist layer 20 is selectively exposed to cure the resin (see FIG. 16).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 17).
In this state, an etching process is performed using the exposed resist layer 20 as a mask, and the ITO film 10 other than the ITO film 10 facing the resist layer 20 is removed (see FIG. 18).
Next, the remaining resist layer 20 on the ITO film 10 is peeled off so that the reflective metal layer 2 and the ITO film 10 are arranged on one pixel (see FIG. 19).

Next, in order to form multistage optical path lengths, the ITO film 10 is again deposited by sputtering, vapor deposition, or the like (see FIG. 20). In this state, in the pixel region where the reflective metal layer 2 and the ITO film 10 are arranged in the previous step, the ITO film 10 is deposited in an overlapping manner, and between the ITO film 10 on other pixels, An optical path length difference is formed.
Next, a resist composition made of a curable resin is applied again on the ITO film 10 to form a resist layer 20 (see FIG. 21).
In this way, a pixel region in which the reflective metal layer 2, the ITO film 10 and the resist layer 20 are disposed on the substrate 1 and covered with a mask 4 which can be partially shielded, and the ITO film 10 is deposited in an overlapping manner. The pixel region adjacent to the pixel region is exposed by irradiating light to cure the resin (see FIG. 22).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 23).
In this state, an etching process is performed using the exposed resist layer 20 as a mask, and the ITO film 10 other than the ITO film 10 facing the resist layer 20 is removed (see FIG. 24).
Next, the resist layer 20 on the remaining ITO film 10 is peeled off, and the pixel region having the ITO film 10 disposed on the substrate 1 so as to overlap the reflective metal layer 2, and the reflective metal layer 2 and ITO A pixel region having the film 10 is formed (see FIG. 25).

Next, in order to form another optical path length, the ITO film 10 is deposited again by sputtering, vapor deposition or the like (see FIG. 26). In this state, in the previous process, in the two pixel regions where the reflective metal layer 2 and the ITO film 10 are arranged, the ITO film 10 is deposited and deposited so as to have different optical path length differences. Above, the optical path length difference due to the thickness of the ITO film 10 layer is formed.
Next, a resist composition made of a curable resin is applied again on the ITO film 10 to form a resist layer 20 (see FIG. 27).
In this way, the reflective metal layer 2, the ITO film 10 and the resist layer 20 are arranged on the substrate 1, and the ITO film 10 is covered with a mask 4 that can partially shield light, and light is applied to the resist layer 20 on each pixel. Is exposed to light to cure the resin (see FIG. 28).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 29).
In this state, an etching process is performed using the exposed resist layer 20 as a mask to remove the ITO film 10 other than the ITO film 10 facing the resist layer 20 (see FIG. 30).
Next, the remaining resist layer 20 on the ITO film 10 is peeled off. In this way, in each pixel region on the substrate 1, an optical path length adjusting layer formed of the ITO film 10 having a different thickness is formed on the reflective metal layer 2 (see FIG. 31).

Next, an organic light emitting layer 7 and a translucent member 8 are laminated in this order on each optical path length adjustment layer in a state having optical path length adjustment layers formed of ITO films 10 having different thicknesses, and an organic electric field The light emitting device 400 is manufactured (see FIG. 32).
In such an organic electroluminescent device 400, the light emitted from the organic light emitting layer 7 corresponds to the optical path lengths d ₁ , d ₂ , and d ₃ of the ITO film 10 formed with different thicknesses, respectively. , Green, and red are extracted from the translucent member 8 as light having a wavelength corresponding to red. That is, the light emitted from the organic light emitting layer 7 is resonated between the translucent member 8 having the optical path lengths d ₁ , d ₂ , and d ₃ and the reflective metal layer 2, and the blue color corresponding to each optical path length. By increasing the light of green, red, and red wavelengths, it is possible to extract from the organic electroluminescent device 400 as blue, green, and red light.

  As described above, in the organic electroluminescent device having the optical path length adjusting layer, high-definition color display using the three primary colors of blue, green, and red is possible. As a material for forming the optical path length adjusting layer, an ITO film is used. In the case of using an inorganic material such as the optical path length difference, formation of a resist layer, etching process using the resist layer as a mask, and stripping of the resist layer are necessary. There is a problem in that the manufacturing process becomes complicated because it must be performed every time the length difference is formed.

Special table 2007-503093 gazette JP 2006-269329 A JP 2004-39311 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention has a first optical path length adjusting layer made of an organic material and a second optical path length adjusting layer made of an inorganic material, and an organic electroluminescence device with improved durability and a manufacturing process are simplified. An object of the present invention is to provide an organic electroluminescent device manufacturing method and an organic electroluminescent display.

Means for solving the problems are as follows. That is,
<1> Of a plurality of pixel regions corresponding to red, green, and blue, at least one pixel region includes a reflective metal layer, a translucent member, an organic electroluminescent element having at least a light emitting layer, and an optical path length adjustment. And an organic electroluminescent device having a resonance structure that resonates light emitted from the organic electroluminescent element,
The organic electroluminescent device is characterized in that the optical path length adjusting layer has a first optical path length adjusting layer made of a light-transmitting resin and a second optical path length adjusting layer made of an inorganic material.
<2> The organic electroluminescence device according to <1>, further including a second optical path length adjustment layer between the first optical path length adjustment layer and the organic electroluminescence element.
<3> The inorganic material in the second optical path length adjusting layer is at least one selected from SiO ₂ , Al ₂ O ₃ , SiON and ZrO _{2, according} to any one of <1> to <2>. Organic electroluminescent device.
<4> The organic electroluminescence device according to any one of <1> to <3>, wherein the thickness of the second optical path length adjustment layer is 5 nm to 30 nm.
<5> An organic electroluminescent display comprising the organic electroluminescent device according to any one of <1> to <4>.
<6> The organic electroluminescence display according to <5>, which is used as a flexible display.
<7> A light-transmitting resin material is formed on a substrate on which a reflective metal layer and a translucent member can be disposed in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue. A light-transmitting resin material film forming step;
A light-transmitting resin layer forming step of forming a light-transmitting resin layer by curing a region including the one pixel region out of the formed light-transmitting resin material;
A first optical path length adjusting layer forming step of developing the light transmissive resin layer after the curing reaction and forming a first optical path length adjusting layer;
A second optical path length adjustment layer forming step of forming a second optical path length adjustment layer made of an inorganic material between the first optical path length adjustment layer and the organic electroluminescent element constituting the one pixel region;
A method for producing an organic electroluminescent device, comprising:
<8> The method for producing an organic electroluminescent device according to <7>, wherein the light transmissive resin material is formed by any one of a vapor phase film forming method, spray coating, and ink jet coating.
<9> The method for producing an organic electroluminescent device according to any one of <7> to <8>, wherein the light transmissive resin material is a photoreactive resin composition.
<10> The method for producing an organic electroluminescent device according to <9>, wherein the photoreactive resin in the photoreactive resin composition has two or more reactive functional groups.
<11> The method for producing an organic electroluminescent device according to any one of <7> to <10>, wherein the second optical path length adjusting layer is formed by any one of a sputtering method and a vapor deposition method.
<12> The first optical path length adjusting layer is formed on a planarizing film, and the planarizing film is formed of the same light transmitting resin material as the light transmitting resin material of the first optical path length adjusting layer. <7> to <11> The method for producing an organic electroluminescent device according to any one of <11>.

  According to the present invention, various problems in the prior art can be solved, and an organic electric field having a first optical path length adjusting layer made of an organic material and a second optical path length adjusting layer made of an inorganic material has improved durability. A light emitting device, a method for manufacturing an organic electroluminescent device that simplifies the manufacturing process, and an organic electroluminescent display can be provided.

FIG. 1 is a schematic diagram (1) showing a manufacturing process of an organic electroluminescent device of the present invention. FIG. 2 is a schematic diagram (2) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 3 is a schematic view (3) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 4 is a schematic view (4) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 5 is a schematic view (5) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 6 is a schematic view (6) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 7 is a schematic view (7) showing the manufacturing process of the organic electroluminescent device of the present invention. FIG. 8 is a schematic view (8) showing the manufacturing process of the organic electroluminescent device of the present invention. FIG. 9 is a schematic diagram (9) showing a manufacturing process of the organic electroluminescent device of the present invention. FIG. 10 is a schematic diagram showing one configuration example of the organic electroluminescent device of the present invention. FIG. 11 is a schematic view showing another configuration example of the organic electroluminescent device of the present invention. FIG. 12 is a schematic view showing still another configuration example of the organic electroluminescent device of the present invention. FIG. 13 is a schematic diagram (1) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 14 is a schematic diagram (2) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 15 is a schematic view (3) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 16 is a schematic diagram (4) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 17 is a schematic diagram (5) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 18 is a schematic diagram (6) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 19 is a schematic view (7) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 20 is a schematic diagram (8) illustrating a manufacturing process of a conventional organic electroluminescent device. FIG. 21 is a schematic view (9) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 22 is a schematic diagram (10) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 23 is a schematic view (11) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 24 is a schematic view (12) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 25 is a schematic view (13) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 26 is a schematic view (14) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 27 is a schematic view (15) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 28 is a schematic view (16) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 29 is a schematic view (17) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 30 is a schematic diagram (18) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 31 is a schematic view (19) showing a manufacturing process of a conventional organic electroluminescent device. FIG. 32 is a schematic diagram (20) illustrating a configuration example of a conventional organic electroluminescent device.

(Organic electroluminescent device)
The organic electroluminescent device of the present invention is an organic electroluminescent device having a reflective metal layer, a translucent member, and at least a light emitting layer in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue. It has an element and an optical path length adjusting layer, and has a resonance structure that resonates light emitted from the organic electroluminescence element, and has a substrate and, if necessary, other members.

  In the organic electroluminescent device, light emitted from the organic light emitting layer emits light having wavelengths corresponding to blue, green, and red corresponding to the optical path length of the optical path length adjusting layer formed with different thicknesses. Although it is possible to take out, in each of the blue, green, and red pixel regions on the viewer side of the organic electroluminescence device, a color filter corresponding to each color is further arranged to provide a higher-definition full-color display. It may be possible.

<Optical path length adjustment layer>
The optical path length adjusting layer includes a first optical path length adjusting layer made of a light-transmitting resin that is an organic material, and a second optical path length adjusting layer made of an inorganic material.

-First optical path length adjustment layer-
The first optical path length adjusting layer is made of a light transmissive resin.
The light-transmitting resin is not particularly limited as long as it has a light-transmitting property and causes a curing reaction in the light-transmitting resin layer described later, and can be appropriately selected according to the purpose. For example, polyester, acrylic resin, methacrylic resin (in this specification, acrylic resin and methacrylic resin may be collectively referred to as acrylate polymer), methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorine Polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, Oren ring-modified polyester, acryloyl compound, a polysiloxane, or the like other organic silicon compounds. These may be used alone or in combination of two or more.

-Photo-curing resin (radical polymerizable monomer)-
As the light transmissive resin, among the exemplified compounds, a photocurable resin is preferable.
There is no restriction | limiting in particular as said photocurable resin, Although it can select suitably according to the objective, At least 1 radical polymerization represented by either the following general formula (1) and the following general formula (2) Is more preferable.
These radical polymerizable monomers preferably have two or more radical polymerizable functional groups. Two or more polymerizable functional groups are preferable in that they can be cross-linked three-dimensionally and the mechanical strength is improved.

In the general formula (1), ^{R 7} represents hydrogen or a methyl group, ^{R 8} represents a hydrogen atom, ^{L 1} is a substituted or unsubstituted alkylene group having 1 to 18 carbon atoms, carbon atoms 1 to 18 substituted or unsubstituted arylene groups, ether groups, imino groups, carbonyl groups, or a monovalent or higher valent linking group in which a plurality of these groups are bonded in series. m1 represents an integer of 1 to 6, and when m1 is 2 or more, R ⁷ and R ⁸ in each repeating unit may be the same or different.

However, the in Formula (2), ^{R 9} represents a hydrogen atom or a methyl ^{group, R 10} represents a hydrogen atom, ^{L 2} is a substituted or unsubstituted alkylene group having 1 to 18 carbon atoms, carbon A substituted or unsubstituted arylene group, an ether group, an imino group, a carbonyl group, or a monovalent or higher valent linking group in which a plurality of these groups are bonded in series is represented. m2 represents an integer of 1 to 6, and when m2 is 2 or more, R ⁹ and R ¹⁰ in each repeating unit may be the same or different.

As the photocurable resin, it is particularly preferable that an acrylate polymer composed of a radical polymerizable monomer having an ethylenically unsaturated double bond represented by the general formula (2) as a main component. Here, the main component means that the content of the polymerizable monomer constituting the light-transmitting resin layer, which will be described later, is the largest, and that it is 80% by mass or more.
Examples of the acrylate polymer include polymers having a structural unit represented by the following general formula (3).

However, in said general formula (3), Z is represented by the following general formula (a) or general formula (b) having a double bond group, and R in the following general formula (a) or (b) ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, * represents a position bonded to the carbonyl group of the general formula (3), and L represents an n-valent linking group. n shows the integer of 1-6. In the case where n is 2 or more, Z in each repeating unit may be the same or different from each other, but at least one Z is represented by the following general formula (a).

In the said General formula (3), 3-18 are preferable, as for carbon number of L, 4-17 are more preferable, 5-16 are still more preferable, and 6-15 are still more preferable.
When n is 2, L represents a divalent linking group. Examples of such a divalent linking group include an alkylene group (for example, 1,3-propylene group, 2,2-dimethyl-1 , 3-propylene group, 2-butyl-2-ethyl-1,3-propylene group, 1,6-hexylene group, 1,9-nonylene group, 1,12-dodecylene group, 1,16-hexadecylene group, etc.) , An ether group, an imino group, a carbonyl group, or a divalent residue in which a plurality of these divalent groups are bonded in series (eg, polyethyleneoxy group, polypropyleneoxy group, propionyloxyethylene group, butyroyloxypropylene group, caproyl) Oxyethylene group, caproyloxybutylene group, etc.). Among these, an alkylene group is particularly preferable.

In the general formula (3), L may have a substituent. Examples of the substituent that can substitute L include an alkyl group (for example, a methyl group, an ethyl group, and a butyl group). ), Aryl group (for example, phenyl group), amino group (for example, amino group, methylamino group, dimethylamino group, diethylamino group, etc.), alkoxy group (for example, methoxy group, ethoxy group, butoxy group, 2-ethylhexyl) Siloxy group etc.), acyl group (eg acetyl group, benzoyl group, formyl group, pivaloyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), hydroxy group, halogen atom (eg fluorine atom) , Chlorine atom, bromine atom, iodine atom), cyano group and the like.
Among these, as the substituent, a group having no oxygen-containing functional group is preferable, and examples of such a group include an alkyl group. That is, when n is 2, L is most preferably an alkylene group having no oxygen-containing functional group. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

  In the general formula (3), when n is 3, L represents a trivalent linking group. As an example of such a trivalent linking group, any hydrogen atom from the above divalent linking group can be used. Or a trivalent residue obtained by removing one, or an arbitrary hydrogen atom is removed from the above-mentioned divalent linking group, and an alkylene group, an ether group, a carbonyl group, and these two bonded in series A trivalent residue substituted with a valent group can be mentioned. Among these, a trivalent residue containing no oxygen-containing functional group obtained by removing one arbitrary hydrogen atom from an alkylene group is preferable. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

  In the general formula (3), when n is 4 or more, L represents a tetravalent or higher linking group, and examples of such a tetravalent or higher linking group are also given. Preferred examples are also given. In particular, a tetravalent residue which does not contain an oxygen-containing functional group and is obtained by removing two arbitrary hydrogen atoms from an alkylene group is preferable. By adopting such a group, it becomes possible to further lower the water vapor transmission rate.

The polymer may have a structural unit not represented by the general formula (3). For example, you may have a structural unit formed when an acrylate monomer and a methacrylate monomer are copolymerized.
In the polymer, the structural unit not represented by the general formula (3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
Examples of the polymer having no structural unit represented by the general formula (3) include polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, poly Examples include ether imide, cellulose acylate, polyurethane, polyether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and fluorene ring-modified polyester.

  In the following, specific examples of the radical polymerizable monomer represented by the general formula (2) will be shown, but the light transmissive resin in the present invention is not limited thereto.

-Acidic monomer-
The light transmissive resin material may further contain an acidic monomer.
By including the acidic monomer, interlayer adhesion is improved.
The acidic monomer means a monomer containing an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid or phosphonic acid.
As the acidic monomer, a monomer containing a carboxylic acid group or a phosphoric acid group is preferred, a (meth) acrylate containing a carboxylic acid group or a phosphoric acid group is more preferred, and a (meth) acrylate having a phosphate ester group is further preferred. preferable.

-(Meth) acrylate having a phosphate ester group ---
As the (meth) acrylate having a phosphoric ester group, a compound represented by the following general formula (P) is more preferably included. By including the (meth) acrylate having the phosphoric ester group, adhesion with the inorganic layer is improved.

However, the general formula (P), ^{Z 1 is, Ac 2 -O-X 2 -} , represents a substituent or a hydrogen atom not having a polymerizable group. Z ² represents Ac ³ —O—X ³ —, a substituent having no polymerizable group, or a hydrogen atom. Ac ¹ , Ac ² and Ac ³ each represents an acryloyl group or a methacryloyl group. X ¹ , X ² and X ³ each represent a divalent linking group.
Examples of the compound represented by the general formula (P) include a monofunctional monomer represented by the following general formula (P-1), a bifunctional monomer represented by the following general formula (P-2), and the following: A trifunctional monomer represented by the general formula (P-3) is preferred.

In the general formulas (P-1) to (P-3), the definitions of Ac ¹ , Ac ² , Ac ³ , X ¹ , X ² and X ³ are the same as those in the general formula (P). In the general formulas (P-1) and (P-2), R ¹ represents a substituent or a hydrogen atom having no polymerizable group, and R ² represents a substituent or a hydrogen atom having no polymerizable group. To express.
In the general formulas (P) and (P-1) to (P-3), X ¹ , X ² and X ³ are the same groups as L1 in the general formula (2). X ¹ , X ² and X ³ are preferably an alkylene group or an alkyleneoxycarbonylalkylene group.
In the general formulas (P) and (P-1) to (P-3), examples of the substituent having no polymerizable group include an alkyl group, an aryl group, and a group obtained by combining these. An alkyl group is preferred.

As carbon number of the said alkyl group, 1-12 are preferable, 1-9 are more preferable, and 1-6 are still more preferable.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
The alkyl group may be linear, branched or cyclic, but a linear alkyl group is preferred. The alkyl group may be substituted with an alkoxy group, an aryl group, an aryloxy group, or the like.

As carbon number of the said aryl group, 6-14 are preferable and 6-10 are more preferable.
Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
The aryl group may be substituted with an alkyl group, an alkoxy group, an aryloxy group, or the like.
In the present invention, only one type of monomer represented by the general formula (P) may be used, or two or more types may be used in combination. When used in combination, the monofunctional monomer represented by the general formula (P-1), the bifunctional monomer represented by the general formula (P-2), and the general formula (P-3) Two or more of the represented trifunctional monomers may be used in combination.
In the present invention, as the polymerizable monomers having a phosphate ester group, commercially available compounds such as KAYAMER series manufactured by Nippon Kayaku Co., Ltd. and Phosmer series manufactured by Unichemical Co., Ltd. may be used as they are. A compound synthesized in (1) may be used.

Although the specific example of an acidic monomer is shown below, this invention is not limited to these.

The thickness of the first optical path length adjusting layer is adjusted so that each subpixel has an optical distance (optical path length) at which light of a predetermined wavelength can efficiently resonate.
Therefore, the optical distance to resonate is determined by the refractive index of the material sandwiched between the light reflecting film and the light semi-transmissive reflecting film, its composition, and thickness, so it is not determined by the optical path length adjusting layer. Absent.
Considering the configuration of a generally used organic electroluminescent layer, the thickness of the optical path length adjusting layer in the red pixel region is preferably a physical thickness of 30 nm to 1,000 nm, and more preferably 150 nm to 350 nm. 200 nm to 250 nm is more preferable.
The thickness of the optical path length adjusting layer in the green pixel region is preferably 5 nm to 800 nm, more preferably 100 nm to 250 nm, and even more preferably 150 nm to 200 nm in terms of physical thickness.
The thickness of the optical path length adjusting layer in the blue pixel region is preferably a physical thickness of 0 nm to 600 nm, more preferably 50 nm to 200 nm, and even more preferably 100 nm to 150 nm.

-Second optical path length adjustment layer-
The constituent material of the second optical path length adjusting layer is not particularly limited as long as it is a transparent and non-conductive inorganic material, and can be appropriately selected according to the purpose. For example, SiO ₂ , Al ₂ O ₃ , Examples thereof include SiON and ZrO ₂ . These may be used individually by 1 type and may use 2 or more types together. Among these, SiO ₂ and Al ₂ O ₃ are particularly preferable in terms of easy film formation.
The method for forming the second optical path length adjusting layer will be described in the method for manufacturing an organic electroluminescent device of the present invention described later.
The thickness of the second optical path length adjusting layer is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 5 nm to 30 nm, and more preferably 5 nm to 15 nm. When the thickness is less than 5 nm, the durability of the organic electroluminescence device may be lowered, and when it exceeds 30 nm, it may be difficult to adjust the optical path length for each pixel.

-Reflective metal layer and translucent member-
The reflective metal layer has a function of reflecting light emitted from the organic light emitting layer.
The translucent member has a function of reflecting or transmitting light emitted from the organic light emitting layer.
The reflective metal layer and the translucent member are disposed to face each other with an organic light emitting layer interposed therebetween, and have a function of resonating light emitted from the organic light emitting layer.
The translucent member is not particularly limited and can be selected according to the purpose. For example, a translucent metal, a translucent dielectric multilayer mirror, and a combination thereof are preferable.
There is no restriction | limiting in particular as said translucent metal, It can comprise using the anode mentioned later.
The translucent dielectric multilayer mirror is not particularly limited and can be appropriately selected according to the purpose. For example, a mirror composed of a dielectric multilayer film composed of a laminate of SiO ₂ , SiN, etc. Etc.
There is no restriction | limiting in particular as said reflection metal layer, It can comprise using the same thing as the cathode mentioned later.

-Board-
There is no restriction | limiting in particular as said board | substrate, Although it can select suitably according to the objective, For example, the glass material, barrier film, etc. which have heat resistance and gas barrier property are preferable.
Specifically, the glass transition temperature (Tg) is preferably made of a transparent material having high heat resistance and at least one of 100 ° C. or higher and a linear thermal expansion coefficient of 40 ppm / ° C. or lower. In addition, a glass transition temperature (Tg) and a linear expansion coefficient can be adjusted with an additive etc.
There is no restriction | limiting in particular as a material of the said board | substrate, According to the objective, it can select suitably, For example, a polyethylene naphthalate (PEN: 120 degreeC), a polycarbonate (PC: 140 degreeC), an alicyclic polyolefin (for example, Japan) Zeon Co., Ltd., ZEONOR 1600: 160 ° C., polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: JP 2001-150584 A) Compound: 162 ° C.), polyimide (for example, manufactured by Mitsubishi Gas Chemical Company, Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic ring Modified Polycarbonate (IP-PC: JP 2000 227603 JP compound: 205 ° C.), acryloyl compound (compound described in JP-A 2002-80616: 300 ° C. or higher), and the like (in parenthesis indicates the Tg). Among these, when transparency is required, it is preferable to use an alicyclic polyolefin.

The light transmittance of the substrate is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
As the light transmittance, for example, the total light transmittance and the amount of scattered light are measured using a method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and the diffuse transmittance is calculated from the total light transmittance. It can be calculated by subtracting.
There is no restriction | limiting in particular as thickness of the said glass material or a barrier film, Although it can select suitably according to the objective, 1 micrometer-800 micrometers are preferable and 10 micrometers-200 micrometers are more preferable.

<Organic electroluminescent device>
The organic electroluminescent element has a pair of electrodes, that is, an anode and a cathode, and a light emitting layer between both electrodes. Examples of the functional layer other than the light emitting layer that can be disposed between both electrodes include a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer.

The organic electroluminescent element preferably has a hole transport layer between the anode and the light emitting layer, and preferably has an electron transport layer between the cathode and the light emitting layer. Furthermore, a hole injection layer may be provided between the hole transport layer and the anode, or an electron injection layer may be provided between the electron transport layer and the cathode.
In addition, a hole transporting intermediate layer (electron blocking layer) may be provided between the light emitting layer and the hole transporting layer, and an electron transporting intermediate layer (hole blocking layer) is provided between the light emitting layer and the electron transporting layer. Layer) may be provided. Each functional layer may be divided into a plurality of secondary layers.

  These functional layers including the light emitting layer can be suitably formed by any of dry film forming methods such as vapor deposition and sputtering, wet coating methods, transfer methods, printing methods, and ink jet methods.

--- Light emitting layer--
The light-emitting layer receives holes from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, receives electrons from a cathode, an electron injection layer, or an electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light.
The light emitting layer includes a light emitting material. The light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material (in the latter case, the light emitting material may be referred to as “light emitting dopant” or “dopant”). The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and two or more kinds may be mixed. The host material is preferably a charge transport material. The host material may be one type or two or more types. Furthermore, the light emitting layer may contain a material that does not have charge transporting properties and does not emit light.

  The thickness of the light emitting layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm from the viewpoint of external quantum efficiency, More preferably, the thickness is 5 nm to 100 nm. Moreover, the said light emitting layer may be 1 layer, or may be two or more layers, and each layer may light-emit with a different luminescent color.

--- Luminescent material ---
As the light emitting material, a phosphorescent light emitting material, a fluorescent light emitting material, or the like can be preferably used. The luminescent dopant in the present invention has an ionization potential difference (ΔIp) and an electron affinity difference (ΔEa) of 1.2 eV>ΔIp> 0.2 eV and / or 1.2 eV> with respect to the host compound. A dopant satisfying the relationship of ΔEa> 0.2 eV is preferable from the viewpoint of driving durability.
The light emitting dopant in the light emitting layer is generally contained in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound that forms the light emitting layer in the light emitting layer. From the viewpoint, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.

<Phosphorescent material>
In general, examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
There is no restriction | limiting in particular as said transition metal atom, According to the objective, it can select suitably, For example, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold | metal | money, silver, copper, platinum etc. are mentioned. Among these, rhenium, iridium, and platinum are preferable, and iridium and platinum are particularly preferable.

  Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .

  The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  Among these, as specific examples of phosphorescent materials, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1 , WO05 / 19373A2, WO2004 / 108857A1, WO2005 / 042444A2, WO2005 / 042550A1, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-235076, JP2003 -123982, JP2002-170684, EP121257, JP2002-226495, JP2 02-234894, JP-A-2001-247659, JP-A-2001-298470, JP-A-2002-173675, JP-A-2002-203678, JP-A-2002-203679, JP-A-2004-357542, JP-A-2006-93542, JP-A-2006- Examples include phosphorescent light emitting compounds described in JP-A-261623, JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, and the like. Among these, Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex are preferable, and Ir complex , Pt complexes, and Re complexes are more preferable, and Ir complexes, Pt complexes, and Re complexes including at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond are particularly preferable. From the viewpoint of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is most preferable.

Specific examples of the phosphorescent material include the following compounds, but are not limited thereto.

<Fluorescent material>
The fluorescent light emitting material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin , Pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compound, condensed polycyclic aromatic compound (anthracene, Phenanthroline, pyrene, perylene, rubrene, or pentacene), 8-quinolinol metal complexes, various metal complexes represented by pyromethene complexes and rare earth complexes, polythiophene , Polyphenylene, polyphenylene vinylene polymer compounds such as organosilanes, or derivatives thereof.

---- Host material ---
As the host material used for the light emitting layer, a hole transporting host material excellent in hole transportability (hereinafter sometimes referred to as “hole transportable host”) and an electron transporting host compound excellent in electron transportability (Hereinafter may be referred to as “electron transporting host”).

<Hole transportable host>
The hole transporting host used in the light emitting layer is not particularly limited and may be appropriately selected depending on the purpose. For example, pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole , Pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic Conductive polymer oligomers such as dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, polythiophenes, etc. Organic silanes, carbon films, or the like derivatives thereof.
Among these, indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives are preferable, compounds having a carbazole group in the molecule are more preferable, and compounds having a t-butyl-substituted carbazole group are particularly preferable.

<Electron transporting host>
There is no restriction | limiting in particular as an electron transport host used for the said light emitting layer, According to the objective, it can select suitably, For example, a pyridine, a pyrimidine, a triazine, an imidazole, a pyrazole, a triazole, an oxazole, an oxadiazo- , Fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine, Or a derivative thereof (which may form a condensed ring with other rings), a metal complex of an 8-quinolinol derivative, a metal phthalocyanine, a metal complex having a benzoxazole or a benzothiazol as a ligand. And various metal complexes. Among these, a metal complex compound is preferable from the viewpoint of durability, and a metal complex having a ligand having at least one nitrogen atom, oxygen atom, or sulfur atom coordinated to a metal is particularly preferable.
Examples of the metal complex electron transporting host include those disclosed in Japanese Patent Application Laid-Open No. 2002-235076, Japanese Patent Application Laid-Open No. 2004-214179, Japanese Patent Application Laid-Open No. 2004-221106, Japanese Patent Application Laid-Open No. 2004-221665, Japanese Patent Application Laid-Open No. 2004-221683, Japanese Patent Application Laid-Open No. 2004-327313, and the like. And the compounds described.

Specific examples of the hole transporting host material and the electron transporting host material include the following compounds, but are not limited thereto.

--- Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. The hole injecting material and hole transporting material used for these layers may be a low molecular compound or a high molecular compound.
Specifically, pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, etc. Is mentioned.

The hole injection layer and the hole transport layer may contain an electron accepting dopant. As the electron-accepting dopant introduced into the hole-injecting layer and the hole-transporting layer, an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.
Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide. In the case of an organic compound, a compound having a nitro group, a halogen, a cyano group, a trifluoromethyl group, or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be given. These may be used individually by 1 type and may use 2 or more types.
The content of the electron-accepting dopant is not particularly limited and varies depending on the type of material, but is preferably 0.01% by mass to 50% by mass with respect to the hole transport layer material, and is 0.05% by mass. More preferably, it is -20 mass%, and it is still more preferable that it is 0.1 mass%-10 mass%.

  The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

--Electron injection layer, electron transport layer--
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles Body, and the like.

The electron injection layer or the electron transport layer may contain an electron donating dopant. The electron-donating dopant introduced into the electron-injecting layer or the electron-transporting layer is not limited as long as it has an electron-donating property and has a property of reducing an organic compound, such as an alkali metal such as Li, an alkaline earth metal such as Mg, Transition metals including rare earth metals and reducing organic compounds are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Examples thereof include Gd and Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
These electron donating dopants may be used alone or in combination of two or more.
The content of the electron donating dopant is not particularly limited and varies depending on the type of the material, but is preferably 0.1% by mass to 99% by mass with respect to the electron transport layer material, and 1.0% by mass. It is more preferable that it is% -80 mass%, and it is still more preferable that it is 2.0 mass%-70 mass%.

  The electron injection layer and the electron transport layer may have a single-layer structure made of one or more of the materials described above, or may have a multilayer structure made up of a plurality of layers having the same composition or different compositions. .

--Hole blocking layer, electron blocking layer--
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the cathode side. .
On the other hand, the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing to the anode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the anode side. .
Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, and phenanthroline derivatives such as BCP. As an example of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be used.
The thickness of the hole blocking layer and the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the hole blocking layer and the electron blocking layer may have a single-layer structure made of one or more of the materials described above, or may have a multilayer structure made up of a plurality of layers having the same composition or different compositions. Good.

--- Electrode--
The organic electroluminescent element includes a pair of electrodes, that is, an anode and a cathode. In view of the properties of the organic electroluminescent element, it is preferable that at least one of the anode and the cathode is transparent.
Usually, the anode only needs to have a function as an electrode for supplying holes to the organic compound layer, and the cathode only needs to have a function as an electrode for injecting electrons into the organic compound layer. The shape, structure, size, and the like are not particularly limited, and can be appropriately selected from known electrode materials according to the use and purpose of the light-emitting element. As a material which comprises an electrode, a metal, an alloy, a metal oxide, an electroconductive compound, or a mixture thereof etc. are mentioned suitably, for example.

  There is no restriction | limiting in particular as said electrode, According to the objective, it can select suitably, It is preferable to comprise the said reflecting metal layer and the semi-transparent metal as said semi-transparent member in the anode and the cathode.

  Specific examples of the material constituting the anode include, for example, tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO). ) Conductive metal oxides, metals such as gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, Examples thereof include organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO. Among these, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like.

  Examples of the material constituting the cathode include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, Examples include lithium-aluminum alloys, magnesium-silver alloys, indium, and rare earth metals such as ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection. Among these, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injecting properties, and materials mainly composed of aluminum are particularly preferable from the viewpoint of excellent storage stability. The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum). Alloy).

  There is no restriction | limiting in particular about the formation method of the said electrode, According to a well-known method, it can carry out. For example, considering the suitability with the material constituting the electrode from among wet methods such as printing methods, coating methods, physical methods such as vacuum deposition methods and sputtering methods, and chemical methods such as CVD and plasma CVD methods. Then, it can be formed on the substrate according to an appropriately selected method. For example, when ITO is selected as the anode material, it can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, or the like. When a metal or the like is selected as the cathode material, one or more of them can be formed simultaneously or sequentially according to a sputtering method or the like.

  In addition, when patterning is performed when forming the electrode, it may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like. A method, a sputtering method, or the like may be performed, or a lift-off method or a printing method may be performed.

-Board-
There is no restriction | limiting in particular as said board | substrate, According to the objective, it can select suitably, For example, inorganic materials, such as a yttria stabilized zirconia (YSZ) and glass (an alkali free glass, soda-lime glass, etc.), a polyethylene terephthalate, a poly Examples include substrates made of organic materials such as polyesters such as butylene phthalate and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin, and poly (chlorotrifluoroethylene).

  There is no restriction | limiting in particular about the shape of the said board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. The shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members. Good. The substrate may be transparent or opaque, and if transparent, it may be colorless and transparent or colored and transparent.

  The substrate may be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface. As the material for the moisture permeation preventing layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.

--Protective layer--
In the present invention, the entire organic electroluminescent element may be protected by a protective layer. As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ , TiO ₂ , metal nitrides such as SiN _x , SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ , CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerization, cyclic in the copolymer main chain Examples thereof include a fluorine-containing copolymer having a structure, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.

  The method for forming the protective layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the MBE (molecular beam epitaxy) method, the cluster ion beam method , Ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method and the like.

--Sealing--
The organic electroluminescent element may be entirely sealed using a sealing container. Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element. The moisture absorbent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, Examples thereof include calcium chloride, magnesium chloride, copper chloride, cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide.
The inert liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, and chlorine-based solvents. Examples include solvents and silicone oils.

Moreover, the method of sealing with the resin sealing layer shown below is also used suitably.
---- Resin sealing layer ---
The organic electroluminescent element preferably suppresses element performance deterioration due to oxygen or moisture from the atmosphere by a resin sealing layer.
The resin material for the resin sealing layer is not particularly limited and may be appropriately selected depending on the purpose. For example, acrylic resin, epoxy resin, fluorine resin, silicon resin, rubber resin, ester resin, etc. Is mentioned. Among these, an epoxy resin is preferable from the viewpoint of the moisture preventing function, and among the epoxy resins, a thermosetting epoxy resin or a photocurable epoxy resin is particularly preferable.
There is no restriction | limiting in particular as a preparation method of the said resin sealing layer, According to the objective, it can select suitably, For example, the method of apply | coating a resin solution, the method of crimping | bonding or thermocompressing a resin sheet, vapor deposition, sputtering, etc. And a dry polymerization method.

---- Sealing adhesive ---
The sealing adhesive has a function of preventing intrusion of moisture and oxygen from the end portion. As the material of the sealing adhesive, the same material as that used for the resin sealing layer can be used. Among these, an epoxy adhesive is preferable from the viewpoint of moisture prevention, and a photocurable adhesive or a thermosetting adhesive is particularly preferable.
It is also preferable to add a filler to the material. As the filler added to the sealant, inorganic materials such as SiO ₂ , SiO (silicon oxide), SiON (silicon oxynitride), SiN (silicon nitride) and the like are preferable. By adding the filler, the viscosity of the sealant is increased, the processing suitability is improved, and the moisture resistance is improved.
The sealing adhesive may contain a desiccant. As the desiccant, for example, barium oxide, calcium oxide, or strontium oxide is preferable. The addition amount of the desiccant with respect to the sealing adhesive is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.05% by mass or more and 15% by mass or less. If the amount is less than this, the effect of adding the desiccant is diminished. On the other hand, when it is more than this, it becomes difficult to uniformly disperse the desiccant in the sealing adhesive, which is not preferable.
In the present invention, the sealing adhesive containing the desiccant can be applied by an arbitrary amount using a dispenser or the like, and the substrates can be sealed by overlapping and curing after application.

  Here, a preferred embodiment of the organic electroluminescence device of the present invention will be described with reference to the drawings.

-First embodiment-
An example of the organic electroluminescence device of the first embodiment will be described with reference to FIG. The organic electroluminescent device 100 is a top emission type organic electroluminescent device.
This organic electroluminescent device 100 has a reflective metal layer 2 on a substrate 1 in each of red, green, and blue pixel regions.
In the red pixel region, first optical path length adjustment layers 3 and 5 made of an organic material are disposed so as to cover the reflective metal layer 2, and a first optical path length adjustment layer 5 made of an inorganic material is disposed on the first optical path length adjustment layer 5. Two optical path length adjusting layers 11 are disposed, and a translucent member 8 facing the reflective metal layer 2 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the red pixel region, the optical path length is adjusted by the first optical path length adjusting layers 3 and 5 and the second optical path length adjusting layer 11, and the first optical path length is adjusted between the reflective metal layer 2 and the translucent member 8. An optical path length d _{3 including the} optical path length adjusting layers 3 and 5 and the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed.
In the green pixel region, a first optical path length adjustment layer 3 is disposed so as to cover the reflective metal layer 2, and a second optical path length adjustment layer 11 is disposed on the first optical path length adjustment layer 3. A translucent member 8 facing the reflective metal layer 2 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the green pixel region, the optical path is adjusted by the first optical path length adjustment layer 3 and the second optical path length adjustment layer 11, and the first optical path length adjustment is performed between the reflective metal layer 2 and the translucent member 8. the optical path length d ₂ and a layer 3 and a second optical path length adjustment layer 11 and the transparent conductive film 6 and the organic light emitting layer 7 is formed.
In the blue pixel region, the second optical path length adjusting layer 11 is disposed so as to cover the reflective metal layer 2, and the half facing the reflective metal layer 2 through the transparent conductive film 6 and the organic light emitting layer 7. A transparent member 8 is arranged. In the blue pixel region, an optical path length d ₁ having the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed between the reflective metal layer 2 and the translucent member 8. .

In the organic electroluminescent device 100 formed in this way, the light emitted from the organic light emitting layer 7 is resonated between the reflective metal layer 2 and the translucent member 8, and the optical path lengths d ₁ , d ₂ , d ₃ is intensified and extracted as blue, green, and red light from the translucent member 8 side.
In addition, the second optical path length adjustment layer 11 also functions as a passivation layer, can prevent moisture from entering from the first optical path length adjustment layer made of an organic material and from the outside, and can improve durability.

-Second Embodiment-
Another example of the organic electroluminescent device of the second embodiment will be described with reference to FIG. The organic electroluminescent device 200 is a top emission type organic electroluminescent device.
In the organic electroluminescent device 200, a first optical path length adjustment layer 3 made of an organic material is disposed so as to cover the reflective metal layer 2 in the red pixel region, and the first optical path length adjustment layer 3 is disposed on the first optical path length adjustment layer 3. A second optical path length adjusting layer 11 made of an inorganic material is disposed, and a translucent member 8 facing the reflective metal layer 2 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the red pixel region, the optical path is adjusted by the first optical path length adjustment layer 3 and the second optical path length adjustment layer 11, and the first optical path length adjustment is performed between the reflective metal layer 2 and the translucent member 8. An optical path length d ₃ having the layer 3, the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed.
In the green pixel region, a second optical path length adjusting layer 11 made of an inorganic material is disposed so as to cover the reflective metal layer 2, and the reflective metal layer 2 is interposed via the transparent conductive film 6 and the organic light emitting layer 7. A semi-transparent member 8 is arranged opposite to the above. In the green pixel region, an optical path length d ₂ having the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed between the reflective metal layer 2 and the translucent member 8. .
In the blue pixel region, the second optical path length adjusting layer 11 made of an inorganic material is disposed so as to cover the reflective metal layer 2, and the translucent member is opposed to the reflective metal layer 2 through the organic light emitting layer 7. 8 is arranged. In the blue pixel region, an optical path length d ₁ having the second optical path length adjusting layer 11 and the organic light emitting layer 7 is formed between the reflective metal layer 2 and the translucent member 8.
In the blue region, the reflective metal layer 2 disposed on the substrate 1 is formed of an electrode material and is configured to exhibit the same electrode action as the transparent conductive film 6.
In the second embodiment, the other points are the same as those in the first embodiment, and thus the description thereof is omitted.
In addition, the second optical path length adjustment layer 11 also functions as a passivation layer, can prevent moisture from entering from the first optical path length adjustment layer made of an organic material and from the outside, and can improve durability.

-Third embodiment-
An example of the organic electroluminescent device of the third embodiment will be described with reference to FIG. The organic electroluminescent device 300 is a bottom emission type organic electroluminescent device.
This organic electroluminescent device 300 has a semi-transparent member 8 on the substrate 1 in each of the red, green, and blue pixel regions.
In the red pixel region, the first optical path length adjustment layers 3 and 5 made of an organic material are disposed so as to cover the translucent member 8, and the first optical path length adjustment layer 5 made of an inorganic material is disposed on the first optical path length adjustment layer 5. The reflective metal layer 2 facing the translucent member 8 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the red pixel region, the optical path length is adjusted by the first optical path length adjusting layers 3 and 5 and the second optical path length adjusting layer 11, and the first optical path length is adjusted between the translucent member 8 and the reflective metal layer 2. An optical path length d ₃ having the optical path length adjusting layers 3 and 5, the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed.
In the green pixel region, the first optical path length adjustment layer 3 made of an organic material is disposed so as to cover the translucent member 8, and the second optical path length adjustment layer 3 made of an inorganic material is disposed on the first optical path length adjustment layer 3. An optical path length adjusting layer 11 is disposed, and a reflective metal layer 2 facing the translucent member 8 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the green pixel region, the optical path is adjusted by the first optical path length adjustment layer 3 and the second optical path length adjustment layer 11, and the first optical path length adjustment is performed between the translucent member 8 and the reflective metal layer 2. An optical path length d ₂ having the layer 3, the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed.
In the blue pixel region, a second optical path length adjusting layer 11 made of an inorganic material is disposed so as to cover the translucent member 8, and the translucent member 8 is interposed via the transparent conductive film 6 and the organic light emitting layer 7. A reflective metal layer 2 is disposed so as to face the surface. In the blue pixel region, an optical path length d ₁ having the second optical path length adjusting layer 11, the transparent conductive film 6, and the organic light emitting layer 7 is formed between the translucent member 8 and the reflective metal layer 2. .
In the third embodiment, the other points are the same as those in the first embodiment, and thus the description thereof is omitted.
In addition, the second optical path length adjustment layer 11 also functions as a passivation layer, can prevent moisture from entering from the first optical path length adjustment layer made of an organic material and from the outside, and can improve durability.

(Method for manufacturing organic electroluminescent device)
The organic electroluminescent device manufacturing method of the present invention includes a light-transmitting resin material film forming step, a light-transmitting resin layer forming step, a first optical path length adjusting layer forming step, and a second optical path length adjusting layer forming. A process, and further includes other processes as necessary.

<Light transmissive resin material film forming process>
The light-transmitting resin material film-forming step is performed on a substrate on which a reflective metal layer and a translucent member can be disposed in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue. This is a step of forming a film of a transparent resin material.

-Film formation-
The film forming method of the light transmissive resin is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a vapor phase film forming method and a coating film forming method. From the point of view of chemical conversion, a vapor phase film forming method is preferable.

There is no restriction | limiting in particular as said vapor-phase film-forming method, Although it can select suitably according to the objective, For example, a flash vapor deposition method, the spray coat method, etc. are preferable.
As the coating film formation method, the light-transmitting resin material may be dissolved in a solvent and formed by spin coating or the like. In this case, however, the structure of the panel (for example, a TFT circuit element disposed on the substrate, etc.) ), The film thickness may be difficult to control, and a desired optical path length difference may not be obtained.
On the other hand, according to the vapor deposition method, the light-transmitting resin material can be deposited without being affected by the flatness of the panel structure.

The film formation conditions by the flash vapor deposition method are not particularly limited and can be appropriately selected according to the purpose. For example, the heating temperature of the monomer is 100 ° C. to 200 ° C., and the degree of vacuum is 1 × 10 ⁻² Pa to 10 Pa is preferable.

<Light transmissive resin layer forming step>
The light transmissive resin layer forming step is a step of forming a light transmissive resin layer by curing a region including the one pixel region in the formed light transmissive resin material.

-Curing reaction-
The reaction for curing the light transmissive resin is not particularly limited and may be appropriately selected depending on the intended purpose. Heat polymerization, light (ultraviolet light, visible light) polymerization, electron beam polymerization, plasma polymerization, or these Combinations can be mentioned.
Among these, it is preferable to carry out exposure in the presence of a photopolymerization initiator and radical polymerization of the radical polymerizable monomer.

In the photopolymerization, the irradiation light is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp.
The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more.
When acrylic acid ester or methacrylic acid ester is used as the radical polymerizable monomer, acrylic acid ester or methacrylic acid ester is subject to polymerization inhibition by oxygen in the air, so the oxygen concentration or oxygen partial pressure during polymerization is lowered. It is preferable.
Examples of such a method include an inert gas replacement method (nitrogen replacement method, argon replacement method, etc.) and a decompression method. Among these, the reduced pressure curing method is more preferable because it has an effect of reducing the dissolved oxygen concentration in the monomer.
When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When reducing the oxygen partial pressure during polymerization by the reduced pressure method, the total pressure is preferably 1,000 Pa or less, and more preferably 100 Pa or less.
In addition, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.
Most preferably, the radical polymerizable monomer film formed by flash vapor deposition is irradiated with energy of ² J / cm ² or more under reduced pressure to perform ultraviolet polymerization. By taking such a method, the polymerization rate can be increased and an organic layer having high hardness can be obtained. The polymerization of the radical polymerizable monomer is preferably performed after the mixture of the monomers is disposed at a target location by vapor deposition.

  The polymerization rate of the radical polymerizable monomer is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and particularly preferably 92% or more. . The polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (acryloyl group and methacryloyl group) in the mixture of monomers. The polymerization rate can be quantified by a red external line absorption method.

-Photopolymerization initiator-
The polymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with light, but a vapor deposition method is preferred. In particular, when a film is formed by a flash vapor deposition method, a polymerization initiator having a melting point of 30 ° C. or lower or a liquid at 1 atm 30 ° C. is preferable. Here, the melting point refers to the temperature at which the solid state changes to the liquid state. The term “liquid” means that fluidity is exhibited when a container containing a polymerization initiator is tilted at 1 atm 30 ° C.
The said polymerization initiator may be used individually by 1 type, and may use 2 or more types together. For example, a photopolymerization initiator that becomes liquid by using two types in combination can also be preferably used.
Since such a photopolymerization initiator actually becomes a liquid state when the organic layer is vacuum-deposited, the radical polymerizable monomer can be cured well with a small amount of the photopolymerization initiator.
In this way, the stable light-transmitting resin layer makes it difficult for the remaining radical-polymerizable monomer-derived gas to be released, and can reduce damage to the adjacent layer.
In the present invention, the amount of the radical residual polymerizable monomer in the light transmissive resin (optical path length adjusting layer described later) is preferably 1 × 10 ⁻² g / m ² or less, preferably 1 × 10 ⁻⁴ g. / M ² or less is more preferable.

  The molecular weight of the photopolymerization initiator is preferably 170 or more, and more preferably 190 or more. When the molecular weight is such, the photopolymerization initiator is less likely to volatilize, and a lightly cured resin layer that is stably cured can be easily obtained. In addition, there is no restriction | limiting in particular as an upper limit of the molecular weight of the said photoinitiator, Although it can select suitably according to the objective, Usually, it is preferable that it is 1,000 or less.

As content of the said polymerization initiator, in the said light transmissive resin material as a composition which forms the said light transmissive resin layer, 10 mass% or less is preferable, 5 mass% or less is more preferable, 2 mass% or less Is more preferable, and 1% by mass or less is particularly preferable.
When the light-transmitting resin material is formed by the vapor phase film-forming method, the amount of the photopolymerization initiator added is smaller than when the light-transmitting resin material is dissolved and applied in a solvent. Even so, since the radical polymerizable monomer can be sufficiently reacted, the amount of the photopolymerization initiator added can be reduced.
Further, by reducing the amount of the photopolymerization initiator added, the amount of the photopolymerization initiator remaining in the light-transmitting resin layer (optical path length adjusting layer) can be reduced, and the amount of gas derived from the photopolymerization initiator can be reduced. Generation can be reduced, and damage to adjacent layers can be reduced.

  Although there is no restriction | limiting in particular as said photoinitiator, When using a gaseous-phase film-forming method, either the compound represented by following General formula (4) and the compound represented by following General formula (5) Compounds containing are preferred.

However, in the general formula (4), R ¹ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 1 to 18 carbon atoms, a carbonyl group, and these groups. R ² represents any one of a plurality of substituents bonded together, and R ² represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 1 to 18 carbon atoms, an amino group, an alkoxy group, An acyl group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, or a cyano group is represented. n1 represents an integer of 0 to 5, and when n1 is 2 or more, R ² in each repeating unit may be the same or different.
Here, R ¹ is preferably any of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted or unsubstituted aryl group having 1 to 18 carbon atoms, and R ² has 1 to 18 carbon atoms. Of these, substituted or unsubstituted alkyl groups are preferred. When R ¹ is a substituted alkyl group having 1 to 18 carbon atoms, the carbon linked to the carbonyl group is preferably substituted with an alkoxy group, a hydroxyl group, or an amino group. n1 is preferably 0 to 3.
As such a compound, a commercial product can be used, and examples of the commercial product include Darocur 1173 (manufactured by Ciba Specialty Chemicals).

However, the general formula (5), R ³ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having from 1 to 18 carbon atoms, an amino group, an alkoxy group, an acyl group Represents an alkoxycarbonyl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, or a cyano group, and R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted group having 1 to 18 carbon atoms. Alternatively, it represents an unsubstituted aryl group, amino group, alkoxy group, acyl group, alkoxycarbonyl group, alkylthio group, arylthio group, hydroxy group, halogen atom, or cyano group. n2 and n3 each represent an integer of 0 to 5, but neither n2 nor n3 is 0. When n2 is 2 or more, R ³ in each repeating unit may be the same or different, and when n3 is 2 or more, R ⁴ in each repeating unit may be the same or different.
R ³ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and R ⁴ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. n2 is preferably 0 to 3, and n3 is preferably 0 to 3.
Examples of such a compound include 2-methylbenzophenone, and for example, commercially available products such as Ezacure TZT (manufactured by Lamberti) can be used.

<First optical path length adjusting layer forming step>
The first optical path length adjustment layer forming step is a step of developing the light-transmitting resin layer after the curing reaction to form a first optical path length adjustment layer.

-Development-
There is no restriction | limiting in particular as the said development method, According to the objective, it can select suitably, For example, ultrasonic development using organic solvents, such as isopropyl alcohol, acetone, toluene, is mentioned.

  In the organic electroluminescence device of the present invention, the first optical path length adjustment layer and the second optical path length adjustment layer are introduced into at least one pixel region of red, green, and blue to have a resonance structure. Do it.

The first optical path length adjusting layer may be directly disposed on the upper surface of the reflective metal layer or the translucent member disposed on the substrate, but from the viewpoint of arranging the first optical path length adjusting layer flatly. May be provided on the reflective metal layer or the translucent member with a flattening film for flattening the shape of the upper surface.
There is no restriction | limiting in particular as said planarization film | membrane, Although it can select suitably according to the objective, It is preferable to form with the same light transmissive resin material as the said light transmissive resin material.

<Second optical path length adjusting layer forming step>
In the second optical path length adjustment layer forming step, a second optical path length adjustment layer made of an inorganic material is formed between the first optical path length adjustment layer and the organic electroluminescent element constituting the one pixel region. It is a process to do.

The second optical path length adjustment layer is formed on the first optical path length adjustment layer, the reflective metal layer, or the translucent member, and is formed in a solid (continuous) pattern without being formed. Is preferable in terms of increasing production efficiency.
The second optical path length adjusting layer is preferably formed by either sputtering or vapor deposition, from the viewpoint that a thin film can be uniformly laminated.

<Other processes>
As said other process, the process of producing an organic electroluminescent element, etc. are mentioned, for example.

  Here, the manufacturing process of the manufacturing method of the organic electroluminescent apparatus of this invention is demonstrated using the schematic shown in FIGS. In addition, about each of the code | symbols 3 and 5 in a figure, since it consists of the same material, it is made to show either a light transmissive resin material, a light transmissive resin layer, or a 1st optical path length adjustment layer.

First, the reflective metal layer 2 is arranged on the substrate 1 corresponding to a plurality of pixels corresponding to red, green, and blue (see FIG. 1).
Next, a light transmissive resin material 3 is formed on the substrate on which the reflective metal layer 2 is disposed by flash vapor deposition (light transmissive resin material film forming step, see FIG. 2).
In this way, with the reflective metal layer 2 and the light-transmitting resin material 3 disposed on the substrate 1, the substrate 1 is covered with a mask 4 that can be partially shielded, and irradiated with light L. The light transmissive resin material 2 in the pixel region adjacent to the pixel is selectively exposed and cured to form the light transmissive resin layer 3 (light transmissive resin layer forming step, see FIG. 3).
This is developed to remove a portion other than the exposed portion from the light transmissive resin layer 3 to form a first optical path length adjusting layer 3 in the first stage (first optical path length adjusting layer forming step, (See FIG. 4).

Next, in order to form a multistage optical path length, the light transmissive resin material 5 is vapor-deposited by a flash vapor deposition method (light transmissive resin material film forming step, see FIG. 5). In this state, in the pixel region in which the reflective metal layer 2 and the first optical path length adjustment layer 3 are arranged in the previous step, the light transmissive resin material 5 is superimposed on the first optical path length adjustment layer 3. An optical path length difference is formed between the other pixel regions which are vapor-deposited and on which the first optical path length adjusting layer 3 is not disposed.
In this way, the reflective metal layer 2, the first optical path length adjusting layer 3, and the light-transmitting resin material 5 are disposed on the substrate 1, and the first optical path is covered with a mask 4 that can partially block light. Of the two pixel regions deposited by overlapping the length adjusting layer 3 and the light-transmitting resin material 5, one pixel region is irradiated with light to be exposed and cured, and the first step in the second stage The light transmissive resin layer 5 is formed (light transmissive resin layer forming step, see FIG. 6).
This is developed to remove portions other than the exposed portion from the first light transmissive resin layer 5 and form the first optical path length adjustment layer 5 in one pixel region (formation of the first optical path length adjustment layer) Process, see FIG. At this stage, the first optical path length adjustment layers 3 and 5 are arranged to overlap in one pixel area, and the first optical path length adjustment layer 3 is arranged in a pixel area adjacent to the pixel area. Become.

Next, a second optical path length made of an inorganic material is formed on the top surfaces of the first optical path length adjusting layer 3 in the first stage, the first optical path length adjusting layer 5 in the second stage, and the reflective metal layer 2. The adjustment layer 11 is solid (second optical path length adjustment layer forming step, see FIG. 8).
Next, the transparent conductive film 6 is disposed on the first optical path length adjustment layer 5 in the pixel region where the first optical path length adjustment layers 3 and 5 and the second optical path length adjustment layer 11 are disposed. At the same time, in the pixel region where the first optical path length adjustment layer 3 is disposed, the transparent conductive film 6 is disposed on the first optical path length adjustment layer 3 and the second optical path length adjustment layer 11 is disposed. In the region, the transparent conductive film 6 is disposed on the second optical path length adjustment layer 11 (see FIG. 9).
Next, in each of the three pixel regions where the transparent conductive film 6 is disposed, the organic light emitting layer 7 and the semitransparent member 8 are laminated in this order on the transparent conductive film 6 to manufacture the organic electroluminescent device 100. (See FIG. 10).
In the organic electroluminescent device 100 manufactured in this manner, the light emitted from the organic light emitting layer 7 is adjusted by the first optical path length adjusting layers 3 and 5 and the second optical path length adjusting layer 11. Corresponding to the lengths d ₁ , d ₂ , and d ₃ , they are extracted from the translucent member 8 as light having wavelengths corresponding to blue, green, and red, respectively.
That is, the light emitted from the organic light emitting layer 7 is resonated between the translucent member 8 having the optical path lengths d ₁ , d ₂ , and d ₃ and the reflective metal layer 2, so that the optical path length depends on each optical path length. By increasing the light of the blue, green, and red wavelengths, it is possible to extract the light from the organic electroluminescent device 100 as blue, green, and red light.

  And according to the said manufacturing process of the organic electroluminescent apparatus 100 of this invention, the process of formation of a resist layer, the etching process which used the resist layer as a mask, and peeling of a resist layer is unnecessary for formation of an optical path length difference. Therefore, the manufacturing process can be greatly simplified as compared with the conventional manufacturing process.

(Organic electroluminescent display)
The organic electroluminescent display of the present invention comprises the organic electroluminescent device of the present invention, and other configurations can be applied as necessary.
As the organic electroluminescent display, since the first optical path length adjusting layer is formed of a light-transmitting resin material and the light-emitting display portion has flexibility, cracking due to stress is unlikely to occur and it can be used as a flexible display. .
In addition, the second optical path length adjustment layer made of an inorganic material also functions as a passivation layer, prevents moisture from entering from the first optical path length adjustment layer made of an organic material and from the outside, and improves durability. Can do.
Moreover, there is no restriction | limiting in particular as said other structure, According to the objective, it can select suitably, All the well-known means can be applied as a matter required for a display.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
-Production of organic electroluminescent devices and organic electroluminescent displays-
Aluminum was deposited to a thickness of 100 nm on the substrate by vacuum deposition, and a reflective electrode layer (reflective metal layer) was formed by photolithography.
Next, a light-transmitting resin material (radical polymerizable monomer, trade name: 1,10-decanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) is formed on the substrate on which the reflective electrode layer is formed by flash vapor deposition. ) To a thickness of 45 nm (light-transmissive resin material film-forming step).
Next, by using an exposure apparatus (apparatus name: KP364N2, manufactured by Dainippon Screen Co., Ltd.), one pixel region was selectively exposed using a mask to form a light transmissive resin layer (light transmissive resin layer). Forming step).
Next, development was performed with 2-propanol to prepare a first optical path length adjusting layer of a first stage having a thickness of 45 nm (first optical path length adjusting layer forming step).

In order to form an optical path length step in a pixel region adjacent to the one pixel region, the light transmissive resin material was again formed to a thickness of 40 nm (light transmissive resin material film forming step).
Next, the light transmissive resin material in the one pixel region and the adjacent pixel region was subjected to selective exposure similar to the above to form a light transmissive resin layer (light transmissive resin layer forming step).
Next, development is performed in the same manner as described above, and a second optical path length adjustment layer having a thickness of 40 nm is formed for the one pixel region, and the same is applied to the pixel region adjacent to the pixel region. A first optical path length adjustment layer in the second stage of thickness was produced (first optical path length adjustment layer forming step).

Boron-doped Si as a target, Ar as a discharge gas, and DC pulse as a power source on the top surfaces of the first optical path length adjustment layer in the first stage, the first optical path length adjustment layer in the second stage, and the reflective metal layer with power applied for plasma discharge, the SiO ₂ was formed by controlling the flow rate of O ₂ as a monitor while the reaction gas plasma emission so that the stoichiometric ratio of SiO _2, the first of the first stage A SiO ₂ film having a thickness of 10 nm was formed as a second optical path length adjusting layer by sputtering on the upper surfaces of the first optical path length adjusting layer, the second stage first optical path length adjusting layer, and the reflective metal layer ( Second optical path length adjusting layer forming step).

  A transparent electrode (made of ITO, IZO, etc., here formed of ITO) was electrically separated and formed for each sub-pixel on the upper surface of the second optical path length adjusting layer. The patterning of the transparent electrode was performed using a film forming method using a shadow mask. The patterning may be performed by film formation on the entire surface and patterning by a photolithography method.

A white organic electroluminescent layer (white OLED) was formed on the upper surface of the transparent electrode using a vacuum film forming apparatus (device name: CM457, manufactured by Tokki Co., Ltd.).
On the upper surface of the white OLED, a metal electrode (aluminum) was formed as a semi-transmissive member using a vacuum film-forming apparatus (apparatus name: CM457, manufactured by Tokki Co., Ltd.).

  Next, the OLED formation region was sealed with a glass can, and each electrode was connected to an external signal control device to manufacture the organic electroluminescence device in Example 1.

The organic electroluminescent display in Example 1 was produced by arranging a plurality of the organic electroluminescent devices.
When the light emitting state of the produced organic electroluminescent display of Example 1 was confirmed, high-definition RGB color development could be confirmed.

(Example 2)
-Production of organic electroluminescent devices and organic electroluminescent displays-
In Example 1, in the second optical path length adjusting layer forming step, the organic of Example 2 was changed in the same manner as in Example 1 except that the SiO ₂ layer having a thickness of 10 nm was changed to an Al ₂ O ₃ layer having a thickness of 9 nm. An electroluminescent device and an organic electroluminescent display were produced.
When the light emission state of the produced organic electroluminescent display was confirmed, the color development of RGB was able to be confirmed with high definition.

(Example 3)
-Production of organic electroluminescent devices and organic electroluminescent displays-
In Example 1, the organic electroluminescence of Example 3 was performed in the same manner as in Example 1 except that in the second optical path length adjusting layer forming step, the SiO ₂ layer having a thickness of 10 nm was changed to a ZrO ₂ layer having a thickness of 7 nm. Devices and organic electroluminescent displays were made.
When the light emission state of the produced organic electroluminescent display was confirmed, the color development of RGB was able to be confirmed with high definition.

Example 4
-Production of organic electroluminescent devices and organic electroluminescent displays-
In Example 1, in the second optical path length adjustment layer forming step, SiO was deposited in a nitrogen atmosphere by an ion plating method, and a SiON layer having a thickness of 9 nm was formed as in Example 1, An organic electroluminescent device and an organic electroluminescent display of Example 4 were produced.
When the light emission state of the produced organic electroluminescent display was confirmed, the color development of RGB was able to be confirmed with high definition.

(Comparative Example 1)
-Production of organic electroluminescent devices and organic electroluminescent displays-
In Example 1, the organic electroluminescent device and the organic electroluminescent display of Comparative Example 1 were manufactured in the same manner as in Example 1 except that the SiO ₂ layer was not formed in the second optical path length adjustment layer forming step. Produced.
When the light emitting state of the produced organic electroluminescent display was confirmed, RGB color development could be confirmed with high definition.

<Durability evaluation>
Defects (DS: dark spots) are generated in 100 pixels after each organic electroluminescent device produced is left at room temperature (25 ° C.) for 3 days and after left at room temperature (25 ° C.) for 60 days. The ratio was observed with an optical microscope.

  The method for producing an organic electroluminescent device of the present invention can be widely used as a method for producing an organic electroluminescent device having a simple production process. The organic electroluminescent device manufactured by the method of manufacturing an organic electroluminescent device of the present invention is highly durable and capable of high-definition full-color display. Therefore, a mobile phone display, a personal digital assistant (PDA), a computer display It is applied in a wide range of fields including automobile information displays, TV monitors, or general lighting.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Reflective metal layer 3, 5 1st optical path length adjustment layer (light transmissive resin material, light transmissive resin layer)
4 Mask 6 Transparent conductive film (anode)
7 Organic Light-Emitting Layer 8 Translucent Member 9 Cathode 10 ITO Film (Optical Path Length Adjustment Layer)
11 Second optical path length adjusting layer 20 Resist layer 100, 200, 300, 400 Organic electroluminescent device

Claims (12)

A reflective metal layer, a translucent member, an organic electroluminescence device having at least a light emitting layer, and an optical path length adjusting layer in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue. An organic electroluminescent device having a resonance structure that resonates light emitted from the organic electroluminescent element,
The organic electroluminescence device, wherein the optical path length adjusting layer includes a first optical path length adjusting layer made of a light-transmitting resin and a second optical path length adjusting layer made of an inorganic material.   The organic electroluminescent device according to claim 1, further comprising a second optical path length adjusting layer between the first optical path length adjusting layer and the organic electroluminescent element. The organic electroluminescent device according to claim 1, wherein the inorganic material in the second optical path length adjusting layer is at least one selected from SiO ₂ , Al ₂ O ₃ , SiON, and ZrO ₂ .   The organic electroluminescent device according to any one of claims 1 to 3, wherein the thickness of the second optical path length adjusting layer is 5 nm to 30 nm.   An organic electroluminescent display comprising the organic electroluminescent device according to claim 1.   The organic electroluminescent display according to claim 5, which is used as a flexible display. A light transmissive resin material is formed on a substrate on which a reflective metal layer and a translucent member can be disposed in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue. A resin material film forming step;
A light-transmitting resin layer forming step of forming a light-transmitting resin layer by curing a region including the one pixel region out of the formed light-transmitting resin material;
A first optical path length adjusting layer forming step of developing the light transmissive resin layer after the curing reaction and forming a first optical path length adjusting layer;
A second optical path length adjustment layer forming step of forming a second optical path length adjustment layer made of an inorganic material between the first optical path length adjustment layer and the organic electroluminescent element constituting the one pixel region;
The manufacturing method of the organic electroluminescent apparatus characterized by including.   The method for producing an organic electroluminescent device according to claim 7, wherein the film formation of the light transmissive resin material is performed by any one of a vapor phase film forming method, spray coating, and ink jet coating.   The method for producing an organic electroluminescent device according to claim 7, wherein the light transmissive resin material is a photoreactive resin composition.   The method for producing an organic electroluminescent device according to claim 9, wherein the photoreactive resin in the photoreactive resin composition has two or more reactive functional groups.   The method for producing an organic electroluminescent device according to claim 7, wherein the second optical path length adjusting layer is formed by any one of a sputtering method and a vapor deposition method.   The first optical path length adjusting layer is formed on a planarizing film, and the planarizing film is formed of the same light transmitting resin material as the light transmitting resin material of the first optical path length adjusting layer. 11. A method for producing an organic electroluminescent device according to any one of 11 above.