JP2016096162A - Method of manufacturing light-emitting display device, light-emitting display device, and light-emitting display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a light-emitting display device or the like for simplifying a manufacturing process of the light-emitting display device having an optical path length adjusting layer.SOLUTION: A method of manufacturing a light-emitting display device includes: a light transmissive resin material deposition process of deposition light transmissive resin material on a substrate capable of arranging and installing a reflecting metal and semi-transparent metal at least in one pixel region out of a plurality of pixel regions corresponding to red, green, and blue; a light transmissive resin layer forming process of forming the light transmissive resin layers by carrying out curing reaction on a region including the one pixel region out of the deposition light transmissive resin material; and an optical path length adjusting layer forming process to develop the light transmissive resin layers after the reaction, and to form an optical path length adjusting layers.SELECTED DRAWING: Figure 9

Description

  The present invention relates to a method for manufacturing a light emitting display device that simplifies the manufacturing process of a light emitting display device having an optical path length adjusting layer, a light emitting display device that has a simple manufacturing process, and a light emitting 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 (organic EL element) as a device that has attracted particular attention in recent years. An organic EL element is an element that emits light in response to an electric signal and is configured using an organic compound as a light-emitting substance. Organic EL 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, white organic EL is used as a means for obtaining three basic colors of red (R), green (G), and blue (B) for full-color expression. In this type of full-color display device, a semi-transparent cathode is further used for the upper electrode, and light of a specific wavelength is obtained due to the multiple interference effect with the light reflecting film. Of the top emission structure that realizes high color reproducibility by taking out only the outside of the organic EL element, and the bottom emission structure using a dielectric multilayer mirror under the translucent or transparent lower electrode for the lower electrode It is being considered.

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 EL element thus formed, an organic EL element 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
(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. To do)
In a full-color display device that combines this type of white organic EL with a color filter, the length of the optical path length L for each pixel is adjusted by changing the thickness of the anode made of an inorganic material such as ITO (Indium Tin Oxide). Thus, light of each color is extracted (see, for example, 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 light emitting display device becomes complicated and the production cost is increased and the productivity is lowered.

For example, a manufacturing process of a light emitting display device having an optical path length adjusting layer according to the prior art will be described below.
First, the reflective metal 2 is arranged on the substrate 1 corresponding to a plurality of pixels corresponding to red, green, and blue (see FIG. 12).
Next, an ITO film 10 is formed on the substrate on which the reflective metal 2 is disposed by sputtering, vapor deposition, or the like (see FIG. 13).
Next, a resist composition made of a curable resin is applied on the ITO film 10 to form a resist layer 20 (see FIG. 14).
In this way, with the reflective metal 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 from light, and irradiated with light L, thereby resist on one pixel. The layer 20 is selectively exposed to cure the resin (see FIG. 15).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 16).
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. 17).
Next, the remaining resist layer 20 on the ITO film 10 is peeled off so that the reflective metal 2 and the ITO film 10 are arranged on one pixel (see FIG. 18).

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. 19). In this state, in the previous step, in the pixel region where the reflective metal 2 and the ITO film 10 are arranged, the ITO film 10 is deposited in an overlapping manner, and the optical path between the ITO film 10 on the other pixels. A 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. 20).
In this way, the reflective metal 2, the ITO film 10, and the resist layer 20 are arranged on the substrate 1, and the pixel area is covered with a mask 4 that can be partially shielded, and the ITO film 10 is deposited thereon, The pixel region adjacent to the pixel region is exposed by irradiating light to cure the resin (see FIG. 21).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 22).
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. 23).
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 with the reflective metal 2, and the reflective metal 2 and the ITO film 10. Are formed (see FIG. 24).

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. 25). In this state, in the previous process, in the two pixel regions where the reflective metal 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. 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. 26).
In this manner, the reflective metal 2, the ITO film 10, and the resist layer 20 are disposed 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. Irradiate and expose to cure the resin (see FIG. 27).
This is developed to remove portions other than the exposed portion from the resist layer 20 (see FIG. 28).
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. 29).
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 2 (see FIG. 30).

Next, the organic light emitting layer 7 and the semi-transmissive metal 8 are laminated in this order on each optical path length adjusting layer in a state having the optical path length adjusting layers formed of the ITO films 10 having different thicknesses. The device 400 is manufactured.
In such a light emitting display 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, blue and green. , And is extracted from the translucent metal 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 transflective metal 8 having the optical path lengths d ₁ , d ₂ , and d ₃ and the reflective metal 2, and blue, green corresponding to each optical path length. By increasing the light of red wavelength, it is possible to take out from the light emitting display device 400 as blue, green and red light.

  As described above, in the light emitting display 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 layer or the like can be used. In the case of using an inorganic material, the formation of the optical path length difference requires steps such as formation of a resist layer, etching treatment using the resist layer as a mask, and stripping of the resist layer. Therefore, there is a problem that the manufacturing process becomes complicated.

Special table 2007-503093 gazette JP 2006-269329 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a method of manufacturing a light emitting display device that simplifies the manufacturing process of a light emitting display device having an optical path length adjusting layer, a light emitting display device that has a simple manufacturing process, and a light emitting display.

Means for solving the above problems are as follows. That is,
<1> Light transmission for forming a light-transmitting resin material on a substrate on which a reflective metal and a semi-transparent member can be disposed in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue A transparent resin material film forming step, and a light transmitting resin layer forming step of forming a light transparent resin layer by curing a region including the one pixel region of the formed light transparent resin material; An optical path length adjusting layer forming step of developing the light transmissive resin layer after the reaction to form an optical path length adjusting layer.
<2> The method for producing a light-emitting display device according to <1>, wherein the light-transmitting resin material film forming step is a step of forming a light-transmitting resin material by a vapor phase film forming method.
<3> The method for producing a light-emitting display device according to <2>, wherein the vapor deposition method is a flash vapor deposition method.
<4> The method for producing a light-emitting display device according to <1>, wherein the light-transmitting resin material film-forming step is a step of forming a light-transmitting resin material by a spray coating method.
<5> The method for producing a light-emitting display device according to <1>, wherein the light-transmitting resin material film forming step is a step of forming a light-transmitting resin material by an inkjet method.
<6> The method for producing a light-emitting display device according to any one of <1> to <5>, wherein the light-transmitting resin material is a photocurable resin.
<7> The method for producing a light-emitting display device according to <6>, wherein the photocurable resin is a radical polymerizable monomer.
<8> The method for producing a light-emitting display device according to <7>, wherein the radical polymerizable monomer has two or more radical polymerizable functional groups.
<9> The method for producing a light-emitting display device according to <7>, wherein the radical polymerizable monomer is a monomer having an ethylenically unsaturated double bond group.
<10> The method for producing a light-emitting display device according to <9>, wherein the monomer having an ethylenically unsaturated double bond group is either acrylic acid or methacrylic acid.
<11> The curing according to any one of <7> to <10>, wherein the curing in the light-transmitting resin layer forming step is performed in the presence of a photopolymerization initiator by radical polymerization of the radical polymerizable monomer. It is a manufacturing method of a light-emitting display device.
<12> The method for producing a light-emitting display device according to any one of <7> to <11>, wherein the residual amount of the radical polymerizable monomer in the optical path length adjusting layer is 1 × 10 ⁻² g / m ² or less. .
<13> The 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 optical path length adjusting layer. > Is a manufacturing method of the light-emitting display device described in the above.
<14> The method for producing a light-emitting display device according to any one of <1> to <5>, wherein the light-transmitting resin is a light-soluble resin.
<15> A substrate in which a reflective metal and a translucent member are disposed in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue, and a light transmissive resin material formed on the substrate. In addition, the light-emitting display device includes an optical path length adjusting layer.
<16> The light-emitting display device according to <15>, which is manufactured by the method for manufacturing the light-emitting display device according to any one of <1> to <14>.
<17> A light emitting display comprising the light emitting display device according to any one of <15> to <16>.
<18> The light-emitting display according to <17>, which is used as a flexible display.

  According to the present invention, there are provided a manufacturing method and a manufacturing process of a light emitting display device that can solve the conventional problems, can achieve the object, and simplify a manufacturing process of a light emitting display device having an optical path length adjusting layer. A simple light-emitting display device and a light-emitting display can be provided.

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

(Method for manufacturing light-emitting display device)
The method for manufacturing a light emitting display device of the present invention includes a light transmissive resin material film forming step, a light transmissive resin layer forming step, and an optical path length adjusting layer forming step, and further for manufacturing a light emitting display device. It comprises other necessary steps.

<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 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 resin material film.

-Light transmissive resin material-
The light-transmitting resin material is not particularly limited as long as it has light-transmitting properties, and can be appropriately selected according to the purpose, and causes a curing reaction in the light-transmitting resin layer (negative type) And those that cause a dissolution reaction in the light-transmitting resin layer (positive type).
There is no restriction | limiting in particular as what produces the curing reaction in the said light-transmissive resin layer (negative type), For example, polyester, an acrylic resin, a methacryl resin (In this specification, an acrylate polymer combining acrylic resin and a methacryl resin. Methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone, polycarbonate, fat Cyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, polysiloxane, other organosilicon Compounds, and the like. These may be used alone or in combination of two or more.
Moreover, there is no restriction | limiting in particular as what produces the dissolution reaction in a light transmissive resin layer (positive type: light soluble resin), According to the objective, it can select suitably, For example, generally as a positive resist Examples thereof include a phenol-based resin, an alkali-soluble resin, and a composition containing a naphthoquinone diazide substituted compound as a photosensitive material. Specifically, a diazonaphthoquinone (DNQ) such as “novolak phenol resin / naphthoquinone diazide substituted compound” is used. ) -Novolac resins, metaparacresol novolac resins such as “novolac resin comprising cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester”, and the like.

-Photo-curing resin (radical polymerizable monomer)-
As the light transmissive resin, among the exemplified compounds, a photocurable resin is preferable.
Although there is no restriction | limiting in particular as said photocurable resin, The radically polymerizable monomer represented by at least one of 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.

General formula (1)
(However, 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 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 by m1. Represents an integer of ˜6, and when m1 is 2 or more, R ⁷ and R ⁸ in each repeating unit may be the same or different.

General formula (2)
(However, in the Formula (2), ^{R 9} represents hydrogen 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 connected in series is represented by m2. Represents an integer of ˜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 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).

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

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 especially 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.) , Ether groups, imino groups, carbonyl groups, and divalent residues in which a plurality of these divalent groups are connected in series (for example, polyethyleneoxy group, polypropyleneoxy group, propionyloxyethylene group, butyroyloxypropylene group, caproyl) Oxyethylene group, caproyloxybutylene group, etc.).
Of these, the alkylene group is preferred.

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.
The acidic monomer is preferably a monomer containing a carboxylic acid group or a phosphoric acid group, more preferably a (meth) acrylate containing a carboxylic acid group or a phosphoric acid group, and even more preferably a (meth) acrylate having a phosphate ester group. .

-((Meth) acrylate having a phosphate 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 a phosphate ester group, adhesion with the inorganic layer is improved.

General formula (P)
(However, in 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} is ^Ac 3 ^-O-X 3 -, Represents a substituent or a hydrogen atom having no polymerizable group, Ac ¹ , Ac ² and Ac ³ each represents an acryloyl group or a methacryloyl group, and X ¹ , X ² and X ³ each represents a divalent linking group; Represent.
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.

Formula (P-1)

General formula (P-2)

General formula (P-3)

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. Represent.
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 more preferable.
Specific 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.
Specific 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, commercially available compounds such as KAYAMER series manufactured by Nippon Kayaku Co., Ltd. and the Phosmer series manufactured by Unichemical Co., Ltd. may be used as they are as the polymerizable monomers having a phosphate group. A newly synthesized compound may be used.

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

-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, it is preferably made of a transparent material having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive.
There is no restriction | limiting in particular as a resin material of such a board | substrate, For example, a polyethylene naphthalate (PEN: 120 degreeC), a polycarbonate (PC: 140 degreeC), an alicyclic polyolefin (For example, Nippon Zeon Co., Ltd. product ZEONOR 1600: 160 ° C.), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of JP 2001-150584 A: 162 ° C.) , Polyimide (for example, Mitsubishi Gas Chemical Co., Ltd. Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: JP 2000-227603 gazette: 205 ° C , Acryloyl compound (compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

The light transmittance of the substrate is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
As the light transmittance, the total light transmittance and the amount of scattered light are measured using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and the diffuse transmittance is subtracted from the total light transmittance. Can be calculated.
Although there is no restriction | limiting in particular as thickness of the said glass material and a barrier film, Typically, it is 1-800 micrometers, and 10 micrometers-200 micrometers are preferable.

-Reflective metal and translucent member-
The reflective metal 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 and the translucent member are disposed to face each other with the 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 examples thereof include a mirror made of a dielectric multilayer film composed of a laminated layer of SiO ₂ and SiN.
There is no restriction | limiting in particular as said reflective metal, It can comprise using the cathode mentioned later.

-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 forming conditions by the flash vapor deposition method are not particularly limited. For example, the heating temperature of the monomer is preferably 100 ° C. to 200 ° C., and the degree of vacuum is preferably about 1 × 10 ^{−2 to} 10 Pa.

<Light transmissive resin layer forming step>
The light-transmitting resin layer forming step is a step of forming a light-transmitting resin layer by curing the region including the one pixel in the formed light-transmitting 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 them, it is preferable to carry out exposure in the presence of a photopolymerization initiator and radical polymerization of a 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 an infrared 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. Thus, when it is molecular weight, the said photoinitiator becomes difficult to volatilize, and also it becomes easy to obtain the light-transmitting resin layer hardened | cured stably. The upper limit of the molecular weight of the photopolymerization initiator is not particularly defined, but is usually 1,000 or less.

The addition amount of the polymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 2% by mass or less in the light transmissive resin material as a composition for forming the light transmissive resin layer. 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.

General formula (4)
(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 from 1 to 18 carbon atoms, a carbonyl group, and these groups Represents any one of a plurality of substituents bonded to each other, 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, and an alkoxy group. , An acyl group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, and a cyano group, 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, for example, a commercially available product such as Darocur 1173 (manufacturer: Ciba Specialty Chemicals) can be adopted.

General formula (5)
(However, in 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 Represents any one of a group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, and a cyano group, and R ⁴ represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, A substituted or unsubstituted aryl group, an amino group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, and a cyano group, each of n2 and n3 is an integer of 0 to 5; represents a, when .n2 none of n2 and n3 is never becomes 0 is 2 or more, R ³ in each repeating unit, the same der And or different, 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 (manufacturer: Lamberti) can be employed.

<Optical path length adjusting layer forming step>
The optical path length adjusting layer forming step is a step of developing the light transmissive resin layer cured by a curing reaction to form the optical path length adjusting 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.

-Optical path length adjustment layer-
In the light-emitting display device of the present invention, the optical path length adjusting layer is introduced into the pixel region of at least one of red, green, and blue to have a resonance structure.
The thickness of the 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 structure of a generally used organic EL light emitting layer, the physical thickness of the optical path length adjusting layer in the red pixel region is preferably 30 nm to 1,000 nm, more preferably 150 nm to 350 nm, and more preferably 200 nm to 250 nm is particularly preferred.
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 particularly 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 0 nm to 600 nm, more preferably 50 nm to 200 nm, and particularly preferably 100 nm to 150 nm in terms of physical thickness.

The optical path length adjusting layer may be directly disposed on the reflective metal or the translucent member disposed on the substrate, but from the viewpoint of arranging the optical path length adjusting layer flat, the reflective metal or the A flattening film for flattening the upper surface shape may be disposed on the upper surface of the translucent member, and may be disposed on the flattening film.
Although there is no restriction | limiting in particular as this planarization film | membrane, It is preferable to form with the same light transmissive resin material as the said light transmissive resin material.

<Other processes>
Examples of the other steps include a step of forming an organic electroluminescent element necessary for a light emitting display device. Hereinafter, the organic electroluminescent element in the present invention will be described.

-Organic electroluminescence 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 in the present invention receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and regenerates the holes and electrons. It is a layer having a function of providing a bonding field to emit light.
The light emitting layer in the present invention contains 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. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.

  Although the thickness of the light emitting layer is not particularly limited, it is usually preferably 2 nm to 500 nm, more preferably 3 nm to 200 nm in terms of external quantum efficiency, and 5 nm to 100 nm. More preferably. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

--- Luminescent material ---
As the light emitting material in the present invention, any of phosphorescent light emitting materials, fluorescent light emitting materials and the like can be suitably 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 contained in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass generally forming the light-emitting layer in the light-emitting layer. To 1 mass% to 50 mass%, and more preferably 2 mass% to 40 mass%.

<Phosphorescent material>
In general, examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
For example, the transition metal atom is not particularly limited, but preferably includes ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum, and more preferably rhenium, iridium. And platinum, more preferably iridium and platinum.

  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- 261623, JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, and the like, and more preferable examples of the light-emitting material include Ir. Complexes, Pt complexes, Cu complexes, Re complexes, W complexes, Rh complexes, Ru complexes, Pd complexes, Os complexes, Eu complexes, Tb complexes, Gd complexes, Dy complexes, and Ce complexes. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or an Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

  Specific examples of the phosphorescent light-emitting material that can be used in the present invention include the following compounds, but are not limited thereto.

<Fluorescent material>
As the fluorescent material, generally, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclohexane Pentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, condensed polycyclic aromatic compounds (such as anthracene, phenanthroline, pyrene, perylene, rubrene, or pentacene), 8 -Various metal complexes such as quinolinol metal complexes, pyromethene complexes and rare earth complexes, polythiophene, polyphenylene, polyphenylene vinylene, and other polymers. Mer compound, organic silane, and may be derivatives of these.

---- Host material ---
As the host material used for the light emitting layer, a hole transporting host material having excellent hole transportability (may be described as a hole transportable host) and an electron transporting host compound having excellent electron transportability (electron transport) May be described as a sex host).

<Hole transportable host>
Specific examples of the hole transporting host used in the light emitting layer include the following materials. 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 dimethylidin compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, Examples thereof include conductive polymer oligomers such as polythiophene, organic silanes, carbon films, and derivatives thereof.
Preferred are indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives, and more preferred are those having a carbazole group in the molecule. In particular, a compound having a t-butyl substituted carbazole group is preferable.

<Electron transporting host>
Specific examples of the electron transporting host used in the light emitting layer include the following materials. Pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyryl Metal complexes of pyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanines, and derivatives thereof (which may form condensed rings with other rings), 8-quinolinol derivatives And various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazol as a ligand. 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 more preferable. Examples of the metal complex electron transporting host are described in, for example, JP-A No. 2002-235076, JP-A No. 2004-214179, JP-A No. 2004-221106, JP-A No. 2004-221665, JP-A No. 2004-221068, JP-A No. 2004-327313, and the like. The compound of this is mentioned.

  Specific examples of the hole transporting host material and the electron transporting host material that can be used in the present invention include, but are not limited to, the following compounds.

--- 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 layer on 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, And the like.

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, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
These electron-accepting dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. More preferably, it is especially 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 a layer on 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, or the like is preferably a layer containing.

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, 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 amount of the electron donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 mass% is particularly preferable.

  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, phenanthroline derivatives such as BCP, and the like. 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 even more preferably 10 nm to 100 nm. In addition, the hole blocking layer and the electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

--- Electrode--
The organic electroluminescent element includes a pair of electrodes, that is, an anode and a cathode. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably 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.

  Although there is no restriction | limiting in particular as said electrode, In the anode and cathode, it is preferable to comprise the said reflective metal and the translucent metal as said translucent member.

  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, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  Specific examples of the material constituting the cathode include, for example, alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, Examples thereof include rare earth metals such as sodium-potassium alloy, lithium-aluminum alloy, magnesium-silver alloy, indium, and 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 injection properties, and materials mainly composed of aluminum are 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). Etc.).

  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, a material constituting the electrode from a wet method such as a printing method, a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. In consideration of the suitability, the film 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, an ion plating 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. It may be performed by sputtering or the like, or may be performed by a lift-off method or a printing method.

-Board-
Examples of the substrate include inorganic materials such as yttria-stabilized zirconia (YSZ) and glass (such as alkali-free glass and soda lime glass), polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, and polyethersulfone. And substrates made of organic materials such as 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. In general, 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. 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 a material for the moisture permeation preventive 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 for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

--Sealing--
Further, 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. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, 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 examples thereof include paraffins, liquid paraffins, fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorinated solvents, and silicone oils. Can be mentioned.

  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 of the resin sealing layer is not particularly limited, and acrylic resin, epoxy resin, fluorine resin, silicon resin, rubber resin, ester resin, or the like can be used. An epoxy resin is preferable from the viewpoint of function. Among the epoxy resins, a thermosetting epoxy resin or a photocurable epoxy resin is preferable.
The method for producing the resin sealing layer is not particularly limited, and examples thereof include a method of applying a resin solution, a method of pressure bonding or thermocompression bonding of a resin sheet, and a method of dry polymerization by vapor deposition or sputtering.

---- 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, epoxy adhesives are preferable from the viewpoint of moisture prevention, and among them, a photocurable adhesive or a thermosetting adhesive is preferable.
It is also preferable to add a filler to the above material. The filler added to the sealant is preferably an inorganic material such as SiO ₂ , SiO (silicon oxide), SiON (silicon oxynitride) or SiN (silicon nitride). 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, barium oxide, calcium oxide, or strontium oxide is preferable. The amount of the desiccant added to the sealing adhesive is preferably 0.01% by mass to 20% by mass, and more preferably 0.05% by mass to 15% by mass. 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 in an arbitrary amount with a dispenser or the like, and the second substrate can be overlaid after application and cured by being cured.

<Manufacturing process>
A manufacturing process of the manufacturing method of the light emitting display device of the present invention thus configured will be described with reference to schematic views 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 has shown either the light transmissive resin material, a light transmissive resin layer, or an optical path length adjustment layer.

First, the reflective metal 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 2 is disposed by flash vapor deposition (light transmissive resin material film forming step, see FIG. 2).
Thus, with the reflective metal 2 and the light-transmitting resin material 3 disposed on the substrate 1, the substrate 4 is partially covered with a mask 4 that can be shielded from light, and irradiated with light L. The light-transmitting resin material 2 in the pixel region adjacent to is selectively exposed and cured to form the light-transmitting resin layer 3 (light-transmitting resin layer forming step, see FIG. 3).
This is developed to remove portions other than the exposed portion from the light-transmitting resin layer 3, thereby forming the optical path length adjusting layer 3 (optical path length adjusting layer forming step, see FIG. 4). When a light-soluble resin is used as the light-transmitting resin, a portion exposed by a positive pattern transfer method may be removed, and the non-exposed optical path length adjusting layer 3 may be formed on the reflective metal 2.

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 previous step, in the pixel region where the reflective metal 2 and the optical path length adjusting layer 3 are arranged, the light-transmitting resin material 5 is deposited on the optical path length adjusting layer 3 to be deposited. An optical path length difference is formed with other pixel regions where 3 is not arranged.
Thus, the reflective metal 2, the optical path length adjusting layer 3, and the light-transmitting resin material 5 are disposed on the substrate 1, and the substrate 4 is covered with a mask 4 that can partially shield the light. Of the two pixel regions on which the transparent resin material 5 is deposited and vapor-deposited, one pixel region is irradiated with light to be cured by exposure to form a light-transmitting resin layer 5 (light-transmitting resin layer) Forming step, see FIG.
This is developed to remove portions other than the exposed portion from the light-transmitting resin layer 5 and form the optical path length adjusting layer 5 in one pixel region (see optical path length adjusting layer forming step, see FIG. 7). At this stage, the optical path length adjustment layers 3 and 5 are arranged to overlap in one pixel area, and the optical path length adjustment layer 3 is arranged in a pixel area adjacent to the pixel area.

Next, the transparent conductive film 6 is disposed on the optical path length adjustment layer 5 in the pixel region where the optical path length adjustment layers 3 and 5 are disposed. At the same time, in the pixel region where the optical path length adjusting layer 3 is disposed, the transparent conductive film 6 is disposed on the optical path length adjusting layer 3 and transparent on the reflective metal 2 in the pixel region where the optical path length adjusting layer is not disposed. A conductive film 6 is provided.
Next, in each of the three pixel regions where the transparent conductive film 6 is disposed, the organic light emitting layer 7 and the semi-transmissive metal 8 are laminated in this order on the transparent conductive film 6 to manufacture the light emitting display device 100 ( (See FIG. 9).
In the light emitting display device 100 manufactured in this way, the light emitted from the organic light emitting layer 7 corresponds to the optical path lengths d ₁ , d ₂ , and d ₃ adjusted by the optical path length adjusting layers 3 and 5. Are extracted from the translucent metal 8 as light of wavelengths corresponding to blue, green and red, respectively.
That is, the light emitted from the organic light emitting layer 7 is resonated between the semi-transparent metal 8 having the optical path lengths d ₁ , d ₂ , and d ₃ and the reflective metal 2, and thus according to each optical path length. By increasing the light of blue, green, and red wavelengths, the light can be extracted from the light emitting display device 100 as blue, green, and red light.

  According to the manufacturing process of the light emitting display device 100 of the present invention, the steps of forming the resist layer, etching using the resist layer as a mask, and stripping the resist layer are not necessary for forming the optical path length difference. Compared with the conventional manufacturing process, the manufacturing process can be greatly simplified.

(Light-emitting display device)
The light emitting display device of the present invention is formed of a substrate having a reflective metal disposed on at least one pixel among a plurality of pixels corresponding to red, green, and blue, and a light transmissive resin material on the substrate. The optical path length adjusting layer is included, and as another configuration, a light-emitting display element necessary for configuring the light-emitting display device is provided.

  The light-emitting display device is not particularly limited as long as it has the above-described configuration, and can be appropriately selected according to the purpose, but is preferably manufactured by the method for manufacturing the light-emitting display device of the present invention, All of the matters described for the method for manufacturing the light emitting display device of the present invention can be applied.

  In the light-emitting display device, light emitted from the organic light-emitting layer extracts 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. However, in each of the blue, green, and red pixel regions on the viewer side of the light emitting display device, a color filter corresponding to each color may be further arranged to enable higher-definition full-color display. .

-First embodiment-
One structural example of the light-emitting display device will be described with reference to FIG. The light emitting display device 100 is a top emission type light emitting display device.
The light-emitting display device 100 includes a reflective metal 2 on a substrate 1 in each pixel region of red, green, and blue.
In the red pixel region, optical path length adjusting layers 3 and 5 are disposed so as to cover the reflective metal 2, and are translucent facing the reflective metal 2 through the transparent conductive film (anode) 6 and the organic light emitting layer 7. A member (cathode) 8 is disposed. In the red pixel region, the optical path length is adjusted by the optical path length adjusting layers 3 and 5, and the optical path length adjusting layers 3 and 5, the transparent conductive film 6, and the organic light emitting layer are interposed between the reflective metal 2 and the translucent member 8. the optical path length d ₃ and a 7 are formed.
In the green pixel region, the optical path length adjusting layer 3 is disposed so as to cover the reflective metal 2, and the translucent member 8 facing the reflective metal 2 is disposed via the transparent conductive film 6 and the organic light emitting layer 7. Has been. In the green pixel region, the optical path is adjusted by the optical path length adjusting layer 3, and the optical path having the optical path length adjusting layer 3, the transparent conductive film 6, and the organic light emitting layer 7 between the reflective metal 2 and the translucent member 8. the length _{d 2} is formed.
In the blue pixel region, a translucent member 8 facing the reflective metal 2 is disposed via the transparent conductive film 6 and the organic light emitting layer 7. In the blue pixel region, an optical path length d ₁ having a transparent conductive film 6 and an organic light emitting layer 7 is formed between the reflective metal 2 and the translucent member 8.

In the light emitting display device 100 formed in this way, the light emitted from the organic light emitting layer 7 is resonated between the reflective metal 2 and the translucent member 8 to have optical path lengths d ₁ , d ₂ , and d ₃ . The light of the corresponding wavelength is intensified and is extracted from the translucent member 8 side as blue, green, and red light, respectively.

-Second Embodiment-
Another light emitting display device 200, which will be described with reference to FIG. 10, is a top emission type light emitting display device.
In the light emitting display device 200, the optical path length adjusting layer 3 is disposed so as to cover the reflective metal 2 in the red pixel region, and is opposed to the reflective metal 2 through the transparent conductive film 6 and the organic light emitting layer 7. A translucent member 8 is disposed. In the red pixel region, the optical path is adjusted by the optical path length adjusting layer 3, and the optical path having the optical path length adjusting layer 3, the transparent conductive film 6, and the organic light emitting layer 7 between the reflective metal 2 and the translucent member 8. the length _{d 3} is formed.
In the green pixel region, a translucent member 8 facing the reflective metal 2 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the green pixel region, an optical path length d ₂ having a transparent conductive film 6 and an organic light emitting layer 7 is formed between the reflective metal 2 and the translucent member 8.
In the blue pixel region, a translucent member 8 facing the reflective metal 2 is disposed with the organic light emitting layer 7 interposed therebetween. In the blue pixel region, an optical path length d ₁ having the organic light emitting layer 7 is formed between the reflective metal 2 and the translucent member 8.
In the blue region, the reflective metal 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.
Since other points are common to the first embodiment, the description thereof is omitted.

-Third embodiment-
One structural example of the light-emitting display device will be described with reference to FIG. The light emitting display device 300 is a bottom emission type light emitting display device.
In the light emitting display device 300, the translucent member 8 is provided on the substrate 1 in each pixel region of red, green, and blue.
In the red pixel region, optical path length adjusting layers 3 and 5 are arranged so as to cover the semitransparent member 8, and the reflective metal 2 facing the translucent member 8 through the transparent conductive film 6 and the organic light emitting layer 7. Is arranged. In the red pixel region, the optical path length is adjusted by the optical path length adjusting layers 3 and 5, and the optical path length adjusting layers 3 and 5, the transparent conductive film 6, and the organic light emitting layer are provided between the translucent member 8 and the reflective metal 2. the optical path length d ₃ and a 7 are formed.
In the green pixel region, the optical path length adjusting layer 3 is disposed so as to cover the translucent member 8, and the reflective metal 2 facing the translucent member 8 is interposed between the transparent conductive film 6 and the organic light emitting layer 7. It is arranged. In the green pixel region, the optical path is adjusted by the optical path length adjusting layer 3, and the optical path having the optical path length adjusting layer 3, the transparent conductive film 6, and the organic light emitting layer 7 between the translucent member 8 and the reflective metal 2. the length _{d 2} is formed.
In the blue pixel region, the reflective metal 2 facing the translucent electrode 8 is disposed through the transparent conductive film 6 and the organic light emitting layer 7. In the blue pixel region, an optical path length d ₁ having a transparent conductive film 6 and an organic light emitting layer 7 is formed between the translucent member 8 and the reflective metal 2.
Since other points are common to the first embodiment, the description thereof is omitted.

(Light-emitting display)
The light-emitting display of the present invention includes the light-emitting display device of the present invention, and other configurations can be applied as necessary.
As the light-emitting display, the optical path length adjusting layer is formed of a light-transmitting resin material, and the light-emitting display portion has flexibility, so that it can be used as a flexible display without cracking due to stress.
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
After depositing 100 nm of aluminum on the substrate by vacuum deposition, and then forming a reflective electrode (reflective metal) by a photolithography process, light transmission is performed by flash deposition on the substrate on which the reflective electrode is formed. The resin material (radically polymerizable monomer, product name: 1,10 decanediol dimethacrylate, manufacturer: Shin-Nakamura Chemical Co., Ltd.) was formed into a 45 nm film (light-transmitting resin material film forming step).
Next, an exposure apparatus (product name: KP364N2, manufacturer: Dainippon Screen) selectively exposed one pixel region using a mask to form a light-transmitting resin layer (light-transmitting resin layer forming step) ).
Next, development was performed with a solvent (solvent name: 2-propanol manufacturer: WAKI) to produce a first-stage optical path length with a thickness of 45 nm (optical path length adjusting layer forming step). The residual amount of radical monomer was 3.0 × 10 ⁻³ g / m ² .

In order to form an optical path length step in the 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 formation step).
Next, the light transmissive resin material in the one pixel region and the adjacent pixel region was selectively exposed in the same manner as described 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-stage optical path length is formed with a thickness of 40 nm for the one pixel region. A first-stage with the same thickness is formed for the pixel region adjacent to the pixel region. Was prepared (optical path length adjusting layer forming step).

  A transparent electrode (made of ITO, IZO, etc., here formed of ITO) is electrically separated and formed for each sub-pixel on the upper surface of the 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 by a vacuum film forming apparatus (product name: CM457, manufacturer: Tokki Co., Ltd.).
On the upper surface of the white OLED, a metal electrode (aluminum) was formed as a light semi-reflective electrode with a vacuum film forming apparatus (product name: CM457, manufacturer: Tokki Co., Ltd.).

  The OLED formation region was sealed with a glass can, and each electrode was connected to an external signal control device to produce a light emitting display device in Example 1.

The light emitting display in Example 1 was manufactured by arranging a plurality of the light emitting display devices.
When the light emitting state of the light emitting display thus manufactured was confirmed, it was possible to confirm the color development of RGB with high definition.

(Example 2)
In the light-transmitting resin material film forming step of Example 1, instead of film formation by flash vapor deposition, film formation by a spin coater (product name: SP-40, manufacturer: Mitsui Seiki) was performed, In the same manner as in Example 1, the light-emitting display device and the light-emitting display in Example 2 were manufactured. The thickness of the optical path length of the first stage was 45 nm, and the thickness of the optical path length of the second stage (and the optical path length of the first stage) was 40 nm.
When the light emitting state of the manufactured light emitting display was confirmed, RGB coloration could be confirmed with high definition.

(Example 3)
Example 1 except that in the light-transmitting resin material film forming step of Example 1, film formation by a spray coater (product name: DC110, manufacturer: Sanmei Electronics Co., Ltd.) was performed instead of film formation by flash vapor deposition. In the same manner as in Example 1, the light emitting display device and the light emitting display in Example 3 were manufactured. The thickness of the optical path length of the first stage was 45 nm, and the thickness of the optical path length of the second stage (and the optical path length of the first stage) was 40 nm.
When the light emitting state of the manufactured light emitting display was confirmed, RGB coloration could be confirmed with high definition.

Example 4
In the light transmissive resin material film forming step of Example 1, instead of film formation by flash vapor deposition, a head cartridge having a droplet ejection amount of 10 pl using an ink jet printer DMP-2831 (manufactured by FDMX), A light-emitting display device and a light-emitting display in Example 4 were manufactured in the same manner as in Example 1 except that film formation by the ink jet method was performed under the condition of a droplet ejection frequency of 10 kHz. The thickness of the optical path length of the first stage was 45 nm, and the thickness of the optical path length of the second stage (and the optical path length of the first stage) was 40 nm.
When the light emitting state of the manufactured light emitting display was confirmed, RGB coloration could be confirmed with high definition.

(Example 5)
A light-emitting display device and a light-emitting display in Example 5 were manufactured in the same manner as in Example 1 except that the light-transmitting resin material film forming step of Example 1 was performed as follows.
That is, 10 g of novolak resin EP4000B (Asahi Organic Materials Co., Ltd.), 2.5 g of the following photosensitive agent, 0.56 g of cross-linking material TEP-G (Asahi Organic Materials Co., Ltd.), and 53 g of a mixture of PEGMEA / siloxane = 1/1 are dissolved. A light transmissive resin material (positive resist material) was prepared.
Examples of the photosensitive agent include 51 parts by mass (0.12 mol) of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and 1,2 -72.5 parts by mass (0.27 mol) of naphthoquinonediazide-4-sulfonic acid chloride was dissolved in 450 mL of tetrahydrofuran, and 28.3 parts by mass (0.28 mol) of triethylamine was added dropwise and reacted at room temperature for 20 hours. Thereafter, the precipitated hydrochloride of triethylamine was removed by filtration and poured into 10 L of ion-exchanged water to obtain a precipitate. The precipitate was agglomerated and vacuum-dried at room temperature for 48 hours.

A 100 nm aluminum film is formed on the substrate by vacuum deposition, and then a reflective electrode (reflective metal) is formed by a photolithography process, and then the light transmissive resin material is sprayed on the substrate on which the reflective electrode is formed. The film was formed by a coater (product name: DC110, manufacturer: Sanmei Electronics).
Next, selective exposure with one pixel area masked was performed by an exposure apparatus (product name: KP364N2, manufacturer: Dainippon Screen) to form a light-transmitting resin layer (light-transmitting resin layer forming step). The thickness of the first stage optical path length was 45 nm, and the thickness of the second stage optical path length (and the first stage optical path length) was 40 nm. The residual radical monomer amount was 2.20 × 10 ⁻³ g / m ² .
When the light emitting state of the manufactured light emitting display was confirmed, RGB coloration could be confirmed with high definition.

  The light emitting display device manufacturing method of the present invention can be widely used as a light emitting display device manufacturing method having a simple manufacturing process, and the light emitting display device manufactured by the manufacturing method is a high-definition full color display. Can be applied in a wide range of fields including mobile phone displays, personal digital assistants (PDAs), computer displays, automotive information displays, TV monitors, or general lighting.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Reflection metal 3, 5 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 (cathode)
10 ITO film (optical path length adjustment layer)
20 resist layer 100, 200, 300, 400 light emitting display device

Claims (18)

A light-transmitting resin material composition is formed by forming a light-transmitting resin material on a substrate in which a reflective metal and a translucent member are disposed in at least one pixel area among a plurality of pixel areas corresponding to red, green, and blue. A membrane process;
A light-transmitting resin layer forming step of forming a light-transmitting resin layer by curing reaction of either the one pixel region or the one pixel region out of the formed light-transmitting resin material; ,
An optical path length adjusting layer forming step of developing the light transmissive resin layer after the curing reaction and forming an optical path length adjusting layer in the one pixel region.   The method for manufacturing a light emitting display device according to claim 1, wherein the light transmissive resin material film forming step is a step of forming a light transmissive resin material by a vapor phase film forming method.   The method of manufacturing a light emitting display device according to claim 2, wherein the vapor deposition method is a flash vapor deposition method.   The method for manufacturing a light-emitting display device according to claim 1, wherein the light-transmitting resin material film forming step is a step of forming a light-transmitting resin material by a spray coating method.   The method for manufacturing a light-emitting display device according to claim 1, wherein the light-transmitting resin material film forming step is a step of forming a light-transmitting resin material by an inkjet method.   The method for manufacturing a light-emitting display device according to claim 1, wherein the light-transmitting resin material is a photocurable resin.   The method for manufacturing a light-emitting display device according to claim 6, wherein the photocurable resin is a radical polymerizable monomer.   The method for producing a light-emitting display device according to claim 7, wherein the radical polymerizable monomer has two or more radical polymerizable functional groups.   The method for producing a light-emitting display device according to claim 7, wherein the radical polymerizable monomer is a monomer having an ethylenically unsaturated double bond group.   The method for producing a light-emitting display device according to claim 9, wherein the monomer having an ethylenically unsaturated double bond group is either an acrylate ester or a methacrylate ester.   The method for producing a light-emitting display device according to claim 7, wherein curing in the light-transmitting resin layer forming step is performed by exposing in the presence of a photopolymerization initiator to radically polymerize a radically polymerizable monomer. . The method for manufacturing a light-emitting display device according to claim 7, wherein the residual amount of the radical polymerizable monomer in the optical path length adjusting layer is 1 × 10 ⁻² g / m ² or less.   The light emitting display according to claim 1, wherein an optical path length adjusting layer is formed on a planarizing film, and the planarizing film is formed of the same light transmissive resin material as the light transmissive resin material of the optical path length adjusting layer. Device manufacturing method.   The method for manufacturing a light-emitting display device according to claim 1, wherein the light-transmitting resin is a light-soluble resin.   A substrate in which a reflective metal and a translucent member are arranged in at least one pixel region among a plurality of pixel regions corresponding to red, green, and blue, and an optical path length formed of a light-transmitting resin material on the substrate A light-emitting display device comprising an adjustment layer.   The light emitting display device according to claim 15, which is manufactured by the method for manufacturing a light emitting display device according to claim 1.   A light-emitting display comprising the light-emitting display device according to claim 15. The light-emitting display according to claim 17, which is used as a flexible display.