JPWO2013105626A1 - Light emitting device and resin composition for forming light emitting device - Google Patents

Abstract

A light-emitting element including a first electrode, a light-emitting layer, a second electrode, and a first resin layer, wherein the first electrode, the light-emitting layer, and the second electrode are stacked in this order, and the first resin The layers are: (a) the side of the first electrode opposite to the side where the light emitting layer is formed, and (b) the side of the second electrode opposite to the side where the light emitting layer is formed. Resin having a glass transition temperature (Tg) of 170 ° C. or higher by differential scanning calorimetry (DSC, heating rate 20 ° C./min) and particles having an average particle size of 0.1 μm to 5 μm And A).

Description

  The present invention relates to a light-emitting element having a specific resin layer and a resin composition for forming a light-emitting element for forming the resin layer.

  The light emitting element has a basic configuration in which a transparent positive electrode layer, a light emitting material layer, and a negative electrode layer are laminated in this order on the surface of a transparent substrate. For example, an organic electroluminescence element injects holes from its positive electrode layer, electrons from its negative electrode layer, into the inside of the light emitting material layer made of organic material, and injects holes and electrons inside the light emitting material layer. This is a light-emitting element that emits light by emission (fluorescence or phosphorescence) when excitons (excitons) are generated by recombination, and the excitons are deactivated. It is taken out from the light emitting element from the transparent substrate side.

  Patent Document 1 discloses a light-emitting element having a high refractive index layer using a high refractive index resin such as polyethersulfone resin or polyetherimide resin.

JP 2004-296438 A

  According to the light emitting element described in Patent Document 1, light generated in the light emitting material layer can be extracted from the transparent substrate side with some efficiency. However, there is a problem that a high refractive index resin such as a polyethersulfone resin or a polyetherimide resin is deteriorated by light emitted from the light emitting material layer.

  In view of the above, an object of the present invention is to provide a light-emitting element that is excellent in light extraction efficiency.

As a result of intensive studies to solve the above problems, the present inventor has a polymer having a specific glass transition temperature and a light-emitting element including a resin layer including particles having a specific particle size. The inventors have found that the above object can be achieved and completed the present invention.
That is, the present invention provides the following [1] to [7].

[1] A light emitting device including a first electrode, a light emitting layer, a second electrode, and a first resin layer, wherein the first electrode, the light emitting layer, and the second electrode are laminated in this order, The first resin layer is
(A) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(B) The side of the second electrode opposite to the side on which the light emitting layer is formed,
Formed on at least one of
It includes a resin having a glass transition temperature (Tg) of 170 ° C. or higher by differential scanning calorimetry (DSC, temperature rising rate 20 ° C./min) and particles (A) having an average particle diameter of 0.1 μm to 5 μm. A light emitting element.

  [2] The light emitting device according to [1], wherein the first resin layer further includes metal oxide fine particles (B) having an average particle diameter of 1 nm or more and less than 100 nm.

[3] Further, the light-emitting element includes a second resin layer, and the second resin layer includes:
(C) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(D) The side of the second electrode opposite to the side on which the light emitting layer is formed,
Formed on at least one of
The glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min) contains a resin having a glass transition temperature of 170 ° C. or higher, and the refractive index measured using light having a wavelength of 632.8 nm is 1.60 or higher. The light-emitting element according to [1] or [2], wherein the light-emitting element is provided.

[4] The second resin layer includes
(C) between the first electrode and the first resin layer; and
(D) Between the second electrode and the first resin layer,
The light emitting device according to [3], wherein the light emitting device is formed on at least one of the above.

  [5] The light emitting device according to any one of [1] to [4], wherein the light emitting device is an organic electroluminescence device.

[6] A light-emitting element forming resin composition for forming the first resin layer of the light-emitting element according to any one of [1] to [5].
[7] A resin composition for forming a light emitting element for forming the second resin layer of the light emitting element according to any one of [3] to [5].

  The light emitting device of the present invention is excellent in light extraction efficiency. Further, since the light-emitting element of the present invention is excellent in durability, it can be used without degrading performance for a long time even under severe use conditions.

It is sectional drawing which shows notionally Embodiment 1 of the light emitting element of this invention. It is sectional drawing which shows notionally Embodiment 2 of the light emitting element of this invention. It is sectional drawing which shows notionally Embodiment 3 of the light emitting element of this invention.

≪Light emitting element≫
Hereinafter, various exemplary embodiments of the light emitting device of the present invention will be described with reference to the drawings. The light emitting device includes a first electrode, a light emitting layer, a second electrode, and a first resin layer. One electrode, the light emitting layer, and the second electrode are laminated in this order, and the first resin layer has a glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min). A resin having a temperature of 170 ° C. or higher (hereinafter also referred to as “polymer (I)”) and particles (A) having an average particle size of 0.1 μm to 5 μm, and
(A) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(B) The side of the second electrode opposite to the side on which the light emitting layer is formed,
There is no particular limitation as long as the light emitting element is formed on at least one of the above.

FIG. 1 shows a light emitting device 10 which is Embodiment 1 of the light emitting device of the present invention. The light emitting element 10 has a structure in which a substrate 11, a first electrode 13, a light emitting layer 15, a second electrode 17, and a first resin layer 18 are laminated in this order. That is, the first resin layer 18 is provided on the surface of the second electrode 17 opposite to the side on which the light emitting layer 15 is provided.
The second electrode 17 is preferably a transmissive electrode. In this case, the light generated in the light emitting layer 15 can be extracted outside the light emitting element 10 through the second electrode 17 and the first resin layer 18. .

  Since the light-emitting element of the present invention includes the first resin layer 18, when light generated in the light-emitting layer 15 passes through the second electrode 17 and enters the air, the light is refracted and the outside of the light-emitting element. The efficiency of being taken out can be increased.

  The light emitting element 10 is preferably a light emitting element in which the refractive index of the second electrode 17, the refractive index of the first resin layer 18, and the refractive index of air (about 1.0) decrease in this order. Moreover, it is preferable that the difference in refractive index between the second electrode 17 and the first resin layer 18 and the difference in refractive index between the first resin layer 18 and air are small. When the second electrode, the first resin layer, and the refractive index of air have such a relationship, the second electrode 17 and the first resin layer are formed in a process in which light generated in the light emitting layer 15 is extracted outside the light emitting element 10. 18 and the interface between the first resin layer 18 and the air are less likely to be totally reflected, and it is considered that the light extraction efficiency is increased.

In FIG. 1, the first resin layer 18 is illustrated as being formed in contact with one surface of the second electrode 17, but there are various types between the first resin layer 18 and the second electrode 17 as necessary. An additional layer may be further provided.
Further, the side of the substrate 11 opposite to the side on which the first electrode 13 is formed, between the substrate 11 and the first electrode 13, between the first electrode 13 and the light emitting layer 15, and between the light emitting layer 15 and the second electrode 17. Various layers may be provided on the opposite side of the first resin layer 18 from the side where the second electrode 17 is formed, as necessary.

  As such various layers, the refractive index decreases from the light emitting element 15 through the first resin layer 18 to the outside of the light emitting element 10 in order to obtain a light emitting element with higher light extraction efficiency. Therefore, the second resin layer or the third resin layer is formed between the second electrode 17 and the first resin layer 18 and / or on the opposite side of the first resin layer 18 from the side on which the second electrode 17 is formed. A layer such as a resin layer may be provided.

  Although not shown in FIG. 1, a known sealing layer for sealing the light emitting element 10 may be further provided, and various modifications are possible.

FIG. 2 shows a light emitting device 20 which is a second embodiment of the light emitting device of the present invention.
The light emitting element 20 has a structure in which a substrate 21, a first resin layer 28, a first electrode 23, a light emitting layer 25, and a second electrode 27 are laminated in this order. That is, the first resin layer 28 is provided on the surface of the first electrode 23 opposite to the surface on which the light emitting layer 25 is provided.
The first electrode 23 is preferably a transmissive electrode. In this case, the light generated in the light emitting layer 25 passes through the first electrode 23, the first resin layer 28, and the substrate 21 and is outside the light emitting element 20. Can be taken out.
The modification of the light emitting element 20 is the same as described above.

The light emitting element 20 is preferably a light emitting element in which the refractive index of the first electrode 23, the refractive index of the first resin layer 28, the refractive index of the substrate 21, and the refractive index of air (about 1.0) decrease in this order.
In consideration of the light extraction efficiency of the light emitting element 20, the substrate 21 is preferably a glass substrate or a transparent plastic substrate having a refractive index smaller than that of the first resin layer 28.
Since the light emitting element 20 includes the first resin layer 28, the light generated in the light emitting layer 25 can be effectively extracted to the outside by light refraction, and the light emitting element has high light extraction efficiency.

FIG. 3 shows a light emitting device 30 which is Embodiment 3 of the light emitting device of the present invention.
The light emitting element 30 has a structure in which a substrate 31, a first or second resin layer 38, a first electrode 33, a light emitting layer 35, a second electrode 37, and a first or second resin layer 39 are laminated in this order. That is, the resin layer 38 is provided on the surface of the first electrode 33 opposite to the surface on which the light emitting layer is provided, and the resin layer 39 is the surface of the second electrode 37 on which the light emitting layer is provided. It is provided on the opposite surface. However, at least one of the resin layers 38 and 39 is a first resin layer. The resin layers 38 and 39 may both be the first resin layer.

The first electrode 33 and the second electrode 37 are preferably transmissive electrodes. In this case, the light generated in the light emitting layer 35 passes through the first electrode 33 and the second electrode 37, and then the resin layer 38, respectively. In addition, the light passes through the resin layer 39 and can be taken out of the light emitting element 30.
The modification of the light emitting element 30 is the same as described above.

In the light emitting element 30, the refractive index of the second electrode 37, the refractive index of the resin layer 39, and the refractive index of air (about 1.0) decrease in this order, the refractive index of the first electrode 33, and the refractive index of the resin layer 38. The light emitting element in which the refractive index, the refractive index of the substrate 31, and the refractive index of air (about 1.0) decrease in this order is preferable.
In consideration of the light extraction efficiency of the light emitting element 30, the substrate 31 is preferably a glass substrate or a transparent plastic substrate having a refractive index smaller than that of the resin layer 38.
Since the light emitting element 20 includes the resin layer 38 and the resin layer 39, light generated in the light emitting layer 35 can be effectively extracted to the outside by light refraction, and the light emitting element has high light extraction efficiency.

<Board>
As the substrate, a substrate used in a general light emitting element can be used, but a glass substrate or a transparent substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. A plastic substrate is preferred.

<First electrode>
The first electrode can be manufactured on the upper surface of the substrate by a vapor deposition method or a sputtering method using a first electrode forming material. When forming a transmissive electrode, the first electrode forming material is transparent and has excellent conductivity, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide ( ZnO) or the like can be used.
When a reflective electrode is formed, magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—) are used as the first electrode forming material. In), magnesium-silver (Mg-Ag), or the like can be used. What is necessary is just to select the thickness of a 1st electrode suitably according to the desired objective.

<Light emitting layer>
The light emitting layer is preferably formed of a material that exhibits a light emission phenomenon when an electric field is applied. Such materials include activated zinc sulfide ZnS: X (where X is an activated element such as Mn, Tb, Cu, Sm), CaS: Eu, SrS: Ce, SrGa ₂ S ₄ : Inorganic electroluminescent (EL) materials such as Ce, CaGa ₂ S ₄ : Ce, CaS: Pb, BaAl ₂ S ₄ : Eu, low molecular dyes such as aluminum complexes of 8-hydroxyquinoline, aromatic amines, anthracene single crystals Conjugated organic EL materials, poly (p-phenylenevinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly (3-alkylthiophene), polyvinylcarbazole, etc. Conventionally used EL materials such as polymer organic EL materials can be used.

  Among these, since the first resin layer contains the polymer (I), the light emitting layer is preferably a layer formed using an organic EL substance. Thus, when a light emitting layer is a layer formed using an organic EL substance, an organic EL element is obtained. The thickness of the light emitting layer is usually 10 to 1000 nm, preferably 30 to 500 nm, and more preferably 50 to 200 nm. The light emitting layer can be formed by a vacuum film formation process such as vapor deposition or sputtering, or a coating process using chloroform or the like as a solvent.

<Second electrode>
The second electrode can be manufactured by vapor deposition or sputtering using a second electrode forming material. As the second electrode forming substance, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg—Ag) and the like.
A transmissive electrode can be obtained by forming a thin film from these substances. Further, a transmissive electrode containing ITO or IZO may be used. What is necessary is just to select the thickness of a 2nd electrode suitably according to the desired objective.
The second electrode is preferably a cathode that is an electron injection electrode.

<First resin layer>
The first resin layer contains at least a polymer (I), particles (A) having an average particle size of 0.1 μm to 5 μm, and an organic solvent (hereinafter also referred to as “specific solvent”). A layer formed from the resin composition is preferred.
Since the light emitting device of the present invention includes the first resin layer, the light emitting device is excellent in light extraction efficiency.

  Such a first resin layer may be included in two or more layers in the light emitting device of the present invention. In this case, two or more first resin layers having the same composition may be included in the light emitting device of the present invention, and two or more first resin layers having different compositions are included in the light emitting device of the present invention. May be.

[Resin having a glass transition temperature (Tg) of 170 ° C. or higher (polymer (I))]
The polymer (I) includes thermoplastic resins such as aromatic polyether polymers (hereinafter also referred to as “polymer (II)”) and polyimide polymers, and silicone-based, epoxy-based, acrylic-based, cyano-based polymers. A thermosetting resin such as acrylate-based or epoxy-based acrylate can be preferably used. In particular, by using a polymer (III), which will be described later, which is a thermoplastic resin, a resin composition having excellent film-forming properties can be obtained, and a light-emitting element having excellent balance in light extraction efficiency, heat resistance, and the like can be obtained.
Polymer (I) may be used individually by 1 type, and may be used in combination of 2 or more type.

[Polymer (I)]
The polymer (I) is a polymer having a glass transition temperature (Tg) of 170 to 350 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min), preferably 240 to 330 ° C., More preferably, it is 250-300 degreeC.
The glass transition temperature of the polymer (I) is measured, for example, using a Rigaku 8230 type DSC measuring apparatus (temperature rising rate 20 ° C./min).

  Such a resin layer containing the polymer (I) is excellent in balance in heat resistance, mechanical strength, electrical characteristics, and the like.

  The polymer (II) is a polymer obtained by a reaction that forms an ether bond in the main chain, and is a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) and the following. A polymer having at least one structural unit (i) selected from the group consisting of structural units represented by formula (2) (hereinafter also referred to as “structural unit (2)”) (hereinafter also referred to as “polymer (III)”) It is preferable that When the polymer has the structural unit (i), an aromatic polyether polymer having a glass transition temperature in the above range is obtained. Such a resin layer containing the polymer (III) is excellent in heat resistance, electrical characteristics and transparency, and has a high refractive index. Moreover, when the resin layer contains the polymer (III), a light emitting device having excellent light extraction efficiency and durability can be obtained.

  In addition, the polymer (II), particularly the polymer (III), has less light absorption in the visible region than the polyethersulfone resin or polyetherimide resin, and therefore the resin is hardly deteriorated by visible light. . For this reason, the light-emitting element provided with the resin layer containing the polymer (II), particularly the polymer (III) is particularly preferable because of its excellent durability.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1.
The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 1 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. An aromatic hydrocarbon group etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group and n-heptyl group.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. Preferable examples include organic groups of formulas 1 to 12.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. And an aryloxy group having 1 to 12 carbon atoms and the like. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.
As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benzine. A triazole group etc. are mentioned.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom. Specifically, an oxazole group, an oxadiazole group, Examples include a benzoxazole group and a benzoxadiazole group.

As R < ¹ > -R < ⁴ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable, a C6-C12 aromatic hydrocarbon group is more preferable, and a phenyl group is further more preferable.

In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

The polymer (III) has a molar ratio of the structural unit (1) to the structural unit (2) (however, the sum of the structural unit (1) and the structural unit (2) is 100). However, it is preferable that the structural unit (1): structural unit (2) = 50: 50 to 100: 0 from the viewpoint that the polymer is excellent in optical properties, heat resistance, mechanical properties, and the like. 1): Structural unit (2) = 70: 30 to 100: 0 is more preferable, and structural unit (1): structural unit (2) = 80: 20 to 100: 0 is more preferable.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer (III) further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). May be. It is preferable that the polymer (III) has such a structural unit (ii) because the mechanical properties of the resin layer obtained from the composition having the polymer (III) are improved.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

  The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. And a group substituted with a chlorine atom, a bromine atom or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom or an iodine atom.

  Examples of the organic group having 1 to 12 carbon atoms including at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms and having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one kind of atom selected from the group consisting of oxygen atom and nitrogen atom is specifically selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

Z in the formula (3) is preferably a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms, and a divalent organic group having 1 to 12 carbon atoms. A hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f. When m is 0, R ⁷ is not a cyano group.

In the polymer (III), the molar ratio of the structural unit (i) to the structural unit (ii) (however, the sum of both ((i) + (ii)) is 100) is an optical property. (I) :( ii) = 50: 50 to 100: 0 is preferable from the viewpoint of becoming a polymer having excellent heat resistance and mechanical properties, and (i) :( ii) = 70: 30 It is more preferable that it is ˜100: 0, and it is more preferable that (i) :( ii) = 80: 20 to 100: 0.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer (III) contains the structural unit (i) and the structural unit (ii) in an amount of 70 mol% or more in the total structural units in view of being a polymer having excellent optical properties, heat resistance, mechanical properties, and the like. It is preferable to contain, and it is more preferable to contain 95 mol% or more in all the structural units.

  Examples of the polymer (III) include a compound represented by the following formula (5) (hereinafter also referred to as “compound (5)”) and a compound represented by the following formula (7) (hereinafter referred to as “compound (7)”). A component containing at least one compound selected from the group consisting of (hereinafter also referred to as “component (A)”) and a component containing a compound represented by the following formula (6) (hereinafter referred to as “component (B)”) It can also be obtained by reacting.

  In said formula (5), X shows a halogen atom independently and a fluorine atom is preferable.

In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently synonymous with X in the formula (5). However, when m is 0, R ⁷ is not a cyano group.

In the formula (6), each R ^a independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (6), R ¹ to R ⁴ and a~d have the same meanings as R ¹ to R ⁴ and a~d each independently the formula (1).

  Specific examples of the compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2, Examples include 5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, and reactive derivatives thereof. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the formula (6) (hereinafter also referred to as “compound (6)”) include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL), 9,9-bis. (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9, Examples include 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  As the compound (7), specifically, 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone (DFDS), 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2′-difluorobenzophenone, 2,2′-difluorodiphenylsulfone, 3,3′-dinitro-4,4′-difluorobenzophenone, 3,3′-dinitro-4,4′-difluorodiphenylsulfone, 4, 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3 , 3′-dinitro-4,4′-dichlorobenzophenone and 3,3′-dinitro-4, 4'-dichlorodiphenyl sulfone and the like can be mentioned. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

It is preferable that at least one compound selected from the group consisting of compound (5) and compound (7) is contained in 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol% to More preferably, it is contained at 100 mol%.
Moreover, it is preferable that (B) component contains the compound represented by following formula (8) as needed. Compound (6) is preferably contained in 100 mol% of component (B) in an amount of 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

In the formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the formula (3), R ^a has the same meaning as R ^a each independently in the formula (6) in.

  Examples of the compound represented by the formula (8) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, and 3,3′-dihydroxy. Diphenylsulfone, 4,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxy) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof Etc. Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

More specifically, the polymer (III) can be synthesized by the method (I ′) shown below.
Method (I ′):
The alkali metal salt obtained after reacting the component (B) with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (compound (6) and / or compound (8), etc.) And (A) component are made to react. In addition, the alkali metal salt of (B) component and (A) component can also be made to react by performing reaction with (B) component and an alkali metal compound in presence of (A) component.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^a in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent used in the reaction include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyllactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (carbon number of alkoxy group) 1-4) etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used. These can be used alone or in combination of two or more.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used. These can be used alone or in combination of two or more.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) is 100 mol% in total of component (A) and component (B). More preferably, it is 50 mol% or more and 52 mol% or less, more preferably more than 50 mol% and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 48 mol%. % Or more and 50 mol% or less, more preferably 48 mol% or more and less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60-250 degreeC, More preferably, it is the range of 80-200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

  The polymer (II) is a polystyrene-reduced weight average molecular weight (Mw) measured by a TOSOH HLC-8220 GPC apparatus (column: TSKgel α-M, developing solvent: tetrahydrofuran (hereinafter also referred to as “THF”)). However, Preferably it is 5,000-500,000, More preferably, it is 15,000-400,000, More preferably, it is 30,000-300,000.

  The polymer (II) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C. or higher, more preferably 475 ° C. or higher, and further preferably 490 ° C. or higher.

As the resin composition for forming a light emitting element, a mixture of the polymer (III) obtained by the method (I ′) and an organic solvent can be used as it is. In this case, the organic solvent used for the reaction is a specific solvent.
The composition is prepared by isolating (purifying) the polymer (III) as a solid component from the mixture of the polymer (III) obtained by the above method and an organic solvent, and then re-dissolving it in a specific solvent. It can also be prepared.

  The method of isolating (purifying) the polymer (III) as a solid component is, for example, reprecipitation of the polymer in a poor solvent of the polymer such as methanol, and subsequent filtration, and then drying the filtrate under reduced pressure. Can be performed.

  As the specific solvent for redissolving the polymer (III), a solvent that easily dissolves the polymer (III) is preferably selected. For example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyrolactone are preferably used from the viewpoints of coating properties and economy. Preferably, methylene chloride, cyclohexanone, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferably used. These solvents can be used alone or in combination of two or more.

  In addition, other specific solvents such as ether organic solvents, ester organic solvents, ketone organic solvents, hydrocarbon organic solvents, alcohols, aiming to improve drying properties, uniformity and surface smoothness during coating. One kind selected from organic organic solvents, or two or more kinds of solvents can be used in appropriate combination. In this case, an organic solvent having a boiling point in the range of 40 to 250 ° C., more preferably 50 to 150 ° C. under atmospheric pressure (1,013 hPa) is preferable, and the polymer (III) is uniformly dissolved and dispersed. It is preferable to be used within the range where it can be used.

  Preferred examples of these other specific solvents include glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate. Esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and methyl amyl ketone Kind. These can be used alone or in combination of two or more.

  In addition, the said specific solvent is used suitably also for the resin composition for light emitting element formation containing polymers (I) other than polymer (III).

[Epoxy resin]
The resin layer containing the epoxy resin is excellent in heat resistance, mechanical strength, adhesion, and the like. Such a resin layer containing an epoxy resin is obtained by using a resin composition for forming a light emitting element including an epoxy compound and a compound capable of curing the epoxy compound (hereinafter also referred to as “curing agent”). Can be formed.

  Specific examples of the epoxy compound include bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; novolac type epoxy compounds such as phenol novolac type epoxy compounds and cresol novolac type epoxy compounds; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3 , 4-epoxycyclohexylmethyl) adipate, vinylcyclohexylene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) azi 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis (3 , 4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, lactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, lactone-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, hydrogenated bisphenol Alicyclic epoxy compounds such as A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol jig Aliphatic epoxy compounds such as cidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether; brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol Halogenated epoxy compounds such as S diglycidyl ether; glycidylamine type epoxy compounds such as tetraglycidylaminophenylmethane, and 9,9-bis [4- (2-glycidyloxypropoxy) -3,5-dimethylphenyl] fluorene And an epoxy compound having a fluorene skeleton. These can be used alone or in combination of two or more.

  Specific examples of the curing agent include amines such as aliphatic amines, aromatic amines and modified amines, polyamide resins, tertiary amines, secondary amines, imidazoles, mercaptans, acid anhydrides, boron trifluoride. Mention may be made of amine complexes, dicyanamides, organic acid hydrazides and the like. These can be used alone or in combination of two or more.

The glass transition temperature of the epoxy resin is preferably 170 to 350 ° C, more preferably 175 to 300 ° C. The glass transition temperature is measured using, for example, Rigaku 8230 type DSC measuring apparatus (temperature rising rate 20 ° C./min).
As the epoxy resin having such a glass transition temperature, it is preferable to use a novolak type epoxy compound as an epoxy compound or an epoxy compound having a fluorene skeleton, and a curing agent comprising a combination of acid anhydrides.

  The concentration of the polymer (I) in the light emitting element forming resin composition is usually 1 to 40% by mass, preferably 5 to 25% by mass, although it depends on the molecular weight of the polymer. When the concentration of the polymer (I) in the composition is in the above range, it is possible to form a resin layer that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

  The viscosity of the resin composition for forming a light emitting element is preferably 50 to 100,000 mPa · s, more preferably 500 to 50,000 mPa · s, although it depends on the molecular weight and concentration of the polymer (I). Preferably it is 1000-20,000 mPa * s. When the viscosity of the composition is within the above range, the resin layer is easily formed during the formation of the resin layer, and the resin layer can be easily molded because the thickness can be easily adjusted.

[Particle (A)]
The resin layer includes particles (A) having an average particle diameter of 0.1 μm to 5 μm. For this reason, it becomes possible to give the said resin layer a light-diffusion function, and also can improve the extraction efficiency of light.
The average particle diameter of the particles (A) is preferably 0.2 to 3 μm, more preferably 0.3 to 2 μm.
The average particle diameter can be measured with a particle distribution measuring apparatus based on the dynamic light scattering method.
The particles (A) can be used alone or in combination of two or more.

Here, in order to impart a light diffusion function, it is preferable to use particles having a large refractive index difference between the particles (A) and the polymer (I). As such particles, particles having a high refractive index are used. Or the particle | grains which have a low refractive index are mentioned.
As the particles having a high refractive index, particles similar to those exemplified as the following metal oxide particles (B), etc. (however, the average particle diameter is in the above range) can be used. The particles having a low refractive index are particles having a refractive index of light of 632.8 nm at 25 ° C. of preferably 1.55 or less, more preferably 1.50 or less, specifically, organic particles. It is preferable to use it.

Examples of the organic particles include polymethyl methacrylate (PMMA) particles, polystyrene particles, and organic crosslinked particles.
The organic crosslinked particles can be produced from a crosslinking monomer. As the crosslinkable monomer, two or more copolymerizable double bonds such as a non-conjugated divinyl compound typified by divinylbenzene or a polyvalent acrylate compound typified by trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, etc. are used. The compound which has can be used preferably. More preferably, it is a compound having two copolymerizable double bonds.
Moreover, as said organic particle, you may use a hollow particle from a viewpoint of low refractive index.

  The addition amount of the particles (A) is preferably adjusted as appropriate in consideration of the specific gravity of the particles themselves and the difference in refractive index from the polymer (I), and is not particularly limited. In order to provide a sufficient light diffusion function, the amount of the particles (A) added is preferably 1 to 2000 parts by mass with respect to 100 parts by mass of the solid content of the light emitting element forming resin composition. Parts, more preferably 2 to 1000 parts by mass, particularly preferably 10 to 100 parts by mass.

When the blending amount of the particles (A) is in the above range, the light diffusion function of the resin layer can be appropriately adjusted while maintaining crack resistance and the like.
In addition, when the particle (A) to be used is a solvent-dispersed sol, the blending amount of the particle (A) means a mass not including a solvent, and the amount of the solvent contained in the sol is the amount of the specific solvent. Count.

[Metal oxide particles (B)]
In order to obtain a light-emitting element having excellent light extraction efficiency, the resin layer preferably contains metal oxide particles (B) having an average particle diameter of 1 nm or more and less than 100 nm. Such particles (B) are fine particles having a refractive index of light having a wavelength of 632.8 nm at 25 ° C. of preferably 1.75 or more, more preferably 1.80 or more, and particularly preferably 1.85 or more. By using the resin layer containing the particles (B) having such a refractive index, a light emitting element that is more excellent in light extraction efficiency can be obtained.
The refractive index is measured using, for example, a prism coupler model 2010 (manufactured by Metricon).

Examples of the particles (B) include metal oxide particles such as zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, barium titanate, and composites thereof. It is done. Among them, zirconium (ZrO ₂ ), titanium oxide (TiO ₂ ), barium titanate (BaTiO ₃ ) fine particles, and titanium oxide fine particles on the surface of silica (SiO ₂ ), zirconium oxide (ZrO ₂ ) or water. Fine particles in which aluminum oxide (Al (OH) ₃ ) is coated to suppress the photocatalytic function of titanium oxide are preferred.
The titanium oxide is not particularly limited as long as it has a TiO ₂ structure, and examples thereof include anatase type, rutile type, brookite type, etc., but the rutile type is most preferable from the viewpoint of suppression of the photocatalytic function and refractive index. .
These particles (B) can be used alone or in combination of two or more.

  The average particle size of the particles (B) is preferably 3 to 70 nm, more preferably 5 to 50 nm. When the average particle diameter is within the above range, a resin layer having excellent transparency can be obtained. The average particle diameter can be measured with a particle distribution measuring apparatus based on the dynamic light scattering method.

  The particles (B) may be in a powder form or a solvent dispersion sol. Examples of the solvent contained in the solvent dispersion sol include 2-butanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, and γ-butyrolactone.

The blending amount of the particles (B) is not particularly limited, but is an amount such that the concentration of the polymer (I) in the resin composition for forming a light emitting element and the viscosity of the resin composition for forming a light emitting element fall within the above ranges. Specifically, it is preferably 0 to 2,000 parts by weight, more preferably 10 to 1,500 parts by weight, still more preferably 30 to 1, based on 100 parts by weight of the polymer (I). 000 parts by mass, particularly preferably 50 to 500 parts by mass. When the blending amount of the particles (B) is in the above range, a light emitting device excellent in light extraction efficiency can be obtained while maintaining transparency and crack resistance.
In addition, when the particle (B) to be used is a solvent-dispersed sol, the blending amount of the particle (B) means a mass not including a solvent, and the amount of the solvent included in the sol is the amount of the specific solvent. Count.

[Dispersant]
The light emitting element forming resin composition preferably contains various dispersants in order to improve the dispersibility of the particles (A) and / or the particles (B).
A dispersing agent can also be used 1 type or in combination of 2 or more types.

  As the dispersant, for example, an aluminum compound can be used. Examples of the aluminum compound include aluminum alkoxide and aluminum β-diketonate complex. Specifically, alkoxide compounds such as triethoxyaluminum, tri (n-propoxy) aluminum, tri (i-propoxy) aluminum, tri (n-butoxy) aluminum, tri (sec-butoxy) aluminum, aluminum tris (methylacetate) Acetate), aluminum tris (ethyl acetoacetate), tris (acetoacetonato) aluminum, aluminum monoacetylacetonatobis (methyl acetate), aluminum monoacetylacetonatobis (ethyl acetate) and other β-diketonate complexes .

  Commercial products of aluminum compounds include AIPD, PADM, AMD, ASBD, aluminum ethoxide, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, aluminum chelate A (W), surface treatment agent OL-1000, algomer, algomer 800AF, algomer 1000SF (manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.

  A nonionic dispersant can also be used as the dispersant. By using a nonionic dispersant, the dispersibility of the metal oxide particles can be enhanced. Examples of the nonionic dispersant include polyoxyethylene alkyl phosphate ester, amide amine salt of high molecular weight polycarboxylic acid, ethylenediamine PO-EO condensate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, alkyl glucoside, polyoxyethylene Fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and fatty acid alkanolamides are preferred. Particularly preferred is a phosphoric ester nonionic dispersant having a polyoxyethylene alkyl structure. As a commercially available product of polyoxyethylene alkyl phosphate, PLAAD ED151 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned.

  The blending amount of the dispersant is not particularly limited as long as the effects of the present invention are not impaired. However, when the dispersant is included, the amount of the dispersant is, for example, about 0.1% relative to 100% by mass of the solid content of the resin composition for light emitting element formation. 1 to 5% by mass.

[Dispersion aid]
The resin composition for forming a light emitting element preferably further contains a dispersion aid in order to improve the dispersibility of the particles (A) and / or the particles (B). As the dispersion aid, one or more selected from acetylacetone and N, N-dimethylacetoacetamide can be suitably used.

  The blending amount of the dispersion aid is not particularly limited as long as the effects of the present invention are not impaired, but when a dispersion aid is included, for example, with respect to 100% by mass of the solid content of the resin composition for light emitting element formation, It is 0-5 mass%.

[Surfactant]
From the viewpoint of obtaining a resin layer having a uniform thickness, it is preferable to add a surfactant to the resin composition for forming a light emitting element. Examples of the surfactant include a silicone-based surfactant and a fluorine-based surfactant. Of these, silicone surfactants are preferred.
Surfactants can be used alone or in combination of two or more.

  Examples of silicone surfactants include, for example, SH28PA (manufactured by Toray Dow Corning Co., Ltd., dimethylpolysiloxane polyoxyalkylene copolymer), Paintad 19, Paintad 54 (manufactured by Toray Dow Corning Co., Ltd., dimethylpolysiloxane). Siloxane polyoxyalkylene copolymer), Silaplane FM0411 (manufactured by JNC Corporation), SF8428 (manufactured by Toray Dow Corning Co., Ltd., dimethylpolysiloxane polyoxyalkylene copolymer (containing OH group in side chain)), BYKUV3510 (Big Chemie Japan Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 (Toray Dow Corning Silicone Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), DC190 (Toray Dowconi Dimethylpolysiloxane-polyoxyalkylene copolymer), Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by JNC Corporation), UV3500, UV3510, UV3530 (Big Chemie) -Japan Co., Ltd.), BY16-004, SF8428 (Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (Wako Pure Chemical Industries, Ltd.).

  Particularly preferred examples include Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, and VPS-1001. In addition, TegoRad 2300, 2200N (manufactured by Tego Chemie), which is a commercial product of a silicone compound having an ethylenically unsaturated group, may also be mentioned.

Examples of the fluorosurfactant include, for example, MegaFuck F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482, F483, F484, F486, F487, F559, F562, F563, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC Corporation) It is done.
Particularly preferred examples include Megafac F559, F562, and F563 having a hydrophilic group and a new oil group.

  The blending ratio of the surfactant is preferably 0 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0 to 100% by mass of the solid content of the resin composition for forming a light emitting element. 0.5-3 mass%. When the compounding quantity of surfactant exceeds 10 mass% with respect to 100 mass% of solid content of the said resin composition for light emitting element formation, there exists a possibility that the refractive index of the resin layer obtained may fall.

Moreover, an anti-aging agent can be further contained in the resin composition for forming a light emitting element, and the durability of the resulting resin layer can be further improved by containing the anti-aging agent.
Preferred examples of the antiaging agent include hindered phenol compounds.

  Examples of hindered phenol compounds that can be used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate), N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro 5.5] undecane, and the like. These can be used alone or in combination of two or more.

  In this invention, it is preferable to use an anti-aging agent in the quantity of 0.01-10 weight part with respect to 100 weight part of said polymers (I).

[Other additives]
The said resin composition for light emitting element formation can contain various additives other than the above in the range which does not impair the effect of this invention. Examples of such additives include curable compounds other than the above components and ultraviolet absorbers.

[Method for Producing Light-Emitting Element Forming Resin Composition]
The resin composition for forming a light emitting element can be prepared by mixing the polymer (I), the particles (A), and other optional components blended as necessary. Usually, it can be prepared by mixing the polymer (I), the particles (A), the specific solvent and other optional components in a predetermined ratio.

In particular, in order to obtain a light-emitting element having high light extraction efficiency, the particles (A) are blended with a composition having a high refractive index (specifically, a composition capable of forming a film having a high refractive index). Is preferred.
As the high refractive index film, the refractive index measured using light having a wavelength of 632.8 nm is preferably 1.60 or more, more preferably 1.65 or more, still more preferably 1.75 or more, more preferably 1.77 to 2.0, particularly preferably 1.80 to 2.0.
The refractive index can be measured using a prism coupler model 2010 (manufactured by Metricon).
The composition capable of forming such a film having a high refractive index is particularly preferable when the composition contains the polymer (I), preferably the polymer (I) having a high refractive index. Is obtained by including 100 parts by mass of the polymer (I) and 50 to 500 parts by mass of the particles (B).

[Method for producing first resin layer]
The method for producing the first resin layer for forming the light emitting device of the present invention is not particularly limited. When the light emitting device 10 is produced using the resin composition for forming the light emitting device, for example, the second electrode 17 is used. A method of removing a specific solvent from the coating film, if necessary, and applying a resin composition for forming a light emitting element on a support made of polyethylene terephthalate (PET) or the like And forming a coating film, and then peeling the coating film from the support and laminating it on the second electrode 17 and the like.

  Since the first resin layer contains the polymer (I), preferably the polymer (II) or the polymer (III), the refractive index tends to be high. Therefore, for example, in the light emitting element 10, when an electrode made of ITO (refractive index: about 2.12) is used as the second electrode 17, the refractive indexes of the second electrode 17, the first resin layer 18, and air are in this order. It is thought that it will become smaller. For this reason, a light emitting element having high light extraction efficiency can be obtained.

  Examples of the method for forming the coating film by applying the resin composition include a roll coating method, a gravure coating method, a spin coating method, a slit coating method, and a method using a doctor blade.

  Although the thickness when apply | coating the said resin composition and forming a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

  Further, the method for removing the specific solvent from the coating film is not particularly limited, and examples thereof include a method of heating the coating film. By heating the coating film, the specific solvent in the coating film can be evaporated and removed. The heating condition may be determined as appropriate so long as the specific solvent evaporates and does not cause thermal deformation or modification of various materials due to heat. For example, the heating temperature is preferably 30 ° C. to 300 ° C., 40 It is more preferable that the temperature is from 250C to 250C, and it is more preferable that the temperature is from 50C to 230C.

  Further, the heating time is preferably 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 150 ° C. for 1 minute to 2 hours, heating is further performed at 100 ° C. to 250 ° C. for 10 minutes to 2 hours. Moreover, you may dry in nitrogen atmosphere or pressure reduction as needed.

  The thickness of the first resin layer is appropriately selected according to a desired application, but is preferably 20 nm to 100 μm, more preferably 80 nm to 50 μm.

  The first resin layer preferably has a glass transition temperature (Tg) of 170-350 ° C., 240-330 ° C. measured by Rigaku 8230 type DSC measuring device (temperature increase rate 20 ° C./min). More preferably, it is more preferably 250 to 300 ° C. When the first resin layer has such a glass transition temperature, heating and heat treatment in forming an electrode or the like on the layer can be performed at a high temperature, and thus the electrode thus obtained has a low resistance. Thus, a light-emitting element having high transmittance and excellent light extraction efficiency and durability can be easily manufactured.

  The first resin layer preferably has a tensile strength of 50 to 200 MPa, and more preferably 80 to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The first resin layer preferably has an elongation at break of 5 to 100%, more preferably 15 to 100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The first resin layer preferably has a tensile modulus of 2.5 to 4.0 GPa, and more preferably 2.7 to 3.7 GPa. The tensile elastic modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The first resin layer has a linear expansion coefficient of preferably 80 ppm / K or less, more preferably 75 ppm / K or less, measured using an SSC-5200 type TMA measuring device manufactured by Seiko Instruments.

  The first resin layer preferably has a humidity expansion coefficient of 15 ppm /% RH or less, and more preferably 12 ppm /% RH or less. The humidity expansion coefficient can be measured using MA (SII Nanotechnology, TMA-SS6100) humidity control option. When the expansion coefficient of the first resin layer is in the above range, it indicates that the dimensional stability (environmental reliability) is high, and therefore it can be suitably used for a light emitting element.

  The first resin layer preferably has a relative dielectric constant of 2.0 to 4.0, more preferably 2.3 to 3.5, and further preferably 2.5 to 3.2. preferable. The relative dielectric constant can be measured using a 4284A type LCR meter manufactured by HP. When the relative dielectric constant is in the above range, the light emitting device including the first resin layer tends to exhibit a stable light emitting state.

  The first resin layer preferably has a total light transmittance in a JIS K7105 transparency test method of 50% or more. The total light transmittance can be measured using a haze meter SC-3H (manufactured by Suga Test Instruments Co., Ltd.).

  When the thickness of the first resin layer is 30 μm, the YI value (yellow index) is preferably 3.0 or less, more preferably 2.5 or less, and 2.0 or less. More preferably. The YI value can be measured using an SM-T type color measuring device manufactured by Suga Test Instruments Co., Ltd.

  When the first resin layer has a thickness of 30 μm, the YI value after heating for 1 hour at 230 ° C. in the air with a hot air dryer is preferably 3.0 or less. Or less, more preferably 2.0 or less.

  In addition, since the said 1st resin layer contains the said particle | grain (A), it is not easy to measure the refractive index.

<Second resin layer>
The light emitting device of the present invention may further have a second resin layer.
The second resin layer is
(C) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(D) The side of the second electrode opposite to the side on which the light emitting layer is formed,
At least one of, preferably
(C ′) between the first electrode and the first resin layer; and
(D ′) between the second electrode and the first resin layer,
Formed on at least one of
The glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min) contains a resin having a glass transition temperature of 170 ° C. or higher, and the refractive index measured using light having a wavelength of 632.8 nm is 1.60 or higher. is there.

The second resin layer is a layer that does not contain the particles (A). Therefore, when the second resin layer is formed in the above (c ′) or (d ′), it can be expected that the electrode surface is flattened.
The second resin layer preferably contains the particles (B) from the viewpoint of obtaining a high refractive index layer.

  Two or more layers of the second resin layer may be included in the light emitting device of the present invention. In this case, two or more second resin layers having the same composition may be included in the light emitting device of the present invention, and two or more second resin layers having different compositions are included in the light emitting device of the present invention. May be.

Such a second resin layer is preferably a layer formed from a resin composition for forming a light emitting element containing at least the polymer (I) and a specific solvent.
About the component contained in this resin composition for light emitting element formation, and the component which may be contained, what is necessary is just the same with having demonstrated the 1st resin layer except the said particle | grain (A).
Moreover, the manufacturing method of a 2nd resin layer should just be the same as the manufacturing method of a 1st resin layer.

The refractive index of the second resin layer measured using light having a wavelength of 632.8 nm is preferably 1.60 or more, more preferably 1.65 or more, and particularly preferably 1.75 or more.
When the refractive index of the second resin layer is in the above range, the light extraction efficiency of the obtained light emitting element is increased.
Since the polymer (I) is contained, a second resin layer having such a refractive index can be obtained.
The refractive index can be measured using a prism coupler model 2010 (manufactured by Metricon).
The physical properties other than the refractive index of the second resin layer may be the same as the physical properties of the first resin layer.

<Third resin layer>
The light emitting device of the present invention may further have a third resin layer. The third resin layer does not contain the particles (A) and (B). Moreover, it is preferable that it is a layer which consists only of resin substantially. Such a third resin layer is preferably provided between the first and / or second resin layer and the substrate when the first and / or second resin layer is provided in contact with the substrate.
Since such a 3rd resin layer is excellent in adhesiveness, it is thought that the light emitting element which the long-term reliability of the light emitting element improved can be obtained.

  Two or more layers of the third resin layer may be included in the light emitting device of the present invention. In this case, two or more third resin layers having the same composition may be included in the light emitting device of the present invention, and two or more third resin layers having different compositions are included in the light emitting device of the present invention. May be.

The third resin layer is preferably a layer formed from a resin composition for forming a light emitting element containing the epoxy resin.
About the component contained in this resin composition for light emitting element formation, and the component which may be contained, what is necessary is just the same with having demonstrated the 1st resin layer except not containing the said particle | grain (A) and (B).
Moreover, the manufacturing method of a 3rd resin layer should just be the same as the manufacturing method of a 1st resin layer.
Further, it may be the same as the physical properties of the first resin layer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(1) Structural analysis The structural analysis of the polymer obtained in the following synthesis example was performed by IR (ATR method, FT-IR, 6700 (manufactured by NICOLET)) and NMR (ADVANCE500 type, manufactured by BRUKAAR).

(2) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) of the polymer obtained in the following synthesis example was measured using an HLC-8220 type GPC apparatus (column: TSKgelα-M, developing solvent: THF) manufactured by TOSOH.

(3) Glass transition temperature (Tg)
The glass transition temperature of the polymer or resin layer for a light-emitting element obtained in the following synthesis example was measured using a Rigaku 8230 type DSC measuring apparatus at a heating rate of 20 ° C./min. In addition, the glass transition temperature of the resin layer for light emitting elements was measured using what peeled the resin layer from the obtained board | substrate with a resin layer for light emitting elements. The results are shown in Table 1 or 2.

(4) Total light transmittance, haze value, and yellow index (YI value)
The resin layer was peeled from the substrate with the light emitting element resin layer obtained in the following examples and comparative examples, and the total light transmittance, haze value, and yellow index (YI value) of the obtained resin layer for light emitting element were measured according to JIS. It measured according to the K7105 transparency test method. Specifically, the total light transmittance was measured using a haze meter SC-3H manufactured by Suga Test Instruments Co., Ltd., and the YI value was measured using a SM-T color meter manufactured by Suga Test Instruments Co., Ltd. Measured (YI before heating).
Also, the resin layer was peeled from the substrate with the light emitting element resin layer obtained in the following examples and comparative examples, and the obtained resin layer for the light emitting element was heated in an air at 200 ° C. for 30 minutes in a hot air dryer. After the measurement, the YI value was measured using an SM-T color measuring device manufactured by Suga Test Instruments Co., Ltd. (YI after heating). The measurement was performed according to JIS K7105 conditions.
The results of total light transmittance, Haze value, and YI value are shown in Table 1 or 2.

(5) Refractive index The refractive index of the resin composition obtained in the following preparation examples is that a film is formed by removing the solvent from the resin composition, and the resulting film is formed into a prism coupler model 2010 (manufactured by Metricon). It measured using. The refractive index was measured using light having a wavelength of 632.8 nm. The results are shown in Table 1 or 2.

(6) Evaluation of element The organic EL element was produced using the board | substrate with a resin layer for light emitting elements or the board | substrate A obtained by the following Example and comparative example, respectively. On each resin layer (resin layer B in the case of Example 6 below, resin layer E in the case of Example 7 below, resin layer G in the case of Example 9 below) or on the surface cleaned with UV ozone (comparison) In Example 1 only), an indium tin oxide (ITO) film having a thickness of 100 nm was formed as a transparent electrode by sputtering. The substrate temperature during sputtering was 160 ° C. The sheet resistance value of the obtained transparent electrode measured with a Loresta GP MCP-T610 type (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), which is a resistivity meter, was 20 Ω / cm ² .
On the surface of the obtained transparent electrode, as a hole transport layer, an oligoaniline derivative (dissolved in aniline pentamer in DMF and doped with 3-fold molar equivalent of 5-sulfosalicylamide) is 70 nm. A 50 nm layer composed of N, N′-bis (1-naphthyl) -N, N′-diphenyl-1,1′-bisphenyl-4,4′-diamine (α-NPD) as a thick layer and a light emitting layer. A 50 nm thick layer made of tris (8-hydroxyquinoline) aluminum (Alq ₃ ) was sequentially formed in this order as a thick layer and an electron transport layer. Subsequently, a magnesium-silver alloy layer was deposited as a cathode on the electron transport layer. The thickness of the cathode at this time was 200 nm.
A voltage of 10 V was applied to the transparent electrode and the cathode of the organic EL device thus prepared, and the amount of light emitted from the surface of the substrate A was measured with a photodiode using an integrating sphere. At this time, the measured value of the element not including the light emitting element resin layer was 1.0. The results are shown in Table 1 or 2.

[Synthesis Example 1]
<Synthesis of polymer>
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile (hereinafter also referred to as “DFBN”), component (B): 9,9-bis (4- Hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) 87.60 g (0.250 mol), potassium carbonate 41.46 g (0.300 mol), N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) 443 g and Toluene 111g was added.
Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. After the generation of water was not observed, the temperature was gradually raised to 160 ° C., and the reaction was allowed to proceed at that temperature for 6 hours.
After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 95.67 g, yield 95%).

The obtained polymer was subjected to structural analysis and measurement of the weight average molecular weight. The results show that the characteristic absorption of the infrared absorption spectrum is 3035 cm ⁻¹ (C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). The weight average molecular weight was 130,000. The obtained polymer had a structural unit (A).
Moreover, the glass transition temperature of the obtained polymer was 270 degreeC.

[Preparation Example 1]
A solution obtained by re-dissolving the polymer obtained in Synthesis Example 1 in cyclohexanone so as to have a polymer concentration of 10% by mass (hereinafter referred to as “resin solution 1”) is added to a polyethylene container capable of being sealed. Next, titanium oxide fine particles (average particle size: 15 nm) surface-treated with aluminum hydroxide were added to the obtained solution so as to be 160 parts by mass with respect to 100 parts by mass of the polymer. Further, 300 parts by mass of zirconia beads having a particle diameter of 0.1 mm (manufactured by Nikkato Co., Ltd.) were added, and the mixture was shaken for 5 hours using a paint shaker (Red Devil) to disperse the titanium oxide fine particles. The resin composition 1 was obtained by removing.
[Example 1]
To the resin composition 1, TITANIX JR-1000 (manufactured by Teika Co., Ltd., average particle diameter: 1 μm), which is titanium oxide particles, is added to the solid content excluding the solvent in the resin composition 1 and the mass of the TITANIX JR-1000. After adding so that ratio might become 90/10, it stirred at 10,000 rpm for 5 minutes at room temperature using the homogenizer, and obtained the coating composition 1 (solid content concentration: 24 mass%).

  One surface of a non-alkali glass plate (trade name: EAGLE XG, Corning, thickness: 0.7 mm) was cleaned with UV ozone as a transparent substrate (hereinafter referred to as “substrate A”). The obtained coating composition 1 was applied to the surface of the substrate A that had been subjected to UV ozone cleaning by spin coating (rotation speed: 1000 rpm, rotation time: 10 seconds). This coated substrate is heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a resin for a light emitting device. A substrate with layer 1 was obtained.

[Preparation Example 2]
DISPERBYK-111 (produced by Big Chemie Japan Co., Ltd.) 10 which is a copolymer containing an acid group as a dispersant with respect to 100 parts by weight of titanium oxide fine particles (average particle size: 15 nm) surface-treated with aluminum hydroxide. Part by weight, 275 parts by weight of cyclohexanone, and 200 parts by weight of zirconia beads having a particle diameter of 0.1 mm (manufactured by Nikkato Co., Ltd.) are added, and the mixture is shaken for 5 hours using a paint shaker (Red Devil). Dispersed. Next, 36 parts by weight of Ogsol PG-100 (Osaka Gas Chemical Co., Ltd., glass transition temperature after curing: 180 ° C.), which is an epoxy compound containing a fluorene group, and trimellitic anhydride ( After dissolving 12 parts by weight of Wako Pure Chemical Industries, Ltd., resin composition 2 was obtained by removing the zirconia beads.

[Example 2]
After further adding TITANIX JR-1000, which is titanium oxide particles, to the resin composition 2 so that the mass ratio of the solid content excluding the solvent in the resin composition 2 and TITANIX JR-1000 is 85/15, the homogenizer Was used and stirred at 10,000 rpm for 5 minutes at room temperature to obtain a coating composition 2 (solid content concentration: 40% by mass).
A substrate with a light emitting element resin layer 2 was obtained in the same manner as in Example 1 except that the coating composition 2 was used in place of the coating composition 1.

[Preparation Example 3]
Resin composition 3 was obtained in the same manner as in Preparation Example 2, except that barium titanate fine particles (average particle size: 50 nm) were used instead of titanium oxide fine particles (average particle size: 15 nm).

[Example 3]
A coating composition 3 (solid content concentration of 40% by mass) was obtained in the same manner as in Example 2 except that it was used in the resin composition 3 obtained instead of the resin composition 2.
A substrate with a light emitting element resin layer 3 was obtained in the same manner as in Example 1 except that the coating composition 3 was used instead of the coating composition 1.

[Preparation Example 4]
Instead of the resin solution 1, Rika Coat PN-20, which is a commercially available transparent polyimide resin (two-component system using 3,3 ′, 4,4′-diphenylsulfone-tetracarboxylic dianhydride as the acid dianhydride) , Glass transition temperature: 270 ° C., polymer concentration: 20% by mass), except that a solution (resin concentration: 10% by mass) diluted with N-methyl-2-pyrrolidone was used. A resin composition 4 was obtained.

[Example 4]
The coating composition 4 (solid content concentration: 24 mass%) was obtained like Example 1 except having used the resin composition 4 instead of the resin composition 1. FIG.
Except having used the coating composition 4 instead of the coating composition 1, it carried out similarly to Example 1, and obtained the board | substrate with the resin layer 4 for light emitting elements.

[Example 5]
In place of TITANIX JR-1000 used in Example 2, SX8782 (P) (average particle size: 1.1 μm, inner pore size: 0, manufactured by JSR Corporation), which is a hollow particle made of crosslinked styrene-acrylic as a polymer composition .9 μm) was added in the same manner as in Example 2 except that the mass ratio of the solid content excluding the solvent in the resin composition 2 to the hollow particles was 97/3. Concentration: 38% by mass) was obtained.
A substrate with a light emitting element resin layer 5 was obtained in the same manner as in Example 1 except that the coating composition 5 was used instead of the coating composition 1.

[Example 6]
The coating composition 2 was applied to the surface of the substrate A that had been subjected to UV ozone cleaning by spin coating (rotation speed: 1000 rpm, rotation time: 10 seconds). This coated substrate is heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere. A substrate was obtained. Next, the resin composition 1 was applied on the resin layer A of the obtained substrate with the resin layer A by a spin coating method (rotation speed: 1000 rpm, rotation time: 10 seconds). The obtained substrate was heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 30 minutes, then taken out from the dryer and cooled to room temperature in the atmosphere. A substrate with a resin layer 6 for a light emitting element was obtained in which the resin layer A formed from the coating composition 2 and the resin layer B formed from the resin composition 1 were laminated in this order.

[Preparation Example 5]
By dissolving 36 parts by weight of Ogsol PG-100, 12 parts by weight of trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane in 950 parts by weight of cyclohexanone. A resin composition 5 was obtained.

[Example 7]
The resin composition 5 was applied to the surface of the substrate A that had been subjected to UV ozone cleaning by spin coating (rotation speed: 2000 rpm, rotation time: 10 seconds). The coated substrate is heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 10 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere. A substrate was obtained. Furthermore, the coating composition 2 was applied on the resin layer C of the obtained substrate with the resin layer C by a spin coating method (rotation speed: 1000 rpm, rotation time: 10 seconds). The coated substrate was heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere. The board | substrate with which the resin layer C and the resin layer D were laminated | stacked in this order was obtained. Further, the resin composition 1 was applied on the resin layer D of the obtained substrate by a spin coating method (rotation speed: 1000 rpm, rotation time: 10 seconds). The coated substrate was heated at 80 ° C. for 3 minutes using a forced stirring dryer, then heated at 180 ° C. for 30 minutes, then taken out from the dryer and cooled to room temperature in the atmosphere. A resin layer for a light emitting device in which a resin layer C formed from the resin composition 5, a resin layer D formed from the coating composition 2, and a resin layer E formed from the resin composition 1 are laminated in this order. A substrate with 7 was obtained.

[Example 8]
Instead of TITANIX JR-1000 used in Example 1, HPS-0500 (manufactured by Toagosei Co., Ltd., average particle size: 0.5 μm) as a silica particle, solid content excluding the solvent in the resin composition 1 and silica A coating composition 6 (solid content concentration: 24 mass%) was obtained in the same manner as in Example 1 except that the addition was performed so that the mass ratio with the particles was 90/10. Except having used the coating composition 6 instead of the coating composition 1, it carried out similarly to Example 1, and obtained the board | substrate with the resin layer 8 for light emitting elements.

[Preparation Example 6]
66 parts by weight of Ogsol PG-100, 18 parts by weight of TITANIX JR-1000, and 400 parts by weight of γ-butyrolactone as a solvent were added, followed by stirring at 10,000 rpm for 5 minutes using a homogenizer. Furthermore, 16 parts by weight of trimellitic anhydride was added, and the mixture was mixed at 200 rpm for 10 minutes at room temperature using a stirring blade to obtain a resin composition 6.

[Example 9]
The resin composition 6 was applied to the surface of the substrate A that had been subjected to UV ozone cleaning by spin coating (rotation speed: 1000 rpm, rotation time: 10 seconds). The coated substrate is heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 150 ° C. for 10 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to attach the resin layer F. A substrate was obtained. Next, the resin composition 1 was applied on the resin layer F of the obtained substrate with the resin layer F by a spin coating method (rotation speed: 1000 rpm, rotation time: 10 seconds). The coated substrate was heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 180 ° C. for 10 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere, whereby the substrate A, The board | substrate with the resin layer 9 for light emitting elements by which the resin layer F formed from the resin composition 6 and the resin layer G formed from the resin composition 1 were laminated | stacked in this order was obtained.

[Preparation Example 7]
A resin composition 7 was obtained in the same manner as in Example 1 except that a solution (polymer concentration: 22.4% by mass) obtained by dissolving the polymer obtained in Synthesis Example 1 in cyclohexanone was used.

[Example 10]
A coating composition 7 (solid content concentration of 24% by mass) was obtained in the same manner as in Example 1 except that the resin composition 7 was used instead of the resin composition 1.
Except having used the coating composition 7 instead of the coating composition 1, it carried out similarly to Example 1, and obtained the board | substrate with the resin layer 10 for light emitting elements.

[Comparative Example 1]
In the evaluation of the element, the substrate A was used.

[Preparation Example 8]
Instead of the resin solution 1, a solution (resin concentration: 10% by mass) obtained by dissolving a commercially available PMMA resin, Parapet HR-S (manufactured by Kuraray Co., Ltd., glass transition temperature 100 ° C.) in cyclohexanone was used. Obtained resin composition 8 in the same manner as in Preparation Example 1.

[Comparative Example 2]
A coating composition 8 (solid content concentration: 24% by mass) was obtained in the same manner as in Example 1 except that the resin composition 8 was used instead of the resin composition 1.
The obtained coating composition 8 was applied to the surface of the substrate A that had been subjected to UV ozone cleaning by spin coating (rotation speed: 1000 rpm, rotation time: 10 seconds). The obtained coated substrate was heated at 80 ° C. for 3 minutes using a forced stirring dryer, followed by heating at 120 ° C. for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a light emitting device. A substrate with a resin layer 11 was obtained.

[Comparative Example 3]
In Example 1, a substrate with a resin layer 12 for a light-emitting element was obtained in the same manner as in Example 1 except that the resin composition 1 (solid content concentration 22 mass%) was used instead of the coating composition 1. It was.

  It has been confirmed that by using the substrate according to the present invention, the surface emission luminance of the organic EL element having a conventional structure is significantly increased.

10, 20, 30: Light-emitting element 11, 21, 31: Substrate 13, 23, 33: First electrode 15, 25, 35: Light-emitting layer 17, 27, 37: Second electrode 18, 28 ,: First resin layer 38, 39: First resin layer or second resin layer (however, at least one is the first resin layer)

[4] The second resin layer includes
(C ′ ) between the first electrode and the first resin layer, and
(D ′ ) between the second electrode and the first resin layer,
The light emitting device according to [3], wherein the light emitting device is formed on at least one of the above.

As such various layers, the refractive index decreases from the light emitting layer 15 through the first resin layer 18 to the outside of the light emitting element 10 in terms of obtaining a light emitting element with higher light extraction efficiency. Therefore, the second resin layer or the third resin layer is formed between the second electrode 17 and the first resin layer 18 and / or on the opposite side of the first resin layer 18 from the side on which the second electrode 17 is formed. A layer such as a resin layer may be provided.

In the light emitting element 30, the refractive index of the second electrode 37, the refractive index of the resin layer 39, and the refractive index of air (about 1.0) decrease in this order, the refractive index of the first electrode 33, and the refractive index of the resin layer 38. The light emitting element in which the refractive index, the refractive index of the substrate 31, and the refractive index of air (about 1.0) decrease in this order is preferable.
In consideration of the light extraction efficiency of the light emitting element 30, the substrate 31 is preferably a glass substrate or a transparent plastic substrate having a refractive index smaller than that of the resin layer 38.
Since the light emitting element 30 includes the resin layer 38 and the resin layer 39, light generated in the light emitting layer 35 can be effectively extracted to the outside by light refraction, and the light emitting element has high light extraction efficiency.

<First electrode>
The first electrode may have use a first electrode forming material can be produced on the upper surface of the substrate or the like by depositing or sputtering. When forming a transmissive electrode, the first electrode forming material is transparent and has excellent conductivity, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide ( ZnO) or the like can be used.
When a reflective electrode is formed, magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—) are used as the first electrode forming material. In), magnesium-silver (Mg-Ag), or the like can be used. What is necessary is just to select the thickness of a 1st electrode suitably according to the desired objective.

The particles (B) may be in a powder form or a solvent dispersion sol. As the solvent contained in the solvent dispersion sol, for example, 2-butanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N- methyl-2-pyrrolidone, propylene grayed recall monomethyl ether, γ- butyrolactone.

Examples of the fluorosurfactant include, for example, MegaFuck F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482, F483, F484, F486, F487, F559, F562, F563, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC Corporation) It is done.
Particularly preferred examples include Megafac F559, F562, F563 having a hydrophilic group and a lipophilic group.

The hindered phenol compound which can be used in the present invention, triethylene glycol - bis [3- (3-tert- butyl-5-methyl-4-hydroxyphenyl) pro pin onato], 1,6-hexanediol Diol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- tert-butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] buta 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Puropione bets, N, N-hexamethylene-bis (3,5-di -tert- butyl-4-hydroxy - hydrocinnamate raw bromide), 1,3,5-trimethyl-2,4,6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro 5.5] undecane, and the like. These can be used alone or in combination of two or more.

[Example 3]
A coating composition 3 (solid content concentration of 40% by mass) was obtained in the same manner as in Example 2 except that the resin composition 3 obtained instead of the resin composition 2 was used.
A substrate with a light emitting element resin layer 3 was obtained in the same manner as in Example 1 except that the coating composition 3 was used instead of the coating composition 1.

Claims (7)

A light-emitting element including a first electrode, a light-emitting layer, a second electrode, and a first resin layer, wherein the first electrode, the light-emitting layer, and the second electrode are stacked in this order, and the first resin Layer
(A) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(B) The side of the second electrode opposite to the side on which the light emitting layer is formed,
Formed on at least one of
It includes a resin having a glass transition temperature (Tg) of 170 ° C. or higher by differential scanning calorimetry (DSC, temperature rising rate 20 ° C./min) and particles (A) having an average particle diameter of 0.1 μm to 5 μm. A light emitting element.   2. The light emitting device according to claim 1, wherein the first resin layer further includes metal oxide fine particles (B) having an average particle diameter of 1 nm or more and less than 100 nm. Furthermore, it is a light emitting device comprising a second resin layer, wherein the second resin layer is
(C) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(D) The side of the second electrode opposite to the side on which the light emitting layer is formed,
Formed on at least one of
The glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min) contains a resin having a glass transition temperature of 170 ° C. or higher, and the refractive index measured using light having a wavelength of 632.8 nm is 1.60 or higher. The light emitting device according to claim 1, wherein the light emitting device is provided. The second resin layer is
(C) between the first electrode and the first resin layer; and
(D) Between the second electrode and the first resin layer,
The light emitting device according to claim 3, wherein the light emitting device is formed on at least one of the above.   The light emitting element of any one of Claims 1-4 whose said light emitting element is an organic electroluminescent element.   The resin composition for light emitting element formation for forming the 1st resin layer of the light emitting element of any one of Claims 1-5.   The resin composition for light emitting element formation for forming the 2nd resin layer of the light emitting element of any one of Claims 3-5.

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