TW201336342A - Light-emitting element and resin composition for forming light-emitting element - Google Patents

Abstract

A light-emitting element comprising 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, and the first The resin layer is formed on at least one of (a) the side opposite to the side on which the light-emitting layer is formed on the first electrode, and (b) the opposite side of the side of the second electrode on which the light-emitting layer is formed, and includes A resin having a glass transition temperature (Tg) of 170 ° C or higher and a particle (A) having an average particle diameter of 0.1 μm to 5 μm by differential scanning calorimetry (DSC, temperature increase rate: 20 ° C /min).

Description

Light-emitting element and resin composition for forming light-emitting element

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 anode electrode layer, a light-emitting material layer, and a cathode electrode layer are laminated in this order on the surface of the transparent substrate. For example, the organic electroluminescence element is: injecting a hole from the anode electrode layer thereof, electrons from the cathode electrode layer into the interior of the luminescent material layer containing the organic material, and recombining the hole and the electron inside the luminescent material layer. In order to generate an exciton, a light-emitting element that emits light by releasing (fluorescence or phosphorescence) light when the exciter is deactivated, and light generated by the light-emitting material layer is emitted from the transparent substrate side to the light-emitting element. external.

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

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-296438

According to the light-emitting element described in Patent Document 1, light generated by the luminescent material layer can be efficiently emitted from the transparent substrate side to some extent. However, there is a problem that the high refractive index resin such as a polyether oxime resin or a polyether fluorene imine resin is deteriorated due to light emitted from the luminescent material layer.

Accordingly, an object of the present invention is to provide a light-emitting element excellent in light emission efficiency.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above object can be attained by a light-emitting element including a resin layer containing a polymer having a specific glass transition temperature, and Contains particles with a specific particle size.

That is, the present invention provides the following [1] to [7].

[1] A light-emitting element comprising: 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 formed on at least one of (a) the side opposite to the side on which the light-emitting layer is formed on the first electrode, and (b) the opposite side of the side of the second electrode on which the light-emitting layer is formed, and A resin having a glass transition temperature (Tg) of 170° C. or higher and a particle having an average particle diameter of 0.1 μm to 5 μm by differential scanning calorimetry (DSC (differential scanning calorimetry) at a temperature increase rate of 20° C./min) (A) ).

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

[3] The light-emitting element according to [1] or [2], further comprising a second resin layer, wherein the second resin layer is formed on (c) the opposite side of the first electrode on which the light-emitting layer is formed. And (d) at least one of the opposite sides of the second electrode on which the light-emitting layer is formed, and including a glass transition temperature (Tg by differential scanning calorimetry (DSC, temperature increase rate: 20° C./min)) The resin having a temperature of 170 ° C or higher and a refractive index measured using light having a wavelength of 632.8 nm is 1.60 or more.

[4] The light-emitting element according to [3], wherein the second resin layer is formed between (c) the first electrode and the first resin layer, and (d) the second electrode and the first resin At least one of the layers.

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

[6] A resin composition for forming a light-emitting element, which is used 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, which is used for forming the second resin layer of the light-emitting element according to any one of [3] to [5].

The light-emitting element of the present invention is excellent in light emission efficiency. Further, the light-emitting element of the present invention is excellent in durability, so even under severe use conditions, Can be used without degrading performance for a long time.

10, 20, 30‧‧‧Lighting elements

11, 21, 31‧‧‧ substrates

13, 23, ‧ ‧ the first electrode

15, 25, 35‧ ‧ luminescent layer

17, 27, 37‧‧‧ second electrode

18, 28‧‧‧1st resin layer

38, 39‧‧‧ a first resin layer or a second resin layer (at least one of which is a first resin layer)

Fig. 1 is a cross-sectional view conceptually showing a first embodiment of a light-emitting device of the present invention.

Fig. 2 is a cross-sectional view conceptually showing a second embodiment of the light-emitting device of the present invention.

Fig. 3 is a cross-sectional view conceptually showing a third embodiment of the light-emitting device of the present invention.

Light-emitting components

Hereinafter, various embodiments of the light-emitting element of the present invention will be described with reference to the drawings. However, the light-emitting element is not particularly limited as long as it is a light-emitting element including a first electrode, a light-emitting layer, and a second electrode. The first resin layer is formed by laminating the first electrode, the light-emitting layer, and the second electrode in this order, and the first resin layer includes glass by differential scanning calorimetry (DSC, temperature increase rate: 20° C./min) a resin having a transition temperature (Tg) of 170 ° C or higher (hereinafter also referred to as "polymer (I)") and particles (A) having an average particle diameter of 0.1 μm to 5 μm, and formed in

(a) at least one of the side opposite to the side on which the light-emitting layer is formed on the first electrode, and (b) the opposite side of the side of the second electrode on which the light-emitting layer is formed.

Fig. 1 shows a light-emitting element 10 which is an embodiment 1 of a light-emitting device of the present invention. The light-emitting element 10 has a structure in which the substrate 11, the first electrode 13, the light-emitting layer 15, the second electrode 17, and the first resin layer 18 are laminated in this order. In other words, the first resin layer 18 is provided on the surface of the second electrode 17 on the side opposite to the side on which the light-emitting layer 15 is provided.

The second electrode 17 is preferably a transmissive electrode. At this time, the light generated by the light-emitting layer 15 passes through the second electrode 17 and the first resin layer 18, and can be emitted to the outside of the light-emitting element 10.

Since the light-emitting element of the present invention includes the first resin layer 18, when light generated by the light-emitting layer 15 enters the air through the second electrode 17, the efficiency of emission to the outside of the light-emitting element can be improved by the refraction of light.

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) are reduced in this order. Further, the difference between the refractive indices of the second electrode 17 and the first resin layer 18 and the difference between the refractive indices of the first resin layer 18 and the air are preferably small. When the refractive index of the second electrode, the first resin layer, and the air has such a relationship, in the step of emitting light generated by the light-emitting layer 15 to the outside of the light-emitting element 10, the second electrode 17 and the first resin layer 18 are formed. The interface and the interface between the first resin layer 18 and the air are less likely to cause total reflection, and therefore it is considered that the light emission efficiency is high.

In FIG. 1, the first resin layer 18 is formed by being in contact with one surface of the second electrode 17, but various layers may be further provided between the first resin layer 18 and the second electrode 17 as needed.

Further, on the side opposite to the side on which the first electrode 13 is formed on the substrate 11, 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, The first resin layer 18 is formed on the opposite side to the side of the second electrode 17, and various layers may be provided as needed.

In order to obtain a light-emitting element having a higher light emission efficiency, the refractive index becomes smaller as the self-luminous element 15 travels toward the outside of the light-emitting element 10 via the first resin layer 18 as a result of obtaining a light-emitting element having a higher light-emitting efficiency. On the opposite side of the second electrode 17 and the first resin layer 18 and/or the side of the first resin layer 18 on which the second electrode 17 is formed, a layer such as a second resin layer or a third resin layer may be provided.

Further, although not shown in FIG. 1, a known sealing layer for sealing the light-emitting element 10 may be further provided, and various modifications can be realized.

Fig. 2 shows a light-emitting element 20 which is an embodiment 2 of the light-emitting element of the present invention.

The light-emitting element 20 has a structure in which the substrate 21, the first resin layer 28, the first electrode 23, the light-emitting layer 25, and the second electrode 27 are laminated in this order. In other words, 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. At this time, the light generated by the light-emitting layer 25 passes through the first electrode 23, the first resin layer 28, and the substrate 21, and can be emitted to the outside of the light-emitting element 20.

The modification of the light-emitting element 20 is the same as described above.

The light-emitting element 20 is preferably a refractive index of the first electrode 23 and a first resin layer. The refractive index of 28, the refractive index of the substrate 21, and the refractive index of air (about 1.0) are reduced in this order.

Further, in consideration of the light emission efficiency of the light-emitting element 20, the substrate 21 is preferably a glass substrate or a transparent plastic substrate having a refractive index lower than that of the first resin layer 28.

Since the light-emitting element 20 has the first resin layer 28, the light generated by the light-emitting layer 25 can be efficiently emitted to the outside by the refraction of light, and becomes a light-emitting element having high light emission efficiency.

Fig. 3 shows a light-emitting element 30 which is an embodiment 3 of the light-emitting element of the present invention.

The light-emitting element 30 has a structure in which the substrate 31, the first or second resin layer 38, the first electrode 33, the light-emitting layer 35, the second electrode 37, and the first or second resin layer 39 are laminated in this order. In other words, 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 provided on the surface of the second electrode 37 on the opposite side to the surface on which the light-emitting layer is provided. However, at least one of the resin layer 38 and the resin layer 39 is a first resin layer. Further, both of the resin layer 38 and the resin layer 39 may be the first resin layer.

The first electrode 33 and the second electrode 37 are preferably penetrating electrodes. In this case, the light generated by the light-emitting layer 35 passes through the first electrode 33 and the second electrode 37, and then passes through the resin layer 38 and the resin layer 39, respectively. It can be emitted to the outside 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) are preferably reduced in this order, and the refractive index of the first electrode 33 and the refractive index of the resin layer 38 are preferably small. The rate, the refractive index of the substrate 31, and the refractive index of air (about 1.0) are reduced in this order.

Further, in consideration of the light-emitting efficiency of the light-emitting element 30, the substrate 31 is preferably a glass substrate or a transparent plastic substrate having a refractive index lower than that of the resin layer 38.

Since the light-emitting element 20 has the resin layer 38 and the resin layer 39, the light generated by the light-emitting layer 35 can be efficiently emitted to the outside by the refraction of light, and becomes a light-emitting element having high light emission efficiency.

<Substrate>

As the substrate, a substrate used in a general light-emitting element can be used, and a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water repellency is preferable.

<first electrode>

The first electrode can be produced on the upper surface of the substrate by a vapor deposition method, a sputtering method, or the like using the first electrode forming material. When the penetrating electrode is formed, indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), or tin oxide (SnO ₂ ) which is transparent and excellent in conductivity can be used as the first electrode forming material. , zinc oxide (ZnO) and the like.

Further, when forming the reflective electrode, magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), or magnesium-indium (Mg-In) can be used as the first electrode forming material. Magnesium-silver (Mg-Ag) and the like. The thickness of the first electrode may be appropriately selected in accordance with a desired purpose.

<Light Emitting Layer>

The light-emitting layer is preferably a light-emitting layer formed by a substance which exhibits a light-emitting phenomenon by applying an electric field. Such an substance can use an electroluminescence (EL) material which has been used until: activation of zinc sulfide ZnS: X (where X is an active element such as Mn, Tb, Cu, Sm), CaS:Eu, SrS:Ce, SrGa ₂ S ₄ : an inorganic electroluminescence (EL) substance such as Ce, CaGa ₂ S ₄ :Ce, CaS:Pb, BaAl ₂ S ₄ :Eu; an aluminum complex of 8-hydroxyquinoline, an aromatic amine, Low molecular weight organic EL material such as ruthenium single crystal; poly(p-phenylacetylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylacetylene], poly(3) A conjugated polymer organic EL material such as -alkylthiophene or polyvinylcarbazole.

Among these, since the first resin layer contains the polymer (I), the light-emitting layer is preferably a layer formed using an organic EL material. As described above, when the light-emitting layer is a layer formed using an organic EL material, an organic EL device can be obtained. The thickness of the luminescent layer is usually from 10 nm to 1000 nm, preferably from 30 nm to 500 nm, and more preferably from 50 nm 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.

<2nd electrode>

The second electrode can be produced by a vapor deposition method, a sputtering method, or the like using the second electrode forming material. Examples of the second electrode forming material include lithium (Li) and magnesium. (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like.

A penetrating electrode can be obtained by forming a film from these materials. Further, it may be a penetrating electrode comprising ITO or IZO. The thickness of the second electrode may be appropriately selected in accordance with the intended purpose.

The second electrode is preferably a cathode which is an electron injecting electrode.

<First resin layer>

The first resin layer is preferably formed of a light-emitting element comprising at least a polymer (I), particles (A) having an average particle diameter of 0.1 μm to 5 μm, and an organic solvent (hereinafter also referred to as "specific solvent"). A layer formed of a resin composition.

Since the light-emitting element of the present invention contains the first resin layer, it is a light-emitting element having excellent light emission efficiency.

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

[Resin (Polymer (I)) having a glass transition temperature (Tg) of 170 ° C or higher]

The polymer (I) can be preferably used, such as an aromatic polyether polymer (hereinafter also referred to as "polymer (II)") and a thermoplastic resin such as a polyamidene polymer, and an anthrone or a ring. A thermosetting resin such as an oxygen-based, acrylic-based, cyanoacrylate-based or epoxy-based acrylate. In particular, by using a thermoplastic resin as described later In the compound (III), a resin composition having excellent film formability can be obtained, and a light-emitting element having sufficiently excellent balance between light emission efficiency and heat resistance can be obtained.

The polymer (I) may be used alone or in combination of two or more.

[Polymer (I)]

The polymer (I) is a polymer having a glass transition temperature (Tg) of 170 ° C to 350 ° C by differential scanning calorimetry (DSC, heating rate 20 ° C / min), preferably 240 ° C to 330 ° C, more preferably Good for 250 ° C ~ 300 ° C.

The glass transition temperature of the polymer (I) is measured, for example, using a Model 8230 DSC measuring apparatus (temperature rising rate: 20 ° C /min) manufactured by Rigaku Corporation.

The resin layer containing such a polymer (I) is sufficiently excellent in balance between heat resistance, mechanical strength, and electrical properties.

The polymer (II) is a polymer obtained by a reaction of forming an ether bond in a main chain, and preferably has a structural unit selected from the following formula (1) (hereinafter also referred to as "structural unit ( 1)") and a polymer of at least one structural unit (i) of a group consisting of structural units (hereinafter also referred to as "structural unit (2)") represented by the following formula (2) (hereinafter also referred to as It is "Polymer (III)"). The polymer has a structural unit (i) and is an aromatic polyether polymer having a glass transition temperature within the above range. The resin layer containing such a polymer (III) is excellent in heat resistance, electrical properties, and transparency, and has a high refractive index. Further, if the resin layer contains the polymer (III), A light-emitting element excellent in light emission efficiency and durability can be obtained.

Further, the polymer (II), particularly the polymer (III), has less absorption of light in the visible light range than the polyether oxime resin or the polyether quinone resin, and thus it is difficult to cause deterioration of the resin due to visible light. Therefore, a light-emitting element including a resin layer containing the above polymer (II), particularly the polymer (III) is preferable because it is excellent in durability.

In the above formula (1), R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms. A~d independently represent an integer of 0~4, preferably 0 or 1.

Examples of the monovalent organic group having 1 to 12 carbon atoms include a monovalent hydrocarbon group having 1 to 12 carbon atoms and a carbon number of 1 to 12 containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. A monovalent organic group or the like.

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 an aromatic hydrocarbon group having 6 to 12 carbon atoms.

The above linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a carbon number of 1 to 8. A linear or branched hydrocarbon group is more preferably a linear or branched hydrocarbon group having 1 to 5 carbon atoms.

Preferred specific examples of the above linear or branched hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl. And positive heptyl.

The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms.

Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; a cyclobutenyl group, a cyclopentenyl group and a cyclohexane group; Alkenyl group such as alkenyl group. 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.

The organic group having 1 to 12 carbon atoms which contains an oxygen atom may, for example, be an organic group containing a hydrogen atom, a carbon atom and an oxygen atom, and preferably includes an ether bond, a carbonyl group or an ester bond, and a total carbon number of the hydrocarbon group. ~12 organic base and so on.

Examples of the organic group having a total carbon number of 1 to 12 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 a carbon number of 6 to 12. An aryloxy group of 12 or an alkoxyalkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a phenoxy group, a propyleneoxy group, a cyclohexyloxy group, and a methoxymethyl group.

Further, the organic group having a total carbon number of 1 to 12 having a carbonyl group may be exemplified by a carbon number. 2 to 12 醯 base and so on. Specific examples thereof include an ethyl group, a propyl group, an isopropenyl group, and a benzamidine group.

The organic group having a total carbon number of 1 to 12 having an ester bond may, for example, be an anthraceneoxy group having 2 to 12 carbon atoms. Specific examples thereof include an ethenyloxy group, a propenyloxy group, a isopropyloxy group, and a benzamidineoxy group.

Examples of the organic group having 1 to 12 carbon atoms and containing a nitrogen atom include an organic group containing a hydrogen atom, a carbon atom and a nitrogen atom, and specific examples thereof include a cyano group, an imidazolyl group, a triazolyl group, a benzimidazolyl group, and a benzotriene group. Azolyl and the like.

Examples of the organic group having 1 to 12 carbon atoms and containing an oxygen atom and a nitrogen atom include an organic group containing a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and specific examples thereof include an oxazolyl group, an oxadiazolyl group, and a benzoxazole group. Azolyl and benzooxadiazolyl and the like.

R ¹ to R ⁴ in the above formula (1) are preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and particularly preferably a phenyl group.

In the above formula (2), R ¹ to R ⁴ and a to d are each independently synonymous with R ¹ to R ⁴ and a to d in the above formula (1), and Y represents a single bond, -SO ₂ - or >C= O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. 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 above formula (1).

In the above polymer (III), the molar ratio of the structural unit (1) to the structural unit (2) (the total of the two (the structural unit (1) + the structural unit (2)) is 100) In terms of an excellent polymer such as optical properties, heat resistance and mechanical properties, the structural unit (1): structural unit (2) = 50:50 to 100:0, more preferably structural unit (1) : Structural unit (2) = 70:30~100:0, especially good for structural unit (1): structural unit (2) = 80:20~100:0.

Here, the mechanical properties refer to properties such as tensile strength, elongation at break, and tensile modulus of elasticity of the polymer.

Further, the polymer (III) may further have 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). . When the polymer (III) has such a structural unit (ii), the mechanical properties of the resin layer obtained from the composition having the polymer (III) are improved, which is preferable.

[Chemical 3]

In the above formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and 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 above formula (1).

Examples of the divalent organic group having 1 to 12 carbon atoms include a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, and at least one selected from the group consisting of an oxygen atom and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms of one atom and a divalent halogenated organic group having 1 to 12 carbon atoms and at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.

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 a divalent aromatic hydrocarbon having 6 to 12 carbon atoms. Hydrocarbyl group and the like.

Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylidene 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 a cycloalkyl group such as a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group, and a cyclohexylene group; a cyclobutene group and a cyclopentene group; And a cyclohexene group such as a cyclohexene group.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a stretching phenyl group, a stretching naphthyl group, and a stretching biphenyl 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, a divalent halogenated aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 2 carbon atoms of 6 to 12 carbon atoms. A halogenated aromatic hydrocarbon group or the like.

The linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms may, for example, be difluoromethylene, dichloromethylene, tetrafluoroethyl, tetrachloroethylene, hexafluorotrimethylene or hexachloro Trimethylene, hexafluoroisopropylidene and hexachloroisopropylidene.

The divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms is exemplified by the fact that at least a part of the hydrogen atoms of the group exemplified in the above-mentioned divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms are a fluorine atom, a chlorine atom, a bromine atom or A group obtained by substituting an iodine atom.

The divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms is exemplified by the fact that at least a part of the hydrogen atoms of the group exemplified as the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Substituted groups, etc.

The organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom may be an organic group containing a hydrogen atom, a carbon atom, and an oxygen atom and/or a nitrogen atom. Further, examples thereof include a divalent organic group having a total carbon number of 1 to 12 including an ether bond, a carbonyl group, an ester bond or a guanamine bond, and a hydrocarbon group.

The divalent halogenated organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom may specifically be selected from the group consisting of oxygen At least one hydrogen atom of the group exemplified in the divalent organic group having 1 to 12 carbon atoms of at least one atom in the group consisting of an atom and a nitrogen atom is substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom The group formed.

Z in the above formula (3) is preferably a single bond, -O-, -SO ₂ -, >C=O or a divalent organic group having 1 to 12 carbon atoms, more preferably 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.

In the above 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 above formula (2), and R ⁵ and R ^{6 are respectively.} And Z, n, e, and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e, and f in the above formula (3). Further, when m is 0, R ^{7 is} not a cyano group.

In the above polymer (III), the molar ratio of the above structural unit (i) to the above structural unit (ii) (the total of both ((i) + (ii)) is 100), and it becomes optical characteristics and heat resistance. In terms of an excellent polymer such as a property or a mechanical property, it is preferably (i): (ii) = 50:50 to 100:0, more preferably (i): (ii) = 70:30 to 100. :0, especially good for (i): (ii) = 80:20~100:0.

Here, the mechanical properties refer to the tensile strength and elongation at break of the polymer and Tensile properties such as elastic modulus.

The polymer (III) is preferably a polymer having excellent optical properties, heat resistance and mechanical properties, etc., and the structural unit (i) and the structural unit (ii) preferably contain 70 in all structural units. Mole% or more, more preferably 95 mol% or more in all structural units.

The polymer (III) can be obtained, for example, by including a compound selected from the following formula (5) (hereinafter also referred to as "compound (5)") and the following formula (7) a component of at least one compound (hereinafter also referred to as "(A) component)) in a group consisting of a compound (hereinafter also referred to as "compound (7)"), and a compound represented by the following formula (6) The component of the compound (hereinafter also referred to as "(B) component") is reacted.

In the above formula (5), X independently represents a halogen atom, preferably a fluorine atom.

[Chemical 6]

In the above formula (7), 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 above formula (2), and X is independent from the above formula. The X in (5) is synonymous. When m is 0, R ^{7 is} not a cyano group.

In the above formula (6), R ^a each independently represents a hydrogen atom, a methyl group, an ethyl group, an ethyl sulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group, and among them, a hydrogen atom is preferred. Further, in the formula (6), R ¹ to R ⁴ and a to d are each independently synonymous with R ¹ to R ⁴ and a to d in the above formula (1).

Specific examples of the above compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, and 2, 6-Dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, and reactive derivatives thereof. Especially in terms of reactivity and economy, etc. It is preferred to use 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile. These compounds may be used in combination of two or more kinds.

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

Specific examples of the above compound (7) include: 4,4'-difluorobenzophenone, 4,4'- 4,4'-difluorodiphenylsulfone (DFDS), 2,4'-difluorobenzophenone, 2,4'-difluorodiphenylanthracene, 2,2'-difluorodiphenyl Methyl ketone, 2,2'-difluorodiphenyl fluorene, 3,3'-dinitro-4,4'-difluorobenzophenone, 3,3'-dinitro-4,4'- Difluorodiphenyl fluorene, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl fluorene, 2,4'-dichlorobenzophenone, 2,4'-dichloro Diphenyl hydrazine, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl fluorene, 3,3'-dinitro-4,4'-dichlorobenzophenone and 3,3'-dinitro-4,4'-dichlorodiphenyl hydrazine. Among these, 4,4'-difluorobenzophenone and 4,4'-difluorodiphenylphosphonium are preferred. These compounds may be used in combination of two or more kinds.

Selected from the group consisting of compound (5) and compound (7) One less compound, preferably 100 mol%, in 100 mol% of the component (A) ~100% by mole, more preferably from 90% by mole to 100% by mole.

Further, the component (B) preferably contains a compound represented by the following formula (8) as needed. The compound (6) is preferably contained in an amount of from 50 mol% to 100 mol%, more preferably from 80 mol% to 100 mol%, and particularly preferably 90 mol%, in 100 mol% of the component (B). %~100% by mole.

In the above 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 above formula (3), and R ^{a is} independently and independently R ^a in the above formula (6) is synonymous.

Examples of the compound represented by the above formula (8) include hydroquinone, resorcin, 2-phenyl hydroquinone, 4,4'-biphenol, and 3,3'-biphenol. , 4,4'-dihydroxydiphenyl hydrazine, 3,3'-dihydroxydiphenyl hydrazine, 4,4'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, 1 , 1'-bi-2-naphthol, 1,1'-bi-4-naphthol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl) ring Hexane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof. Among the above compounds, resorcin, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane are preferred. Alkane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, in terms of reactivity From the viewpoint of mechanical properties, it is preferred to use 4,4'-biphenol. These compounds may be used in combination of two or more kinds.

More specifically, the above polymer (III) can be synthesized by the method (I') shown below.

Process (I'): The (B) component is reacted 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 the obtained The alkali metal salt is reacted with the component (A). Further, by reacting the component (B) with an alkali metal compound in the presence of the component (A), the alkali metal salt of the component (B) can be reacted with the component (A).

Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali metal hydroxides such as lithium hydride, potassium hydride and sodium hydride; alkali metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide; An alkali metal carbonate such as lithium, potassium carbonate or sodium carbonate; an alkali metal hydrogencarbonate such as lithium hydrogencarbonate, potassium hydrogencarbonate or sodium hydrogencarbonate. These may be used alone or in combination of two or more.

The alkali metal compound is used in an amount of from 1 to 3 equivalents, preferably from 1.1 times to 2 times, based on all -OR ^a in the above component (B). The equivalent weight is particularly preferably 1.2 times to 1.5 times equivalent.

In addition, the organic solvent used in the reaction may be: N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-two A Keto-2-imidazolidone, γ-butyl lactone, cyclobutyl hydrazine, dimethyl hydrazine, diethyl hydrazine, dimethyl hydrazine, diethyl hydrazine, diisopropyl hydrazine, diphenyl Anthracene, diphenyl ether, benzophenone, dialkoxybenzene (carbon number: 1 to 4 of alkoxy group), and trialkoxybenzene (carbon number of alkoxy group: 1 to 4). Among these solvents, polar organic compounds having a high dielectric constant such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, cyclobutyl hydrazine, diphenyl hydrazine, and dimethyl hydrazine are particularly preferred. Solvent. These may be used alone or in combination of two or more.

Further, in the above reaction, a solvent which azeotropes with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole or phenethyl ether may be further used. . These may be used alone or in combination of two or more.

When the ratio of the component (A) to the component (B) is 100 mol%, the component (A) is preferably 45 mol% or more and 55 mol%. More preferably, it is 50 mol% or more and 52 mol% or less, more preferably 50 mol% or more and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less. Preferably, it is 48% by mole or more and 50% by mole or less, and more preferably 48% by mole or more and less than 50% by mole.

Further, the reaction temperature is preferably from 60 ° C to 250 ° C, more preferably from 80 ° C to 200 ° C. The reaction time is preferably from 15 minutes to 100 hours, more preferably from 1 hour to 24 hours.

The above polymer (II) is manufactured by Tosoh (TOSOH) HLC-8220 The polystyrene-equivalent weight average molecular weight (Mw) measured by a GPC (gel permeation chromatography) apparatus (column: TSKgelα-M, developing solvent: tetrahydrofuran (hereinafter also referred to as "THF")) is preferably 5,000. ~500,000, more preferably 15,000~400,000, especially preferably 30,000~300,000.

The above polymer (II) by thermogravimetric analysis (Thermo Gravimetric The thermal decomposition temperature measured by Analysis, TGA) is preferably 450 ° C or higher, more preferably 475 ° C or higher, and particularly preferably 490 ° C or higher.

The above resin composition can be directly used as the resin composition for forming a light-emitting element. A mixture of the polymer (III) obtained in (I') with an organic solvent. At this time, the organic solvent used in the above reaction is a specific solvent.

In addition, the above composition can also be prepared by: The mixture of the polymer (III) and the organic solvent obtained by the method is isolated (purified) from the polymer (III) in the form of a solid component, and then dissolved again in a specific solvent.

The side of the above polymer (III) is isolated (purified) in the form of a solid component The method can be carried out, for example, by reprecipitating the polymer in a poor solvent of a polymer such as methanol, followed by filtration, followed by drying the filtrate under reduced pressure or the like.

The specific solvent for re-dissolving the above polymer (III) is preferably selected: Those which easily dissolve the above polymer (III). For example, it is preferably used: dichloromethane, tetrahydrofuran, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyl From the viewpoint of coatability and economy, lactone, cyclohexanone, N,N-dimethylacetamide and N-methyl-2- are preferably used. Pyrrolidone. These solvents may be used alone or in combination of two or more.

In addition, in order to achieve drying or uniformity during coating, surface smoothness For the improvement, etc., one type or two or more types of solvents selected from other specific solvents, such as an ether-based organic solvent, an ester-based organic solvent, a ketone-based organic solvent, a hydrocarbon-based organic solvent, or an alcohol-based organic solvent, may be appropriately combined. And use. In this case, the boiling point at atmospheric pressure (1,013 hPa) is preferably from 40 ° C to 250 ° C, more preferably from 50 ° C to 150 ° C, and it is preferred that the polymer (III) is uniformly dissolved. Used within the scope of dispersion.

Preferred examples of these other specific solvents include ethylene glycol monoethyl ether and C. Glycol ethers such as diol monomethyl ether; ethylene glycol alkyl ether acetate such as ethyl cellosolve, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate; ethyl lactate, 2-hydroxypropionic acid Ester and other esters; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; methyl ethyl ketone, methyl isobutyl ketone, 2 a ketone such as heptanone, cyclohexanone or methyl amyl ketone. These may be used alone or in combination of two or more.

Further, the specific solvent described above can also be preferably used for a resin composition for forming a light-emitting element comprising the polymer (I) other than the polymer (III).

[epoxy resin]

The resin layer containing the above epoxy resin is sufficiently excellent in balance between heat resistance, mechanical strength, and adhesion. A resin layer containing such an epoxy resin can be obtained by using an epoxy compound and a compound capable of hardening the epoxy compound ( The resin composition for forming a light-emitting element, which is also referred to as a "hardener", is formed.

Specific examples of the epoxy compound include bisphenol A diglycidyl ether and bisphenol F. a bisphenol type epoxy compound such as diglycidyl ether or bisphenol S diglycidyl ether; a novolak type epoxy compound such as a phenol novolak type epoxy compound or a cresol novolak type epoxy compound; 3', 4'- 3,4-epoxycyclohexylmethyl epoxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane , bis(3,4-epoxycyclohexylmethyl) adipate, vinyl epoxy cyclohexane, 4-vinyl epoxy cyclohexane, bis(3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, 3',4'-epoxy-6'-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl ester, methylene bis (3, 4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene (3,4-epoxycyclohexanecarboxylate), epoxidized tetrabenzyl alcohol, lactone modification 3', 4 '-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, lactone modified epoxidized tetrahydrobenzyl alcohol, epoxycyclohexane, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F II An alicyclic epoxy compound such as glycidyl ether or hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin tricondensate An aliphatic epoxy compound such as oleyl ether or trimethylolpropane triglycidyl ether; halogenated brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Epoxy compound; glycidylamine type epoxy compound such as tetraglycidylaminophenylmethane; and 9,9-bis[4-(2-glycidoxyoxypropoxy)-3,5-dimethyl An epoxy compound having an anthracene skeleton such as phenylphenyl group or the like. These may be used alone or in combination of two or more.

Specific examples of the above hardener include aliphatic amines, aromatic amines, and modified amines. Amines, polyamine resins, tertiary amines, secondary amines, imidazoles, thiols, acid anhydrides, boron trifluoride amine complexes, dicyanoguanamines, and organic acid hydrazines. These may be used alone or in combination of two or more.

The glass transition temperature of the epoxy resin is preferably from 170 ° C to 350 ° C, more preferably It is 175 ° C ~ 300 ° C. The glass transition temperature is measured, for example, using a Model 8230 DSC measuring apparatus (temperature rising rate: 20 ° C /min) manufactured by Rigaku Corporation.

As an epoxy resin having such a glass transition temperature, an epoxy compound It is preferable to use a novolac type epoxy compound or an epoxy compound having an anthracene skeleton, and it is preferred to use a combination comprising an acid anhydride.

Concentration of the polymer (I) in the resin composition for forming a light-emitting element The degree also depends on the molecular weight of the polymer, and is usually from 1% by mass to 40% by mass, preferably from 5% by mass to 25% by mass. When the concentration of the polymer (I) in the composition is in the above range, it is possible to form a resin layer which is thick in film formation, is less likely to cause pinholes, and is excellent in surface smoothness.

Further, the viscosity of the resin composition for forming a light-emitting element is also dependent on The molecular weight or concentration of the polymer (I) is preferably 50 mPa. s~100,000 mPa. s, more preferably 500 mPa. s~50,000 mPa. s, especially good for 1000 mPa. s~20,000 mPa. s. When the viscosity of the composition is in the above range, the composition in the formation of the resin layer is excellent in the retention property, and the thickness is easily adjusted, so that the resin layer is easily formed.

[Particle (A)]

The resin layer contains particles (A) having an average particle diameter of 0.1 μm to 5 μm. Therefore, the light diffusion function can be imparted to the above resin layer, and the light emission efficiency can be improved.

The average particle diameter of the particles (A) is preferably from 0.2 μm to 3 μm, more preferably from 0.3 μm to 2 μm.

Further, the average particle diameter can be measured by a particle distribution measuring apparatus which uses a dynamic light scattering method as a measuring principle.

One type of the particles (A) may be used or two or more types may be used in combination.

Here, in order to impart a light diffusing function, it is preferred to use particles having a large difference in refractive index between the particles (A) and the polymer (I). Examples of such particles include particles having a high refractive index or particles having a low refractive index. .

As the particles having a high refractive index, the same particles as those exemplified as the metal oxide particles (B) described below (wherein the average particle diameter is in the above range) can be used. Further, the particles having a low refractive index are particles having a refractive index of light of 632.8 nm at 25 ° C, preferably 1.55 or less, more preferably 1.50 or less. Specifically, organic particles are preferably used.

Examples of the organic particles include polymethyl methacrylate (PMMA) particles, polystyrene particles, and organic crosslinked particles.

The above organic crosslinked particles can be produced from a crosslinkable monomer. The crosslinkable monomer is preferably a non-conjugated divinyl compound typified by divinylbenzene or represented by trimethylolpropane trimethacrylate or trimethylolpropane triacrylate. a compound having two or more copolymerizable double bonds, such as a polyvalent acrylate compound Things. More preferably, it is a compound having two copolymerizable double bonds.

Further, in view of the fact that the organic particles have a low refractive index, hollow particles can be used.

The amount of addition of the particles (A) is preferably adjusted as appropriate in consideration of the specific gravity of the particles themselves and the refractive index difference of the polymer (I), and is not particularly limited, and physical strength and sufficient strength are applied to the resin layer. In the light-diffusing function, the amount of the particles (A) to be added is preferably 1 part by mass to 2000 parts by mass, more preferably 2 parts by mass, per 100 parts by mass of the solid content of the resin composition for forming a light-emitting element. 1000 parts by mass, particularly preferably 10 parts by mass to 100 parts by mass.

When the amount of the particles (A) is in the above range, the light diffusion function of the resin layer can be appropriately adjusted while maintaining the crack resistance and the like.

When the particles (A) to be used are solvent-dispersed sols, the amount of the particles (A) to be added means the mass of the solvent, and the amount of the solvent contained in the sol is calculated as the amount of the specific solvent.

[Metal Oxide Particles (B)]

In the above-mentioned resin layer, in order to obtain a light-emitting element having excellent light emission efficiency, metal oxide particles (B) having an average particle diameter of 1 nm or more and less than 100 nm are preferably blended. 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 a resin layer containing particles (B) having such a refractive index, a light-emitting element having more excellent light emission efficiency can be obtained.

Further, the refractive index is measured, for example, using a prism coupler Model 2010 (manufactured by Metricon Co., Ltd.).

Examples of the particles (B) include metal oxide particles such as zirconia, titanium oxide, zinc oxide, cerium oxide, indium oxide, cerium oxide, tin oxide, cerium oxide, barium titanate, and a composite of these. Among them, fine particles of zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ) or barium titanate (BaTiO ₃ ) are preferably used, and cerium oxide (SiO ₂ ) and zirconium oxide (ZrO) are coated on the surface of the fine particles of titanium oxide. ₂ ) or aluminum hydroxide (Al(OH) ₃ ) to suppress the photocatalytic function of titanium oxide.

The titanium oxide is not particularly limited as long as it has a TiO ₂ structure, and examples thereof include an anatase type, a rutile type, and a brookite type. The above is preferable in terms of suppressing the photocatalytic function and the refractive index. Rutile type.

These particles (B) may be used alone or in combination of two or more.

The average particle diameter of the above particles (B) is preferably from 3 nm to 70 nm, more preferably from 5 nm to 50 nm. When the average particle diameter is within the above range, a resin layer excellent in transparency can be obtained. Further, the average particle diameter can be measured by a particle distribution measuring apparatus which uses a dynamic light scattering method as a measuring principle.

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

The amount of the above particles (B) to be formulated is not particularly limited, and is preferably as above. The concentration of the polymer (I) in the resin composition for forming a light-emitting element or the viscosity of the resin composition for forming a light-emitting element is used in the above range, and specifically, 100 parts by mass based on 100 parts by mass of the polymer (I). It is preferably 0 parts by mass to 2,000 parts by mass, more preferably 10 parts by mass to 1,500 parts by mass, particularly preferably 30 parts by mass to 1,000 parts by mass, particularly preferably 50 parts by mass to 500 parts by mass. When the amount of the particles (B) is in the above range, a light-emitting element having excellent light emission efficiency can be obtained while maintaining transparency or crack resistance.

When the particles (B) to be used are solvent-dispersed sols, the amount of the particles (B) to be added means the mass of the solvent, and the amount of the solvent contained in the sol is calculated as the amount of the specific solvent.

[Dispersant]

In the resin composition for forming a light-emitting element, in order to improve the dispersibility of the particles (A) and/or particles (B), it is preferred to contain various dispersants.

The dispersing agent may be used alone or in combination of two or more.

As the above dispersant, for example, an aluminum compound can be used. Examples of the aluminum compound include an alkane alumina and a β-diketone aluminum complex. Specific examples thereof include alkoxides such as triethoxyaluminum, tri(n-propoxy)aluminum, tris(isopropoxy)aluminum, tri(n-butoxy)aluminum, and tris(t-butoxy)aluminum. Compound, tris(methylacetamidineacetic acid) aluminum, tris(ethylacetamethyleneacetate)aluminum, tris(acetamidineacetone)aluminum, monoethylammonium acetonate bis(methylacetate)aluminum, monoethylammonium acetonide bis(ethyl Acetic acid) β-diketone complex such as aluminum.

Commercial products of aluminum compounds include: AIDD, PADM, AMD, ASBD, Aluminium Ethoxide, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, Alumichelate M, Alumichelate D, Alumichelate A (W), Surface Treatment Agent OL-1000, ALGOMER, ALGOMER 800AF , ALGOMER 1000SF (the above is manufactured by Kawaken Fine Chemicals Co., Ltd.).

A nonionic dispersing agent can also be used for the above dispersing agent. By using non-ion A dispersant that increases the dispersibility of the metal oxide particles. The above nonionic dispersant is preferably a polyoxyethylene alkyl phosphate, a guanamine amine salt of a high molecular weight polycarboxylic acid, or a propylene oxide-ethylene oxide (PO-EO). Condensate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, alkyl glucoside, polyoxyethylene fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Esters and fatty acid alkanolamines. Particularly preferred are phosphate-based nonionic dispersants having a polyoxyethylene alkyl structure. Commercially available products of polyoxyethylene alkyl phosphates include PLAAD ED151 manufactured by Kaneko Kasei Co., Ltd., and the like.

The amount of the above dispersing agent is not provided as long as the effect of the present invention is not impaired. In particular, when the dispersant is contained, the solid content of the resin composition for forming a light-emitting element is 100% by mass, for example, 0.1% by mass to 5% by mass.

[Dispersing Aid]

In the resin composition for forming a light-emitting element, in order to improve particles (A) And/or the dispersibility of the particles (B), preferably further comprising a dispersing aid. The dispersing aid can be preferably used in an amount of at least one selected from the group consisting of acetamidine acetone and N,N-dimethylacetamide.

The amount of the dispersing agent is not particularly limited as long as the effect of the present invention is not impaired, and when the dispersing aid is contained, the solid content of the resin composition for forming the light-emitting element is 100% by mass, for example, 0% by mass. ~5 mass%.

[Surfactant]

In the resin composition for forming a light-emitting element, from the viewpoint of obtaining a resin layer having a uniform thickness, it is preferred to prepare a surfactant. Examples of the surfactant include an anthrone-based surfactant, a fluorine-based surfactant, and the like. Among them, an anthrone-based surfactant is preferred.

One type of the surfactants may be used or two or more types may be used in combination.

Examples of the anthrone-based surfactants include SH28PA (manufactured by Dow Corning Toray Co., Ltd., dimethyl polyoxyalkylene polyoxyalkylene copolymer), PAINTAD 19, and PAINTAD 54 (east). Manufactured by Lidao Corning Co., Ltd., dimethyl polyoxyalkylene polyoxyalkylene copolymer), Silaplane FM0411 (manufactured by JNC), SF8428 (made by Toray Dow Corning), dimethyl Polyoxyalkylene polyoxyalkylene copolymer (the side chain contains OH group)), BYKUV3510 (made by BYK-Chemie Japan Co., Ltd., dimethyl polyoxyalkylene-polyoxyalkylene) Copolymer), DC57 (Dow Corning Toray Silicone (manufactured by Dow Corning), dimethyl polyoxyalkylene-polyoxyalkylene copolymer), DC190 (Manufactured by Toray Dow Corning) Dimethyl polyoxane-polyoxyalkylene Base copolymer), Silaplane FM-4411, Silaplane FM-4421, Silaplane FM-4425, Silaplane FM-7711, Silaplane FM-7721, Silaplane FM-7725, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane FM-DA26, Silaplane FM0711, Silaplane FM0721, Silaplane FM-0725, Silaplane TM-0701, Silaplane TM-0701T (made by Jie Enzhi), UV3500, UV3510, UV3530 ( Manufactured by BYK Chemical Co., Ltd., BY16-004, SF8428 (manufactured by Toray Dow Corning), VPS-1001 (manufactured by Wako Pure Chemicals Co., Ltd.).

Particularly good examples are: Silaplane FM-7711, Silaplane FM-7721, Silaplane FM-7725, Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0425, Silaplane FM0711, Silaplane FM0721, Silaplane FM-0725, VPS-1001. Further, commercially available products of an anthranone compound having an ethylenically unsaturated group, that is, TegoRad 2300 and 2200N (manufactured by Tego Chemie Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include, for example, MEGAFAC F-114, MEGAFAC F410, MEGAFAC F411, MEGAFAC F450, MEGAFAC F493, MEGAFAC F494, MEGAFAC F443, MEGAFAC F444, MEGAFAC F445, MEGAFAC F446, MEGAFAC F470, MEGAFAC F471, MEGAFAC F472SF, MEGAFAC F474, MEGAFAC F475, MEGAFAC R30, MEGAFAC F477, MEGAFAC F478 MEGAFAC F479, MEGAFAC F480SF, MEGAFAC F482, MEGAFAC F483, MEGAFAC F484, MEGAFAC F486, MEGAFAC F487, MEGAFAC F559, MEGAFAC F562, MEGAFAC F563, MEGAFAC F172D, MEGAFAC F178K, MEGAFAC F178RM, MEGAFAC ESM-1, MEGAFAC MCF350SF, MEGAFAC BL20, MEGAFAC R08, MEGAFAC R61, MEGAFAC R90 (manufactured by Dainippon Ink and Chemicals, DIC).

Particularly preferred examples are MEGAFAC F559, MEGAFAC F562, and MEGAFAC F563 having a hydrophilic group and a new oily group.

The blending ratio of the surfactant is 100% by mass, preferably 0% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, even more preferably 0.5% by mass based on the solid content of the resin composition for forming a light-emitting element. Mass%~3 mass%. When the amount of the surfactant is more than 10% by mass based on 100% by mass of the solid content of the resin composition for forming a light-emitting element, the refractive index of the obtained resin layer is lowered.

Further, the resin composition for forming a light-emitting element may further contain an anti-aging agent, and by containing an anti-aging agent, the durability of the obtained resin layer can be further improved.

The anti-aging agent is preferably a hindered phenol-based compound.

The hindered phenol-based compound which can be used in the present invention is exemplified by triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6- Hexanediol-double [3-(3,5-Di-t-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-tributyl-4-hydroxyphenyl)propionate], 1,1,3-tri[2] -methyl-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy]-5-tert-butylphenyl]butane, 2,2-thio -diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Octadecyl ester), N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, and 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl]-2,4 , 8,10-tetraoxaspiro[5.5]undecane, and the like. These may be used alone or in combination of two or more.

In the present invention, the anti-aging agent is preferably used in an amount of from 0.01 part by weight to 10 parts by weight per 100 parts by weight of the polymer (I).

[Other additives]

The resin composition for forming a light-emitting element may include various additives other than the above insofar as the effects of the present invention are not impaired. Examples of such an additive include a curable compound other than the above components and an ultraviolet absorber.

[Method for Producing Resin Composition for Forming Light-emitting Element]

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 needed. The polymer (I), the particles (A), and the specific solvent can usually be obtained in a specific ratio. It is prepared by mixing with other optional ingredients.

In particular, in order to obtain a light-emitting element having high light emission efficiency, it is preferable to mix the particles (A) in a composition having a high refractive index (specifically, a composition of a film capable of forming a high refractive index).

The refractive index of the high refractive index film 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, particularly preferably 1.77 to 2.0, and most preferably 1.80. 2.0.

The refractive index can be measured using a 稜鏡 coupler Model 2010 (manufactured by Metricen).

A composition for forming such a high refractive index film, wherein the composition comprises the above polymer (I), preferably by containing a polymer (I) having a high refractive index, particularly preferably by containing a polymer (I) 100 parts by mass and 50 parts by weight to 500 parts by mass of the particles (B).

[Method for Producing First Resin Layer]

The method of producing the first resin layer of the light-emitting element of the present invention is not particularly limited, and when the light-emitting element 10 is produced, for example, the resin composition for forming a light-emitting element is directly applied to the second electrode 17 or the like. Further, a coating film is formed, and then a specific solvent is removed from the coating film as needed; and the resin composition for forming a light-emitting element is applied onto a support including polyethylene terephthalate (PET) or the like. A method of forming a coating film, and then peeling the coating film from the support, and laminating it on the second electrode 17, or the like.

The first resin layer contains a polymer (I), preferably contains a polymerization. Since the substance (II) or the polymer (III) has a tendency to have a high refractive index. Therefore, in the light-emitting element 10, for example, when an electrode including ITO (refractive index of about 2.12) is used as the second electrode 17, the refractive indices of the second electrode 17, the first resin layer 18, and the air become smaller in this order. . Therefore, a light-emitting element having high light emission efficiency can be obtained.

A method of applying the above resin composition to form a coating film can be exemplified by roll coating. Method, gravure coating method, spin coating method, slit coating method, and a method using a doctor blade.

The thickness at the time of coating the above resin composition to form a coating film is not particularly limited The ratio is, for example, 1 μm to 250 μm, preferably 2 μm to 150 μm, more preferably 5 μm to 125 μm.

Further, the method of removing the above specific solvent from the coating film is not particularly limited. For example, the method of heating a coating film is mentioned. The specific solvent in the coating film can be removed by evaporation by heating the coating film. The heating conditions may be determined by evaporating the specific solvent, and may be appropriately determined without causing thermal deformation or modification of various materials by heat. For example, the heating temperature is preferably from 30 ° C to 300 ° C, more preferably 40 ° C. 250 ° C, especially preferably 50 ° C ~ 230 ° C.

Further, the heating time is preferably from 10 minutes to 5 hours. In addition, heating can It is carried out by two or more stages. Specifically, it is dried at a temperature of 30 ° C to 150 ° C for 1 minute to 2 hours, and then further heated at 100 ° C to 250 ° C for 10 minutes to 2 hours. Further, drying may be carried out under a nitrogen atmosphere or under reduced pressure as needed.

The thickness of the above first resin layer is appropriately selected depending on the intended use. Preferably, it is preferably from 20 nm to 100 μm, more preferably from 80 nm to 50 μm.

In addition, the 8230 type of the first resin layer manufactured by Rigaku Corporation The glass transition temperature (Tg) measured by the DSC measuring device (temperature rising rate: 20 ° C / min) is preferably from 170 ° C to 350 ° C, more preferably from 240 ° C to 330 ° C, and particularly preferably from 250 ° C to 300 ° C. When the first resin layer has such a glass transition temperature, heating or heat treatment when an electrode or the like is formed on the layer can be performed at a high temperature, and thus the electrode thus obtained has low resistance and high transmittance, and can be easily A light-emitting element excellent in light emission efficiency and durability is produced.

The tensile strength of the first resin layer is preferably 50 MPa to 200 MPa. More preferably 80 MPa to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

The elongation at break of the first resin layer is preferably 5% to 100%, more preferably It is 15%~100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by Instron Corporation).

The tensile modulus of the first resin layer is preferably 2.5 GPa to 4.0. GPa is better than 2.7 GPa to 3.7 GPa. The tensile modulus of elasticity can be measured using a tensile tester 5543 (manufactured by Instron Corporation).

Seiko Instruments using the above first resin layer The linear expansion coefficient measured by the company's SSC-5200 TMA measuring device is preferably 80 ppm/K or less, more preferably 75 ppm/K or less.

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

The specific dielectric constant of the first resin layer is preferably from 2.0 to 4.0, more preferably 2.3~3.5, especially good is 2.5~3.2. The specific dielectric constant can be measured using a 4284A inductance capacitance resistance (LCR) meter manufactured by Hewlett Packard (HP). When the specific dielectric constant is in the above range, the light-emitting element including the first resin layer tends to exhibit a stable light-emitting state.

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

YI value (yellow index) when the first resin layer has a thickness of 30 μm It is preferably 3.0 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. The YI value can be measured using an SM-T type color measuring device manufactured by a Suga test machine.

The first resin layer is dried by a hot air dryer at a thickness of 30 μm. The YI value after heating at 230 ° C for 1 hour in the atmosphere is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.

Further, since the first resin layer contains the particles (A), it is not It is easy to measure the refractive index.

<2nd resin layer>

The light-emitting element of the present invention may further comprise a second resin layer.

The second resin layer is formed on

(c) at least one of the side opposite to the side on which the light-emitting layer is formed on the first electrode, and (d) at least one of the side opposite to the side on which the light-emitting layer of the second electrode is formed, preferably (c') At least one of the first electrode and the first resin layer and (d') between the second electrode and the first resin layer includes a differential scanning calorimeter (DSC, temperature increase rate of 20 ° C) The resin having a glass transition temperature (Tg) of 170 ° C or more and a refractive index measured by using a light having a wavelength of 632.8 nm is 1.60 or more.

The second resin layer is a layer containing no such particles (A). Therefore, when the second resin layer is formed in the above (c') or (d'), it is expected that the surface of the electrode is flattened.

Further, in the second resin layer, a layer having a high refractive index or the like is obtained, and the particles (B) are preferably contained.

The second resin layer may include two or more layers in the light-emitting device of the present invention. In this case, the second resin layer having the same composition may include two or more layers in the light-emitting device of the present invention, and the second resin layer having different compositions may include two or more layers in the light-emitting device of the present invention.

Preferably, the second resin layer contains at least a polymer (I) and a specific A layer formed of a resin composition for forming a light-emitting element of a solvent.

The components contained in the resin composition for forming a light-emitting element and the components which may be contained may be the same as those described in the first resin layer except that the particles (A) are not contained.

Further, the method for producing the second resin layer may be the same as the method for producing the first resin layer.

The refractive index of the second resin layer measured by 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-emitting efficiency of the obtained light-emitting element is increased.

Since the above polymer (I) is contained, the second resin layer having such a refractive index can be obtained.

The refractive index can be measured using a 稜鏡 coupler Model 2010 (manufactured by Metricen).

In addition, 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.

<3rd resin layer>

The light-emitting element of the present invention may further comprise a third resin layer. The third resin layer does not contain the particles (A) and the particles (B). Further, a layer containing substantially only a resin is preferable. When the first resin layer and/or the second resin layer are brought into contact with the substrate, the third resin layer is preferably provided on the first resin layer and/or the second tree. Between the lipid layer and the substrate.

Since such a third resin layer is excellent in adhesiveness, it is considered that a light-emitting element having improved long-term reliability of a light-emitting element can be obtained.

The third resin layer may include two or more layers in the light-emitting device of the present invention. In this case, the third resin layer having the same composition may include two or more layers in the light-emitting device of the present invention, and the third resin layer having a different composition may include two or more layers in the light-emitting device of the present invention.

The third resin layer is preferably a layer formed of a resin composition for forming a light-emitting element including the epoxy resin.

The component and the component which may be contained in the resin composition for forming a light-emitting element may be the same as those described in the first resin layer, except that the particles (A) and the particles (B) are not contained.

Further, the method for producing the third resin layer may be the same as the method for producing the first resin layer.

Further, it may be the same as the physical properties of the first resin layer.

[Examples]

Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by these examples.

(1) Structural analysis

The structural analysis of the polymer obtained in the following synthesis example is by infrared spectroscopy (IR) (Attenuated Total Reflex (Attenuated Total) Reflection, ATR) method, Fourier transform infrared spectroscopy (FT-IR), 6700 (manufactured by NICOLET), and nuclear magnetic resonance (NMR) (ADVANCE500 type, Made by Bruker (BRUKAR).

(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: TSKgel α-M, developing solvent: THF) manufactured by Tosoh.

(3) Glass transition temperature (Tg)

The glass transition temperature of the polymer or the light-emitting element resin layer obtained in the following synthesis example was measured using a Model 8230 DSC measuring apparatus manufactured by Rigaku Corporation at a temperature increase rate of 20 ° C/min. In addition, the glass transition temperature of the resin layer for a light-emitting element is measured by using a substrate-releasing resin layer from which the obtained resin layer for a light-emitting element is attached. The results are shown in Table 1 or Table 2.

(4) Total light transmittance, haze value and yellow index (YI value)

The substrate peeling resin layer of the resin layer for light-emitting elements obtained in the following Examples and Comparative Examples was attached, and the obtained light-emitting element resin layer was measured for total light transmittance, haze value, and yellow according to JIS K7105 transparency test method. Index (YI value). Specifically, the total light transmittance was measured using a haze meter SC-3H manufactured by a Suga test machine, and the YI value (YI before heating) was measured using an SM-T type color measuring instrument manufactured by a Suga test machine.

Further, the light-emitting elements obtained in the following examples and comparative examples were attached. The substrate of the resin layer was peeled off from the resin layer, and the obtained resin layer for a light-emitting element was heated at 200 ° C for 30 minutes in a hot air dryer, and then an SM-T type color measuring device manufactured by a Suga test machine was used. The YI value (YI after heating) was measured. In addition, the measurement was carried out in accordance with the conditions of JIS K7105.

The results of the total light transmittance, the haze value, and the YI value are shown in Table 1 or Table 2.

(5) Refractive index

The refractive index of the resin composition obtained in the following preparation example is obtained by The resin composition was removed from the solvent to form a film, and the obtained film was measured using a tantalum coupler Model 2010 (manufactured by Metricen Co., Ltd.). In addition, the refractive index was measured using light having a wavelength of 632.8 nm. The results are shown in Table 1 or Table 2.

(6) Evaluation of components

An organic EL device was produced using a substrate or a substrate A to which a resin layer for a light-emitting element obtained in the following examples and comparative examples was attached. In each of the resin layers (the resin layer B in the following Example 6, the resin layer E in the following Example 7, the resin layer G in the following Example 9), or the ultraviolet (UV) ozone cleaning. On the surface (Comparative Example 1 only), an indium tin oxide (ITO) film was formed as a transparent electrode by a sputtering method at a thickness of 100 nm. Further, the substrate temperature at the time of sputtering was set to 160 °C. The sheet resistance of the obtained transparent electrode was 20 Ω/cm ² as measured by a Loresta GP MCP-T610 type (manufactured by MITSUBISHI CHEMICAL ANALYTECH Co., Ltd.) as a resistivity meter.

On the surface of the obtained transparent electrode, sequentially formed in this order: an oligoaniline derivative as a hole transport layer (dissolving an aniline pentamer in dimethylformamide (N, N-Dimethyl formamide, a layer of 70 nm thick in which DMF) is doped with 3 times molar equivalent of 5-sulfosalicylideneamine, and contains N,N'-bis(1-naphthyl) as a light-emitting layer a layer of 50 nm thick of -N,N'-diphenyl-1,1'-bisphenyl-4,4'-diamine (α-NPD), which contains tris(8-hydroxyquinoline) as an electron transport layer A layer of 50 nm thick of porphyrin) aluminum (Alq ₃ ). Next, a magnesium-silver alloy layer was vapor-deposited on the electron transport layer as a cathode. The film thickness of the cathode at this time was set to 200 nm.

A voltage of 10 V was applied to the transparent electrode and the cathode of the organic EL device thus produced, and the amount of light emitted from the surface of the substrate A was measured by using a photodiode of the integrating sphere. In addition, at this time, the measured value of the element which does not contain the resin layer for light-emitting elements was 1.0. The results are shown in Table 1 or Table 2.

[Synthesis Example 1]

<Synthesis of Polymer>

In a 3 L four-necked flask, (A) component: 2,6-difluorobenzonitrile (hereinafter also referred to as "DFBN") 35.12 g (0.253 mol), and (B) component: 9,9-double (4-hydroxyphenyl) hydrazine (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 111 g of toluene.

Next, a four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube, and a cooling tube.

Next, after the inside of the flask was substituted with nitrogen, the obtained product was obtained at 140 ° C. The solution was reacted for 3 hours, and the generated water was removed from the Dean-Stark tube at any time. After the formation of water was no longer found, the temperature was slowly raised to 160 ° C and reacted at this temperature for 6 hours.

After cooling to room temperature (25 ° C), the resulting salt is removed by filter paper, The filtrate was poured into methanol to precipitate again, and the filtrate (residue) was separated 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 structural analysis of the obtained polymer and the measurement of the weight average molecular weight were carried out. As a result, the characteristic absorption of the infrared absorption spectrum is located at 3035 cm ^-1 (CH stretching), 2229 cm ^-1 (CN), 1574 cm ^-1 , 1499 cm ^-1 (absorption of the aromatic ring skeleton), and 1240 cm ^-1 (-O- The weight average molecular weight is 130,000. The obtained polymer has a structural unit (A).

Further, the glass transition temperature of the obtained polymer was 270 °C.

[Preparation Example 1]

The polymer obtained in Synthesis Example 1 was made to have a polymer concentration of 10 a solution in which the amount of % is dissolved in cyclohexanone again (hereinafter referred to as "resin solution 1"), added to a sealable polyethylene container, and then in the resulting solution, relative to the polymer 100 Titanium oxide fine particles (average particle diameter: 15 nm) surface-treated with aluminum hydroxide were added in a form of 160 parts by mass. Then, 300 parts by mass of zirconia beads (manufactured by NIKKATO Co., Ltd.) having a particle diameter of 0.1 mm was added, and the mixture was shaken for 5 hours using a paint shaker (RED DEVIL) to disperse the titanium oxide fine particles. Resin composition 1 was obtained by removing zirconia beads.

[Example 1]

In the above resin composition 1, more added as titanium oxide particles TITANIX JR-1000 (manufactured by TAYCA Co., Ltd., average particle diameter: 1 μm), so that the mass ratio of the solid content of the solvent-removed material 1 to the TITANIX JR-1000 is 90/10, and then The coating composition 1 (solid content concentration: 24% by mass) was obtained by stirring at room temperature at 10,000 rpm for 5 minutes using a homogenizer.

UV ozone cleaning (hereinafter referred to as "substrate A") was performed on one surface of an alkali-free glass plate (trade name: EAGLE XG, manufactured by Corning Co., Ltd., thickness: 0.7 mm) as a transparent substrate. On the UV ozone-cleaned surface of the substrate A, the obtained coating composition 1 was applied 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, and then heated at 180 ° C for 30 minutes, and then taken out from the dryer. The substrate was cooled to room temperature in the atmosphere to obtain a resin layer 1 with a light-emitting element.

[Preparation Example 2]

Titanium oxide microparticles relative to surface treatment with aluminum hydroxide (average Particle size: 15 nm) 100 parts by weight, 10 parts by weight of DISPERBYK-111 (manufactured by Japan Biotech Co., Ltd.), 275 parts by weight of cyclohexanone, and 0.1 particle diameter of a copolymer containing an acid group as a dispersing agent. 200 parts by mass of zirconia beads (manufactured by Nippon Kasei Co., Ltd.) of mm were shaken for 5 hours using a paint shaker (Red Magic Co., Ltd.) to disperse titanium oxide fine particles. Next, 36 parts by weight of OGSOL PG-100 (Osaka Gas Chemicals (manufactured by Osaka Gas Chemicals Co., Ltd.), cured glass transition temperature: 180 ° C), which is an epoxy compound containing a mercapto group, is dissolved in the obtained dispersion liquid. 12 parts by weight of trimellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), and then zirconia beads were removed to obtain Resin Composition 2.

[Embodiment 2]

Further added as the titanium oxide particles in the above resin composition 2 TITANIX JR-1000, the mass ratio of the solid content of the solvent removed from the resin composition 2 to TITANIX JR-1000 was 85/15, and then the mixture was stirred at 10,000 rpm for 5 minutes at room temperature using a homogenizer to obtain a coating composition. 2 (solid content concentration: 40% by mass).

Coating composition 2 is used instead of coating composition 1, in addition to In the same manner as in the first embodiment, a substrate having the resin layer 2 for light-emitting elements was obtained.

[Preparation Example 3]

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

[Example 3]

The obtained resin composition 3 was used instead of the resin composition 2, except Further, in the same manner as in Example 2, Coating Composition 3 (solid content concentration: 40% by mass) was obtained.

Coating composition 3 is used instead of coating composition 1, in addition to In the same manner as in the first embodiment, a substrate having the resin layer 3 for light-emitting elements was obtained.

[Preparation Example 4]

Instead of the above resin solution 1, it is used by N-methyl-2-pyrrolidone The commercially available transparent polyimine resin, RIKACOAT PN-20 (using 3,3',4,4'-diphenylanthracene-tetracarboxylic dianhydride as the two component system of acid dianhydride, glass transition temperature: 270 Resin composition 4 was obtained in the same manner as in Preparation Example 1, except that a solution (resin concentration: 10% by mass) of a solution (concentration: 20% by mass) was obtained.

[Example 4]

Resin composition 4 is used instead of resin composition 1, in addition to In the same manner as in Example 1, a coating composition 4 (solid content concentration: 24% by mass) was obtained.

Coating composition 4 is used instead of coating composition 1, in addition to In the same manner as in the first embodiment, a substrate having the resin layer 4 for light-emitting elements was obtained.

[Example 5]

Instead of the TITANIX JR-1000 used in the second embodiment, it is added as A polymer composed of a crosslinked styrene-acrylic acid-containing hollow particle, SX8782 (P) (manufactured by JSR, average particle diameter: 1.1 μm, inner pore diameter: 0.9 μm), to remove the solvent from the above resin composition 2 A coating composition 5 (solid content concentration: 38% by mass) was obtained in the same manner as in Example 2 except that the mass ratio of the solid content to the hollow particles was 97/3.

Coating composition 5 is used instead of coating composition 1, in addition to In the same manner as in the first embodiment, a substrate having the resin layer 5 for light-emitting elements was obtained.

[Embodiment 6]

On the UV-ozone-cleaned surface of substrate A, by spin coating (rotation speed: The above coating composition 2 was applied at 1000 rpm and a rotation time: 10 seconds. The coated substrate was heated at 80 ° C for 3 minutes using a forced stirring dryer, and then heated at 180 ° C for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a substrate with the resin layer A attached thereto. . Next, the resin composition 1 was applied onto the resin layer A of the obtained resin layer A-attached substrate 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, and then heated at 180 ° C for 30 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a substrate A laminated in this order. The resin layer A formed of the composition 2 and the resin layer B formed of the resin composition 1 are coated with the resin layer 6 for a light-emitting element.

[Preparation Example 5]

By making OGSOL PG-100 36 parts by weight, trimellitic anhydride (and 12 parts by weight, and 2 parts by weight of 3-glycidoxypropyltrimethoxydecane, were dissolved in 950 parts by weight of cyclohexanone to obtain a resin composition 5, which was produced by Wako Pure Chemical Industries, Ltd.

[Embodiment 7]

On the UV-ozone-cleaned surface of substrate A, by spin coating (rotation speed: The above resin composition 5 was applied at 2000 rpm and a rotation time: 10 seconds. The coated substrate was heated at 80 ° C for 3 minutes using a forced stirring dryer, and then heated at 180 ° C for 10 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a substrate with the resin layer C attached thereto. . Next, the coating composition 2 was applied onto the resin layer C of the obtained resin layer C-attached 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, and then heated at 180 ° C for 30 minutes, and then taken out from the dryer and cooled to room temperature in the air to obtain a substrate A laminated in this order. A substrate of the resin layer C and the resin layer D. Next, the resin composition 1 was applied onto 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, and then heated at 180 ° C for 30 minutes, and then taken out from the dryer and cooled to room temperature in the air to obtain a substrate A laminated in this order. a resin layer C formed of the resin composition 5, a resin layer D formed of the coating composition 2, and a resin layer E formed of the resin composition 1 The substrate with the resin layer 7 for light-emitting elements is attached.

[Embodiment 8]

Instead of the TITANIX JR-1000 used in the embodiment 1, it is added as HPS-0500 (manufactured by East Asia Synthetic Co., Ltd., average particle diameter: 0.5 μm) of the cerium oxide particles, and the mass ratio of the solid component of the solvent-removing material 1 to the cerium oxide particles is 90/10, In the same manner as in Example 1, a coating composition 6 (solid content concentration: 24% by mass) was obtained. A substrate having the resin layer 8 for light-emitting elements was obtained in the same manner as in Example 1 except that the coating composition 6 was used instead of the coating composition 1.

[Preparation Example 6]

Add OGSOL PG-100 66 parts by weight, TITANIX JR-1000 18 After parts by weight and 400 parts by weight of γ-butyrolactone as a solvent, the mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer. Then, 16 parts by weight of trimellitic anhydride was added, and the resin composition 6 was obtained by mixing at room temperature for 10 minutes at room temperature using a stirring blade.

[Embodiment 9]

On the UV-ozone-cleaned surface of substrate A, by spin coating (rotation speed: The above resin composition 6 was applied at 1000 rpm and a rotation time: 10 seconds. The coated substrate was heated at 80 ° C for 3 minutes using a forced stirring dryer, and then heated at 150 ° C for 10 minutes, and then taken out from the dryer and cooled to room temperature in the atmosphere to obtain a substrate with the resin layer F attached thereto. . Next, on the resin layer F of the obtained substrate with the resin layer F, it was coated by a spin coating method (rotation speed: 1000 rpm, rotation time: 10 seconds). The above resin composition 1. The coated substrate was heated at 80 ° C for 3 minutes using a forced stirring dryer, and then heated at 180 ° C for 10 minutes, and then taken out from the dryer and cooled to room temperature in the air to obtain a substrate A laminated in this order. A resin layer F formed of the resin composition 6 and a substrate of the resin layer G formed of the resin composition 1 with the resin layer 9 for a light-emitting element.

[Preparation Example 7]

The solution obtained by dissolving the polymer obtained in Synthesis Example 1 in cyclohexanone was used. Resin composition 7 was obtained in the same manner as in Example 1 except that the liquid (polymer concentration: 22.4% by mass) was used.

[Embodiment 10]

Resin composition 7 is used instead of resin composition 1, in addition to In the same manner as in Example 1, a coating composition 7 (solid content concentration: 24% by mass) was obtained.

Coating composition 7 is used instead of coating composition 1, in addition to In the same manner as in the first embodiment, a substrate having the resin layer 10 for light-emitting elements was obtained.

[Comparative Example 1]

In the evaluation of the above elements, the substrate A was used.

[Preparation Example 8]

Instead of the above resin solution 1, a commercially available PMMA resin is used. Parapet HR-S (manufactured by Kuraray Co., Ltd., glass transition temperature: 100 ° C) was dissolved in cyclohexanone (resin concentration: 10% by mass), and In the same manner as in Preparation Example 1, Resin Composition 8 was obtained.

[Comparative Example 2]

Resin composition 8 is used instead of resin composition 1, in addition to In the same manner as in Example 1, a coating composition 8 (solid content concentration: 24% by mass) was obtained.

On the UV-ozone-cleaned surface of substrate A, by spin coating (rotation speed: The obtained coating composition 8 was applied at 1000 rpm, rotation time: 10 seconds. The obtained coated substrate was heated at 80 ° C for 3 minutes using a forced stirring dryer, and then heated at 120 ° C for 30 minutes, and then taken out from the dryer and cooled to room temperature in the air to obtain a resin with a light-emitting element. The substrate of layer 11.

[Comparative Example 3]

In Example 1, the above resin composition 1 (solid content concentration) was used. A substrate having the resin layer 12 for a light-emitting element was obtained in the same manner as in Example 1 except that the coating composition 1 was replaced by the above-mentioned coating composition.

It was confirmed that the surface light-emitting luminance of the organic EL element of the prior structure was greatly increased by using the substrate of the present invention.

10‧‧‧Lighting elements

11‧‧‧Substrate

13‧‧‧1st electrode

15‧‧‧Lighting layer

17‧‧‧2nd electrode

18‧‧‧1st resin layer

Claims (7)

A light-emitting element comprising 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, and the first resin The layer is formed on at least one of (a) the side opposite to the side on which the light-emitting layer is formed on the first electrode, and (b) the opposite side of the side of the second electrode on which the light-emitting layer is formed, and includes The glass transition temperature (Tg) of the differential scanning calorimetry (DSC, temperature rising rate: 20 ° C /min) was 170 ° C or more, and the particles (A) having an average particle diameter of 0.1 μm to 5 μm. The light-emitting element according to claim 1, wherein the first resin layer further contains metal oxide fine particles (B) having an average particle diameter of 1 nm or more and less than 100 nm. The light-emitting element according to claim 1 or 2, further comprising a second resin layer, wherein the second resin layer is formed on (c) the opposite side of the first electrode on which the light-emitting layer is formed And (d) at least one of the opposite sides of the second electrode on which the light-emitting layer is formed, and including a glass transition temperature (Tg by differential scanning calorimetry (DSC, temperature increase rate: 20° C./min)) The resin having a temperature of 170 ° C or higher and a refractive index measured using light having a wavelength of 632.8 nm is 1.60 or more. The illuminating element according to claim 3, wherein the second tree is The lipid layer is formed in at least one of (c) the first electrode and the first resin layer, and (d) the second electrode and the first resin layer. The light-emitting element according to any one of claims 1 to 4, wherein the light-emitting element is an organic electroluminescence element. A resin composition for forming a light-emitting element, which is used for forming the first resin layer of the light-emitting element according to any one of the first to fifth aspects of the invention. A resin composition for forming a light-emitting element, which is used for forming the second resin layer of the light-emitting element according to any one of claims 3 to 5.