JP2016040348A - Resin composition and light-emitting element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition from which a resin layer excellent in optical characteristics, particularly, having a high refractive index can be formed by a heat treatment at a lower temperature in a shorter time, while having little coloring by the heat treatment.SOLUTION: The resin composition comprises an aromatic polyether polymer and inorganic oxide fine particles, in which the inorganic oxide fine particles are surface-modified with at least one compound selected from a fluorine-containing silane coupling agent, a cyano group-containing phosphate compound, and a cyano group-containing phosphonate. The inorganic oxide fine particles are at least one of titanium oxide, zirconium oxide, and barium titanate.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing metal oxide particles surface-treated with a specific modifier, and a light emitting device having a resin layer obtained from the resin composition.

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

  In this case, in order to increase the light extraction efficiency, it is considered that a light-emitting element in which the refractive index of the transparent positive electrode layer and air decreases in this order is preferable. In order to obtain a light emitting device having such a structure, it is known to provide a resin layer or the like on the air side of the transparent positive electrode layer. Usually, since the transparent positive electrode layer has a high refractive index, the resin layer includes Therefore, it is required to be transparent and have a high refractive index in accordance with the transparent positive electrode layer.

As such a resin layer, Patent Document 1 describes a resin layer containing an aromatic polyether polymer having a glass transition temperature of 230 to 350 ° C.
On the other hand, it has been known to increase the refractive index by blending inorganic fine particles in a polymer matrix (Patent Document 2, etc.).

JP 2012-221554 A JP2013-040239A

  By using the resin layer described in Patent Document 1, it is possible to obtain a resin layer that exhibits a certain degree of light extraction efficiency. However, in order to further increase the light extraction efficiency, a resin layer having a higher refractive index is desired.

  In order to adjust the refractive index by blending inorganic oxide fine particles in the polymer matrix, it is necessary to uniformly disperse the inorganic oxide fine particles in the polymer matrix in order to adjust the refractive index to the desired refractive index. Necessary. For example, Patent Document 2 discloses that a nanocomposite composed of inorganic oxide fine particles is used for polyimide having a high refractive index polymer, but when the inorganic oxide fine particles are uniformly mixed with polyimide, a nitrogen atmosphere is disclosed. Underneath, heat treatment at high temperature (˜300 ° C.) for a long time (2 hours or more) is necessary, and the resulting resin layer has a high haze and is highly colored by the high temperature heat treatment.

  When a high refractive index layer is used as a layer for improving the light extraction efficiency of an organic electroluminescence device, if the coloring due to the thermal load during the production of the organic electroluminescence device is large, light loss occurs due to absorption, resulting in a decrease in light extraction efficiency. It is necessary to suppress the coloring of the high refractive index layer as low as possible.

  Accordingly, an object of the present invention is to provide a resin composition that is excellent in optical properties, particularly capable of forming a resin layer having a high refractive index by heat treatment at a lower temperature and in a shorter time, and is less colored by heat treatment.

  As a result of intensive studies to solve the above problems, the present inventor can achieve the above object by using a composition comprising metal oxide particles surface-treated with a specific modifier and a specific polymer. As a result, the present invention has been completed.

Configuration examples of the present invention are the following [1] to [7].
[1] A resin composition comprising an aromatic polyether polymer and inorganic acid fine particles, wherein the inorganic oxide particles comprise a fluorine-containing silane coupling agent, a cyano group-containing phosphate ester compound, and a cyano group-containing A resin composition characterized by being surface-modified with at least one selected from phosphonic acid ester compounds.
[2] The resin composition according to claim 1, wherein the inorganic oxide fine particles are at least one of titanium oxide, zirconium oxide, and barium titanate.
[3] The resin composition according to [1] or [2], wherein the inorganic oxide fine particles have an average particle diameter of 1 nm to 100 nm.
[4] The resin composition of [1] to [3], wherein the fluorine-containing silane coupling agent is represented by the following general formula (1).

（式（１）中、Ｘは一価のハロゲン原子、炭素数１〜５のアルコキシ基を示し、Ｘが複数の場合、それぞれは同一でも異なっても良い。ｎは１〜１０の整数、ｍは１〜５の整数、ｐは１〜３の整数を示す。）
[5]前記シアノ基含有リン酸エステル化合物が、下記一般式（２）で表される化合物である[1]〜[3]の樹脂組成物。

(In formula (1), X represents a monovalent halogen atom or an alkoxy group having 1 to 5 carbon atoms, and when X is plural, each may be the same or different. N is an integer of 1 to 10, m Represents an integer of 1 to 5, and p represents an integer of 1 to 3.)
[5] The resin composition of [1] to [3], wherein the cyano group-containing phosphate ester compound is a compound represented by the following general formula (2).

（式（２）中、Ｒ¹はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基を示す。ｑは０〜１０の整数、ｒは１〜５の整数を示す。）
[6]前記シアノ基含有ホスホン酸エステル化合物が、下記一般式（３）で表される化合物である[1]〜[3]の樹脂組成物。

(In formula (2), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Q represents an integer of 0 to 10, and r represents an integer of 1 to 5.)
[6] The resin composition of [1] to [3], wherein the cyano group-containing phosphonic acid ester compound is a compound represented by the following general formula (3).

（式（３）中、Ｒ¹はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基を示す。ｑは０〜１０の整数、ｒは１〜５の整数を示す。）
[7]基板と第一電極と発光層と第二電極と[1]〜[6]の樹脂組成物からなる樹脂層とを備える発光素子であって、前記基板と前記第一電極と前記発光層と前記第二電極とがこの順に積層されてなり、前記樹脂層は、
（ａ）前記第一電極の、前記発光層が形成された側とは反対側、および、
（ｂ）前記第二電極の、前記発光層が形成された側とは反対側、
の少なくとも一方に形成された発光素子。

(In formula (3), R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Q represents an integer of 0 to 10, and r represents an integer of 1 to 5.)
[7] A light emitting device comprising a substrate, a first electrode, a light emitting layer, a second electrode, and a resin layer made of the resin composition of [1] to [6], wherein the substrate, the first electrode, and the light emitting The layer and the second electrode are laminated in this order, and the resin layer is
(A) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(B) The side of the second electrode opposite to the side on which the light emitting layer is formed,
A light emitting device formed on at least one of the above.

  According to the present invention, the specific surface-modified inorganic acid fine particles are combined with the aromatic polyether polymer, so that the optical properties are excellent, and in particular, a high refractive index resin layer is formed at a lower temperature in a shorter time. It is possible to provide a resin composition that is small in color by heat treatment. Therefore, by using such a resin composition, a light emitting element or the like having excellent light extraction efficiency can be obtained.

  In addition, since the resin layer obtained using the resin composition of the present invention is excellent in durability, it is possible to obtain a light-emitting element or the like whose performance is not easily lowered over a long period even under severe use conditions. .

≪Resin composition≫
The resin composition according to the present invention includes an aromatic polyether polymer (hereinafter also referred to as “polymer (I)”), a fluorine-containing silane coupling agent, a cyano group-containing phosphate ester compound, and a cyano group-containing resin. Inorganic oxide fine particles (hereinafter referred to as “particle (I)”) surface-modified with one or more compounds selected from phosphonate compounds.

According to such a resin composition, a resin layer having excellent optical characteristics and a particularly high refractive index can be formed.
Although the refractive index depends on the composition ratio of the polymer and particles (I) and the dispersion state of the particles (I), it is larger than that when the resin layer is formed by the polymer (I) alone, and is 1.70 or more. Is preferable, 1.75 or more is more preferable, and 1.83 or more is more preferable. By using a resin composition having a refractive index in the above range, a light emitting element having high light extraction efficiency can be obtained. The refractive index can be measured using a prism coupler model 2010 (manufactured by Metricon).

  Conventionally, if the refractive index is increased, the transmittance is decreased, and if the transmittance is increased or the transmittance of the resin is maintained, a resin layer having a high refractive index cannot be obtained. By using the resin composition of the present invention, a resin layer having a high total light transmittance can be formed even though the refractive index is high. If the resin composition of the present invention is used, a total light transmittance of 80% or more can be achieved.

The total light transmittance can be measured using a haze guard 2 (manufactured by Toyo Seiki Seisakusho).
The resin composition of the present invention is not particularly limited as long as it includes the [A] polymer (I) and the [B] particles (I). However, the [C] dispersant, [ D] a solvent, and [E] may contain other components.

Hereinafter, each component will be described.
[A] Aromatic polyether polymer (polymer (I))
The polymer (I) has a Tg of 200 to 350 ° C, preferably 220 to 330 ° C, more preferably 250 to 300 ° C.

The Tg can be measured using a Rigaku 8230 DSC measuring apparatus.
When the resin composition of the present invention contains such a polymer (I), a resin layer excellent in heat resistance, mechanical strength, electrical characteristics and the like can be obtained.

The refractive index of the polymer (I) used in the present invention, measured by the method described herein, is in the range of 1.62 to 1.68.
The resin composition of the present invention may contain one type of polymer (I) or two or more types of polymers (I).

  The polymer (I) is not particularly limited as long as it is an aromatic polyether polymer, such as polyethersulfone resin, polyetherimide resin, polyetheramide resin, polyetherketone resin, polyphenylene oxide resin, and the like. However, it is preferably a polymer obtained by a reaction that forms an ether bond in the main chain, and is a structural unit represented by the following formula (3) (hereinafter also referred to as “structural unit (3)”). And a polymer having at least one structural unit (i) selected from the group consisting of structural units represented by the following formula (4) (hereinafter also referred to as “structural unit (4)”) (hereinafter referred to as “polymer (II) It is also referred to as “)”. When the polymer has the structural unit (i), it becomes a polyether polymer having Tg in the above range. When the resin composition of the present invention contains such a polymer (II), a resin layer having excellent heat resistance, durability, electrical characteristics and transparency and having a high refractive index can be easily formed. . Furthermore, by using a resin composition containing the polymer (II), a light emitting device having excellent light extraction efficiency can be obtained.

  In addition, the polymer (II) has less light absorption in the visible region than the polyethersulfone resin and the polyetherimide resin, and the resin is hardly deteriorated by visible light or heat. For this reason, the resin layer containing the polymer (II) is preferable because it is particularly excellent in durability and is less colored by heat.

前記式（３）中、Ｒ²〜Ｒ⁵は、それぞれ独立に炭素数１〜１２の１価の有機基を示す。ａ〜ｄは、それぞれ独立に０〜４の整数を示し、好ましくは０または１である。

In said formula (3), R < ² > -R < ⁵ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1.

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

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

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

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

As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.
Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

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

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

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

  Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

  As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

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

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

As R < ² > -R < ⁵ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable, a C6-C12 aromatic hydrocarbon group is more preferable, and a phenyl group is further more preferable.

前記式（４）中、Ｒ²〜Ｒ⁵およびａ〜ｄは、それぞれ独立に前記式（3）中のＲ²〜Ｒ⁵およびａ〜ｄと同義であり、Ｚは、単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁶およびＲ⁷は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｔは、０または１を示す。但し、ｔが０の時、Ｒ⁶はシアノ基ではない。fおよびgは、それぞれ独立に０〜４の整数を示し、好ましくは０である。

In the formula (4), R ² to R ⁵ and a~d has the same meaning as R ² to R ⁵ and a~d each independently the formula (3), Z represents a single bond, -SO _2- or> C = O, R ⁶ and R ⁷ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and t represents 0 or 1. However, when t is 0, R ⁶ is not a cyano group. f and g each independently represent an integer of 0 to 4, preferably 0.

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (3).
The polymer (II) has a molar ratio of the structural unit (3) to the structural unit (4) (provided that the total of both (structural unit (3) + structural unit (4)) is 100.) However, it is preferable that the structural unit (3): structural unit (4) = 50: 50 to 100: 0 from the viewpoint of becoming a polymer having excellent optical properties, heat resistance, mechanical properties, and the like. 3): Structural unit (4) = 70: 30 to 100: 0 is more preferable, and structural unit (3): structural unit (4) = 80: 20 to 100: 0 is more preferable.

Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.
The polymer (II) further comprises at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5). You may have. It is preferable that the polymer (II) has such a structural unit (ii) because the mechanical properties of the resin layer obtained using the resin composition having the polymer (II) are improved.

前記式（５）中、Ｒ⁸およびＲ⁹は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Jは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｕは、０または１を示す。ｈおよびiは、それぞれ独立に０〜４の整数を示し、好ましくは０である。

In the formula (5), R ⁸ and R ⁹ each independently represent a monovalent organic group having 1 to 12 carbon atoms, J represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and u represents 0 or 1. h and i each independently represent an integer of 0 to 4, preferably 0.

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (3).
The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

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

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

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

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

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

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

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

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

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

As J in the formula (5), a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms is preferable, and a divalent organic group having 1 to 12 carbon atoms is preferable. A hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

前記式（６）中、Ｒ⁶、Ｒ⁷、Z、ｔ、ｆおよびｇは、それぞれ独立に前記式（４）中のＲ⁶、Ｒ⁷、Z、t、fおよびgと同義であり、Ｒ⁸、Ｒ⁹、J、ｕ、ｈおよびｉは、それぞれ独立に前記式（５）中のＲ⁸、Ｒ⁹、J、ｕ、ｈおよびｉと同義である。なお、ｔが０の時、Ｒ⁶はシアノ基ではない。

In the formula (6), R ⁶ , R ⁷ , Z, t, f and g are each independently synonymous with R ⁶ , R ⁷ , Z, t, f and g in the formula (4), R ^8, R ^9, J, u, h and i are each R ⁸ in independent to the formula ^{(5), R 9, J} , u, synonymous with h and i. When t is 0, R ⁶ is not a cyano group.

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

Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.
The polymer (II) contains the structural unit (i) and the structural unit (ii) in an amount of 70 mol% or more in the total structural units from the viewpoint of becoming a polymer excellent in optical properties, heat resistance, mechanical properties, and the like. It is preferable to include, and more preferably 95 mol% or more in all the structural units.

  Examples of the polymer (II) include a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”) and a compound represented by the following formula (9) (hereinafter “compound (8)”). And a component (hereinafter also referred to as “component (A)”) containing at least one compound selected from the group consisting of a compound represented by the following formula (8) (hereinafter referred to as “(B)”. ) Component ") can be obtained by reaction.

前記式（７）中、Qは独立してハロゲン原子を示し、フッ素原子が好ましい。

In the formula (7), Q independently represents a halogen atom, preferably a fluorine atom.

前記式（９）中、Ｒ⁶、Ｒ⁷、Z、t、fおよびgは、それぞれ独立に前記式（４）中のＲ⁶、Ｒ⁷、Z、t、fおよびgと同義であり、Qは、独立に前記式（７）中のQと同義である。但し、ｔが０の時、Ｒ６はシアノ基ではない。

In the formula (9), R ⁶ , R ⁷ , Z, t, f and g are each independently synonymous with R ⁶ , R ⁷ , Z, t, f and g in the formula (4), Q is independently synonymous with Q in the formula (7). However, when t is 0, R6 is not a cyano group.

前記式（８）中、Ｒ^aは、それぞれ独立に水素原子、メチル基、エチル基、アセチル基、メタンスルホニル基またはトリフルオロメチルスルホニル基を示し、この中でも水素原子が好ましい。なお、式（８）中、Ｒ²〜Ｒ⁵およびａ〜ｄは、それぞれ独立に前記式（３）中のＲ²〜Ｒ⁵およびａ〜ｄと同義である。

In the formula (8), each R ^a independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (8), R ² to R ⁵ and a~d have the same meanings as R ² to R ⁵ and a~d each independently to the formula (3).

  Specific examples of the compound (7) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2, Examples include 5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, and reactive derivatives thereof. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the formula (8) (hereinafter also referred to as “compound (8)”) include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL), 9,9- Bis (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9 , 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  As the compound (9), specifically, 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone (DFDS), 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2′-difluorobenzophenone, 2,2′-difluorodiphenylsulfone, 3,3′-dinitro-4,4′-difluorobenzophenone, 3,3′-dinitro-4,4′-difluorodiphenylsulfone, 4, 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3 , 3′-dinitro-4,4′-dichlorobenzophenone and 3,3′-dinitro-4, 4'-dichlorodiphenyl sulfone and the like can be mentioned. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

  It is preferable that at least one compound selected from the group consisting of the compound (7) and the compound (9) is contained in 80 mol% to 100 mol% in 100 mol% of the component (A), More preferably, it is contained at 100 mol%.

  Moreover, (B) component may contain the compound (henceforth "compound (10)") represented by following formula (10) as needed. Compound (8) is preferably contained in 100 mol% of component (B) in an amount of 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

前記式（１０）中、Ｒ⁸、Ｒ⁹、J、ｈ、iおよびｕは、それぞれ独立に前記式（５）中のＲ⁸、Ｒ⁹、Ｊ、ｈ、ｉおよびｕと同義であり、Ｒ^aは、それぞれ独立に前記式（８）中のＲ^aと同義である。

In the formula (10), R ⁸ , R ⁹ , J, h, i and u are each independently synonymous with R ⁸ , R ⁹ , J, h, i and u in the formula (5); R ^a has the same meaning as R ^a each independently in the formula (8) in.

  Examples of the compound (10) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, 3,3′-dihydroxydiphenylsulfone, 4 , 4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxyphenyl) propane, Examples include 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof. . Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

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

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

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

The polymer (I) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C. or higher, more preferably 475 ° C. or higher, and further preferably 490 ° C. or higher.
As the resin composition of the present invention, a mixture of the polymer (II) obtained by the method (I ′) and an organic solvent may be used as it is.

[B] Particle (I)
Inorganic oxide fine particles The inorganic oxide fine particles used in the resin composition of the present invention include titanium oxide, zirconium oxide, barium titanate, yttria-added zirconium oxide, lead zirconate, strontium titanate, tin titanate, tin oxide, Examples thereof include bismuth oxide, niobium oxide, tantalum oxide, potassium tantalate, tungsten oxide, cerium oxide, lanthanum oxide, gallium oxide, and silicon dioxide / zirconium dioxide / tin dioxide / potassium oxide-containing titanium oxide. One kind of inorganic oxide fine particles may be used alone, two or more kinds of different kinds may be used, and two or more kinds having different average particle diameters may be used. Of these, titanium oxide, zirconium oxide, and barium titanate having a high refractive index are preferably used. Titanium oxide has two types of crystal structures, a rutile type and an anatase type. Since anatase type has high photocatalytic activity, it is preferable to use a rutile type. As the inorganic oxide fine particles, it is most preferable to use barium titanate having a high refractive index and low photocatalytic activity.

  The inorganic oxide fine particles have an average particle diameter of preferably 1 nm or more and less than 100 nm, more preferably 3 to 70 nm, and particularly preferably 5 to 50 nm. If the average particle size is less than 1 nm, the particles become unstable and secondary aggregation occurs, and the resin composition coating film may become cloudy. On the other hand, when the average particle diameter is 100 nm or more, the resin composition coating film becomes non-uniform, the transparency of the coating film is impaired, and the transmittance may be significantly reduced. When the average particle diameter is within the above range, a resin layer having excellent transparency can be obtained. The average particle diameter can be measured with a particle distribution measuring apparatus based on the dynamic light scattering method.

In the present invention, the average particle size of the inorganic oxide fine particles is an average particle size evaluated in a fine particle dispersion (which may contain the polymer (I)), and may be referred to as a dispersed particle size.
The inorganic oxide fine particles blended in the resin composition of the present invention may be in the form of a powder or a solvent-dispersed sol. Examples of the solvent contained in the solvent dispersion sol include 2-butanol, methanol, ethanol, 2-methoxyethanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, γ-butyrolactone, N, N-dimethylacetamide may be mentioned. Of these solvents, 2-methoxyethanol, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide are particularly preferable.

  The blending amount of the inorganic oxide fine particles is preferably 30 to 99% by mass, more preferably 40 to 95% by mass, and still more preferably 100% by weight of the resin composition comprising the polymer (I) and the particles (I). It is 45-90 mass%. When the blending amount of the inorganic oxide fine particles is within the above range, a resin layer having a particularly high refractive index and excellent transparency can be obtained, and a light emitting element having excellent light extraction efficiency can be obtained. In addition, when inorganic oxide microparticles | fine-particles are solvent dispersion sol, the compounding quantity of inorganic oxide microparticles means the mass which does not contain a solvent.

Surface modifier The inorganic oxide fine particles used in the resin composition of the present invention has one surface selected from fluorine-containing silane coupling agents, cyano group-containing phosphate compounds, and cyano group-containing phosphonate compounds. Those whose surface is modified with the above compounds are used. When the inorganic oxide fine particles are surface-modified with such a surface modifier, the dispersibility in the resin composition containing the polymer can be increased, and the high refractive index, high light transmittance, low Haze and It is possible to obtain a resin layer having excellent optical characteristics such as a low extinction coefficient.

  As the fluorine-containing silane coupling agent, a silane coupling agent represented by the following general formula (1) is used.

式（１）中、ｎは１〜１０の整数、ｍは１〜５の整数を示す。

In formula (1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5.

  X represents a group selected from a halogen atom, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. When X is plural, each group may be the same or different. p shows the integer of 1-3.

As a specific example of the silane coupling agent represented by the general formula (1),
CF ₃ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₄ Si (OCH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CH ₂ ) ₃ SiCl ₃
CF ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,
CF ₃ CH ₂ Si (CH ₃ ) (OCH ₂ CH ₃ ) ₂
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₂ CH ₃ ) ₂ ,
CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₂ CH ₃ ) ₂ ,
C ₂ F ₅ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇ CH ₂ Si (OCH ₃ ) ₃ ,
C ₄ F ₉ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
C ₃ F ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
C ₂ F ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
C ₃ F ₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C ₄ F ₉ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
C ₅ F ₁₁ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C ₆ F ₁₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
C ₇ F ₁₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₃ SiCl (CH ₃ ) ₂ , CF ₃ (CH ₂ ) ₃ SiCl ₂ (OCH ₃ ) and the like can be mentioned. Although the said silane coupling agent may be used individually by 1 type, you may use 2 or more types. Among these compounds, CF ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ is preferably used.

  The amount of the coupling agent (1) used is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 1% by mass with respect to the inorganic oxide fine particles. It is.

  As the cyano group-containing phosphate compound, a compound represented by the following general formula (2) is used.

式（２）中、Ｒ¹は水素原子、炭素数１〜１０のアルキル基を示す。Ｙは-（ＣＨ₂）q−、-（ＣＨ₂）q−Ｏ−から選ばれる基であり、ｑは０〜１０の整数を示す。ｒは１〜５の整数を示す。
一般式（２）で示される化合物の具体例としては、以下等が挙げられる。

In formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Y is _{- (CH 2) q -,} - (CH 2) a group selected from q-O-, q is an integer of 0. r shows the integer of 1-5.
Specific examples of the compound represented by the general formula (2) include the following.

上記シアノ基含有リン酸エステル化合物は単独で用いることもできるが、２種以上を用いることもできる。

Although the said cyano group containing phosphate ester compound can also be used independently, 2 or more types can also be used.

  As the cyano group-containing phosphonate compound, a compound represented by the following general formula (3) is used.

式（３）中、Ｒ¹はそれぞれ独立に水素原子、炭素数１〜１０のアルキル基を示す。ｑは０〜１０の整数、ｒは１〜５の整数を示す。
一般式（３）で示される化合物の具体例としては、以下等が挙げられる。

In Formula (3), R ¹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. q represents an integer of 0 to 10, and r represents an integer of 1 to 5.
Specific examples of the compound represented by the general formula (3) include the following.

上記シアノ基含有ホスホン酸エステル化合物は単独で用いることもできるが、２種以上を用いることもできる。

Although the said cyano group containing phosphonic acid ester compound can also be used independently, 2 or more types can also be used.

The cyano group-containing phosphate compound and the cyano group-containing phosphonate compound can be used alone or both can be used simultaneously.
Among these compounds,

が好適に用いられる。

Are preferably used.

  The amount of the cyano group-containing phosphate compound and the cyano group-containing phosphonate compound is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass, based on the inorganic oxide fine particles. More preferably, it is 0.5-1 mass%.

  As the surface modification method, a known method can be adopted. For example, a surface modifier is added to the inorganic oxide fine particle dispersion, and the mixture is heated and mixed as necessary to react with the surface. What is necessary is just to separate.

[C] Dispersant Usually, an anionic dispersant, a cationic dispersant, a nonionic dispersant, or the like is used to disperse the inorganic oxide fine particles in the polymer.

  Conventionally, in order to uniformly disperse the inorganic oxide fine particles in the polymer, it is necessary to add a large amount of a dispersant, so that there is a problem that the refractive index of the obtained resin composition is lowered. Furthermore, since these dispersants have low thermal stability at high temperatures, there is a problem that the resin composition is highly colored at high temperatures, which causes problems such as a decrease in light extraction efficiency when used in a light emitting device. There are many cases.

  In contrast, in the present invention, a fluorine-containing silane coupling agent, a phosphoric acid ester compound, and a phosphonic acid ester compound are used as a surface modifier for inorganic oxide fine particles, so that the dispersant can be used with a small amount or no use. The fine particles can be uniformly dispersed in the polymer, and a resin composition having a high refractive index can be obtained. In addition, since these fluorine-containing silane coupling agents, phosphate ester compounds, and phosphonate ester compounds are excellent in thermal stability at high temperatures, it is possible to obtain a resin composition in which coloring at high temperatures is suppressed, and high light A light extraction high refractive index layer having an extraction efficiency can be obtained.

  The amount of the dispersant used is appropriately selected in consideration of the refractive index and transparency, but when the total of the polymer (I) and the inorganic oxide (I) is 100% by mass, it is 5% by mass or less. This is not necessary.

[D] Solvent The resin composition of the present invention may contain a solvent as necessary.
A solvent may be used individually by 1 type and may use 2 or more types.

  Such a solvent is preferably a solvent capable of uniformly dissolving and dispersing the polymer (I), and the solvents mentioned as the organic solvent used in the synthesis of the polymer (II) A similar solvent may be used (referred to as a first solvent).

  Preferred solvents (first solvent) include, for example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and γ-butyrolactone. From the viewpoints of properties and economy, preferably, methylene chloride, cyclohexanone, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are used.

  In addition, aiming at improving the drying property, uniformity, surface smoothness, etc. during coating, for example, selected from ether organic solvents, ester organic solvents, ketone organic solvents, hydrocarbon organic solvents, alcohol organic solvents It is preferable to use an appropriate combination of one kind or two or more kinds of second solvents. In this case, a low boiling point organic solvent having a boiling point under atmospheric pressure (1,013 hPa) of 200 ° C. or lower, more preferably in the range of 50 to 150 ° C. is preferable.

  When the resin composition of the present invention contains a solvent, a resin layer having a high refractive index can be easily formed because the solvent is a low boiling point organic solvent, and the resin layer can be formed at a low temperature of 200 ° C. or lower. Since it can form, the base material etc. in which a resin layer is formed are not restrict | limited, It is preferable.

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

  Although the said solvent is based also on the molecular weight of polymer (I), it is preferable to be used in the range which can dissolve polymer (I) uniformly, Specifically, in the resin composition of this invention It is desirable to use the polymer (I) in such an amount that the concentration is usually 1 to 40% by mass, preferably 5 to 25% by mass. When the concentration of the polymer (I) in the resin composition of the present invention is in the above range, it is possible to form a resin layer that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

[E] Other components The resin composition of the present invention may contain other components other than the above [A] to [D] as long as the effects of the present invention are not impaired.

  Examples of the other components include dispersion aids such as acetylacetone, particles such as metal oxide particles and organic particles, surfactants such as silicone surfactants, anti-aging agents such as hindered phenol compounds, and curable compounds. And ultraviolet absorbers.

<Method for producing resin composition>
The resin composition of the present invention is prepared by mixing the polymer (I), the surface-modified inorganic oxide fine particles (I), and other optional components blended as necessary, such as a solvent. Can do.

  In particular, in order to obtain a resin layer excellent in optical properties such as high refractive index, high light transmittance, low haze and low extinction coefficient, it is considered preferable to improve the dispersibility of the inorganic oxide fine particles. From the standpoint of obtaining such a resin composition with improved dispersibility, the production method of the resin composition of the present invention includes inorganic oxide fine particles surface-modified with a silane coupling agent and phosphoric acid (phosphonic acid) ester. A method of uniformly stirring the uniformly dispersed solution and a solution in which the polymer (I) is dissolved in a solvent is preferable.

≪Coating composition≫
In the coating composition of the present invention, the resin composition itself can be used, or the resin composition and the second solvent having a boiling point (under atmospheric pressure (1,013 hPa)) of 200 ° C. or lower are mixed. You can also

Each of the resin composition and the solvent used in the coating composition may be used alone or in combination of two or more.
The solvent having a boiling point of 200 ° C. or lower is preferably a solvent having a boiling point of 50 to 150 ° C., and more preferably water-insoluble.

Examples of such a solvent include the same solvents as the low boiling point organic solvent.
The viscosity of the resin composition for coating depends on the molecular weight and concentration of the polymer (I), but is preferably 50 to 100,000 mPa · s, more preferably 500 to 50,000 mPa · s, and still more preferably 1000 to It is 20,000 mPa · s. In consideration of handling properties, it may be mixed with an organic solvent so as to adjust the viscosity within this range. When the viscosity of the resin composition is in the above range, the resin composition is excellent in the retention property when the resin layer is formed using the coating composition, and the thickness can be easily adjusted. It is.

≪Resin layer≫
The resin layer of the present invention is not particularly limited, but is preferably formed using the resin composition, and is preferably formed from the coating composition.

Since the resin layer of the present invention contains polymer (I), preferably polymer (II), the refractive index tends to be high. For this reason, a resin layer having high light extraction efficiency can be obtained.
Furthermore, since the specific surface-modified inorganic oxide fine particles having high dispersibility are included together with the polymer (I), a transparent resin layer having a high refractive index and excellent heat resistance can be formed. For this reason, such a resin layer can be used suitably as a material of a light emitting element.

  Specifically, the resin layer of the present invention is formed by coating the coating composition on a substrate or a member (eg, a layer constituting an optical element) in which the resin layer is used, and then forming a coating film. Depending on the method, the solvent can be removed from the coating film.

  Although it does not restrict | limit especially as said board | substrate, The glass substrate or transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is desirable.

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

  Further, the method for removing the solvent from the coating film is not particularly limited, and examples thereof include a method of heating the coating film. By heating the coating film, the solvent in the coating film can be evaporated and removed. The heating conditions may be determined as appropriate as long as the solvent evaporates and does not cause thermal deformation or modification of various materials due to heat. For example, the heating temperature is preferably 30 ° C to 200 ° C.

  The heating time is preferably 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 150 ° C. for 1 minute to 2 hours, heating is further performed at 100 ° C. to 200 ° C. for 10 minutes to 2 hours. Further, if necessary, heating may be performed under a nitrogen atmosphere or under reduced pressure. Preferably, after drying at 60 to 100 ° C. for 20 minutes to 1 hour, 200 to 260 ° C. for 20 minutes to 1 hour, more preferably after drying at 80 ° C. for 30 minutes and then heating at 250 ° C. for 30 minutes.

  In the present invention, since the resin composition is used, the resin layer can be formed by heat treatment at a low temperature for a short time. For this reason, since the heat load at the time of manufacturing a light emitting element can be reduced, coloring and deformation can be reduced.

  The thickness of the resin layer is appropriately selected according to the desired application, but is preferably 20 nm to 100 μm, more preferably 80 nm to 50 μm, and still more preferably 100 nm to 10 μm.

  The resin layer has a refractive index at a wavelength of 632.8 nm of preferably 1.70 or more, more preferably 1.75 or more, and further preferably 1.83 or more. By using a resin layer having a refractive index in the above range, a light emitting element having high light extraction efficiency can be obtained.

The refractive index can be measured using a prism coupler model 2010 (manufactured by Metricon).
The total light transmittance measured based on JIS K7361 at a thickness of about 2 μm is preferably 80% or more, more preferably 85% or more, and particularly preferably 87% or more. A resin layer having a refractive index in the above range is excellent in light transmittance, and by using the resin layer, a light emitting element or the like having higher light extraction efficiency can be obtained.

The total light transmittance can be measured using a haze guard 2 (manufactured by Toyo Seiki Seisakusho).
The resin layer has a Tg of 8230 type DSC measuring apparatus (temperature increase rate 20 ° C./min) manufactured by Rigaku, preferably 230 to 350 ° C., more preferably 240 to 330 ° C., and further preferably 250 to 300 ° C. It is. When the resin layer has such a Tg, heating and heat treatment when forming an electrode or the like on the layer can be performed at a high temperature. Therefore, the electrode obtained in this way has low resistance and high transmittance. Thus, a light-emitting element having excellent light extraction efficiency and durability can be easily manufactured.

The resin layer has a Haze measured based on JIS K7136 at a thickness of about 2 μm, preferably 30% or less, more preferably 25% or less, and even more preferably 10% or less. A resin layer having a haze in the above range is excellent in light transmittance, and by using the resin layer, a light emitting element or the like having higher light extraction efficiency can be obtained.
Haze can be measured using a haze guard 2 (manufactured by Toyo Seiki Seisakusho).

The resin layer has an extinction coefficient (k value) of 30 × 10 ⁻⁴ or less, more preferably 2 × 10 ⁻⁴ or less after heating at 200 ° C. for 30 minutes in the atmosphere. A resin layer having a k value in the above range is excellent in light transmittance and durability, and by using the resin layer, a light emitting element or the like having higher light extraction efficiency can be obtained.

Specifically, the k value can be measured by the method described in the Examples below.
The resin layer preferably has a tensile strength of 50 to 200 MPa, and more preferably 80 to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

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

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

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

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

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

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

  When the resin layer has a thickness of 30 μm, the YI value after heating for 1 hour at 230 ° C. in the air with a hot air dryer is preferably 3.0 or less, and 2.5 or less. More preferably, it is 2.0 or less.

≪Light emitting element≫
The light emitting device of the present invention includes a first electrode, a light emitting layer, a second electrode, and the resin layer, and the first electrode, the light emitting layer, and the second electrode are laminated in this order. The resin layer is (a) the side of the first electrode opposite to the side where the light emitting layer is formed, and (b) the side of the second electrode opposite to the side where the light emitting layer is formed. , At least one of them.
Since such a light emitting element includes the resin layer, the light extraction efficiency is high and the durability is excellent.

[First electrode]
The first electrode can be manufactured by vapor deposition or sputtering using a first electrode forming material. When forming a transmissive electrode, the first electrode forming material is transparent and has excellent conductivity, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide ( ZnO) or the like can be used.

  When a reflective electrode is formed, magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—) are used as the first electrode forming material. In), magnesium-silver (Mg-Ag), or the like can be used. What is necessary is just to select the thickness of a 1st electrode suitably according to the desired objective.

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

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

[Second electrode]
The second electrode can be manufactured by vapor deposition or sputtering using a second electrode forming material. As the second electrode forming substance, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg—Ag) and the like.

  A transmissive electrode can be obtained by forming a thin film from these substances. Further, a transmissive electrode containing ITO or IZO may be used. What is necessary is just to select the thickness of a 2nd electrode suitably according to the desired objective.

The second electrode is preferably a cathode that is an electron injection electrode.
The second electrode is preferably a transmissive electrode. In this case, light generated in the light emitting layer preferably passes through the second electrode and the resin layer and is extracted outside the light emitting element.

  Since this light-emitting element includes the resin layer, when light generated in the light-emitting layer passes through the second electrode and enters the air, the light is refracted to increase the efficiency of being extracted outside the light-emitting element. A light emitting element in which the refractive index of the second electrode, the refractive index of the resin layer, and the refractive index of air (about 1.0) become smaller in this order is preferable. Moreover, it is preferable that the difference in refractive index between the second electrode and the resin layer and the difference in refractive index between the resin layer and air are small. When the refractive index of the second electrode, the resin layer, and air is in such a relationship, the interface between the second electrode and the resin layer, the resin layer, and the step of extracting the light generated in the light emitting layer to the outside of the light emitting element Since it becomes difficult to totally reflect at the interface with air, it is considered that the light extraction efficiency is increased.

Note that the light emitting element may be further provided with various layers as necessary.
Further, a known sealing layer for sealing the light emitting element may be further provided, and various modifications are possible.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
(1) Structural analysis The structural analysis of the polymer obtained in the following synthesis example was performed by IR (ATR method, FT-IR, 6700 (manufactured by NICOLET)) and NMR (ADVANCE500 type, manufactured by BRUKAAR).

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

(3) Glass transition temperature (Tg)
The glass transition temperature of the polymer obtained in the following synthesis example, or the resin layer for evaluation obtained in the following examples and comparative examples, was measured using a Rigaku 8230 DSC measuring apparatus using a temperature increase rate of 20 ° C./min. As measured.

(4) Optical characteristics About the resin layer for evaluation obtained by the following Example and comparative example, the total light transmittance was measured based on JISK7361 and JISK7136, respectively. Specifically, the total light transmittance was measured using a Toyo Seiki Seisakusho Co., Ltd. haze guard 2.

  The extinction coefficient (= k value) at a wavelength of 450 nm was determined by heating the evaluation resin layers obtained in the following Examples and Comparative Examples in the air at 200 ° C. for 30 minutes in the atmosphere, and then Hitachi, Ltd. The transmittance and reflectance of the evaluation resin layer are measured using a spectrophotometer U-4100 manufactured by High Technology, and the thickness of the evaluation resin layer is further measured by a reflective spectral film thickness meter FE manufactured by Otsuka Electronics Co., Ltd. -3000 and calculated from Beer's law.

  The refractive indexes of the evaluation resin layers obtained in the examples and comparative examples were measured using a prism coupler model 2010 (manufactured by Metricon). The refractive index was measured using a wavelength of 632.8 nm.

[Synthesis Example 1]
<Synthesis of polymer>
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, component (B): 87.60 g (0,9,9-bis (4-hydroxyphenyl) fluorene 250 mol), 41.46 g (0.300 mol) of potassium carbonate, 443 g of N, N-dimethylacetamide (DMAc) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

  Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 95.67 g, yield 95%).

The resulting polymer was subjected to structural analysis and Mw measurement. The results show that the characteristic absorption of the infrared absorption spectrum is 3035 cm ⁻¹ (CH stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). ) And Mw was 130,000. The obtained polymer had the following structural unit (A). Moreover, the glass transition temperature of the obtained polymer was 280 degreeC.

[Preparation Example 1]
<Preparation of Barium Titanate Nanoparticle Dispersion (1)>
A reaction vessel equipped with a stirrer was charged with 55.83 g of 2-methoxyethanol, 1.318 g of barium metal and 2.305 g of tetraethyl orthotitanate were added under a nitrogen atmosphere, and completely dissolved with stirring to prepare a metal alkoxide solution. . Subsequently, this solution was heated to reflux for 2 hours, and a mixed solution of 32.40 g of deionized water and 26.62 g of 2-methoxyethanol was added and stirred for 5 hours in a thermostatic bath maintained at 70 ° C. to obtain barium titanate nanoparticles. A dispersion was prepared. After ultrasonic irradiation for 30 minutes, 0.462 g of diethyl (4-cyanobenzyl) phosphonate and 0.390 g of 3,3,3-trifluoropropyltrimethoxysilane were added and reacted at 70 ° C. for 1 hour. After cooling to room temperature, the solid content was collected by centrifugation, and 4 mL of N-methyl-2-pyrrolidone (NMP) was added to obtain an NMP dispersion of barium titanate nanoparticles.

Example 1
The polymer obtained in Synthesis Example 1 was dissolved in DMAc so that the polymer concentration was 4.7% by mass (the polymer obtained in Synthesis Example 1 was dissolved in DMAc so that the polymer concentration became 24% by mass. 1.75 g of the barium titanate nanoparticle dispersion (1) is added to 0.175 g of a solution (hereinafter also referred to as “resin solution (1)”), and a rotating / revolving mixer (Awatori) is added. A mixed solution was prepared by stirring for 5 minutes. The dispersion particle diameter of the barium titanate particles in the obtained mixed solution was 21 nm calculated from the measured transmittance at a wavelength of 632 nm using the Rayleigh scattering formula. The obtained mixed solution was filtered with a filter having a pore size of 5 μm, and then spin-coated on a glass substrate. This coated substrate was heated at 80 ° C. for 30 minutes using a forced stirring dryer, then heated at 250 ° C. for 30 minutes, then taken out from the dryer and cooled to room temperature in the atmosphere to about 1.7 μm. A thick film was obtained. The refractive index of the obtained coating layer is 1.87. The total light transmittance was 87%, and the extinction coefficient was 2 × 10 ⁻⁴ .

Example 2
A mixed solution was prepared and a coated substrate was prepared in the same manner as in Example 1 except that 1.331 g of the barium titanate nanoparticle dispersion (1) was added to 0.279 g of the resin solution (1). The dispersed particle diameter of the barium titanate particles in the obtained mixed solution was 21 nm. The resulting coating layer has a thickness of 2.2 μm and a refractive index of 1.87. The total light transmittance was 87%, and the extinction coefficient was 2 × 10 ⁻⁴ .

Example 3
A mixed solution and a coated substrate were prepared in the same manner as in Example 1 except that 2.130 g of the barium titanate nanoparticle dispersion (1) was added to 0.842 g of the resin solution (1). The dispersed particle diameter of the barium titanate particles in the obtained mixed solution was 21 nm. The resulting coating layer has a thickness of 2.0 μm and a refractive index of 1.87. The total light transmittance was 87%, and the extinction coefficient was 2 × 10 ⁻⁴ .

Example 4
A mixed solution and a coated substrate were prepared in the same manner as in Example 1 except that 1.684 g of the barium titanate nanoparticle dispersion (1) was added to 2.130 g of the resin solution (1). The dispersed particle diameter of the barium titanate particles in the obtained mixed solution was 21 nm. The resulting coating layer has a thickness of 2.2 μm and a refractive index of 1.87. The total light transmittance was 87%, and the extinction coefficient was 2 × 10 ⁻⁴ .

Example 5
A mixed solution was prepared and a coated substrate was prepared in the same manner as in Example 1 except that 3.087 g of the barium titanate nanoparticle dispersion (1) was added to 3.124 g of the resin solution (1). The dispersed particle diameter of the barium titanate particles in the obtained mixed solution was 21 nm. The obtained coating layer has a thickness of 1.5 μm and a refractive index of 1.87. The total light transmittance was 87%, and the extinction coefficient was 2 × 10 ⁻⁴ .

[Preparation Example 2]
<Preparation of Barium Titanate Nanoparticle Dispersion (2)>
11 parts by mass of Marbon AC-F3 (polyoxyethylene secondary alkyl ether) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. with respect to 100 parts by mass of barium titanate (Sigma Aldrich, less than 100 nm primary particle size) in a PFA container, propylene glycol Add 192 parts by weight of monomethyl ether, add 900 parts by weight of zirconia beads having a particle size of 0.1 mm (manufactured by Nikkato), shake using paint conditioner (manufactured by RED DEVIL) for 1 hour, and titanate After barium nanoparticles were dispersed in propylene glycol monomethyl ether, the zirconia beads were removed to obtain a barium titanate nanoparticle dispersion (2).

Comparative Example 1
The mixed solution and the coated substrate were prepared in the same manner as in Example 1 except that the coating liquid composition was prepared in the same manner as in Example 1 except that the barium titanate nanoparticle dispersion (2) was used. went. The dispersion diameter of the barium titanate particles in the obtained mixed solution was 800 nm. The obtained coating layer had a thickness of 2.0 μm, a refractive index of 1.72, a total light transmittance of 70%, an extinction coefficient of 5 × 10 ⁻² and coloring after drying.

Claims (7)

  A resin composition comprising an aromatic polyether polymer and inorganic acid fine particles, wherein the inorganic oxide particles comprise a fluorine-containing silane coupling agent, a cyano group-containing phosphate ester compound, and a cyano group-containing phosphonate ester A resin composition characterized by being surface-modified with at least one selected from compounds.   The resin composition according to claim 1, wherein the inorganic oxide fine particles are at least one of titanium oxide, zirconium oxide, and barium titanate.   The resin composition according to claim 1 or 2, wherein the inorganic oxide fine particles have an average particle diameter of 1 nm to 100 nm. The said fluorine-containing silane coupling agent is represented by following General formula (1), The resin composition of any one of Claims 1-3 characterized by the above-mentioned.

(In formula (1), X represents a monovalent halogen atom or an alkoxy group having 1 to 5 carbon atoms, and when X is plural, each may be the same or different. N is an integer of 1 to 10, m Represents an integer of 1 to 5, and p represents an integer of 1 to 3.) The resin composition according to any one of claims 1 to 3, wherein the cyano group-containing phosphate ester compound is a compound represented by the following general formula (2).

(In formula (2), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Q represents an integer of 0 to 10, and r represents an integer of 1 to 5.) The resin composition according to any one of claims 1 to 3, wherein the cyano group-containing phosphonic acid ester compound is a compound represented by the following general formula (3).

(In formula (3), R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Q represents an integer of 0 to 10, and r represents an integer of 1 to 5.) A light emitting device comprising a substrate, a first electrode, a light emitting layer, a second electrode, and a resin layer comprising the resin composition according to any one of claims 1 to 6, wherein the substrate, the first electrode, The light emitting layer and the second electrode are laminated in this order, and the resin layer is
(A) a side of the first electrode opposite to the side on which the light emitting layer is formed; and
(B) The side of the second electrode opposite to the side on which the light emitting layer is formed,
A light emitting device formed on at least one of the above.