KR20120008445A - Luminescent element and composition for forming particle-containing layer - Google Patents

Abstract

PURPOSE: A light emitting device and a composition material for particle containing layer formation are provided to arrange a particle containing layer with a hardening material of a specific composition material, thereby improving light emitting efficiency by improving the refractive index of the particle containing layer. CONSTITUTION: A first electrode(13) is arranged on a substrate(11). A light-emitting layer(15) is arranged on the first electrode. A second electrode(17) is arranged on the light-emitting layer. A particle-containing layer(18) is arranged on the second electrode. Light generated from the light-emitting layer is extracted to the outside of a light emitting device(10) by passing the second electrode and particle-containing layer.

Description

LUMINESCENT ELEMENT AND COMPOSITION FOR FORMING PARTICLE-CONTAINING LAYER}

The present invention relates to a light emitting element and a composition used as a material of the particle-containing layer constituting the light emitting element.

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 stacked in this order on the surface of a transparent substrate. For example, the organic electroluminescent device injects holes from the positive electrode layer and electrons from the negative electrode layer into the light emitting material layer made of an organic material, and holes inside the light emitting material layer. An exciton (exciton) is produced by recombination of electrons and electrons, and the light emitting element emits light by emission of light (fluorescence and phosphorescence) when the excitons are deactivated. Light generated in the light emitting material layer is taken out of the light emitting element from the side of the transparent substrate.

Patent Literature 1 discloses a light emitting device having a high refractive index layer using high refractive index resins such as polyether sulfone resin and polyetherimide resin.

Japanese Patent Laid-Open No. 2004-296438

By using the transparent conductive substrate of patent document 1, the light which a light emitting element emits can be taken out efficiently to some extent from the side of a transparent substrate. However, there exists a problem that high refractive index resins, such as a polyether sulfone resin and a polyether imide resin, deteriorate by the light which a light emitting element emits.

Therefore, an object of the present invention is to provide a light emitting device having improved luminous efficiency and durability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that the said objective could be achieved by the light emitting element provided with the particle | grain containing layer containing a specific component, and completed this invention.

That is, this invention provides the following [1]-[7].

[1] a substrate, a first electrode, a light emitting layer, a second electrode, and a particle containing layer, wherein the substrate, the first electrode, the light emitting layer, and the second electrode are laminated in this order; The first electrode is formed on at least one side opposite to the side on which the light emitting layer is formed and on the side opposite to the side on which the light emitting layer is formed of the second electrode, and the particle-containing layer comprises the following component (A) and A light emitting device comprising the cured product of the composition for forming a particle-containing layer containing the component (B):

(A) at least one polymer selected from siloxane-based polymers, titanoxane-based polymers and these copolymers;

(B) metal oxide particles.

[2] The light emitting element according to the above [1], wherein the light emitting element is an organic electroluminescent element.

[3] The light emitting device according to [1] or [2], wherein the particle-containing layer is provided between the substrate and the first electrode.

[4] Any of the above [1] to [3], wherein the polymer is a polymer obtained by condensation of at least one compound selected from a compound represented by the following General Formula (1) and a compound represented by the following General Formula (2). Light emitting element described in:

(R ¹ ) _p Si (X) _4-p ... (One)

[In General Formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3;

(R ¹ ) _p Ti (X) _4-p ... (2)

[In General Formula (2), R <^1> is a non-hydrolyzable organic group whose carbon number is 1-12, X is a hydrolysable group, and p is an integer of 0-3.].

[5] The light emitting element according to any one of [1] to [4], wherein a compounding amount of the component (B) is 50 to 2,000 parts by mass with respect to 100 parts by mass of the component (A).

[6] The light emitting device according to any one of [1] to [5], in which the component (B) is a fine particle having a number average primary particle diameter of 1 to 100 nm.

[7] A composition for forming a particle-containing layer, comprising the following component (A) and (B) as a composition for forming the particle-containing layer of the light emitting device according to any one of the above [1] to [6]:

(A) at least one polymer selected from siloxane-based polymers, titanoxane-based polymers and these copolymers;

(B) metal oxide particles.

The light emitting element of this invention is equipped with the particle | grain containing layer which consists of hardened | cured material of a specific composition, and since the refractive index of the said particle | grain containing layer is high, it has the outstanding luminous efficiency.

Moreover, since the light emitting element of this invention is excellent also in durability, it can be used, even under severe use conditions, without degrading performance over a long term.

1 is a cross-sectional view conceptually showing Embodiment 1 of a light emitting device of the present invention.
Fig. 2 is a sectional view conceptually showing Embodiment 2 of the light emitting device of the present invention.
3 is a cross-sectional view conceptually showing Embodiment 3 of a light emitting device of the present invention.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, various embodiment examples of the light emitting element of this invention are described with reference to drawings.

In FIG. 1, the light emitting element 10 is Embodiment 1 of the light emitting element of this 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 particle containing layer 18 are sequentially stacked. The second electrode 17 is a transmissive electrode, and the light generated by the light emitting layer 15 may pass through the second electrode 17 and the particle-containing layer 18 and may be extracted to the outside of the light emitting device 10.

As the board | substrate 11, although the board | substrate used with a general light emitting element can be used, the glass substrate or transparent plastic substrate which is excellent in mechanical strength, thermal stability, transparency, surface smoothness, handling property, and waterproofness is preferable.

The first electrode 13 is formed by supplying a material for forming the first electrode to the upper surface of the substrate 11 by vapor deposition, sputtering, or the like. The 1st electrode 13 has the 1st surface which contact | connects the light emitting layer 15 mentioned later, and the 2nd surface which contact | connects the board | substrate 11. As shown in FIG. As the material for forming the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like which is transparent and excellent in conductivity can be used. Alternatively, when magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or the like is used, The electrode 13 can be formed as a reflective electrode.

The light emitting layer 15 is formed by a material exhibiting a light emission phenomenon by applying an electric field. Examples of such a substance include activated zinc oxide ZnS: X (where X is an activated element such as Mn, Tb, Cu, Sm, etc.), CaS: Eu, SrS: Ce, and SrGa ₂ S ₄ : Ce, CaGa. _{2 S 4: Ce, CaS:} Pb, BaAl 2 S 4: a low (低) dye molecule-based aluminum complex, such as an aromatic amine, an anthracene single crystal of 8-hydroxyquinoline inorganic EL materials conventionally used, such as Eu Organic EL materials, poly (p-phenylenevinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly (3-alkylthiophene) Conventionally used organic EL materials, such as conjugated polymer type organic EL materials, such as polyvinylcarbazole, can be used. The thickness of the light emitting layer 15 is 10-1000 nm normally, Preferably it is 30-500 nm, More preferably, it is 50-200 nm. The light emitting layer 15 can be formed by a vacuum film forming process such as vapor deposition or sputtering, or a coating process using chloroform or the like as a solvent.

The second electrode 17 is a cathode which is an electron injection electrode. Examples of the metal for forming the second electrode 17 include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), and magnesium-indium (Mg-In). And magnesium-silver (Mg-Ag). By forming these metals in a thin film, a transmissive electrode can be obtained. On the other hand, in order to obtain the light emitting element of the top emission system which takes out light from the element side, the transmissive electrode using ITO and IZO can also be formed.

The particle containing layer 18 is a hardened | cured material of the composition for particle | grain containing layer formation containing the following (A) component and the following (B) component.

Each component used for this invention is demonstrated in detail.

[(A) component; Siloxane-based polymers, titanoxane-based polymers and at least one polymer selected from these copolymers]

As the at least one polymer selected from the siloxane polymer, the titanoxane polymer and these copolymers, for example, at least one compound selected from the compound represented by the following general formula (1) and the compound represented by the following general formula (2) And polymers formed by condensation.

(R ¹ ) _p Si (X) _4-p ... (One)

[In General Formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3;

(R ¹ ) _p Ti (X) _4-p ... (2)

[In General Formula (2), R <^1> is a non-hydrolyzable organic group whose carbon number is 1-12, X is a hydrolysable group, and p is an integer of 0-3.].

Hydrolyzable groups represented by X in General formula (1) and General formula (2) are usually heated in the temperature range of room temperature (25 degreeC)-100 degreeC in presence of a non-catalyst and excess water, and a valence such as an alkoxy group Degradable groups are groups that can be hydrolyzed to produce silanol groups or titanol groups. In addition, the hydrolyzable group may be further condensed after hydrolysis to form a siloxane condensate or a titanoxane condensate.

The subscript p in General formula (1) is an integer of 0-3, Preferably it is an integer of 0-2.

It is preferable that the at least 1 sort (s) of polymer chosen from a siloxane type polymer, a titanoxane type polymer, and these copolymers contain a silanol group or a titanol group. The number of hydroxyl groups contained in the silanol group and the titanol group is preferably 15 to 300%, more preferably 30 to 250%, further preferably 50 to the total of the number of silicon atoms and titanium atoms in the polymer. It is-200%. When the number of hydroxyl groups contained in the silanol group and the titanol group is within the above range with respect to the sum of the number of silicon atoms and titanium atoms in the polymer, a composition for forming a particle-containing layer having excellent dispersibility of metal oxide particles is obtained. A film that is high and excellent in transparency, heat resistance, crack resistance and light resistance is obtained.

In the siloxane polymer, a microhydrolyzable hydrolyzable group may remain in part. The siloxane polymer may be a partial condensate obtained by condensation of some silanol groups or hydrolyzable groups.

The organic group R ¹ in General Formula (1) and General Formula (2) is a non-hydrolyzable organic group having 1 to 12 carbon atoms. The non-hydrolyzable property in organic group R <^1> means that it is a property to remain stable as it is on the conditions by which hydrolyzable group X hydrolyzes.

As the organic group R ^1, for example, there may be mentioned hydrocarbon groups of 1 to 12 carbon atoms, a halogenated hydrocarbon group of 1 to 12 carbon atoms and the like. The organic group R ¹ may be linear, branched, cyclic, or a combination thereof. In addition, the organic group R ¹ may have a structural unit containing a hetero atom. Group includes such structural units, may be mentioned an ether bond, an ester bond, sulfide bond or the like, Examples of the organic group R ¹ comprising such a combination, for example, having an epoxy group such as an oxetanyl group, an oxiranyl group, The group etc. which have a (meth) acryloyloxy group are mentioned.

In view of the organic group R in the ^first 1 to 12 carbon atoms carbide as a hydrogen group, a reactivity and the obtained film of the crack resistance, and preferably hydrocarbon group having 1 to 8 carbon atoms, more preferably hydrocarbon group having from 1 to 4 carbon atoms . Specifically, aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclo Aromatic hydrocarbon groups, such as an alicyclic hydrocarbon group, such as a hexyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, and a benzyl group, are mentioned, A methyl group, an ethyl group, n-propyl group, isopropyl group, t-butyl group, a phenyl group, It is preferable that it is a methylphenyl group, and it is more preferable that it is a methyl group and an ethyl group.

Further, the organic halogen atom-substituted hydrocarbon group having 1 to 12 carbon atoms in R ^1, may be a fluorinated hydrocarbon group, a chlorinated hydrocarbon group, a group brominated hydrocarbon, more preferably a fluorinated hydrocarbon group. Carbon number of the said hydrocarbon group becomes like this. Preferably it is 1-4 from a viewpoint of reactivity and the crack tolerance of the film | membrane obtained.

Specifically, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, perfluoro-n-propyl Group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-t-butyl group, and a fluoromethyl group, difluoromethyl group, and trifluoromethyl group And a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a perfluoro-t-butyl group, and a fluoromethyl group and di It is more preferable that they are a fluoromethyl group, a trifluoromethyl group, a 2,2, 2- trifluoroethyl group, and a pentafluoroethyl group.

As hydrolyzable group X in General formula (1) and (2), a hydrogen atom, a halogen atom, a C1-C12 alkoxy group, a C1-C12 halogenated alkoxy group, C2-C12 acyl jade And a halogenated acyloxy group having 2 to 12 carbon atoms may be mentioned. A methoxy group, an ethoxy group, etc. are mentioned as a preferable example of a C1-C12 alkoxy group. Preferred examples of the halogen atom include fluorine, chlorine, bromine and iodine. Preferable examples of the acyloxy group include an acetoxy group, propionyloxy group, butyloyloxy and the like.

The specific example of the hydrolyzable silane compound (Hereinafter, it may abbreviate as a silane compound) represented by General formula (1) is demonstrated.

Examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane and trimeth Oxysilane, triethoxysilane, etc. are mentioned.

Examples of the silane compound having three hydrolyzable groups include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane and ethyltributoxy Silane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, d ₃ -methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane Etc. can be mentioned.

Examples of the silane compound having two hydrolyzable groups include dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, and the like.

Examples of the silane compound having one hydrolyzable group include trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, and the like.

The specific example of the hydrolyzable titanium compound represented by General formula (2) (hereinafter, it may abbreviate as a titanium compound) is demonstrated.

Examples of the titanium compound having four hydrolyzable groups include tetrachlorotitanium, tetra aminotitanium, tetraacetitanium titanium, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium, tetrabenzyloxytitanium and trimeth Oxytitanium, triethoxytitanium, and the like.

Examples of the titanium compound having three hydrolyzable groups include methyltrichlorotitanium, methyltrimethoxytitanium, methyltriethoxytitanium, methyltributoxytitanium, ethyltrimethoxytitanium, ethyltriisopropoxytitanium and ethyltributoxy Titanium, butyltrimethoxytitanium, pentafluorophenyltrimethoxytitanium, phenyltrimethoxytitanium, d ₃ -methyltrimethoxytitanium, nonafluorobutylethyltrimethoxytitanium, trifluoromethyltrimethoxytitanium Etc. can be mentioned.

Examples of the titanium compound having two hydrolyzable groups include dimethyldichlorotitanium, dimethyldiaminotitanium, dimethyldiacetoxytitanium, dimethyldimethoxytitanium, diphenyldimethoxytitanium and dibutyldimethoxytitanium.

Examples of the titanium compound having one hydrolyzable group include trimethylchlorotitanium, trimethyltitanium, tributyltitanium, trimethylmethoxytitanium and tributylethoxytitanium.

The molecular weight of the at least 1 sort (s) of polymer chosen from the siloxane type polymer, titanoxane type polymer which are (A) component, and these copolymers is demonstrated. Such molecular weight can be measured as a weight average molecular weight of polystyrene conversion using gel permeation chromatography (hereinafter sometimes referred to as GPC) using tetrahydrofuran in the mobile phase.

The weight average molecular weight of the siloxane polymer, the titanoxane polymer, and at least one polymer selected from these copolymers is preferably 500 to 100,000, more preferably 800 to 30,000, still more preferably 1,000 to 5,000. When the said value is less than 500, there exists a tendency for the crack tolerance at the time of formation of a cured film to fall. When the said value exceeds 100,000, there exists a tendency for the dispersibility of the metal oxide particle which is (B) component to fall.

The catalyst for obtaining at least one kind of polymer selected from a siloxane polymer, a titanoxane polymer and these copolymers is preferably at least one compound selected from a metal chelate compound, an acidic compound and a basic compound. It is more preferable.

(d-1) metal chelate compounds

The metal chelate compound which can be used as a catalyst is represented by following General formula (2).

R ¹⁵ _e M (OR ¹⁶ ) _fe ????? (2)

(Wherein, R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group or an aryl group, f represents the valence of the metal M, and e represents an integer of 1 to f).

Here, the metal M is preferably at least one metal selected from Group IIIB metals (aluminum, gallium, indium, thallium) and Group IVA metals (titanium, zirconium, hafnium), and titanium, aluminum, and zirconium are more preferred. desirable.

Examples of the chelating agent represented by R ¹⁵ include CH ₃ COCH ₂ COCH ₃ , CH ₃ COCH ₂ COOC ₂ H ₅ , and the like.

As an alkyl group or aryl group represented by R <^16> , the alkyl group or aryl group represented by R <^1> in the said General formula (1) is mentioned.

As a suitable embodiment of the metal chelate compound,

(CH ₃ (CH ₃ ) HCO) _{4- t} Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (CH ₃ (CH ₃ ) HCO) _{4- t} Ti (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₄ H ₉ O) _{4- t} Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₄ H ₉ O) _{4- t} Ti (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₂ H ₅ (CH ₃ ) CO) _{4- t} Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _{4- t} Ti (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(CH ₃ (CH ₃ ) HCO) _{4- t} Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (CH ₃ (CH ₃ ) HCO) _{4- t} Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₄ H ₉ O) _{4- t} Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₄ H ₉ O) _{4- t} Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₂ H ₅ (CH ₃ ) CO) _{4- t} Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _{4- t} Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(CH ₃ (CH ₃ ) HCO) _{3- t} Al (CH ₃ COCH ₂ COCH ₃ ) _t , (CH ₃ (CH ₃ ) HCO) _{3- t} Al (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₄ H ₉ O) _{3- t} Al (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₄ H ₉ O) _{3- t} Al (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t ,

(C ₂ H ₅ (CH ₃ ) CO) _{3- t} Al (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _{3- t} Al (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t etc. are mentioned.

The amount of the metal chelate compound is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 100 parts by mass of the total amount of the silane compound and the titanium compound (hereinafter also referred to as a silane compound). It is-5 mass parts. When the said amount is less than 0.0001 mass part, the applicability | paintability of a coating film may be inferior, and when it exceeds 10 mass parts, polymer growth cannot be controlled and gelation may arise.

When hydrolytically condensing a hydrolyzable silane compound in the presence of a metal chelate compound, it is preferable to use 0.5 to 20 moles of water per mole of the total amount of the silane compound and the like, and particularly preferably 1 to 10 moles of water. When the amount of water is less than 0.5 mole, the hydrolysis reaction does not proceed sufficiently, and problems may occur in coating properties and storage stability. When it exceeds 20 moles, precipitation or gelation of the polymer during the hydrolysis and condensation reaction occurs. There is a case. In addition, water is preferably added intermittently or continuously.

These metal chelate compounds can be used individually by 1 type or in combination of 2 or more types.

(d-2) acidic compounds

As an acidic compound which can be used as a catalyst, an organic acid or an inorganic acid can be illustrated and an organic acid is preferable.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid and gallic acid. , Butyric acid, melit acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloro Acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, mal acid Lonic acid, the hydrolyzate of glutaric acid, the hydrolyzate of maleic anhydride, the hydrolyzate of phthalic anhydride, etc. are mentioned.

As an inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc. are mentioned, for example.

Especially, an organic acid is preferable at the point that there is little concern of precipitation and gelation of a polymer in reaction of hydrolysis condensation (hydrolysis and subsequent condensation), and the compound which has a carboxyl group is more preferable among these.

Among the compounds having a carboxyl group, acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid, maleic anhydride and the like Organic acids of are particularly preferred.

These acidic compounds can be used individually by 1 type or in combination of 2 or more type.

The amount of the acidic compound is preferably 0.0001 to 10 parts by mass, and more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the silane compound or the like (complete hydrolysis condensate conversion). When the said quantity is less than 0.0001 mass part, the applicability | paintability of a coating film may be inferior, and when it exceeds 10 mass parts, a hydrolysis condensation reaction may advance rapidly and may gelatinize.

When hydrolytically condensing a silane compound or the like in the presence of an acidic compound, it is preferable to use 0.5 to 20 moles of water per mole of the total amount of the silane compound and the like, and particularly preferably 1 to 10 moles of water. If the amount of water is less than 0.5 mole, the hydrolysis reaction may not proceed sufficiently, and problems may occur in coating properties and storage stability. When the amount of water exceeds 20 moles, precipitation or gelation of the polymer in the hydrolysis condensation reaction may occur. There is a case. In addition, water is preferably added intermittently or continuously.

(d-3) basic compound

As a basic compound which can be used as a catalyst, For example, methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N- Methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine , N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- ( Aminomethyl) propanolamine, N- (aminomethyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammon Hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, ammonia, sodium hydroxide, potassium hydroxide, tetra hydroxide Methyl ammonium, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, etc. are mentioned.

The amount of the basic compound is preferably 0.00001 to 10 mol, more preferably 0.00005 to 5 mol, with respect to 1 mol of the total amount of hydrolyzable groups such as a silane compound. When the said amount is less than 0.00001 mol, hydrolysis condensation may not fully advance, and when it exceeds 10 mol, the storage stability of the obtained hydrolysis-condensation thing may fall.

[(B) component; Metal oxide particles]

In this invention, in order to obtain the hardened | cured material which has a high refractive index, it is preferable to use the metal oxide particle which has a high refractive index. Such metal oxide particles are fine particles having a refractive index of light having a wavelength of 400 nm at 25 ° C. of preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1.70 or more. Examples of such metal oxide particles include zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and metal oxide particles such as these composites. Among them, fine particles of zirconium oxide (ZrO ₂₎ are preferred.

The titanium oxide is not particularly limited as long as it has a TiO ₂ structure, and examples thereof include anatase type, rutile type, and brookite type.

These metal oxide particles can be used individually by 1 type or in combination of 2 or more type.

The number average primary particle diameter of the metal oxide particle which is (B) component becomes like this. Preferably it is 1-100 nm, More preferably, it is 3-70 nm, Especially preferably, it is 5-50 nm. When the number average primary particle diameter is in the above range, a cured product excellent in transparency can be obtained.

The metal oxide particle which is (B) component may be powder shape, or may be a solvent dispersion sol before mixing with (A) component and (C) component. As the solvent, for example, an organic solvent is used. Examples of the organic solvent include 2-butanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, and the like.

The compounding quantity of (B) component becomes like this. Preferably it is 50-2,000 mass parts, More preferably, it is 100-1,500 mass parts, More preferably, it is 150-1,000 mass parts with respect to 100 mass parts of (A) component. If the amount is less than 50 parts by mass, the refractive index of the cured film (cured product of the composition) may decrease, and the luminous efficiency of the light emitting device may decrease. If the amount exceeds 2,000 parts by mass, sufficient crack resistance may not be obtained. There is no fear.

In addition, when (B) component is a solvent dispersion sol, the compounding quantity of (B) component means the mass which does not contain a solvent. In addition, when (B) component is a solvent dispersion sol, the quantity of the organic solvent as a solvent of (B) component shall comprise a part of compounding quantity of the organic solvent which is (C) component.

Although the compounding quantity of the sum total of (A) component and (B) component is not specifically limited, 50-100 mass% from a heat resistant viewpoint of the particle content layer obtained with respect to 100 mass% of component total amounts of the composition except an organic solvent. It is preferable that it is, It is more preferable that it is 70-100 mass%, It is further more preferable that it is 80-100 mass%, It is especially preferable that it is 90-100 mass%.

[(C) component; Organic solvent]

In this invention, the storage stability of a composition can be improved and a suitable viscosity can be provided by mix | blending an organic solvent.

As an organic solvent, an ether type organic solvent, an ester type organic solvent, a ketone type organic solvent, a hydrocarbon type organic solvent, an alcohol type organic solvent, etc. are mentioned. As an organic solvent, it is preferable to use the organic solvent which the boiling point in atmospheric pressure (1,013 hPa) exists in 50-250 degreeC, and can disperse | distribute each component uniformly.

Examples of such organic solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monoalcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. Sulfur solvents and the like. These organic solvents are used individually by 1 type or in combination of 2 or more types.

Among the organic solvents, monoalcohol solvents, polyhydric alcohol solvents, and ketone solvents are preferable from the viewpoint of further improving the storage stability of the composition. Examples of preferred compounds of these solvents include propylene glycol monomethyl ether, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, methanol, ethanol, 2-butanol and the like. These preferable compounds are used individually by 1 type or in combination of 2 or more types.

In the present invention, the type of organic solvent is preferably selected in consideration of the coating method of the composition. For example, in order to easily obtain the cured film (hardened | cured material of a composition) which has a uniform thickness, when using spin coating method, as an organic solvent, glycol ethers, such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, are mentioned. ; 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; It is preferable to use gamma -butyl olactone and the like.

Especially preferred organic solvents are ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and the like.

The compounding quantity of (C) component (organic solvent) becomes like this. Preferably it is 50-20,000 mass parts, More preferably, it is 100-1,000 mass parts with respect to 100 mass parts of total amounts of the component except the said organic solvent. If it is in the said preferable range, the storage stability of a composition can be improved and a moderate viscosity can be provided, and the high refractive index cured film which has a uniform thickness can be formed easily.

Although the addition method of (C) component is not restrict | limited, For example, you may add when manufacturing (A) component, you may add when preparing the dispersion liquid containing (B) component, (A) You may add when mixing a component and (B) component.

[(D) component; Dispersant]

The composition for forming a particle-containing layer of the present invention may contain various dispersants in order to improve the dispersibility of the metal oxide particles.

As a dispersing agent, an aluminum compound can be used, for example. As an example of an aluminum compound, an aluminum alkoxide, an aluminum (beta) -diketonate complex, etc. are mentioned. Specifically, alkoxide compounds, such as triethoxy aluminum, tri (n-propoxy) aluminum, tri (i-propoxy) aluminum, tri (n-butoxy) aluminum, and tri (sec-butoxy) aluminum, aluminum Β- such as tris (methylacetoacetate), aluminum tris (ethylacetoacetate), tris (aceacetonate) aluminum, aluminum monoacetylacetonate bis (methylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate) And diketonate complexes.

As a commercial item of an aluminum compound, AIPD, PADM, AMD, ASBD, aluminum ethoxide, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, aluminum chelate A (W), surface treatment agent OL-1000, Algomar (ALGOMAR), Algorma 800AF, Algorithm 1000SF (above, Kawaken Fine Chemical Co., Ltd.), etc. can be used.

As a dispersing agent, a nonionic dispersing agent can also be used. Dispersibility can be improved by using a nonionic dispersing agent. The nonionic dispersant used in the present invention is preferably a phosphate ester nonionic dispersant having a polyoxyethylene alkyl structure.

Although the compounding quantity of a dispersing agent is not specifically limited, When it contains a dispersing agent, it is 0.1-5 mass% with respect to 100 mass% of component total amounts of the composition except the organic solvent.

[(E) component; Dispersion Aids]

The composition for forming a particle-containing layer of the present invention may further contain a dispersing aid in order to increase dispersibility. As the dispersion aid, one or more selected from acetylacetone, N, N-dimethylacetoacetamide, and the like can be suitably used.

Although the compounding quantity of a dispersal auxiliary agent is not specifically limited, When it contains a dispersion auxiliary agent, it is 0.1-5 mass% with respect to 100 mass% of component total amounts of the composition except the organic solvent.

[(F) component; Surfactants]

When apply | coating the composition for particle | grain containing layer formation of this invention to a base material etc. by spin coating, it is preferable to mix | blend surfactant from a viewpoint of obtaining the coating film which has a uniform thickness. As surfactant used by this invention, silicone type surfactant, fluorine type surfactant, etc. are mentioned. Especially, surfactant of silicone type is preferable.

As an example of silicone type surfactant, SH28PA (made by Toray Dow Corning Co., dimethyl polysiloxane-polyoxyalkylene copolymer), Painted (PAINTAD) 19, 54 (made by Tole Dow Corning Co., dimethyl, for example) Polysiloxane-Polyoxyalkylene Copolymer), FM-0411 (SILAPLANE, Chisso Co., Ltd.), SF8428 (Toreda Corning Co., Ltd., Dimethyl Polysiloxane-Polyoxyalkylene Copolymer (Contains Side Chain OH) )), BYKUV3510 (manufactured by Big Chem Japan Japan, dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 (Torre Dow Corning Silicon Silicon Co., Ltd., dimethyl polysiloxane-polyoxyalkylene copolymer), DC190 (Toray Dow Corning Silicone Co., Ltd., dimethylpolysiloxane-polyoxyalkylene copolymer), silaplen FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM -0411, FM-0421, FM-0 425, FM-DA11, FM-DA21, FM-DA26, FM-0711, FM-0721, FM-0725, TM-0701, TM-0701T (manufactured by Tosso Co., Ltd.), UV3500, UV3510, UV3530 (Big Chemie? Japan Co., Ltd.), BY16-004, SF8428 (made by Toray Dow Corning Silicon Co., Ltd.), VPS-1001 (made by Wako Pure Chemical Industries Ltd.), etc. are mentioned. As a particularly preferable example, silaplen FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-0711, FM-0721, FM-0725, VPS-1001, etc. are mentioned. . Moreover, as a commercial item of the silicone compound which has an ethylenically unsaturated group, TegoRad 2300, 2200N (made by Tego Chemical Co., Ltd.), etc. are mentioned, for example.

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

The blending ratio of the component (F) is preferably 0 to 10% by mass, more preferably 0.1 to 5% by mass, particularly preferably 0.5 to 3 with respect to 100% by mass of the total component of the composition excluding the organic solvent. It is mass%. When the said amount exceeds 10 mass%, there exists a possibility that the refractive index of the hardened | cured material of a composition may fall.

[(G) component; Dehydrating agent]

The composition for particle-containing layer formation of this invention may also contain a dehydrating agent. By adding the dehydrating agent, the radiation curing reaction of the composition can be promoted, and the storage stability of the composition can be further improved.

The dehydrating agent used in the present invention is a compound that converts water into a substance other than water by a chemical reaction, or a compound that converts water into a substance that does not affect radiation curability and storage stability by physical adsorption or inclusion. Is defined. By containing a dehydrating agent, two characteristics in which storage stability and radiation curability oppose can be improved, without impairing the light resistance and heat resistance of a composition. For this reason, the dehydrating agent effectively absorbs water invading from the outside, thereby improving the storage stability of the composition, and in the condensation reaction of the radiation curing reaction, the dehydrating agent sequentially absorbs the generated water, thereby causing radiation of the composition. It is thought that it is because hardenability improves.

[(H) component; Acid generator]

The composition for particle-containing layer formation of this invention may contain an acid generator. An acid generator is defined as a compound which can generate an acid by light irradiation or heating.

Here, light irradiation means irradiation of ionizing radiation, such as infrared rays, visible rays, an ultraviolet-ray, and X-rays, an electron beam, (alpha) ray, (beta) ray, (gamma) ray.

Moreover, as a photo-acid generator which can generate an acid by light irradiation, the onium salt (compound of 1st group) which has a structure represented by General formula (3), or the structure represented by General formula (4) And sulfonic acid derivatives (compounds in the second group) to have.

[R ² _a R ³ _b R ⁴ _c R ⁵ _d W] ^{+ m} [MZ _{m + n} ] ^-m (3)

[A general formula (3), cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or -N≡N, R ^2, R ^3, R ⁴ and R ⁵ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) -m is the same as the valence of W. In addition, M is a metal or metalloid constituting the center atom of the halide complex [MX _{m + n} ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, or Co. Z is, for example, a halogen atom or an aryl group such as F, Cl, Br, m is a net charge of a halide complex ion, and n is a valency of M;

Q _s- [S (= O) ₂ -R ⁶ ] _t (4)

[In general formula (4), Q is a monovalent or divalent organic group, R <^6> is a C1-C12 monovalent organic group, subscript s is 0 or 1, and subscript t is 1 or 2.].

First, the onium salt, which is a compound of the first group, is a compound capable of releasing an acidic active substance by receiving light. Among these compounds of the first group, more effective onium salts are aromatic onium salts, and particularly preferably diaryl iodonium salts represented by the following general formula (5).

^{[R 7 -Ar 1 -I + -Ar} 2 -R 8] [Y -] (5)

[In General Formula (5), R <^7> and R <^8> is a monovalent organic group, respectively, may be same or different, At least one of R <^7> and R <^8> has a C4 or more alkyl group, Ar <^1> and Ar ² are each an aromatic group, a well may be the same or different, Y ^- is an anion selected from; ^- 1 is the divalent anion, periodic table group 3, the group 5 or fluoride _{^{anion, ClO 4 -, CF 3 -SO}} 3.

Moreover, when the example of the sulfonic acid derivative represented by General formula (4) as a compound of 2nd group is shown, disulfone, disulfonyl diazomethane, disulfonyl methane, sulfonyl benzoyl methane, imide sulfonate, benzo Insulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates. Moreover, in the sulfonic acid derivative represented by General formula (4), More preferably, they are imide sulfonates, More preferably, they are trifluoromethyl sulfonate derivatives in imide sulfonate.

The addition amount (content rate) of a photo-acid generator is demonstrated. Although the addition amount of a photo-acid generator is not restrict | limited especially, It is preferable to make the total solid amount of the composition for particle | grain containing layer formation into 100 mass parts, and to set it as the value within 15 mass parts normally. When the said addition amount exceeds 15 mass parts, there exists a tendency for the light resistance and heat resistance of the hardened | cured material obtained to fall.

[(I) component; Other additives]

The composition for particle-containing layer formation of this invention can contain various additives of that excepting the above within the range which does not impair the effect of this invention. As such an additive, curable compounds other than the said component, antioxidant, a ultraviolet absorber, etc. are mentioned, for example.

[Method for Producing Composition for Forming Particle-Containing Layer]

The composition for particle-containing layer formation of this invention is prepared by mixing the said components (A)-(C) and the other arbitrary components mix | blended as needed. Usually, a particle-containing layer by mixing component (A) (siloxane type polymer, etc.), component (B) (metal oxide particles), and other components optionally added at a predetermined ratio in component (C) (organic solvent). The composition for formation can be prepared.

[Curing film]

Preferably the refractive index of the cured film which is the hardened | cured material of the composition for particle | grain containing layer formation of this invention is 1.6 or more. If the said refractive index is 1.6 or more, the luminous efficiency of a light emitting device will become high. Although the film thickness of a cured film is not specifically limited, According to the kind of light emitting element, it can determine suitably within the range of 50 nm-100 micrometers, for example.

Since the light emitting element of this invention is equipped with the particle containing layer 18, when the light produced | generated in the light emitting layer 15 passes through the 2nd electrode 17 and enters in air, it emits light by the principle of constructive interference. The efficiency taken out to the outside of the device can be increased, which can greatly contribute to the improvement of the luminous efficiency of the light emitting device.

In FIG. 1, the particle-containing layer 18 is illustrated as being formed in contact with one surface of the second electrode 17, but various layers may be provided between the particle-containing layer 18 and the second electrode 17 as necessary. It may be provided additionally. Although not shown in FIG. 1, various modifications are possible, such as a sealing layer having a known structure for sealing the light emitting element 10 may be further provided on the particle containing layer 18.

In FIG. 2, the light emitting element 20 is Embodiment 2 of the light emitting element of this invention.

The light emitting element 20 has a structure in which a substrate 21, a particle-containing layer 28, a first electrode 23, a light emitting layer 25, and a second electrode 27 are sequentially stacked. The first electrode 23 is a transmissive electrode, and the light generated in the light emitting layer 25 passes through the first electrode 23 and the particle-containing layer 28, and may be extracted to the outside of the light emitting device 20. The particle-containing layer 28 is formed on the surface of the first electrode 23 opposite to the surface on which the light emitting layer is formed. The detailed description about each layer which comprises the light emitting element 20 is the same as that of the above-mentioned. The particle-containing layer 28 made of a polymer obtained by condensation of the silane compound or the like has a high refractive index, and the light generated in the light emitting layer 25 can be effectively taken out to the outside by the principle of constructive interference. It may have a light efficiency characteristic.

In FIG. 3, the light emitting element 30 is Embodiment 3 of the light emitting element of this invention.

The light emitting element 30 has a structure in which a substrate 31, a particle containing layer 38, a first electrode 33, a light emitting layer 35, a second electrode 37, and a particle containing layer 39 are sequentially stacked. The first electrode 33 and the second electrode 37 are transmissive electrodes, and the light generated in the light emitting layer 35 passes through the first electrode 33 and the second electrode 37, and then each contains a particle-containing layer. Pass through the 38 and the particle-containing layer 39, it can be taken out of the light emitting element (30). The detailed description about each layer which comprises the light emitting element 30 is the same as that of the above-mentioned. The particle-containing layer 38 and the particle-containing layer 39 made of a polymer obtained by condensation of the silane compound or the like have a high refractive index, and light generated in the light-emitting layer 35 can be effectively extracted to the outside by the principle of constructive interference. As such, it may have improved light efficiency characteristics.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.

[Preparation of (A) Component]

Synthesis Example 1

To a flask with a stirrer and a reflux tube, methyltrimethoxysilane (45.7 g), tetraethoxysilane (12.33 g), propylene glycol monomethyl ether (19.56 g), and oxalic acid (0.03 g) were added and stirred, After the solution was obtained, the solution was heated to set the temperature of the liquid to 60 ° C. Subsequently, distilled water (22.38 g) was added dropwise, and after completion of dropwise addition, the solution was stirred at 100 ° C for 3 hours. Then, it concentrated under reduced pressure and finally obtained (A) component (propylene glycol monomethyl ether solution) which adjusted solid content to 30 mass%. This is called "A-1".

Synthesis Example 2

In a flask with a stirrer and a reflux tube, methyltrimethoxysilane (17.89g), phenyltrimethoxysilane (35.80g), tetraethoxysilane (3.42g), propylene glycol monomethyl ether (24.84g), and oxalic acid (0.03 g) was added and stirred to obtain a solution, and then the solution was heated to set the temperature of the liquid to 60 ° C. Subsequently, distilled water (18.02 g) was added dropwise, and after completion of dropwise addition, the solution was stirred at 100 ° C for 3 hours. Then, it concentrated under reduced pressure and finally obtained (A) component (propylene glycol monomethyl ether solution) which adjusted solid content to 30 mass%. This is called "A-2".

Table 1 shows the component compositions of "A-1" and "A-2".

As "A-3", OX-SQ 'ME-20 by Toagosei Co., Ltd. was used.

As "A-4", the tetramethylol methane triacrylate by Shin-Nakamura Chemical Co., Ltd. was used.

[Preparation of Composition 1]

Propylene glycol monomethyl ether in an amount of 21.0 g of zirconium oxide (primary average particle diameter: 15 nm), 29.7 g of "A-1" (solid content of 8.9 g), and 70 g of the total weight of the organic solvent as the component (B). Into a container, 350 g of zirconia beads (NIKKATO) manufactured by 0.1 mm in diameter were added thereto, and the mixture was stirred at 1500 rpm for 10 hours with a bead mill to form fine particles of zirconium oxide ((B) component). Was dispersed.

0.10 g of a dimethyl polysiloxane-polyoxyalkylene copolymer was added to the dispersion liquid of the obtained zirconium oxide microparticles | fine-particles, and the composition "J-1" was obtained.

In addition, compositions "J-2", "J-4", and "J-6" were prepared like composition "J-1" except having used the component shown in Table 2. A component composition etc. are shown in Table 2.

[Preparation of Composition 2]

As the component (B), 15.9 g of zirconium oxide fine particles (number average primary particle diameter: 15 nm), 1.9 g of PLADD'ED-151 (compound name: polyoxyethylene alkyl phosphate ester), tri (sec-butoxy) aluminum 2.2 g, acetylacetone 0.9 g, 2-butanol 2.3 g, methyl ethyl ketone 54.3 g, and propylene glycol monomethyl ether 15.7 g were placed in a container, and 300 g of zirconia beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm were added thereto. And bead mill were stirred at 1500 rpm for 10 hours to disperse the fine particles of zirconium oxide (component (B)).

To 77.5 g of the dispersion containing fine particles of zirconium oxide obtained, 22.4 g of "A-1" (solid content of 6.7 g) and 0.1 g of a dimethylpolysiloxane-polyoxyalkylene copolymer were added to obtain a composition "J-3". . A component composition etc. are shown in Table 2.

[Preparation 3 of Composition]

As component (B), 15.91 g of zirconium oxide fine particles (number average primary particle diameter: 15 nm), 1.91 g of PLADD'ED-151, 2.20 g of tri (sec-butoxy) aluminum, 0.85 g of acetylacetone, and 2.30 of 2.30 g and 70.00 g of methyl ethyl ketone were placed in a container, and 350 g of zirconia beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm were added thereto, followed by stirring at 1500 rpm for 10 hours with a bead mill to form zirconium oxide fine particles (B). Dispersed.

To 93.17 g of the obtained dispersion of zirconium oxide fine particles, 5.73 g of "A-4" and 1.0 g of Irgacure184 (manufactured by BASF Corporation) and 0.1 g of a dimethyl polysiloxane-polyoxyalkylene copolymer were added as a photopolymerization initiator. "J-5" was obtained. A component composition etc. are shown in Table 2.

[Preparation of Composition 4]

Under a nitrogen stream, 42.54 g (125 mmol) of tetra-n-butoxytitanium and 26.53 g (250 mmol) of diethylene glycol were added to a solvent (n-butanol, 60 mL) and mixed. In parallel with this, 4.5 g (250 mmol) of ion-exchanged water and 0.085 g (1.25 mmol) of hydrazine hydrochloride were added to the solvent (n-butanol, 100 mL) and mixed. The obtained two types of mixed solutions were combined and stirred and mixed for 2 hours in the incubator adjusted to 25 degreeC, and the composition "J-7" was obtained.

EXAMPLES 1-4, COMPARATIVE EXAMPLES 1-3

Each of the said composition "J-1"-"J-4" (Examples 1-4) and "J-5"-"J-7" (Comparative Examples 1-3) was evaluated as follows. .

<Evaluation of the composition>

(1) dispersion particle diameter

About the microparticles | fine-particles in the obtained composition, the volume average particle diameter in 25 degreeC was measured with the dynamic light-scattering type | mold particle size distribution measuring apparatus by Horiba Seisakusho Corporation. The thing whose volume average particle diameter is less than 50 nm was "(circle)", 50 nm or more, and less than 100 nm made "(triangle | delta)" and the thing of 100 nm or more "x". The results are shown in Table 3.

<Production of a cured film>

? Composition "J-1"-"J-5", "J-7"

The composition was dispensed on a 4 inch diameter fused quartz or silicon substrate, spin-coated to a thickness of about 1 μm, and heated at 120 ° C. for 1 minute and at 150 ° C. for 60 minutes to form a cured film (film thickness: 1 Μm) was produced.

? Composition "J-6"

The composition was dispensed on a 4 inch diameter molten quartz or silicon substrate, spin coated to a thickness of about 1 μm, and heated at 120 ° C. for 1 minute. Then, the ultraviolet-ray was irradiated so that exposure amount might be 2000mJ / cm <2> in air | atmosphere using the contact mask aligner, and then it heated at 150 degreeC for 60 minutes, and produced the cured film.

<Characteristic Evaluation of Cured Film>

The following characteristics were measured and evaluated about the said cured film. The results are shown in Table 3.

(2) curability

The surface of the said cured film was touched with a finger, and it was made into "(circle)" that the thing without stickiness was "x" and the thing with stickiness.

(3) crack resistance

The external appearance of the said cured film was observed visually, and the thing without a crack was made into "(circle)", and the thing with a crack was made into "x".

(4) transparency

The transmittance | permeability (%) in wavelength 400nm of the said cured film was measured using the spectrophotometer made from Nihon Bunco. The case where the transmittance | permeability was 90% or more was made into "(circle)" and the case of less than 90% was made into "x".

(5) refractive index

The refractive index in 23 degreeC and the wavelength 633 nm was measured using the prism coupler made from a METRICON Corporation. The case where refractive index is 1.6 or more was made into "(circle)" and the case of less than 1.6 was made into "x".

(6) heat resistance

The cured film was heat-processed at the temperature of 300 degreeC for 5 minutes using oven. "(Circle)" and the case of 10% or more were made into "x" for the case where the fall (rate of reduction of transmittance) of the transmittance | permeability of the cured film before and behind a process was less than 10%.

10, 20, 30: light emitting element
11, 21, 31: substrate
13, 23, 33: first electrode
15, 25, 35: light emitting layer
17, 27, 37: second electrode
18, 28, 38, 39: particle containing layer

Claims (7)

A substrate, a first electrode, a light emitting layer, a second electrode and a particle containing layer,
The substrate, the first electrode, the light emitting layer, and the second electrode are stacked in this order;
The particle-containing layer is formed on at least one side of the first electrode on the side opposite to the side where the light emitting layer is formed and on the side opposite to the side on which the light emitting layer is formed of the second electrode,
The said particle containing layer is hardened | cured material of the composition for particle | grain containing layer formation containing the following (A) component and (B) component, The light emitting element characterized by the above-mentioned:
(A) at least one polymer selected from siloxane-based polymers, titanoxane-based polymers and these copolymers;
(B) metal oxide particles. The method of claim 1,
The light emitting element whose light emitting element is an organic electroluminescent element. The method of claim 1,
A light emitting element comprising the particle-containing layer between the substrate and the first electrode. 4. The method according to any one of claims 1 to 3,
A light emitting device wherein the polymer is a polymer obtained by condensation of at least one compound selected from a compound represented by the following General Formula (1) and a compound represented by the following General Formula (2):
(R ¹ ) _p Si (X) _4-p ... (One)
[In General Formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3;
(R ¹ ) _p Ti (X) _4-p ... (2)
[In General Formula (2), R <^1> is a non-hydrolyzable organic group whose carbon number is 1-12, X is a hydrolysable group, and p is an integer of 0-3.]. 4. The method according to any one of claims 1 to 3,
The light emitting element whose compounding quantity of the said (B) component is 50-2,000 mass parts with respect to 100 mass parts of said (A) components. 4. The method according to any one of claims 1 to 3,
The said (B) component is a light emitting element whose number average primary particle diameter is 1-100 nm fine particles. A composition for forming the particle-containing layer of the light emitting device according to any one of claims 1 to 3, comprising the following component (A) and component (B):
(A) at least one polymer selected from siloxane-based polymers, titanoxane-based polymers and these copolymers;
(B) metal oxide particles.

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