WO2015011929A1 - Dispositif électroluminescent - Google Patents

Dispositif électroluminescent Download PDF

Info

Publication number
WO2015011929A1
WO2015011929A1 PCT/JP2014/003927 JP2014003927W WO2015011929A1 WO 2015011929 A1 WO2015011929 A1 WO 2015011929A1 JP 2014003927 W JP2014003927 W JP 2014003927W WO 2015011929 A1 WO2015011929 A1 WO 2015011929A1
Authority
WO
WIPO (PCT)
Prior art keywords
sealing layer
polymetalloxane
light emitting
group
mass
Prior art date
Application number
PCT/JP2014/003927
Other languages
English (en)
Japanese (ja)
Inventor
望月　誠
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Publication of WO2015011929A1 publication Critical patent/WO2015011929A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a light emitting device having a sealing layer for sealing a light emitting element.
  • the light emitting element is generally sealed with a transparent resin or the like.
  • a composition for sealing a light emitting element a composition containing a silicone resin or an epoxy resin is common.
  • phenyl silicone resin has low permeability to hydrogen sulfide gas. Therefore, phenylsilicone resin is used for many sealing members for the purpose of suppressing corrosion of the metal material of the light emitting device.
  • a light-emitting device used in an outdoor environment is required to have a high barrier property against hydrogen sulfide gas; a phenyl silicone resin does not have a sufficient gas barrier property.
  • phenyl silicone resins are required to be further improved in terms of adhesion to a substrate, transparency, light resistance, and the like.
  • Patent Document 1 describes a sealing layer made of a cured product of perhydropolysilazane.
  • Patent Documents 2 and 3 describe a sealing layer made of a cured product of tetrafunctional alkoxysilane.
  • Patent Documents 4 to 6 describe techniques for forming a sealing layer containing siloxane by a sol-gel method.
  • JP 2012-19062 A Japanese Patent No. 3275308 JP 2003-197976 A JP 2004-231947 A JP 2002-33517 A Japanese Patent Laid-Open No. 2002-203989
  • the cured product of polysilazane disclosed in Patent Document 1 is brittle and the sealing layer is liable to break. Further, since the film is fragile, it is difficult to sufficiently increase the thickness of the sealing layer, and it is difficult to obtain a sufficient gas barrier property.
  • the cured product of tetrafunctional alkoxysilane described in the above-mentioned Patent Document 2 or 3 is an incomplete glass body usually containing 10% by mass or more of silanol.
  • tetrafunctional alkoxysilanes have a large amount of components that are eliminated during dehydration and dealcoholization condensation. Therefore, the alkoxysilane has a large shrinkage at the time of curing, and the film is likely to crack.
  • the temperature of the device is likely to increase during driving; the temperature of the device may change from room temperature to about 200 ° C.
  • the difference between the thermal expansion coefficient of the sealing layer and the thermal expansion coefficient of the substrate is large, peeling is likely to occur at the interface between the sealing layer and the substrate.
  • the phosphor material functions as an aggregate of layers. For this reason, when phosphor particles are not added, there is a problem that a transparent, crack-free, glass-like sealing layer cannot be obtained. Furthermore, the technique described in Patent Document 5 also includes an inorganic light scattering agent in the sealing layer. In this case, when the inorganic light scattering agent is not included, the glass-like sealing is transparent and has no cracks. It was difficult to obtain a stop layer.
  • molten glass is not practical because it has a high handling temperature of 350 ° C. or higher and may damage the light emitting element.
  • an object of the present invention is to provide a light-emitting device that has excellent gas barrier properties and is less likely to crack or peel off even if used for a long period of time.
  • a light emitting device comprising: a substrate; a light emitting element disposed on the substrate; and a sealing layer that covers the light emitting element and the substrate surface and includes polymetalloxane, the polymetalloxane
  • the amount of silicon oxide component in the polymetalloxane is 30 to 94% by mass with respect to the total amount, and the amount of hydrocarbon component in the polymetalloxane is 5 to 50% by mass with respect to the total amount of the polymetalloxane.
  • the light emitting device wherein the amount of the oxide component of the group 4 or group 13 metal element in the polymetalloxane is 1 to 30% by mass with respect to the total amount of the polymetalloxane.
  • the sealing layer contains a cyclic ether compound, and the amount of the cyclic ether compound is 0.5 to 5.0% by mass with respect to the total amount of the sealing layer.
  • the sealing layer of the light emitting device of the present invention has a high gas barrier property and is excellent in light resistance and heat and moisture resistance.
  • the light emitting device of the present invention includes a substrate 1, a light emitting element 2, and a sealing layer 3 that covers the substrate 1 and the light emitting element 2.
  • the sealing layer 3 includes polymetalloxane; the polymetalloxane includes a silicon oxide component, a hydrocarbon component, and an oxide component of a group 4 or group 13 metal element.
  • the silicon oxide component refers to silicon and oxygen constituting a siloxane bond in the polymetalloxane;
  • the hydrocarbon component refers to an organic group bonded to a metal element in the polymetalloxane; a group 4 or group 13 metal
  • the oxide component of the element refers to a group 4 or group 13 metal element that forms a metalloxane bond in polymetalloxane and oxygen bonded to the metal element.
  • the sealing layer is made of a cured product of tetrafunctional alkoxysilane or polysilazane
  • the film is likely to crack during film formation, and it is difficult to sufficiently enhance the gas barrier property.
  • the difference between the thermal expansion coefficient of the sealing layer and the thermal expansion coefficient of the substrate is large, there is also a problem that peeling is easily caused at the interface between the substrate and the sealing layer due to thermal shock.
  • the polymetalloxane contained in the sealing layer 3 of the light emitting device 100 of the present invention contains some organic groups (hydrocarbon components) bonded to metal elements. Therefore, the crosslinking density of the sealing layer 3 is not excessively increased, and cracks are hardly generated when the sealing layer 3 is formed. As a result, the sealing layer 3 hardly transmits hydrogen sulfide gas, and corrosion of the electrode and the like covered with the sealing layer 3 is suppressed. Moreover, since the hydrocarbon component is contained in the polymetalloxane, the sealing layer has a relatively high flexibility. Therefore, the sealing layer 3 easily follows the deformation of the substrate 1, and even if the temperature of the light emitting device 100 changes, it is difficult to peel off at the interface between the substrate 1 and the sealing layer 3.
  • the polymetalloxane includes a metalloxane bond containing a group 4 or group 13 metal element.
  • the group 4 or group 13 metal element forms a strong metalloxane bond with an OH group or the like present on the substrate surface. Therefore, the substrate 1 and the sealing layer 3 are firmly adhered.
  • oxides of Group 4 or Group 13 metal elements often form nano-sized clusters in polymetalloxane.
  • Such a cluster develops a photocatalytic effect; it converts hydrogen sulfide gas, which is highly corrosive to metal, to sulfur dioxide gas, which is less corrosive. Therefore, a metal electrode or the like covered with the sealing layer 3 including such clusters is very unlikely to corrode.
  • the type of the light emitting element 2 included in the light emitting device 100 of the present invention is not particularly limited, and may be a semiconductor laser element, an LED element, or the like.
  • the light emitting device of the present application will be described by taking the case where the light emitting element 2 is an LED element as an example.
  • the LED device in which the light emitting element 2 is an LED element is not particularly limited in its configuration as long as the device includes the substrate 1, the LED element 2, and the sealing layer 3.
  • Examples of the LED device of the present invention include the following two LED devices, but the present invention is not limited to this.
  • a light emitting device includes, for example, a substrate 1, an LED element 2 formed on the substrate 1, and the LED element 2 as shown in the schematic cross-sectional view of FIG. And a sealing layer 3 covering the surface of the substrate 1 and a wavelength conversion layer 4 formed on the sealing layer 3.
  • part of the light emitted from the LED element 2 is converted into light having a different wavelength by the wavelength conversion layer 4.
  • the light emitted from the LED element 2 and the light converted in wavelength by the wavelength conversion layer 4 are mixed, and light of a desired color is emitted from the LED device 100.
  • the substrate 1 is a member for holding the LED element 2.
  • the substrate 1 may have a lead electrode 11.
  • the lead electrode 11 is a member that supplies electricity to the LED element 2 from a power source (not shown) arranged outside the substrate 1.
  • the lead electrode 11 may also serve as a reflection layer for reflecting the light from the LED element 2 and the light from the wavelength conversion layer 4 to the light extraction surface side.
  • the shape of the lead electrode 11 is appropriately selected according to the type and application of the light emitting device 100.
  • the substrate 1 may have a cavity (concave portion) as shown in FIG. 1 or may have a flat plate shape.
  • the shape of the cavity that the substrate 1 has is not particularly limited. For example, it may be a truncated cone shape, and may be a truncated pyramid shape, a cylindrical shape, a prismatic shape, or the like.
  • the substrate 1 preferably has insulating properties and heat resistance, and is preferably made of a ceramic resin or a heat resistant resin.
  • the heat resistant resin include liquid crystal polymer, polyphenylene sulfide, aromatic nylon, epoxy resin, hard silicone resin, polyphthalic acid amide and the like.
  • the substrate 1 may contain an inorganic filler.
  • the inorganic filler can be titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, glass fiber, and the like.
  • the method for producing the substrate 1 is not particularly limited, and may be a known method.
  • the substrate 1 having the lead electrodes 11 is obtained by integrally molding a lead frame having a desired shape and a resin.
  • the LED element 2 is disposed on a substrate. It is electrically connected to an external electrode or the like and emits light of a specific wavelength. The connection with the external electrode is performed through a metal wiring or the like, and may be performed through, for example, the lead electrode 11 formed on the substrate surface.
  • the wavelength of the light emitted from the LED element 2 is not particularly limited.
  • the LED element 2 may be, for example, an element that emits blue light (light of about 420 nm to 485 nm) or an element that emits ultraviolet light.
  • the configuration of the LED element 2 is not particularly limited.
  • the LED element 2 is an element that emits blue light
  • the LED element 2 includes an n-GaN compound semiconductor layer (cladding layer), an InGaN compound semiconductor layer (light emitting layer), and a p-GaN compound semiconductor layer. It may be a laminate of (cladding layer) and a transparent electrode layer.
  • the LED element 2 may have a light emitting surface of 200 to 300 ⁇ m ⁇ 200 to 300 ⁇ m, for example.
  • the height of the LED element 2 is usually about 50 to 200 ⁇ m. In the LED device 100 shown in FIG. 1, only one LED element 2 is disposed on the substrate 1, but a plurality of LED elements 2 may be disposed on the substrate 1.
  • connection method between the LED element 2 and the metal wiring is not particularly limited.
  • the LED element 2 and the metal wiring (lead electrode 11) may be connected via the protruding electrode 12.
  • the LED element 2 and the metal wiring (lead electrode 11) may be connected via a wire 14.
  • a mode in which the LED element 2 and the metal wiring are connected via the protruding electrode 12 is referred to as a flip chip type.
  • a mode in which the LED element 2 and the metal wiring are connected via the wire 14 is referred to as a wire bonding type.
  • an underfill material 13 may be filled in a gap between the LED element 2 and the substrate 1.
  • the underfill material 13 can be a silicone resin, an epoxy resin, or the like. Moreover, you may consist of a material similar to the sealing layer 3 mentioned later.
  • the sealing layer 3 is a layer that covers the surfaces of the LED element 2 and the substrate 1.
  • substrate 1 means the surface in which the LED element 2 of the board
  • the sealing layer 3 may be a layer that covers the entire surface of the substrate 1 on which the LED element 2 is mounted; it may be a layer that covers only the LED element 2 and its peripheral part.
  • the sealing layer 3 preferably covers a metal member such as the lead electrode 11 or the reflective layer on the substrate 1. When a member made of metal is covered with the sealing layer 3, the metal is difficult to corrode, and the light extraction efficiency of the light emitting device 100 is unlikely to decrease with time.
  • the thickness of the sealing layer 3 is not particularly limited, but is preferably 0.1 ⁇ m or more and 15 ⁇ m or less, more preferably 0.3 ⁇ m or more and 4 ⁇ m or less, and further preferably 0.8 ⁇ m or more and 2 ⁇ m or less. If the sealing layer 3 is excessively thick, distortion is likely to occur during the formation of the sealing layer 3, and cracks may occur. On the other hand, if the thickness of the sealing layer 3 is excessively thin, the LED layer 2, the lead electrode 11 and the like are not sufficiently protected by the sealing layer 3, and the deterioration with time may not be sufficiently suppressed.
  • the thickness of the sealing layer 3 is the maximum thickness of the sealing layer 3 disposed on the upper surface of the LED element 2.
  • the layer thickness is measured using a laser holo gauge.
  • the sealing layer 3 contains polymetalloxane as described above. It is preferable that 80 mass% or more of polymetalloxane is contained with respect to the total mass of the sealing layer 3, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more. When the polymetalloxane content is 80% by mass or more, the gas barrier property of the sealing layer 3 is likely to be increased, and the adhesion between the substrate 1 and the sealing layer 3 is also likely to be improved.
  • the sealing layer 3 may contain other components such as a cyclic ether compound as necessary.
  • the polymetalloxane may be a compound having a metalloxane bond in the structure, and may be a polymer of a metal alkoxide or a metal chelate.
  • inorganic oxide fine particles to be described later can also be a kind of polymetalloxane.
  • the amount of the silicon oxide component in the polymetalloxane relative to the total amount of the polymetalloxane is 30 to 94% by mass, preferably 40 to 80% by mass, and more preferably 60 to 70% by mass.
  • the amount of the hydrocarbon component in the polymetalloxane relative to the total amount of the polymetalloxane is 5 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 35% by mass.
  • the amount of the oxide component of the group 4 or group 13 metal element in the polymetalloxane relative to the total amount of the polymetalloxane is 1 to 30% by mass, preferably 10 to 28% by mass, and more preferably 15 to 25% by mass.
  • the amount of the silicon oxide component, the amount of the hydrocarbon component, and the amount of the oxide component of the group 4 or group 13 metal element in the polymetalloxane is a composition ratio of a metal chelate or a metal alkoxide for preparing the polymetalloxane. And adjust according to the kind of inorganic oxide fine particles.
  • the amount of hydrocarbon component in polymetalloxane relative to the total amount of polymetalloxane can be determined by the following method.
  • the organic matter contained in the sealing layer 3 is sufficiently removed by an extraction method or the like. Thereafter, the sealing layer is baked at 500 ° C. for about 1 hour, and the weight reduction amount due to the calcination is measured; the weight reduction amount is defined as the weight of the hydrocarbon component.
  • the amount of the silicon oxide component in the polymetalloxane and the oxide component of the group 4 or group 13 metal element in the polymetalloxane relative to the total amount of the polymetalloxane is determined after the hydrocarbon component amount is specified (firing).
  • the stop layer is analyzed by ICP; the amount of silicon and the weight ratio of group 4 or group 13 metal elements are specified and calculated.
  • the polymer of metal alkoxide or metal chelate contained in polymetalloxane is a monomer of alkoxysilane or aryloxysilane (silane compound) or a polymer thereof (oligomer) and group 4 or It is obtained by polymerizing a metal alkoxide or metal chelate (metal compound) of a group 13 metal element by a known method.
  • the monomer of the silane compound can be a bifunctional alkoxysilane compound, a trifunctional alkoxysilane compound, or a tetrafunctional alkoxysilane compound.
  • the oligomer of the silane compound may be a compound in which several to several tens of monomers of the silane compound are polymerized.
  • Examples of the bifunctional alkoxysilane compound include a compound represented by the following general formula (II).
  • R 5 each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R 4 represents a hydrogen atom or an alkyl group.
  • bifunctional alkoxysilane compound examples include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxy Propoxysilane, ethoxypentyloxysilane, ethoxyphenyloxysilane, methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylmethoxyphenyloxysilane, ethyldipropoxysilane, ethyl Methoxypropoxysilane, ethyldipentyloxysilane, ethyldiphenyloxysilane,
  • Examples of the trifunctional alkoxysilane compound include a compound represented by the following general formula (III).
  • R 2 each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • R 1 represents a hydrogen atom or an alkyl group.
  • trifunctional alkoxysilane compound examples include trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane, Dipropoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxy Silane, monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane Monohydrosilane compounds such as monophenyloxydieth,
  • each R 3 independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • tetrafunctional alkoxysilane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxymono.
  • the oligomer of the silane compound is obtained by mixing a bifunctional alkoxysilane compound, a trifunctional alkoxysilane compound, and a tetrafunctional alkoxysilane compound in a desired ratio and reacting them in the presence of an acid catalyst, water, and a solvent.
  • the oligomer of the silane compound preferably has a weight average molecular weight measured by GPC (gel permeation chromatograph) of 500 to 20000, more preferably 1000 to 10,000, and still more preferably 1500 to 6000. If the degree of polymerization of the oligomer is too high, the viscosity of the coating solution may increase or the components may precipitate.
  • the molecular weight of the oligomer of the silane compound is adjusted by the reaction time, temperature, water concentration, and the like.
  • the group 4 or group 13 metal alkoxide or metal chelate may be a compound represented by the following general formula (V).
  • M m + X n Y mn (V) M represents a Group 4 or Group 13 metal element.
  • m represents the valence of M and represents 3 or 4.
  • n represents the number of X groups and is an integer of 2 or more and 4 or less. However, m ⁇ n.
  • the group 4 or group 13 metal element represented by M is preferably aluminum, zirconium, or titanium, and particularly preferably zirconium.
  • a cured product of an alkoxide or chelate containing a zirconium element does not have an absorption wavelength in a light emission wavelength region (particularly blue light (wavelength 420 to 485 nm)) of a general LED element. For this reason, light from the LED element 2 is not easily absorbed by the cured product of zirconium alkoxide or chelate.
  • the hydrolyzable group represented by X may be a group that is hydrolyzed with water to form a hydroxyl group.
  • the hydrolyzable group include a lower alkoxy group having 1 to 5 carbon atoms, an acetoxy group, a butanoxime group, a chloro group and the like.
  • all the groups represented by X may be the same group or different groups.
  • the hydrolyzable group represented by X is hydrolyzed when the metal element forms a metalloxane bond with a hydroxyl group or silane compound on the surface of the substrate. Therefore, the compound produced after hydrolysis is preferably neutral and light boiling. Therefore, the group represented by X is preferably a lower alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group or an ethoxy group.
  • the monovalent organic group represented by Y may be a monovalent organic group contained in a general silane coupling agent. Specifically, the aliphatic group, alicyclic group, aromatic group, fatty acid having 1 to 1000 carbon atoms, preferably 500 or less, more preferably 100 or less, further preferably 40 or less, and particularly preferably 6 or less. It may be a ring aromatic group.
  • the organic group represented by Y may be an aliphatic group, an alicyclic group, an aromatic group, or a group in which an alicyclic aromatic group is bonded via a linking group.
  • the linking group may be an atom such as O, N, or S, or an atomic group containing these.
  • the organic group represented by Y may have a substituent.
  • substituents include halogen atoms such as F, Cl, Br, and I; vinyl group, methacryloxy group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, Organic groups such as nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group and phenyl group are included.
  • metal alkoxide or metal chelate containing the aluminum element represented by the general formula (V) include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide and the like. It is.
  • metal alkoxide or metal chelate containing a zirconium element represented by the general formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium.
  • Examples include tetra n-butoxide, zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide, dibutoxyzirconium bis (ethylacetoacetate) and the like.
  • metal alkoxide or metal chelate containing the titanium element represented by the general formula (V) include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium.
  • examples include tetramethoxypropoxide, titanium tetra n-propoxide, titanium tetraethoxide, titanium lactate, titanium bis (ethylhexoxy) bis (2-ethyl-3-hydroxyhexoxide), titanium acetylacetonate, and the like.
  • metal alkoxides or metal chelates exemplified above are a part of commercially available organometallic alkoxides or metal chelates.
  • the metal alkoxides or metal chelates shown in the list of coupling agents and related products in Chapter 9 “Optimum Utilization Technology of Coupling Agents” published by Science and Technology Research Institute are also applied to the composition for forming a reflective layer.
  • a part of polymetalloxane may be an inorganic oxide fine particle.
  • the inorganic oxide fine particles may be zirconium oxide fine particles, silicon oxide fine particles, titanium oxide fine particles, zinc oxide fine particles, aluminum oxide fine particles, zeolite fine particles, imogolite and the like.
  • the inorganic oxide fine particles may be spherical, rod-shaped, or string-shaped.
  • the average particle diameter of the inorganic oxide fine particles is preferably 1 nm or more and 50 ⁇ m or less.
  • the average particle diameter of the inorganic oxide fine particles is measured, for example, by a Coulter counter method.
  • the inorganic oxide fine particles may be porous.
  • the specific surface area is preferably 200 m 2 / g or more.
  • the viscosity of the composition for forming the sealing layer 3 is likely to increase, and unevenness is hardly generated in the sealing layer 3.
  • the content of the inorganic oxide fine particles is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass with respect to the total mass of the sealing layer 3. If the amount of the inorganic oxide is less than 0.5% by mass, the effect of improving the strength of the sealing layer 3 cannot be obtained. On the other hand, when the amount of the inorganic oxide exceeds 50% by mass, the sealing layer 3 becomes brittle and the strength of the sealing layer 3 decreases.
  • the surface of the inorganic oxide may be treated with a silane coupling agent or a titanium coupling agent. By the surface treatment, compatibility between the inorganic fine particles and the polysiloxane or the solvent is increased.
  • the sealing layer 3 may contain a cyclic ether compound.
  • metal ions may be generated from a metal wiring (for example, the lead electrode 11) or the like under wet heat, move to the sealing layer 3, and precipitate (migrate).
  • the sealing layer 3 contains a cyclic ether compound, the outflowing metal ions are captured, and corrosion (migration or the like) of the metal wiring (the lead electrode 11 or the like) is suppressed.
  • the cyclic ether compound contained in the sealing layer 3 may be a cyclic compound represented by the following general formula (A). (—CH 2 —CH 2 —Z—) n (A)
  • Z represents O, NR (R represents hydrogen or an alkylene group having 1 to 1000 carbon atoms), or S.
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • S represents S.
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • n represents an integer of 1 or more.
  • the structure of the cyclic ether compound may contain a benzene ring or the like as shown in the following formula (B).
  • cyclic ether compound contained in the sealing layer 3 include 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown-7-ether, and dibenzo-ether. 18-crown-6-ether, diaza-18-crown-6-ether and the like.
  • the cyclic ether compound contained in the sealing layer is preferably a 15- to 21-membered ring compound, more preferably an 18-membered ring compound.
  • the amount of the cyclic ether compound contained in the sealing layer 3 is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass with respect to the total mass of the sealing layer 3. %, And more preferably 1.0 to 2.0% by mass.
  • the sealing layer 3 contains a cyclic ether compound in an amount of 0.1% by mass or more, corrosion of metal wiring and the like is suppressed.
  • the amount of the cyclic ether compound contained in the sealing layer 3 is obtained by immersing the sealing layer 3 in a solvent and extracting the cyclic ether compound in the solvent. Then, it is calculated from the weight of the extracted cyclic ether compound and the weight of the sealing layer 3.
  • the sealing layer 3 is formed by applying the sealing layer composition containing the silane compound, metal compound, inorganic oxide fine particles, cyclic ether compound, and the like described above.
  • the layer is preferably obtained by heat curing.
  • a film obtained by polymerizing a silane compound or a metal compound is relatively dense, and it is difficult for hydrogen sulfide gas and moisture to pass therethrough.
  • a solvent may be contained in the composition for sealing layers as needed.
  • the coating method of the sealing layer composition is not particularly limited, and may be blade coating, spin coating coating, dispenser coating, spray coating, or the like.
  • the coating method of the sealing layer composition is spray coating, the thickness of the sealing layer 3 tends to be thin.
  • the method for heat-curing the sealing layer composition is not particularly limited, but the coating film is preferably heated to 100 ° C. or higher, more preferably 150 to 300 ° C.
  • the composition for sealing layers is heated to 100 ° C. or higher, the aforementioned silane compound or metal compound undergoes dehydration condensation, and the aforementioned polymetalloxane is obtained. If the heating temperature at this time is less than 100 ° C., water generated during the dehydration condensation of the silane compound, the solvent contained in the composition for the sealing layer, and the like are not sufficiently removed, and the light resistance of the sealing layer 3 and the like. May be reduced.
  • the wavelength conversion layer 4 is a layer that converts light of a specific wavelength emitted from the LED element 2 into light of another specific wavelength.
  • the wavelength conversion layer 4 may be a layer in which phosphor particles are dispersed in a transparent resin.
  • the phosphor particles are excited by the wavelength of light emitted from the LED element 2 (excitation wavelength), and emit fluorescent light having a wavelength different from the excitation wavelength.
  • excitation wavelength the wavelength of light emitted from the LED element 2
  • fluorescent light having a wavelength different from the excitation wavelength.
  • blue light is emitted from the LED element 2
  • phosphor particles that emit yellow fluorescence are added to the wavelength conversion layer 4, an LED device that emits white light is obtained.
  • the phosphor particles that emit yellow fluorescence include YAG (yttrium, aluminum, garnet) phosphors.
  • the YAG phosphor emits yellow (wavelength 550 nm to 650 nm) fluorescence using blue light (wavelength 420 nm to 485 nm) emitted from the blue LED element as excitation light.
  • the phosphor particles contained in the wavelength conversion layer 4 are obtained, for example, by 1) mixing a suitable amount of a fluoride such as ammonium fluoride as a flux with a predetermined composition and pressurizing it to obtain a molded body, and 2) The molded body thus obtained is packed in a crucible and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a sintered body.
  • a fluoride such as ammonium fluoride as a flux
  • the mixed raw material having a predetermined composition can be obtained by sufficiently mixing oxides of Y, Gd, Ce, Sm, Al, La, Ga, or compounds that easily become oxides at high temperatures in a stoichiometric ratio.
  • the mixed raw material having a predetermined composition can be obtained by mixing 1) a solution in which rare earth elements of Y, Gd, Ce, and Sm are dissolved in an acid with a stoichiometric ratio and oxalic acid to obtain a coprecipitated oxide. 2) It can also be obtained by mixing this coprecipitated oxide with aluminum oxide or gallium oxide.
  • the kind of the phosphor is not limited to the YAG phosphor, and other phosphors such as a non-garnet phosphor not containing Ce may be used.
  • the average particle diameter of the phosphor particles is preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the larger the particle size of the phosphor particles the higher the light emission efficiency (wavelength conversion efficiency).
  • the particle diameter of the phosphor particles is too large, a gap generated at the interface between the phosphor particles and the binder resin in the wavelength conversion layer 4 becomes large. Thereby, the intensity
  • the average particle diameter of the phosphor particles can be measured, for example, by a Coulter counter method.
  • the amount of phosphor particles contained in the wavelength conversion layer 4 is preferably 5 to 15% by mass, more preferably 9 to 11% by mass, based on the total mass of the wavelength conversion layer 4.
  • the transparent resin contained in the wavelength conversion layer 4 is not particularly limited as long as it is a thermosetting resin transparent to visible light.
  • transparent resins include methyl silicone resins, epoxy-modified silicone resins, alkyd-modified silicone resins, acrylic-modified silicone resins, polyester-modified silicone resins, and phenyl silicone resins; epoxy resins; acrylic resins; methacrylic resins; Transparent resin and the like.
  • a silicone resin is particularly preferable.
  • the thickness of the wavelength conversion layer 4 is usually preferably 25 ⁇ m to 5 mm, more preferably 1 to 3 mm. If the wavelength conversion layer 4 is too thick, the phosphor particle concentration in the wavelength conversion layer 4 becomes excessively low and the phosphor particles may not be uniformly dispersed.
  • the wavelength conversion layer 4 is prepared by preparing a wavelength conversion layer composition containing the resin or the precursor thereof and phosphor particles, and applying and curing the composition so as to cover the LED element 2 and the sealing layer 3. Obtained.
  • the method for applying the wavelength conversion layer composition is appropriately selected depending on the type of the binder component, and may be, for example, dispenser application. Moreover, the hardening method and hardening conditions of the composition for wavelength conversion layers are suitably selected by the kind of binder component.
  • An example of the curing method is heat curing.
  • the LED device includes, for example, a substrate 1, an LED element 2 formed on the substrate 1, and the LED element 2 as shown in the schematic cross-sectional view of FIG. And a sealing layer 3 ′ covering the surface of the substrate 1.
  • the sealing layer 3 ′ includes phosphor particles.
  • part of the light emitted from the LED element 2 is converted into light having a different wavelength by the sealing layer 3 ′ (hereinafter referred to as “wavelength conversion type sealing layer”). Then, the light emitted from the LED element 2 and the light converted by the wavelength conversion type sealing layer 3 ′ are mixed, and light of a desired color is emitted from the LED device 100.
  • the LED device 100 may include a translucent layer (not shown) or the like for protecting the LED element 2 from an external impact on the wavelength conversion type sealing layer 3 ′ as necessary.
  • substrate 1 and LED element 2 in a 2nd aspect may be the same as the board
  • the wavelength conversion type sealing layer 3 ′ is a layer that covers the LED element 2 and the surface of the substrate 1.
  • the wavelength conversion type sealing layer 3 ′ may be a layer covering the entire surface of the substrate 1 on which the LED element 2 is mounted; it is a layer covering only the LED element 2 and its peripheral part. Also good.
  • the wavelength conversion type sealing layer 3 ′ preferably covers a member made of metal such as the lead electrode 11 formed on the substrate 1. When the member made of metal is covered with the wavelength conversion type sealing layer 3 ′, the metal is hardly corroded, and the light extraction efficiency of the light emitting device 100 is not easily lowered over time.
  • the thickness of the wavelength conversion type sealing layer 3 ′ is not particularly limited, and is set according to the amount of phosphor required by the LED device 100. However, it is preferable that the particle diameter of the phosphor particles contained in the wavelength conversion type sealing layer 3 ′ is thicker. Specifically, it is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and further preferably 20 ⁇ m or more. If the thickness of the wavelength conversion type sealing layer 3 ′ is less than 10 ⁇ m, the phosphor particles are not sufficiently retained, and the phosphor particles may be peeled off. When the phosphor particles are peeled off, chromaticity variations are likely to occur in the irradiation light of the LED device 100. Further, when the phosphor particles are peeled off, voids are easily generated in the wavelength conversion type sealing layer 3 ′, and the gas barrier property of the wavelength conversion type sealing layer 3 ′ is also lowered.
  • the thickness of the wavelength conversion type sealing layer 3 ′ is preferably less than 500 ⁇ m. If the thickness of the wavelength conversion type sealing layer 3 ′ is 500 ⁇ m or more, the concentration of the phosphor particles is likely to be uneven; the chromaticity of the emitted light from the LED device 100 is likely to be uneven.
  • the thickness of the wavelength conversion type sealing layer 3 ′ is the maximum thickness of the wavelength conversion type sealing layer 3 ′ disposed on the upper surface of the LED element 2.
  • the layer thickness is measured using a laser holo gauge.
  • the wavelength conversion type sealing layer 3 ′ contains polymetalloxane and phosphor particles as described above.
  • the polymetalloxane is preferably contained in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass with respect to the total mass of the wavelength conversion type sealing layer 3 ′. is there.
  • the amount of polymetalloxane is 5% by mass or more, the gas barrier property of the wavelength conversion type sealing layer 3 ′ is likely to increase, and the adhesion between the substrate 1 and the wavelength conversion type sealing layer 3 ′ is also likely to increase.
  • the amount of polymetalloxane contained in the wavelength conversion type sealing layer 3 ′ exceeds 40% by mass, the amount of phosphor particles contained in the wavelength conversion type sealing layer 3 ′ becomes relatively small. As a result, sufficient fluorescence may not be obtained from the wavelength conversion type sealing layer 3 ′.
  • the polymetalloxane contained in the wavelength conversion type sealing layer 3 ′ can be the same as the polymetalloxane contained in the sealing layer 3 of the first aspect.
  • the wavelength conversion type sealing layer 3 ′ may contain clay mineral particles as a kind of polymetalloxane.
  • the clay mineral particles are contained in the wavelength conversion type sealing layer composition for forming the wavelength conversion type sealing layer 3 ′, the viscosity of the wavelength conversion type sealing layer composition increases, Sedimentation is suppressed. Therefore, the concentration unevenness of the phosphor particles in the wavelength conversion type sealing layer 3 ′ is suppressed.
  • clay mineral particles include layered silicate minerals, imogolite, allophane and the like.
  • the layered silicate mineral is preferably a swellable clay mineral having a mica structure, a kaolinite structure, or a smectite structure, and particularly a swellable clay mineral having a smectite structure rich in swelling properties.
  • layered silicate minerals include natural or synthetic hectorite, saponite, stevensite, hydelite, montmorillonite, nontrite, bentonite, laponite, and other smectite clay minerals, Na-type tetralithic fluoromica, Li-type Non-swelling mica genus clay minerals such as swellable mica genus clay minerals such as tetrasilic fluorinated mica, Na type fluorine teniolite, Li type fluorine teniolite, muscovite, phlogopite, fluorine phlogopite, sericite, potassium tetrasilicon mica , And vermiculite and kaolinite, or mixtures thereof.
  • Examples of commercial products of clay mineral particles include Laponite XLG (synthetic hectorite analogue manufactured by LaPorte, UK), Laponite RD (Synthetic hectorite analogue produced by LaPorte, UK), Thermabis (Synthetic product, Henkel, Germany) Hectorite-like substance), smecton SA-1 (saponite-like substance manufactured by Kunimine Industry Co., Ltd.), Bengel (natural bentonite sold by Hojun Co., Ltd.), Kunivia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), bee gum ( Natural hectorite manufactured by Vanderbilt, USA, Daimonite (synthetic swellable mica manufactured by Topy Industries, Ltd.), Micromica (synthetic non-swellable mica, manufactured by Coop Chemical Co., Ltd.), Somasifu (Coop Chemical Co., Ltd.) ) Synthetic swelling mica), SWN (Synthetic s
  • the clay mineral particles are preferably at least one selected from the group consisting of layered silicate minerals, imogolite, and allophane. These particles have a very large surface area, and a small amount tends to increase the viscosity of the wavelength conversion type sealing layer composition.
  • the content of the clay mineral particles is preferably 0.5 to 20% by mass and more preferably 0.5 to 10% by mass with respect to the total mass of the wavelength conversion type sealing layer 3 '.
  • the content of the clay mineral particles contained in the wavelength conversion type sealing layer 3 ′ is less than 0.5% by mass, the above thickening effect cannot be sufficiently obtained.
  • the amount of the layered silicate mineral exceeds 20% by mass, the strength of the wavelength conversion type sealing layer 3 ′ decreases.
  • the phosphor particles are preferably contained in an amount of 60 to 95% by mass, more preferably 70 to 90% by mass, and further preferably 75 to 85% by mass with respect to the total mass of the wavelength conversion type sealing layer 3 ′. %. If the amount of the phosphor particles is less than 60% by mass, there is a possibility that sufficient fluorescence cannot be obtained from the wavelength conversion type sealing layer 3 ′. On the other hand, when the amount of the phosphor exceeds 95% by mass, the amount of polymetalloxane is relatively reduced, and the gas barrier property and the adhesion between the substrate 1 and the wavelength conversion type sealing layer 3 ′ tend to be lowered.
  • the phosphor particles contained in the wavelength conversion type sealing layer 3 ′ can be the same as the phosphor particles contained in the wavelength conversion layer 4 of the first embodiment.
  • the wavelength conversion type sealing layer 3 ′ may contain other components such as a cyclic ether compound as necessary.
  • a cyclic ether compound as necessary.
  • the amount of the cyclic ether compound contained in the wavelength conversion type sealing layer 3 ′ is preferably 0.1 to 5.0% by mass, more preferably based on the total mass of the wavelength conversion type sealing layer 3 ′. It is 0.5 to 3.0% by mass, and more preferably 1.0 to 2.0% by mass.
  • the wavelength conversion type sealing layer 3 ′ contains a cyclic ether compound in an amount of 0.1% by mass or more, corrosion of metal wiring and the like is sufficiently suppressed.
  • the cyclic ether compound contained in the wavelength conversion type sealing layer 3 ′ can be the same as the cyclic ether compound contained in the sealing layer 3 of the first embodiment.
  • the wavelength conversion type sealing layer 3 ′ is a wavelength conversion type sealing containing polymetalloxane and its precursor (the aforementioned silane compound, metal compound, inorganic oxide fine particles), phosphor particles, cyclic ether compound, clay mineral particles, and the like. It may be a layer obtained by applying a composition for a stop layer and heat-curing it. A solvent may be contained in the composition for wavelength conversion type sealing layers as needed.
  • the coating method and the curing method of the wavelength conversion type sealing layer composition may be the same as the film forming method of the sealing layer 3 of the first aspect.
  • the wavelength conversion type sealing layer 3 ′ is a phosphor dispersion in which a polymetalloxane precursor (the above-mentioned silane compound or metal compound), phosphor particles, clay mineral particles, inorganic oxide fine particles and the like are dispersed in a solvent. It may also be a layer obtained by coating the liquid separately and heating and curing them. Specifically, the phosphor dispersion liquid is applied and the phosphor particles are arranged in a desired region, and then the polymetalloxane precursor is applied so as to cover the phosphor particles and cured.
  • a polymetalloxane precursor the above-mentioned silane compound or metal compound
  • the phosphor dispersion liquid may be a dispersion liquid in which phosphor particles and clay mineral particles are dispersed in a solvent.
  • the phosphor dispersion liquid may further contain inorganic oxide fine particles, a cyclic ether compound, and the like.
  • the solvent of the phosphor dispersion liquid preferably contains alcohols.
  • alcohols include monohydric alcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, and the like, preferably ethylene glycol Dihydric or higher polyhydric alcohols such as propylene glycol, 1,3-butanediol, 1,4-butanediol, and the like.
  • the phosphor dispersion liquid may contain two or more kinds of alcohols. When a divalent or higher alcohol is contained, the viscosity of the phosphor dispersion liquid is likely to increase, and sedimentation of the phosphor particles as a dispersoid is suppressed.
  • the method for applying the phosphor dispersion liquid is not particularly limited, and may be blade coating, spin coating coating, dispenser coating, spray coating, or the like. By spray coating, the wavelength conversion type sealing layer 3 ′ tends to be thin. After application of the phosphor dispersion liquid, the coating film is dried as necessary.
  • a polymetalloxane precursor (the aforementioned silane compound or metal compound) is applied so as to cover the phosphor particles.
  • the coating solution may contain a solvent as necessary.
  • the coating method is not particularly limited, and examples thereof include blade coating, spin coating coating, dispenser coating, and spray coating. By spray coating, the wavelength conversion type sealing layer 3 ′ tends to be thin.
  • the coating is heated to 100 ° C. or higher, preferably 150 to 300 ° C., to dry and cure the polymetalloxane precursor (the aforementioned silane compound or metal compound). If the heating temperature is less than 100 ° C., water, solvent and the like generated during dehydration condensation of the silane compound are not sufficiently removed, and the light resistance of the wavelength conversion type sealing layer 3 ′ may be lowered.
  • the LED device 100 may include a translucent layer on the wavelength conversion type sealing layer 3 ′.
  • the light transmissive layer functions to protect the LED element 2 from external impacts, gases, and the like.
  • the light transmissive layer may be a layer made of a transparent resin such as a silicone resin or an epoxy resin.
  • the thickness of the light transmitting layer is preferably 25 ⁇ m to 5 mm, more preferably 1 to 3 mm. Generally, it is difficult to make the thickness of the translucent layer containing the transparent resin 25 ⁇ m or less. On the other hand, from the viewpoint of miniaturization of the LED device, the thickness of the translucent layer is preferably 5 mm or less.
  • the thickness of the light transmissive layer means the maximum thickness of the light transmissive layer formed on the light emitting surface of the LED element 2. The thickness of the translucent layer can be measured with a laser holo gauge.
  • the translucent layer is obtained by applying and curing the resin or a precursor thereof so as to cover the wavelength conversion type sealing layer 3 ′.
  • the method of applying the resin or its precursor is appropriately selected according to the type of resin, and can be, for example, dispenser application.
  • the curing method and curing conditions for the resin or its precursor are appropriately selected depending on the type of resin.
  • An example of the curing method is heat curing.
  • the above-described light-emitting device is further provided with other optical components (such as a lens) to form various optical members.
  • the light-emitting device of the present invention is excellent in gas barrier properties, light resistance, heat resistance, and the like, and is therefore suitable for lighting for vehicles, lighting for outdoor use, and the like.
  • the obtained fired product was pulverized, washed, separated, and dried to obtain yellow phosphor particles having an average particle diameter of about 10 ⁇ m.
  • the emission wavelength of excitation light with a wavelength of 465 nm was measured, it had a peak wavelength at a wavelength of approximately 570 nm.
  • LED devices A-1 to A-10 were produced by the following method. These LED devices have the configuration shown in FIG. Specifically, it includes a substrate 1, an LED element 2, a sealing layer 3 that does not contain a phosphor, and a wavelength conversion layer 4 that is a resin layer in which the phosphor is dispersed.
  • ⁇ LED device A-1 (Example 1)> A substrate 1 having a cavity (opening diameter 3 mm, cavity bottom diameter 2 mm, wall surface angle 60 °) at the center as shown in FIG. 1 was prepared. A lead electrode 11 is formed on the substrate 1. And the lead electrode 11 of the said board
  • substrate 1 and LED element 2 (cuboid shape; 200 micrometers x 300 micrometers x 100 micrometers) were flip-chip mounted.
  • composition A-1 was prepared.
  • the LED element sealing layer composition A-1 was applied with a spray device (TS-MSP-400, manufactured by Taitec Solutions) so as to cover the LED element and the surface of the cavity of the substrate.
  • the sealing layer composition A-1 was baked at 150 ° C. for 1 hour to obtain a sealing layer having a thickness of 1.0 ⁇ m.
  • the phosphor particles described above were dispersed in a silicone resin (OE6630, manufactured by Toray Dow Co., Ltd.) to prepare a wavelength conversion layer composition.
  • the amount of the phosphor particles was 10% by mass with respect to the total amount of the composition for wavelength conversion layer.
  • the composition for wavelength conversion layers was dripped on the sealing layer with the dispenser, and it baked at 150 degreeC for 1 hour.
  • the thickness of the obtained wavelength conversion layer was 2.5 mm.
  • Example 2 to 9 and Comparative Examples 1 to 3 An LED device (A-2 to A-2) was prepared in the same manner as in Example 1 except that the sealing layer composition A-1 was changed to the sealing layer compositions (A-2 to A-12) shown in Table 1. A-12) was produced.
  • the component ratio of the polymetalloxane in the sealing layers formed in Examples 1 to 9 and Comparative Examples 1 to 3 was specified as follows.
  • Each of the sealing layer compositions (A-1 to A-12) having the same composition as in Examples 1 to 9 and Comparative Examples 1 to 3 was applied on a quartz substrate in an amount of 1.0 g, and 150 ° C. For 1 hour.
  • cured material (sealing layer) of the composition for sealing layers was peeled from the quartz substrate, and the weight was measured.
  • the sealing layer was immersed in acetone and sonicated for 1 hour. Then, the presence or absence of a component (cyclic ether) extracted into acetone was confirmed, and when there was an extract, its weight was measured. Furthermore, the extracted component was subjected to NMR measurement to identify the chemical structure of the composition.
  • a component cyclic ether
  • the sealing layer was sufficiently dried, the weight of the sealing layer was measured again. And it baked at 500 degreeC for 1 hour, and measured the weight after baking. Further, the volatile component during firing was subjected to gas chromatograph mass spectrometry (GC-MS), and it was confirmed that the volatile component was a hydrocarbon component.
  • GC-MS gas chromatograph mass spectrometry
  • ⁇ Adhesion> The adhesion of the sealing layer of the LED device was evaluated. Specifically, a cycle of ⁇ 40 ° C. (30 minutes) and 100 ° C. (30 minutes) was repeated using an LED device using a heat shock tester (TSA-42EL; manufactured by Espec Corp.). After this test, the LED device was examined for non-lighting due to peeling of the sealing layer, and the adhesion was evaluated according to the following criteria. ⁇ : No lighting in 2000 cycles of heat shock ⁇ : No lighting in 1500 cycles or more and less than 2000 cycles ⁇ : No lighting in 1000 cycles or more of heat shock, less than 1500 cycles ⁇ : No lighting in less than 1000 cycles of heat shock Occurrence
  • ⁇ Crack resistance evaluation> About the sealing layer of the LED device, appearance observation was performed at a magnification of 1000 times by SEM (VE7800, manufactured by Keyence) before forming the wavelength conversion layer. The crack resistance was evaluated according to the following criteria. ⁇ : There is no crack with a length of 5 ⁇ m or more in the sealing layer. ⁇ : There are 1 to 5 cracks with a length of 5 ⁇ m or more in the sealing layer. X: A crack with a length of 5 ⁇ m or more in the sealing layer. There are 5 or more
  • ⁇ Hydrogen sulfide gas resistance evaluation> The LED device was subjected to sulfidation resistance evaluation based on a JIS standard gas exposure test (JIS C60068-2-43). The LED device was exposed to an environment of 15 ppm hydrogen sulfide gas, a temperature of 25 ° C., and a relative humidity of 75% RH for 1000 hours. The total luminous flux was measured for the LED devices before and after exposure, and the resistance to hydrogen sulfide gas was evaluated according to the following criteria. The total luminous flux was measured with a spectral radiance meter (CS-2000, manufactured by Konica Minolta Sensing).
  • CS-2000 spectral radiance meter
  • Total luminous flux to initial ratio (total luminous flux value after exposure to hydrogen sulfide gas / total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) is 96% or more
  • total luminous flux to initial ratio (total luminous flux value after exposure to hydrogen sulfide gas) / Total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) is 92% or more and less than 96%
  • initial luminous flux to initial ratio total luminous flux value after exposure to hydrogen sulfide gas / total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) 92% or less
  • the composition for light emitting element sealing layer was apply
  • permeability before and behind processing for 150 hours by a metal halide lamp light resistance tester (M6T, Suga Test Instruments Co., Ltd.) for 100 hours was measured, and the light resistance evaluation was performed on the following reference
  • ⁇ Heat and heat resistance evaluation> Wet and heat resistance of the LED device was evaluated. Specifically, the LED device was continuously energized in a humid heat environment with a temperature of 85 ° C. and a relative humidity of 85% RH. The total luminous flux value 1000 hours after the start of energization was measured, and the ratio to the total luminous flux value before the energization start (total luminous flux value after test / total luminous flux value before test ⁇ 100) was calculated. The value was evaluated according to the following criteria.
  • the silicon oxide component is 30 to 94% by mass
  • the hydrocarbon component is 5 to 50% by mass
  • the metal oxide component is 1 to 30% by mass with respect to the total mass of the polymetalloxane.
  • metal oxide component (zirconium oxide component) in the polymetalloxane exceeds 30% by mass (Comparative Example 3), cracks are likely to occur, and the resistance to sulfurization and heat-and-moisture resistance decreased. If the metal oxide component (zirconium oxide component) is excessive, distortion is likely to occur inside, and it is assumed that cracks have occurred.
  • the sealing layer contained 0.5 to 5% by mass of the cyclic ether compound (Examples 6 and 7), the heat and humidity resistance was very good. Usually, metal ions are generated from a metal electrode or the like formed on a substrate by humidity or heat, and the metal electrode or the like is corroded. On the other hand, when a cyclic ether compound is contained in the sealing layer, the metal ion is trapped by the cyclic ether compound. As a result, it is presumed that the corrosion of the metal was suppressed and the total luminous flux value did not decrease.
  • LED devices B-1 to B-12 were produced by the following method. These LED devices have the configuration shown in FIG. Specifically, it has the board
  • LED device B-1 (Example 10) 1 g of phosphor particles, 0.05 g of MK-100 (synthetic mica, manufactured by Corp Chemical), 0.05 g of RX300 (average particle size of primary particles: 7 nm, specific surface area: 300 m 2 / g, manufactured by Nippon Aerosil Co., Ltd.) Then, 1.5 g of propylene glycol was mixed to prepare a phosphor dispersion.
  • a substrate similar to that in Example 1 was prepared, and the lead electrode 11 of the substrate 1 and the LED element 2 (cuboid: 200 ⁇ m ⁇ 300 ⁇ m ⁇ 100 ⁇ m) were flip-chip mounted. Thereafter, the phosphor dispersion liquid described above was spray-coated on the substrate 1. Then, it was made to dry at 50 degreeC for 1 hour, and the fluorescent substance particle was arrange
  • the sealing layer composition A-1 is covered with a spray device (TS-MSP-400, manufactured by Taitec Solutions Co., Ltd.) so as to cover the side surface and mounting portion of the LED element on which the phosphor particles are arranged. Applied. Thereafter, the sealing layer composition A-1 was baked at 150 ° C. for 1 hour to obtain an LED device B-1 having a sealing layer (wavelength conversion type sealing layer) having a thickness of 20 ⁇ m.
  • a spray device T-MSP-400, manufactured by Taitec Solutions Co., Ltd.
  • LED devices B-2 to B-12 as in Example 10, except that the sealing layer composition A-1 was changed to the sealing layer compositions A-2 to A-12, respectively.
  • Example 10 Example 11 to 18 and Comparative Examples 4 to 6
  • LED devices B-2 to B-12 as in Example 10, except that the sealing layer composition A-1 was changed to the sealing layer compositions A-2 to A-12, respectively.
  • the silicon oxide component is 30 to 94% by mass
  • the hydrocarbon component is 5 to 50% by mass
  • the metal oxide component is 1 to 30% by mass with respect to the total mass of the polymetalloxane.
  • metal oxide component (zirconium oxide component) in the polymetalloxane exceeds 30% by mass (Comparative Example 6), cracks are likely to occur, and the resistance to sulfurization and heat-and-moisture resistance decreased. If the metal oxide component (zirconium oxide component) is excessive, distortion is likely to occur inside, and it is assumed that cracks have occurred.
  • the light emitting device of the present invention is excellent in gas barrier properties, heat and humidity resistance, and light resistance. Therefore, it is useful for lighting used outdoors or indoors.
  • LED device Light emitting device

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Led Device Packages (AREA)

Abstract

La présente invention aborde le problème de pourvoir à un dispositif électroluminescent qui possède d'excellentes propriétés de barrière aux gaz et ne subit presque pas de fissuration ni d'écaillage dans une couche d'étanchéité même s'il est utilisé pendant une longue durée. Un dispositif électroluminescent comprend un substrat, un élément électroluminescent qui est disposé sur le substrat, et une couche d'étanchéité qui couvre l'élément électroluminescent et la surface du substrat et contient du polymétalloxane, la teneur en oxyde de silicium dans le polymétalloxane étant de 30-94% en masse par rapport à la quantité totale du polymétalloxane, la teneur en hydrocarbures dans le polymétalloxane étant de 5-50% en masse par rapport à la quantité totale du polymétalloxane, et la teneur en oxydes d'éléments métalliques du groupe 4 ou 13 dans le polymétalloxane étant de 1-30% en masse par rapport à la quantité totale du polymétalloxane.
PCT/JP2014/003927 2013-07-26 2014-07-25 Dispositif électroluminescent WO2015011929A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013155812 2013-07-26
JP2013-155812 2013-07-26

Publications (1)

Publication Number Publication Date
WO2015011929A1 true WO2015011929A1 (fr) 2015-01-29

Family

ID=52392993

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/003927 WO2015011929A1 (fr) 2013-07-26 2014-07-25 Dispositif électroluminescent

Country Status (1)

Country Link
WO (1) WO2015011929A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010182970A (ja) * 2009-02-06 2010-08-19 Seiko Instruments Inc 発光デバイスの製造方法
WO2013099193A1 (fr) * 2011-12-26 2013-07-04 コニカミノルタ株式会社 Agent de scellement pour un dispositif à del, dispositif à del et procédé de production de dispositif à del

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010182970A (ja) * 2009-02-06 2010-08-19 Seiko Instruments Inc 発光デバイスの製造方法
WO2013099193A1 (fr) * 2011-12-26 2013-07-04 コニカミノルタ株式会社 Agent de scellement pour un dispositif à del, dispositif à del et procédé de production de dispositif à del

Similar Documents

Publication Publication Date Title
WO2014104295A1 (fr) Dispositif électroluminescent
US9708492B2 (en) LED device and coating liquid used for production of same
WO2013099193A1 (fr) Agent de scellement pour un dispositif à del, dispositif à del et procédé de production de dispositif à del
WO2013180259A1 (fr) Produit d'étanchéité pour dispositif émettant de la lumière, dispositif émettant de la lumière l'utilisant et procédé de fabrication de dispositif émettant de la lumière
WO2016121855A1 (fr) Roue de couleur pour dispositif d'affichage du type à projection, procédé de fabrication de cette roue, et dispositif d'affichage du type à projection comportant cette roue
WO2014103326A1 (fr) Liquide de revêtement et dispositif à del pourvu d'une couche réfléchissante formée d'un produit durci dudit liquide de revêtement
JP2014022508A (ja) Ｌｅｄ装置及びその製造方法
JP2014130871A (ja) 発光装置
JP2015153856A (ja) 発光装置及びその製造方法
WO2014030342A1 (fr) Dispositif à del et procédé pour sa fabrication
JP2014138081A (ja) 発光装置、波長変換・光拡散素子及びそれらの製造方法、光拡散セラミック層形成用組成物
JP2016154179A (ja) 発光装置、及びその製造方法
JP5910340B2 (ja) Ｌｅｄ装置、及びその製造方法
JP2015195269A (ja) 発光装置及びその製造方法
JP5729327B2 (ja) Ｌｅｄ装置の製造方法
WO2013180258A1 (fr) Produit d'étanchéité pour dispositif émettant de la lumière, dispositif émettant de la lumière l'utilisant et procédé de fabrication pour dispositif émettant de la lumière
WO2014103330A1 (fr) Dispersion de luminophore, dispositif à del et procédé de fabrication associé
WO2015049865A1 (fr) Agent d'étanchéité pour éléments électroluminescents et dispositif à led
JP2014127495A (ja) Ｌｅｄ装置、及びその製造方法
WO2015011929A1 (fr) Dispositif électroluminescent
JP2014160713A (ja) Ｌｅｄ装置の製造方法
WO2016024604A1 (fr) Composition de polysilsesquioxane contenant des microparticules inorganiques, son procédé de production, dispositif électroluminescent, et son procédé de fabrication.
JP2016181535A (ja) 発光装置、および発光装置製造用の塗布液
WO2013105514A1 (fr) Dispositif del
WO2016047745A1 (fr) Liquide de revêtement, procédé de production de dispositif à del l'utilisant, et dispositif à del

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14828705

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 14828705

Country of ref document: EP

Kind code of ref document: A1