WO2014103326A1 - 塗布液、及びその硬化物からなる反射層を備えるled装置 - Google Patents
塗布液、及びその硬化物からなる反射層を備えるled装置 Download PDFInfo
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- WO2014103326A1 WO2014103326A1 PCT/JP2013/007664 JP2013007664W WO2014103326A1 WO 2014103326 A1 WO2014103326 A1 WO 2014103326A1 JP 2013007664 W JP2013007664 W JP 2013007664W WO 2014103326 A1 WO2014103326 A1 WO 2014103326A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/50—Wavelength conversion elements
- H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
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- 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
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- 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
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
- H01L2224/85909—Post-treatment of the connector or wire bonding area
- H01L2224/8592—Applying permanent coating, e.g. protective coating
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- 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 an LED device including a coating layer and a reflective layer made of a cured product thereof.
- a phosphor such as a YAG phosphor has been placed in the vicinity of a gallium nitride (GaN) blue LED (Light Emitting Diode) chip, and has received blue light and blue light emitted from the blue LED chip.
- GaN gallium nitride
- An LED device that obtains white light by mixing yellow light emitted from a phosphor is widely used.
- various phosphors are arranged in the vicinity of the blue LED chip, and blue light emitted from the blue LED chip and red light and green light emitted from the phosphor upon receiving blue light are mixed to obtain white light.
- Equipment has also been developed.
- White LED devices have a variety of uses, for example, there is a demand as an alternative to fluorescent lamps and incandescent lamps.
- Such an illuminating device has a configuration in which a plurality of white LED devices are combined, and how to increase the light extraction efficiency of each white LED device is important in realizing cost reduction and long life. come.
- a reflector having a high light reflectance is disposed around the LED element.
- Such a reflector is generally formed of metal plating or the like.
- a reflector made of metal plating cannot be formed on the entire surface of the substrate in order to prevent electrical conduction. Therefore, there is a problem that light is absorbed by the substrate in the region where the reflector is not formed.
- Patent Document 1 a reflector in which metal plating is covered with a resin layer
- Patent Document 2 a reflector in which metal plating is covered with a white resin layer
- the reflector is made of resin, or when the reflector surface made of metal plating is coated with resin as in the technique of Patent Document 1, the resin deteriorates due to heat or light, and the light reflection of the reflective layer over time. There is a problem that the property is lowered or electricity is conducted. In particular, in applications where a large amount of light is required, such as in-vehicle headlights, the resin is likely to deteriorate.
- an object of the present invention is to provide a reflective layer for an LED device that can reflect light efficiently with little deterioration over a long period of time, and a coating liquid for obtaining the reflective layer.
- the present invention relates to the following inventions.
- R4 the ratio of the tetrafunctional silane compound
- the following formula 1 and formula 2 0 ⁇ R2 ⁇ 20 (Formula 1) 0 ⁇ R4 / R3 ⁇ 3 (Formula 2)
- the coating solution according to 1 above wherein at least one selected from the group consisting of the bifunctional silane compound, the trifunctional silane compound, and the tetrafunctional silane compound is polymerized in advance.
- the coating solution contains at least one selected from the group consisting of metal oxide fine particles having an average particle size of 5 nm to less than 100 nm, inorganic particles having an average particle size of 100 nm to 100 ⁇ m, and clay mineral particles.
- the coating solution according to 1 or 2 further contained. 4).
- the clay mineral particles are at least one selected from the group consisting of layered silicate minerals, imogolite, and allophane. 5.
- An LED device comprising: a substrate; an LED element disposed on the substrate; a reflective layer disposed at least around the LED element on the substrate; and a wavelength conversion layer covering the LED element and the reflective layer.
- the reflective layer includes a white pigment, a silane compound, and a solvent, and the ratio of the bifunctional silane compound in the total amount of the silane compound is R2 (mol%), and the ratio of the trifunctional silane compound is R3 (mol%).
- a reflective layer for an LED device that can reflect light efficiently with little deterioration over a long period of time is provided, and as a result, light can be efficiently extracted over a long period of time. LED device is provided.
- the ratio of the bifunctional silane compound in the total amount of (B) silane compound is R2 (mol%)
- the ratio of the trifunctional silane compound is R3 (mol%)
- the ratio of the tetrafunctional silane compound is R4 (mol%).
- the following formula 1 and formula 2 0 ⁇ R2 ⁇ 20 (Formula 1) 0 ⁇ R4 / R3 ⁇ 3 (Formula 2) Both conditions are satisfied.
- R2 is 20 or more, the adhesion between the layer obtained by curing the coating solution and the substrate is lowered. Moreover, the gas barrier property of the layer obtained by hardening
- the value of R4 / R3 in Formula 2 exceeds 3, there is a risk of cracks occurring during film formation. Therefore, the value of R4 / R3 is preferably 3 or less, more preferably 0 ⁇ R4 / R3 ⁇ 2, and further preferably 0 ⁇ R4 / R3 ⁇ 1.
- the ratio of the bifunctional silane compound, the trifunctional silane compound, and the tetrafunctional silane compound of the silane compound in the coating solution can be obtained from a solid Si-NMR spectrum of a sample obtained by drying and solidifying the coating solution at 150 ° C. .
- NMR Nuclear Magnetic Resonance
- the following schematic diagram (A) shows the Si—O net structure ignoring the tetrahedral structure.
- the schematic diagram (B) shows a case where a part of the oxygen atom O is substituted with another member (here, —H) in the Si—O net structure.
- the schematic diagram (A) derived from the tetrafunctional silane compound, the atoms (Q 4 ) bonded to four —OSi and the three —OSi bonded to each other as shown in the schematic (B). There are atoms (Q 3 ) and the like.
- a silicon atom that is, silicon derived from a bifunctional silane compound in which two oxygen atoms are bonded and two other atoms (usually carbon) are bonded is generally referred to as a D site.
- D site silicon atom
- the peak derived from the D site is also observed as each peak of D 0 to D n (D n peak group), which is further than the peak group of Q n and T n. It is observed as a multimodal peak in the region on the high magnetic field side (usually the region with a chemical shift of ⁇ 3 to ⁇ 40 ppm).
- FIG. 6 is an example of a solid Si-NMR spectrum of a polymer of a silane compound.
- the horizontal axis indicates the chemical shift
- the vertical axis indicates “relative strength” depending on the amount of the compound having each structure.
- D11 indicates actual measurement data.
- D12 indicates data modeled by a Gaussian function.
- D13 shows a difference spectrum.
- the peak P11 represents the D n peak group, the peak top of the D n peak group is present in the vicinity of chemical shift -20.0Ppm.
- the peak P12 represents the T n peak group, the peak top of the T n peak group is present in the vicinity of chemical shift -60.0Ppm.
- the peak P13 represents a Q n peak group, the peak top of the Q n peak group is present in the vicinity of a chemical shift -100.0 ⁇ -110 ppm. That is, FIG. 6 shows that the polymer contains silicon derived from a bifunctional silane compound, silicon derived from a trifunctional silane compound, and silicon derived from a tetrafunctional silane compound.
- the area ratio of the respective peak groups of D n , T n , and Q n is equal to the molar ratio of silicon atoms placed in the environment corresponding to each peak group. Therefore, the ratio of the area of each peak group to the total area of the Q n peak group, the T n peak group, and the D n peak group is the silane compound (tetrafunctional group) with respect to the total molar amount of silicon atoms contained in the coating solution. Silane compound, trifunctional silane compound, and bifunctional silane compound).
- the coating liquid of the present invention is not easily cracked when the coating film is cured. Moreover, the layer obtained by hardening
- the application of the coating liquid of the present invention is not particularly limited as long as such characteristics can be utilized, but the coating liquid of the present invention is suitable for a coating liquid for forming a reflective layer of an LED device.
- the coating solution is a reflection layer forming coating solution will be described as an example.
- White pigment The white pigment contained in the coating solution is not particularly limited as long as it is highly reflective particles.
- White pigments are calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc sulfide, aluminum hydroxide, boron nitride, It may be at least one selected from aluminum nitride, potassium titanate, barium titanate, aluminum titanate, strontium titanate, calcium titanate, magnesium titanate, hydroxyapatite, and the like. Among these, a mixture of one or a combination of two or more selected from the group consisting of titanium oxide, aluminum oxide, barium sulfate, zinc oxide, and boron nitride is preferable.
- the resulting reflective layer has high thermal conductivity. As a result, heat generated from the light emitting chip can be quickly released from the substrate. Therefore, the temperature of the LED device can be kept low, and the device life can be extended.
- the average primary particle diameter of the white pigment is preferably 100 nm or more and 20 ⁇ m or less, more preferably greater than 100 nm and 10 ⁇ m or less, and further preferably 200 nm to 2.5 ⁇ m.
- the “average primary particle size” refers to the value of D50 measured with a laser diffraction particle size distribution meter. Examples of the laser diffraction particle size distribution measuring device include a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation.
- the amount of the white pigment contained in the coating solution is preferably 60 to 95% by mass and more preferably 70 to 90% by mass with respect to the total mass of components other than the solvent contained in the coating solution. If the amount of the white pigment is less than 60% by mass, the resulting reflective layer may not have sufficient light reflectivity, and the light extraction efficiency may not increase. On the other hand, when the content of the white pigment exceeds 95% by mass, the amount of the binder is relatively reduced, and the strength of the reflective layer may be lowered, or the white pigment may be lost from the reflective layer.
- the total amount of the silane compound contained in the coating solution is preferably 5 to 40% by mass and more preferably 10 to 30% by mass with respect to the total mass of components other than the solvent contained in the coating solution.
- the total amount of the silane compound is less than 5% by mass, the white pigment is not sufficiently retained by the polymer of the silane compound in the resulting reflective layer. As a result, pigment powder is easily generated on the surface of the reflective layer.
- the total amount of a silane compound exceeds 40 mass%, it will become easy to produce shrinkage
- trifunctional silane compounds include trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane, di Propoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxysilane Monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane, monofluoro Monohydrosilane compounds such as nyloxydieth
- R 2 represented by the general formula (III) of these trifunctional silane compounds is a methyl group
- the hydrophobicity of the resulting reflective layer surface becomes low.
- the composition for forming a wavelength conversion layer becomes easy to spread.
- the adhesion between the reflective layer and the wavelength conversion layer is enhanced.
- the trifunctional silane compound in which R 2 represented by the general formula (III) is a methyl group include methyltrimethoxysilane and methyltriethoxysilane, and methyltrimethoxysilane is particularly preferable.
- 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 silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxymonomethoxy.
- Silane trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, Triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Silane, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxy
- bifunctional silane compound examples include compounds 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 silane compound examples include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxy.
- the oligomer of a silane compound is obtained by mixing a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound in a desired ratio and reacting them in the presence of an acid catalyst, water, and a solvent.
- the molecular weight of the oligomer is adjusted by the reaction time, temperature, water concentration, and the like.
- solvents for preparing oligomers include monohydric alcohols such as methanol, ethanol, propanol and n-butanol; alkyl carboxylic acid esters such as methyl-3-methoxypropionate and ethyl-3-ethoxypropionate; ethylene Polyhydric alcohols such as glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexanetriol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, pro Monoethers of polyhydric alcohols such as lenglycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol
- the solvent contained in the coating solution is not particularly limited as long as it is compatible with the silane compound and can uniformly disperse the white pigment and the like, but at least one of a monohydric alcohol and a dihydric or higher polyhydric alcohol is used. It is preferably included. When monohydric alcohol is contained, the coating solution is likely to spread and spread easily. On the other hand, when the polyhydric alcohol is contained, the viscosity of the coating solution is likely to increase, and the white pigment is difficult to settle.
- monohydric alcohols examples include methanol, ethanol, propanol, butanol and the like.
- the content of the monohydric alcohol is preferably 10 to 50% by mass and more preferably 20 to 40% by mass with respect to the entire coating solution.
- the polyhydric alcohol may be either a diol or a triol.
- the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, and preferably ethylene glycol, propylene glycol, 1,3-butane. Diol, 1,4-butanediol and the like are included.
- the content of the polyhydric alcohol is preferably 10 to 50% by mass and more preferably 20 to 40% by mass with respect to the entire coating solution.
- the solvent may contain water.
- water When water is contained in the coating solution, water enters between the layers of the clay mineral particles, the clay mineral particles swell, and the viscosity of the coating solution is more likely to increase.
- the total amount of the solvent contained in the coating solution is preferably 20 to 80% by mass, more preferably 30 to 70% by mass with respect to the total amount of the coating solution. If the total amount of the solvent is excessively small, the viscosity of the coating solution increases and the coating stability decreases. On the other hand, when the total amount of the solvent is excessively large, the viscosity of the coating solution becomes low, and the white pigment may settle in the coating solution.
- the coating liquid may contain clay mineral particles.
- clay mineral particles include layered silicate minerals, imogolite, allophane and the like.
- the layered silicate mineral is preferably a clay mineral having a mica structure, a kaolinite structure, or a smectite structure.
- Layered silicate mineral particles tend to form a card house structure when the coating solution is left standing.
- the viscosity of the coating solution is greatly increased.
- the card house structure is apt to collapse when a certain pressure is applied, whereby the viscosity of the coating solution is lowered. That is, when the layered silicate mineral particles are contained in the coating solution, the viscosity of the coating solution increases in a stationary state, and the viscosity of the coating solution decreases when a certain pressure is applied.
- layered silicate minerals include natural or synthetic hectrite, saponite, stevensite, hydelite, montmorillonite, nontrinite, bentonite, laponite and other smectite clay minerals, and Na-type tetralithic fluoric mica.
- Non-swelling mica such as swellable mica genus clay minerals such as Li-type tetralithic fluorine mica, Na-type fluorine teniolite, Li-type fluorine teniolite, muscovite, phlogopite, fluorine phlogopite, sericite, potassium tetrasilicon mica Genus clay minerals, vermiculite and kaolinite, or mixtures thereof.
- swellable mica genus clay minerals such as Li-type tetralithic fluorine mica, Na-type fluorine teniolite, Li-type fluorine teniolite, muscovite, phlogopite, fluorine phlogopite, sericite, potassium tetrasilicon mica Genus clay minerals, 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 can increase the viscosity of the coating solution in a small amount.
- the content of clay mineral particles is preferably from 0.1 to 5% by mass, more preferably from 0.2 to 2% by mass, based on the total mass of the coating solution.
- the content of clay mineral particles is small, the viscosity of the coating solution is difficult to increase, and the white pigment tends to settle.
- the content of the clay mineral particles is excessive, the viscosity of the coating solution becomes too high, and the coating solution may not be discharged uniformly from the coating device.
- the surface of the clay mineral particles may be modified (surface treatment) with an ammonium salt or the like in consideration of compatibility with the solvent in the coating solution.
- the coating liquid may contain metal oxide fine particles having an average particle diameter of 5 nm or more and less than 100 nm.
- metal oxide fine particles When metal oxide fine particles are contained in the coating solution, irregularities are generated on the surface of the resulting reflective layer, and an anchor effect is exhibited between the reflective layer and the wavelength conversion layer. As a result, the adhesion between the reflective layer and the wavelength conversion layer is very good.
- metal oxide fine particles when metal oxide fine particles are contained in the coating solution, the stress generated in the film during polycondensation or drying of the polysiloxane is alleviated, and cracks are suppressed from occurring in the resulting reflective layer.
- the type of metal oxide fine particles is not particularly limited, but is relatively easy to obtain from the group of aluminum oxide, zirconium oxide, zinc oxide, tin oxide, yttrium oxide, cerium oxide, titanium oxide, copper oxide, and bismuth oxide. One or more selected metal oxide fine particles are preferable.
- the surface of the metal oxide fine particles may be treated with a silane coupling agent or a titanium coupling agent. By the surface treatment, the compatibility between the metal oxide fine particles and the polysiloxane or the solvent is increased.
- the average particle diameter of the metal oxide fine particles is preferably 5 to 100 nm, more preferably 5 to 80 nm, still more preferably 5 to 50 nm in consideration of the respective effects described above. By setting the average particle diameter in such a range, fine irregularities can be formed on the surface of the reflective layer, and the anchor effect described above can be obtained.
- the average particle diameter of the metal oxide fine particles can be measured, for example, by a Coulter counter method.
- the metal oxide fine particles may be porous, and the specific surface area is preferably 200 m 2 / g or more. When the metal oxide fine particles are porous, impurities are adsorbed in the porous voids.
- the amount of metal oxide fine particles contained in the coating solution is preferably 0.1 to 20% by mass, and preferably 5 to 10% by mass, based on the total mass of components other than the solvent contained in the coating solution. More preferred. If the amount of the metal oxide fine particles is too small, the above-described anchor effect is not sufficient. On the other hand, if the amount is too large, the amount of polysiloxane is relatively reduced, and the strength of the resulting reflective layer may be reduced.
- the coating liquid may contain inorganic particles having an average particle size of 100 nm or more and 100 ⁇ m or less. A gap generated at the interface between the white pigment particles and the clay mineral particles is filled with inorganic particles, and the viscosity of the coating liquid is increased.
- the inorganic particles include oxide particles such as silicon oxide, fluoride particles such as magnesium fluoride, or a mixture thereof.
- the inorganic particles are preferably oxide particles, and particularly preferably silicon oxide.
- the surface of the inorganic particles may be treated with a silane coupling agent or a titanium coupling agent. By the surface treatment, the compatibility between the inorganic particles and the polysiloxane or the solvent is increased.
- the content of inorganic particles in the coating solution is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass with respect to the total mass of the coating solution. This is because if the inorganic particles exceed 10% by mass, cracks are likely to occur during the formation of the reflective layer, and if it is less than 0.1%, the thickening effect of the coating solution is reduced.
- the average particle diameter of the inorganic particles is preferably 100 nm or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less from the viewpoint of filling a gap generated at the interface between the white pigment particles and the clay mineral particles.
- the average particle diameter of the inorganic particles can be measured, for example, by a Coulter counter method.
- the coating solution preferably further contains a silane coupling agent.
- silane coupling agent When the silane coupling agent is contained in the coating solution, the adhesion between the resulting reflective layer and the substrate is increased, and the durability of the LED device is improved.
- silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethy
- the amount of the silane coupling agent contained in the coating solution is preferably 0.5 to 10% by mass, and preferably 1 to 7% by mass, based on the total mass of components other than the solvent contained in the coating solution. More preferable. If the amount of the silane coupling agent is too small, the adhesion between the resulting reflective layer and the substrate is not sufficiently increased, and if it is too large, the heat resistance may be lowered.
- the coating solution may contain a metal alkoxide or metal chelate containing a metal element other than Si element.
- the metal alkoxide or metal chelate forms a metalloxane bond with the above-mentioned silane compound or a hydroxyl group present on the substrate surface during the formation of the reflective layer. Since the metalloxane bond is very strong, when the coating liquid contains a metal alkoxide or a metal chelate, the adhesion between the resulting reflective layer and the substrate is enhanced.
- a part of the metal alkoxide or metal chelate forms a nano-sized cluster composed of a metalloxane bond in the cured film (reflective layer) of the coating solution. Due to the photocatalytic effect of this cluster, it is possible to oxidize a highly corrosive sulfide gas or the like existing in the vicinity of the LED device and change it to a sulfur dioxide gas or the like having a low corrosivity.
- the metal element contained in the metal alkoxide or metal chelate is preferably a group 4 or group 13 metal element other than Si, and a compound represented by the following general formula (V) is preferable.
- M m + X n Y mn (V) M represents a group 4 or group 13 metal element (excluding Si), and m represents the valence of M (3 or 4).
- X represents a hydrolyzable group, and n represents the number of X groups (an integer of 2 or more and 4 or less). However, m ⁇ n. Y represents a monovalent organic group.
- 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 zirconium alkoxide or chelate 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. That is, the light from the LED element is hardly absorbed by the cured product.
- 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 and released during the formation of the reflective layer. Therefore, the compound produced after hydrolysis from the group represented by X 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 represented by the general formula (V) include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide and the like.
- metal alkoxide or metal chelate of zirconium represented by the general formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n- Examples include butoxide, zirconium tetra-i-butoxide, zirconium tetra-t-butoxide, zirconium dimethacrylate dibutoxide, dibutoxyzirconium bis (ethylacetoacetate) and the like.
- metal alkoxide or metal chelate of the titanium element represented by the general formula (V) include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium tetra Examples include methoxypropoxide, 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.
- 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 the National Institute of Science and Technology are also applicable to the present invention.
- the amount of metal alkoxide or metal chelate contained in the coating solution is preferably 1 to 10% by mass, more preferably 2 to 7 parts by mass, based on the total mass of components other than the solvent contained in the coating solution. preferable. If the content is too small, the effect of improving the adhesion cannot be obtained, and if the content is too large, the storage stability of the coating solution decreases.
- the preparation method of the coating liquid may be a method of mixing raw materials such as a white pigment, a silane compound, a solvent, metal oxide fine particles, inorganic particles, clay mineral particles, and a silane coupling agent in a lump.
- the raw materials may be mixed in advance and the mixed solution may be mixed later.
- either one or both of inorganic particles and clay mineral particles may be dispersed in a solvent and then mixed with the remaining components.
- the white pigment In order to enhance the dispersibility of the white pigment, it is preferable to disperse the white pigment at least once with the following apparatus.
- the white pigment When the white pigment is dispersed with the following apparatus, aggregation of the white pigment is reduced, and a denser and highly reflective coating film is obtained.
- Mixing / dispersing device is, for example, a magnetic stirrer, an ultrasonic dispersing device, a homogenizer, a stirring mill, a blade kneading stirring device, a thin-film swirling type dispersing device, a high-pressure impact dispersing device, a rotation and revolution mixer, etc. Can be done.
- All known devices can be used as the stirring device used for stirring the mixed solution.
- Ultra Turrax manufactured by IKA Japan
- TK homomixer manufactured by Primix
- TK pipeline homomixer manufactured by Primics
- TK Philmix manufactured by Primix
- Claremix manufactured by M Technique
- Medialess stirrers such as Claire SS5 (manufactured by M Technique), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko), Viscomill (manufactured by IMEX), Apex Mill (manufactured by Kotobuki Industries), Star mill (Ashizawa, manufactured by Finetech), DMPA / S Superflow (manufactured by Nihon Eirich), MP Mill (manufactured by Inoue Seisakusho), spike mill (manufactured by Inoue Seisakusho), Mighty mill (manufactured by In
- the viscosity of the coating solution is preferably more than 5 mPa ⁇ s and 500 mPa ⁇ s or less. If the viscosity of the coating solution is lower than the lower limit, the white pigment will settle and the concentration will easily change inside the coating apparatus. As a result, the coating stability is deteriorated. On the other hand, when it becomes higher than the upper limit, the pressure loss of the dispenser gradually decreases and the discharge amount increases. As a result, the coating stability tends to deteriorate.
- the coating method of the coating liquid is not particularly limited, and may be a coating method using a general coating device such as a dispenser, a jet dispenser, or a spray device. Moreover, the curing method and curing conditions of the coating solution are appropriately selected depending on the type of silane compound and the like. An example of the curing method is heat curing.
- the coating film is heated after the coating solution is applied.
- the heating temperature is preferably 20 to 200 ° C, more preferably 25 to 150 ° C. If the heating temperature is less than 20 ° C, the solvent in the coating film may not be sufficiently evaporated. On the other hand, if the temperature exceeds 200 ° C., the LED element may be adversely affected.
- the drying / curing time is preferably from 0.1 to 120 minutes, more preferably from 5 to 60 minutes from the viewpoint of production efficiency.
- FIG. 1 is a top view of an LED device 100A according to the embodiment.
- FIG. 2 is a cross-sectional view of the LED device 100A according to the embodiment.
- the LED element 2 will be described by taking a wire bonding type as an example.
- the LED device 100 ⁇ / b> A includes a substrate 1, an LED element 2 disposed on the substrate 1, and a reflective layer 21 disposed at least around the LED element 2 on the substrate 1. And the wavelength conversion layer 11 covering the LED element 2 and the reflective layer 21.
- the LED device 100A includes the reflective layer 21 that reflects the emitted light or the like of the LED element 2 to the light extraction surface side.
- the reflective layer 21 is obtained by heating and curing the coating liquid according to the above-described embodiment.
- 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 wavelength of 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.
- only one LED element 2 is arranged on the substrate 1, but a plurality of LED elements 2 may be arranged on the substrate 1.
- the reflective layer 21 is a layer that reflects the emitted light from the LED element 2 and the fluorescence emitted by the phosphor contained in the wavelength conversion layer 11 to the light extraction surface side of the LED device 100A. By providing the reflective layer 21, the amount of light extracted from the light extraction surface of the LED device 100A increases.
- the reflective layer 21 is formed on the surface of the substrate 1 at least outside the region where the LED elements 2 are arranged.
- the arrangement region of the LED element 2 refers to a light emitting surface of the LED element 2 and a connection part between the LED element 2 and the metal part (metal electrode part) 3. That is, the reflective layer 21 is formed in a region that does not hinder the emission of light from the LED element 2 and the connection between the LED element 2 and the metal part (metal electrode part) 3.
- the reflective layer 21 is formed in at least the peripheral region of the LED element 2.
- the reflective layer 21 is also formed on the inner wall surface 1b of the cavity. This is because when the reflective layer 21 is formed on the cavity inner wall surface 1b, the light traveling in the horizontal direction on the surface of the wavelength conversion layer 11 can be reflected by the reflective layer 21 and extracted.
- the reflection layer of the conventional LED device is generally metal plating.
- metal plating cannot be formed on the entire surface of the substrate in order to prevent electrical conduction. Therefore, there is a problem that light is absorbed by the substrate in the region where the metal plating is not formed.
- a reflection layer made of a resin layer in which light diffusion particles are dispersed has been proposed, but is easily deteriorated by light emitted from the LED element, heat, or the like. Therefore, when the LED device is used for a long period of time, the light extraction from the LED device may be deteriorated due to deterioration of the resin.
- the reflective layer 21 of the LED device 100A according to the embodiment is a layer in which a white pigment is bound with a binder (cured product of a silane compound), and electricity is not conducted. That is, in the LED device 100A according to the embodiment, the reflective layer 21 can be formed in an arbitrary region of the substrate 1 and can be formed in a gap between metal portions. Therefore, light can be efficiently extracted from the LED device 100A. Furthermore, the reflective layer 21 of the LED device 100 ⁇ / b> A according to the embodiment is difficult to be decomposed even when receiving heat or light from the LED element 2. Therefore, the light reflectivity of the reflective layer 21 does not change over a long period, and good light extraction performance is maintained for a long period.
- the thickness of the reflective layer 21 is preferably 5 to 30 ⁇ m, more preferably 5 to 20 ⁇ m. If the thickness of the reflective layer 21 exceeds 30 ⁇ m, cracks are likely to occur in the reflective layer 21. On the other hand, when the thickness of the reflective layer 21 is less than 5 ⁇ m, the light reflectivity of the reflective layer 21 is not sufficient, and the light extraction efficiency may not be increased.
- the amount of the binder contained in the reflective layer 21 is preferably 5 to 40% by mass, more preferably 10 to 30% by mass with respect to the total mass of the reflective layer 21. . If the amount of the binder is less than 5% by mass, the white pigment cannot be sufficiently retained by the binder, and pigment powder tends to be generated on the surface of the reflective layer 21. On the other hand, when the amount of the binder exceeds 40% by mass, the amount of the white pigment is relatively decreased, and the light reflectivity of the reflective layer 21 may not be sufficiently increased.
- the binder includes a polymer (cured product) of a trifunctional silane compound, a tetrafunctional silane compound, or a bifunctional silane compound, or a polymer of these oligomers (cured product).
- the amount of the component derived from the bifunctional silane compound (hereinafter also referred to as “bifunctional component”) with respect to the total amount of the component derived from the silane compound contained in the binder of the reflective layer 21 is less than 20 mol%. If the binder contains a bifunctional component, the reflective layer 21 is unlikely to crack. However, if the amount of the bifunctional component is 20 mol% or more, the ratio of the polar component composed of Si—O is reduced, so that the adhesion of the reflective layer 21 to the substrate 1 is reduced, and peeling easily occurs at these interfaces. Become.
- tetrafunctional component The molar ratio of the component derived from the tetrafunctional silane compound (hereinafter also referred to as “tetrafunctional component”) to the component derived from the trifunctional silane compound contained in the binder (hereinafter also referred to as “trifunctional component”) is 0 or more. 3 or less.
- the adhesion of the reflective layer 21 to the substrate 1 is improved.
- the molar ratio exceeds 3
- the degree of crosslinking of the silane compound polymer increases. Cracks are likely to occur in the reflective layer 21.
- the ratio of the bifunctional component, trifunctional component, and tetrafunctional component of the silane compound contained in the binder can be determined by the aforementioned solid Si-NMR.
- the configuration of the LED device 100A is not particularly limited, and various configurations can be taken.
- the LED element 2 is not limited to the wire bonding type, for example, as shown in FIG. 3, a metal part (metal electrode part) 3B disposed on the substrate 1 and a flip connected via the protruding electrode 5 It may be a chip type.
- the shape of the cavity shown in FIGS. 1 and 2 is not particularly limited, and may be, for example, a truncated pyramid shape, a columnar shape, a prismatic shape, or the like.
- substrate 1 may be flat form as FIG. 4, FIG. 5 shows, for example.
- the reflective layer 21 ⁇ / b> D may be formed not only in the peripheral region of the LED element 2 but also between the substrate 1 ⁇ / b> C and the LED element 2. That is, the LED element 2 may be disposed on the reflective layer 21D. Since the reflection layer 21D is also formed between the substrate 1C and the LED element 2, the reflection layer 21D reflects the light that goes around the back surface side of the LED element 2, so that the light extraction efficiency from the LED device 100D is increased. It is.
- silane compound solutions 1 to 10 Each component was mixed in the component ratio shown in Table 1 below to prepare silane compound solutions 1 to 10.
- Silane compound solution 1 Tetramethoxysilane 7.8% by mass, methyltrimethoxysilane 2.2% by mass, methanol 35% by mass, acetone 35% by mass, water 19.99% by mass and nitric acid 0.01% by mass were mixed. After stirring at 0 ° C. for 3 hours, the reaction was carried out at 26 ° C. with stirring for 3 days to obtain a silane compound solution 1 containing a polysiloxane oligomer. When the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 1800. Further, when solid Si-NMR was measured using a solid obtained by curing the solution at 150 ° C. as a sample, peaks corresponding to the Q component and the T component were observed. The ratio of T component, R4 / R3, was 3.2.
- Silane compound solution 2 A mixture of 7.5% by mass of tetramethoxysilane, 2.5% by mass of methyltrimethoxysilane, 35% by mass of methanol, 35% by mass of acetone, 19.99% by mass of water and 0.01% by mass of nitric acid, After stirring at 0 ° C. for 3 hours, the reaction was carried out with stirring at 26 ° C. for 3 days to obtain a silane compound solution 2 containing a polysiloxane oligomer. When the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 2000. Further, when solid Si-NMR was measured using a solid obtained by curing the solution at 150 ° C. as a sample, peaks corresponding to the Q component and the T component were observed. The T component ratio, R4 / R3, was 2.7.
- Silane compound solution 3 Silane compound solution 3 was obtained by mixing 20% by mass of methyltriethoxysilane, 60% by mass of ethanol, 19.99% by mass of water and 0.01% by mass of hydrochloric acid. When a solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C. as a sample, only a peak corresponding to the T component was observed.
- Silane compound solution 4 A mixture of 17% by mass of methyltriethoxysilane, 3% by mass of dimethyldiethoxysilane, 60% by mass of ethanol, 19.99% by mass of water and 0.01% by mass of hydrochloric acid was stirred at 28 ° C. for 2 days, and polysiloxane A silane compound solution 4 containing an oligomer was obtained.
- the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 2300.
- solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C. as a sample, and peaks corresponding to the T component and the D component were observed. When the area ratio of the peaks was calculated, the content rate of the D component in the total silicon compound was 17.5 mol%.
- silane compound solution 5 16% by weight of methyltriethoxysilane, 4% by weight of dimethyldiethoxysilane, 60% by weight of ethanol, 19.99% by weight of water and 0.01% by weight of hydrochloric acid were mixed and stirred for 2 days at 28 ° C.
- a silane compound solution 5 containing an oligomer was obtained.
- the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 2400.
- solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C. as a sample, and peaks corresponding to the T component and the D component were observed. When the area ratio of the peaks was calculated, the content ratio of the D component in the total silicon compound was 23.1 mol%.
- Silane compound solution 6 Tetraethoxysilane 4.3% by mass, methyltrimethoxysilane 4.3% by mass, dimethyldimethoxysilane 1.4% by mass, methanol 70% by mass, water 19.99% by mass and nitric acid 0.01% by mass were mixed.
- the mixture was stirred at 25 ° C. for 6 days to obtain a silane compound solution 6 containing a polysiloxane oligomer.
- the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 1600. Further, solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C.
- Silane compound solution 7 3.9% by mass of tetraethoxysilane, 3.9% by mass of methyltrimethoxysilane, 1.6% by mass of dimethyldimethoxysilane, 70% by mass of methanol, 19.99% by mass of water and 0.01% by mass of nitric acid were mixed. The mixture was stirred at 25 ° C. for 6 days to obtain a silane compound solution 7 containing a polysiloxane oligomer. When the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 1500.
- solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C. as a sample, and peaks corresponding to the Q component, the T component, and the D component were observed.
- the area ratio of the peaks was calculated, the ratio of the Q component to the T component, R4 / R3, was 0.9, and the content of the D component in the total silicon compound was 21.9 mol%.
- silane compound solution 8 Tetraethoxysilane 7.2% by mass, methyltrimethoxysilane 1.8% by mass, dimethyldimethoxysilane 1% by mass, methanol 70% by mass, water 19.99% by mass and nitric acid 0.01% by mass, The mixture was stirred at 25 ° C. for 6 days to obtain a silane compound solution 8 containing a polysiloxane oligomer.
- the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 1600. Further, solid Si-NMR measurement was performed using a solid obtained by curing the solution at 150 ° C.
- Silane compound solution 9 9.6% by weight of methyltrimethoxysilane, 10.7% by weight of tetramethoxysilane, 70.5% by weight of n-butanol / methyl-3-methoxypropionate (1: 1 solution), 9.19% by weight of water, Nitric acid 0.01% by mass was stirred for 3 hours to cause a hydrolysis reaction. Then, the reaction solution containing a siloxane polymer was obtained by making it react at 26 degreeC for 2 days. The mass average molecular weight (Mw) of the siloxane polymer in the reaction solution was 1600.
- Silane compound solution 10 15% by mass of methyltriethoxysilane was dissolved and mixed in 80% by mass of ethylene glycol dimethyl ether. Next, a mixture of 4.99% by mass of pure water and 0.01% by mass of concentrated nitric acid was added dropwise while slowly stirring, then stirred for about 3 hours, and then allowed to stand at room temperature for 6 days to obtain a solution. This solution was distilled under reduced pressure at 120 to 140 mmHg and 40 ° C. for 1 hour to obtain a silane compound solution 10. When the molecular weight of the polysiloxane oligomer in the obtained solution was measured by GPC, the weight average molecular weight in terms of polystyrene was 1800. Further, when solid Si-NMR was measured using a solid obtained by curing the solution at 150 ° C. as a sample, only a peak corresponding to the T component was observed.
- Silicia 470 Silica (Silicia 470, manufactured by Fuji Silysia Chemical) average particle size of 14 ⁇ m
- SP-1 Silica (Microbead SP-1, manufactured by JGC Catalysts & Chemicals) Average particle size 5 ⁇ m
- VM2270 Silica (VM-2270, manufactured by Dow Corning) average particle size 5-15 ⁇ m
- SS-50F Silica (Nip seal SS-50F, manufactured by Tosoh Silica) Average particle size 1.2 ⁇ m (Metal oxide fine particles)
- Alu-C Alumina (AEROXIDE Alu-C, manufactured by Nippon Aerosil) average primary particle size 13 nm
- ZR-210 ZrO 2 particles (TECNADIS-Zr-210, manufactured by TECNAN) Average particle size 10 to 15 nm Ti-
- Examples 1 to 21 and Comparative Examples 1 to 4 As shown in Tables 3 and 4, the white pigment, the silane compound solution, and the adjustment liquid were mixed at the mixing ratios shown in Tables 3 and 4 to prepare Samples 1 to 25. Specifically, the white pigment (A) and the silane compound solution (B) prepared by the above method were mixed, and mixed and dispersed by the method shown in Table 3 below. And the liquid mixture of a white pigment (A) and a silane compound solution (B) was mixed with the adjustment liquid (C) prepared by the above-mentioned method, and it mixed and disperse
- ⁇ Reflectance measurement> The coating solution was applied to a transparent 1 mm glass plate and cured by heat treatment at 150 ° C. for 1 hour to prepare a measurement sample having a reflective layer having a thickness of 20 ⁇ m. Then, the reflectance of each sample was measured with a spectrophotometer V-670 (manufactured by JASCO Corporation). The evaluation results were judged as follows. ⁇ : Reflectance at a wavelength of 500 nm was 95% or more ⁇ : Reflectance at a wavelength of 500 nm was 90% or more and less than 95% ⁇ : Reflectance at a wavelength of 500 nm was less than 90%
- ⁇ Tape peeling experiment> A coating solution was applied on a silver plate and cured by heat treatment at 150 ° C. for 1 hour to prepare a measurement sample having a reflective layer having a thickness of 20 ⁇ m.
- the work of attaching Nichiban cello tape (registered trademark) (24 mm) to the formed reflective layer and immediately peeling it off was repeated 20 times. And the state of the reflective layer was observed with the microscope for every operation
- X The peeling of the reflective layer occurred at the time of 15 times of work.
- Table 4 shows the following. It was found that when the ratio of the bifunctional silane compound exceeds 20% by mass, the adhesion to the substrate is lowered (Comparative Examples 2 and 3 using the silane compound solutions 5 and 7). From the comparison between Comparative Examples 1 and 4 using silane compound solutions 1 and 8 and Examples 1 to 21 using other silane compound solutions, the value of tetrafunctional silane compound / 3 functional silane compound exceeds 3. It was found that cracks occurred during film formation.
- Example 15 by comparing Example 15 and Example 21, it was found that by preliminarily polymerizing and oligomerizing the silane compound, shrinkage during heat curing was suppressed and cracks were less likely to occur.
- Example 14 From the comparison between Example 14 and Examples 1 to 12 and 15 to 21, it was found that the reflectance was lowered when the white pigment content was low.
- Example 13 From comparison between Example 13 and Examples 1 to 12 and 15 to 21, it was found that if the white pigment content was too high, the amount of binder was insufficient and powder was likely to come out from the surface.
Abstract
Description
しかし、金属メッキからなるリフレクタは、電気の導通を防ぐため、基板全面に形成することができない。そのため、リフレクタが形成されていない領域では、基板に光が吸収されてしまう、という問題があった。
1.白色顔料と、シラン化合物と、溶媒と、を含む塗布液であって、前記シラン化合物総量中の2官能シラン化合物の比率をR2(モル%)、3官能シラン化合物の比率をR3(モル%)、4官能シラン化合物の比率をR4(モル%)、としたときに、下記式1及び式2
0≦R2<20 (式1)
0≦R4/R3≦3 (式2)
の両条件を満たす、塗布液。
3.前記塗布液が、前記白色顔料とは別に、平均粒径5nm以上100nm未満の金属酸化物微粒子、平均粒径100nm以上100μm以下の無機粒子、粘土鉱物粒子、からなる群から選ばれる少なくとも1種をさらに含有する、上記1または2に記載の塗布液。
4.前記粘土鉱物粒子が、層状ケイ酸塩鉱物、イモゴライト、アロフェン、からなる群から選ばれる少なくとも1種である、上記3に記載の塗布液。
5.前記塗布液がシランカップリング剤をさらに含有する、上記1~4のいずれか1つに記載の塗布液。
7.前記白色顔料が、酸化チタン、酸化アルミニウム、硫酸バリウム、酸化亜鉛、窒化ホウ素からなる群から選ばれる少なくとも1種である、上記1~6のいずれか1つに記載の塗布液。
8.前記塗布液の粘度が5mPa・sを超え、500mPa・s以下である、上記1~7のいずれか1つに記載の塗布液。
9.前記塗布液の加熱硬化後の固形分中の白色顔料の濃度が60質量%以上、95質量%以下である、上記1~8のいずれか1つに記載の塗布液。
0≦R2<20 (式1)
0≦R4/R3≦3 (式2)
の両条件を満たす、塗布液を加熱硬化して得られる、LED装置。
11.前記反射層は、前記LED素子の配置領域を除く前記基板上に配置されている、上記10に記載のLED装置。
12.前記反射層は、前記基板と前記LED素子の間に形成されている上記10に記載のLED装置。
実施形態に係る塗布液には、(A)白色顔料と、(B)シラン化合物と、(C)溶媒と、が含まれる。塗布液には、平均粒径5nm以上100nm未満の金属酸化物微粒子や、平均粒径100nm以上100μm以下の無機粒子、粘土鉱物粒子、シランカップリング剤等がさらに含まれてもよい。
0≦R2<20 (式1)
0≦R4/R3≦3 (式2)
の両条件が満たされる。
4官能シラン化合物の重合体は、SiO2・nH2Oの示性式で表されるが、構造的には、ケイ素原子Siの四面体の各頂点に酸素原子Oが結合され、これらの酸素原子Oに更にケイ素原子Siが結合してネット状に広がった構造を有する。
(白色顔料)
塗布液に含まれる白色顔料は、反射性の高い粒子であれば、特に制限されない。
白色顔料は、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸マグネシウム、硫酸バリウム、硫酸カルシウム、酸化亜鉛、酸化マグネシウム、酸化カルシウム、酸化チタン、酸化アルミニウム、酸化ジルコニウム、硫化亜鉛、水酸化アルミニウム、窒化ホウ素、窒化アルミニウム、チタン酸カリウム、チタン酸バリウム、チタン酸アルミニウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、ヒドロキシアパタイト、等から選ばれる少なくとも一種でありうる。中でも酸化チタン、酸化アルミニウム、硫酸バリウム、酸化亜鉛及び窒化ホウ素の群より選ばれる1種又は2種以上の組合せからなる混合物が好ましい。
塗布液中に含まれるシラン化合物は、前述のように、2官能シラン化合物、3官能シラン化合物、または4官能シラン化合物でありうる。シラン化合物は、モノマーの状態であってもよいが;これらの重合物(オリゴマー)であってもよい。シラン化合物が、あらかじめ数個~数十個のモノマーが重合したオリゴマーであると、塗布液を硬化させたときの収縮が少なくなり、クラックが発生しにくくなる。
3官能シラン化合物の例には、下記一般式(III)で表される化合物が含まれる。
R1Si(OR2)3 (III)
上記一般式中、R2は、それぞれ独立にアルキル基またはフェニル基を表し、好ましくは炭素数1~5のアルキル基、またはフェニル基を表す。また、R1は、水素原子またはアルキル基を表す。
4官能シラン化合物の例には、下記一般式(IV)で表される化合物が含まれる。
Si(OR3)4 …(IV)
上記一般式(IV)中、R3はそれぞれ独立にアルキル基またはフェニル基を表し、好ましくは炭素数1~5のアルキル基、またはフェニル基を表す。
2官能シラン化合物の例には、下記一般式(II)で表される化合物が含まれる。
R4 2Si(OR5)2 (II)
上記一般式(II)中、R5はそれぞれ独立にアルキル基またはフェニル基を表し、好ましくは炭素数1~5のアルキル基、またはフェニル基を表す。また、R4は水素原子またはアルキル基を表す。
シラン化合物のオリゴマーは、2官能シラン化合物、3官能シラン化合物、及び4官能シラン化合物を所望の比率で混合し、酸触媒、水、溶媒の存在下で反応させて得られる。オリゴマーの分子量は、反応時間、温度、水の濃度等により調整される。
塗布液に含まれる溶媒は、シラン化合物と相溶性があり、白色顔料等を均一に分散可能であれば特に制限されないが、1価のアルコールおよび2価以上の多価アルコールの少なくともいずれか一方が含まれることが好ましい。1価のアルコールが含まれると、塗布液が濡れ広がりやすくなり、塗布し易くなる。一方、多価アルコールが含まれると、塗布液の粘度が高まりやすく、白色顔料が沈降し難くなる。
塗布液には、粘土鉱物粒子が含まれてもよい。塗布液に粘土鉱物粒子が含まれると、塗布液の粘度が高まり、白色顔料の沈降が抑制される。粘土鉱物粒子の例には、層状ケイ酸塩鉱物、イモゴライト、アロフェン等が含まれる。層状ケイ酸塩鉱物は、雲母構造、カオリナイト構造、またはスメクタイト構造を有する粘土鉱物が好ましい。
塗布液には、平均粒径が5nm以上100nm未満の金属酸化物微粒子が含まれてもよい。塗布液中に金属酸化物微粒子が含まれると、得られる反射層表面に凹凸が生じ、反射層と波長変換層との間にアンカー効果が発現する。その結果、反射層と波長変換層との密着性が非常に良好となる。また、塗布液に金属酸化物微粒子が含まれると、ポリシロキサンの重縮合時や乾燥時に膜に生じる応力が緩和され、得られる反射層にクラックが生じることが抑制される。
塗布液には、平均粒径100nm以上100μm以下の無機粒子が含まれてもよい。白色顔料粒子と粘土鉱物粒子との界面に生じる隙間が無機粒子によって埋まり、塗布液の粘度が高まる。
無機粒子の表面は、シランカップリング剤やチタンカップリング剤で処理されていてもよい。表面処理によって、無機粒子と、ポリシロキサンや溶媒との相溶性が高まる。
塗布液には、さらにシランカップリング剤が含まれることが好ましい。塗布液にシランカップリング剤が含まれると、得られる反射層と基板との密着性が高まり、LED装置の耐久性が向上する。
塗布液には、Si元素以外の金属元素を含む金属アルコキシドまたは金属キレートが含まれてもよい。金属アルコキシドまたは金属キレートは、反射層成膜時に、前述のシラン化合物や、基板表面に存在する水酸基と、メタロキサン結合を形成する。当該メタロキサン結合は非常に強固であるため、塗布液に金属アルコキシドまたは金属キレートが含まれると、得られる反射層と基材との密着性が高まる。
Mm+XnYm-n (V)
一般式(V)中、Mは4族または13族の金属元素(Siを除く)を表し、mはMの価数(3または4)を表す。Xは加水分解性基を表し、nはX基の数(2以上4以下の整数)を表す。ただし、m≧nである。Yは1価の有機基を表す。
塗布液の調液方法は、白色顔料、シラン化合物、溶媒、金属酸化物微粒子、無機粒子、粘土鉱物粒子、シランカップリング剤等の原料を、一括して混合する方法であってもよく、複数の原料を予め混合して、後から混合液同士を混合する方法であってもよい。
混合液の撹拌、分散は、例えば、マグネチックスターラー、超音波分散装置、ホモジナイザー、撹拌ミル、ブレード混練撹拌装置、薄膜旋回型分散機、高圧衝撃式分散装置、自転公転ミキサーなどで行うことができる。
塗布液の粘度は、5mPa・sを超え、500mPa・s以下であることが好ましい。塗布液の粘度が上記下限値よりも低いと、白色顔料が沈降し、塗布装置内部で濃度が変化しやすくなる。その結果、塗布安定性が悪くなる。一方、上限値よりも高くなると、ディスペンサの圧損が徐々に小さくなり吐出量が多くなる。その結果、塗布安定性が悪くなりやすい。
塗布液の塗布方法は、特に制限されず、例えばディスペンサ、ジェットディスペンサ、スプレー装置等の一般的な塗布装置による塗布方法でありうる。また、塗布液の硬化方法や硬化条件は、シラン化合物の種類等によって適宜選択する。硬化方法の一例として、加熱硬化が挙げられる。
以下に、塗布液の硬化物からなる反射層を含むLED装置について説明する。
図1は、実施形態に係るLED装置100Aの上面図を示す。図2は、実施形態に係るLED装置100Aの断面図を示す。ここでは、LED素子2として、ワイヤボンディング型のものを例に挙げて説明する。
反射層21は、LED素子2の配置領域を除く基板1上に配置されている。反射層21は、基板1の円錐台状のキャビティ(凹部)の底面1aから側面1bに連続して、すり鉢状に配置されている。反射層21は、上面視において、波長変換層11の外周に波長変換層11と同心円状のリング状に形成されている。
基板1は、絶縁性及び耐熱性を有することが好ましく、セラミック樹脂や耐熱性樹脂からなることが好ましい。耐熱性樹脂の例には、液晶ポリマー、ポリフェニレンスルフィド、芳香族ナイロン、エポキシ樹脂、硬質シリコーンレジン、ポリフタル酸アミド等が含まれる。
LED素子2が出射する光の波長は特に制限されない。LED素子2は、例えば青色光(420nm~485nm程度の光)を発する素子であってもよく、紫外光を発する素子であってもよい。
反射層21は、LED素子2からの出射光や、波長変換層11に含まれる蛍光体が発する蛍光を、LED装置100Aの光取り出し面側に反射する層である。反射層21が配設されることで、LED装置100Aの光取り出し面から取り出される光量が増加する。
上記のように、本発明は実施形態によって記載したが、この開示の一部をなす論述及び図面はこの発明を限定するものであると理解すべきではない。この開示から当業者には様々な代替実施の形態、実施例及び運用技術が明らかとなろう。
さらに基板1は、例えば図4、図5に示されるように、平板状であってもよい。
下記表1に示される成分比で各成分を混合し、シラン化合物溶液1~10を調製した。
テトラメトキシシラン7.8質量%と、メチルトリメトキシシラン2.2質量%とメタノール35質量%とアセトン35質量%と水19.99質量%と硝酸0.01質量%とを混合して、23℃で3時間撹拌した後、26℃で3日間撹拌しながら反応させ、ポリシロキサンオリゴマーを含有するシラン化合物溶液1を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は1800であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分と、T成分に対応するピークがみられ、それぞれの面積比から、Q成分とT成分の比、R4/R3は、3.2であった。
テトラメトキシシラン7.5質量%と、メチルトリメトキシシラン2.5質量%とメタノール35質量%とアセトン35質量%と水19.99質量%と硝酸0.01質量%とを混合して、23℃で3時間撹拌した後、26℃で3日間撹拌しながら反応させ、ポリシロキサンオリゴマーを含有するシラン化合物溶液2を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は2000であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分と、T成分に対応するピークがみられ、それぞれの面積比から、Q成分とT成分の比、R4/R3は、2.7であった。
メチルトリエトキシシラン20質量%とエタノール60質量%と水19.99質量%と塩酸0.01質量%とを混合して、シラン化合物溶液3を得た。この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、T成分に対応するピークのみがみられた。
メチルトリエトキシシラン17質量%とジメチルジエトキシシラン3質量%とエタノール60質量%と水19.99質量%と塩酸0.01質量%とを混合して、28℃で2日間撹拌し、ポリシロキサンオリゴマーを含有するシラン化合物溶液4を得た。
得られた溶液中の、ポロシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は2300であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、T成分と、D成分に対応するピークがみられた。ピークの面積比を計算したところ、全ケイ素化合物中のD成分の含有率は17.5モル%であった。
メチルトリエトキシシラン16質量%とジメチルジエトキシシラン4質量%とエタノール60質量%と水19.99質量%と塩酸0.01質量%とを混合して、28℃で2日間撹拌し、ポリシロキサンオリゴマーを含有するシラン化合物溶液5を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は2400であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、T成分と、D成分に対応するピークがみられた。ピークの面積比を計算したところ、全ケイ素化合物中のD成分の含有率は23.1モル%であった。
テトラエトキシシラン4.3質量%とメチルトリメトキシシラン4.3質量%とジメチルジメトキシシラン1.4質量%とメタノール70質量%と水19.99質量%と硝酸0.01質量%とを混合して、25℃で6日間撹拌し、ポリシロキサンオリゴマーを含有するシラン化合物溶液6を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は1600であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分とT成分とD成分に対応するピークがみられた。ピークの面積比を計算したところ、Q成分とT成分の比、R4/R3は、0.9であり、全ケイ素化合物中のD成分の含有率は18.2モル%であった。
テトラエトキシシラン3.9質量%とメチルトリメトキシシラン3.9質量%とジメチルジメトキシシラン1.6質量%とメタノール70質量%と水19.99質量%と硝酸0.01質量%とを混合して、25℃で6日間撹拌し、ポリシロキサンオリゴマーを含有するシラン化合物溶液7を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は1500であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分とT成分とD成分に対応するピークがみられた。ピークの面積比を計算したところ、Q成分とT成分の比、R4/R3は、0.9であり、全ケイ素化合物中のD成分の含有率は21.9モル%であった。
テトラエトキシシラン7.2質量%とメチルトリメトキシシラン1.8質量%とジメチルジメトキシシラン1質量%とメタノール70質量%と水19.99質量%と硝酸0.01質量%とを混合して、25℃で6日間撹拌し、ポリシロキサンオリゴマーを含有するシラン化合物溶液8を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は1600であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分とT成分とD成分に対応するピークがみられた。ピークの面積比を計算したところ、Q成分とT成分の比、R4/R3は、3.4であり、全ケイ素化合物中のD成分の含有率は14.8モル%であった。
メチルトリメトキシシラン9.6質量%、テトラメトキシシラン10.7質量%、n-ブタノール/メチル-3-メトキシプロピオネート(1:1溶液)70.5質量%、水9.19質量%、硝酸0.01質量%を3時間撹拌して加水分解反応させた。
その後、26℃で2日間反応させることにより、シロキサンポリマーを含む反応溶液を得た。反応溶液中のシロキサンポリマーの質量平均分子量(Mw)は1600であった。
上記反応溶液400gに、n-ブタノール100gおよびメチル-3-メトキシプロピオネート100gを混合し、シリカ系被膜形成用塗布液を得たシラン化合物溶液9を得た。
この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、Q成分と、T成分に対応するピークがみられ、それぞれの面積比から、Q成分とT成分の比、R4/R3は、1.0であった。
メチルトリエトキシシラン15質量%をエチレングリコールジメチルエーテル80質量%に溶解しかき混ぜた。次いで、純水4.99質量%と濃硝酸0.01質量%を混合したものを、ゆっくりかき混ぜながら滴下した後、約3時間かき混ぜ、その後室温で6日間静置させて溶液を得た。この溶液を120~140mmHg、40℃にて1時間減圧蒸留し、シラン化合物溶液10を得た。
得られた溶液中の、ポリシロキサンオリゴマーの分子量をGPCにより測定したところ、ポリスチレン換算の重量平均分子量は1800であった。
また、この溶液を150℃で硬化させた固体を試料として、固体Si-NMRの測定を行ったところ、T成分に対応するピークのみがみられた。
表2に示に示される成分比で各成分を配合した。当該混合液を表2に示される分散方法で混合して、調整液1~12を作製した。表2及び表3中の略号は以下の成分を表す。
BD:1,3-ブタンジオール
PG:プロピレングリコール
IPA:イソプロピルアルコール
EtOH:エタノール
(無機粒子)
サイリシア470:シリカ(サイリシア470、富士シリシア化学製)平均粒径14μm
SP-1:シリカ (マイクロビードSP-1、日揮触媒化成製)平均粒径5μm
VM2270:シリカ(VM-2270、ダウコーニング製)平均粒径5~15μm
SS-50F:シリカ(ニップシールSS-50F、東ソー・シリカ製)平均粒径1.2μm
(金属酸化物微粒子)
Alu-C:アルミナ(AEROXIDE Alu-C、日本アエロジル製)平均一次粒径13nm
ZR-210:ZrO2粒子(TECNADIS-Zr-210、TECNAN社製)平均粒径10~15nm
Ti-210:TiO2粒子(TECNADIS-TI-210、TECNAN社製)平均粒径10~15nm
(粘土鉱物粒子)
MK-100:合成雲母(ミクロマイカMK-100、コープケミカル製)
ME-100:合成雲母(ソマシフME-100、コープケミカル製)
SWN:スメクタイト(ルーセンタイトSWN、コープケミカル社製)
クニピアF:モンモリロナイト(クニピアF、クニミネ工業製)
(シランカップリング剤)
KBM-403:3-グリシドキシプロピルトリメトキシシラン(KBM-403、信越シリコーン製)
KBM-903:3-アミノプロピルトリメトキシシラン(KBM-903、信越シリコーン製)
KBM-802:3-メルカプトプロピルメチルジメトキシシラン(KBM-802、信越シリコーン製)
KBE-846:ビス(トリエトキシシリルプロピル)テトラスルフィド(KBE-846、信越シリコーン製)
(白色顔料)
酸化チタン:CR-93 石原産業製
酸化チタン:CR-95 石原産業製
酸化アルミニウム:HD-11 ニッカトー製
硫酸バリウム:NFJ-3-1999 山西物産製
窒化ホウ素:AP-100S MARUKA製
表3及び表4に示されるように、白色顔料と、シラン化合物溶液と、調整液とを、表3及び表4に記載の混合比で混合し、サンプル1~サンプル25を調製した。
具体的には、白色顔料(A)と上述の方法で調製されたシラン化合物溶液(B)とを混合し、下記表3に示される方法で混合・分散した。そして、上述の方法で調製された調整液(C)に、白色顔料(A)及びシラン化合物溶液(B)の混合液を混合し、下記表3に示される方法で混合・分散した。
<粘度評価>
塗布液の粘度は、振動式粘度計VISCOMATE MODEL VM-10A(セコニック社製)を用いて測定した。測定温度は25℃とし、振動子を液体に浸漬してから、1分後の測定値を使用した。
ディスペンサーのシリンジに塗布液を充填し、一定の条件下において、連続で10回のディスペンスを行い、滴下された液の合計質量を求めた。続いて、シリンジをそのまま保持した状態で、10分毎に同様の操作を行い、4時間後に同条件下において、連続で10回のディスペンスを行い、滴下された液の合計質量を求めた。
下記式により、質量変化率を算出した。
最初の10回で滴下された塗布液の合計質量をA、
4時間後の10回で滴下された塗布液の合計質量をBとしたとき、
質量変化率=((B-A)/A)×100%
塗布量安定性を以下のように分類した。
○:質量変化率が3%未満であった。
△:質量変化率が3%以上であった。
銀板上に塗布液を塗布し、150℃、1時間の熱処理により、硬化させて、厚さ20μmの反射層を備えた測定サンプルを作製した。このときの反射層の状態を目視で観察し、以下のように判断した。
○:反射層にクラックがみられなかった
△:反射層に僅かなクラックが発生したが、反射層の欠落はみられなかった
×:反射層にクラックが発生し、反射層の一部が基板から欠落した
透明な1mmのガラス板に塗布液を塗布し、150℃、1時間の熱処理により、硬化させて、厚さ20μmの反射層を備えた測定サンプルを作製した。そして、分光光度計V-670(日本分光株式会社製)により、各サンプルの反射率を測定した。評価結果の判断は、以下のように行った。
○:波長500nmにおける反射率が95%以上であった
△:波長500nmにおける反射率が90%以上、95%未満であった
×: 波長500nmにおける反射率が90%未満であった
銀板上に塗布液を塗布し、150℃、1時間の熱処理により、硬化させて、厚さ20μmの反射層を備えた測定サンプルを作製した。形成された反射層にニチバン製セロテープ(登録商標)(24mm)を貼り付け、直ちに剥がす作業を20回繰り返して行った。そして、各回の作業毎に反射層の状態を顕微鏡により観察し、以下のように判断した。
◎:20回作業後も反射層の剥離がみられず、テープの表面に何も付着しなかった。
○:15回作業後は剥離がみられなかったが、20回作業後には、僅かに剥離がみられた。
△:剥離は生じなかったが、1回目の作業後に、テープの表面に、白色顔料の粉が僅かに付着した。
×:15回作業時点で反射層の剥離が発生していた。
2官能シラン化合物の比率が20質量%を超えると、基材への密着性が低下することが分かった(シラン化合物溶液5及び7を用いた比較例2及び3)。
シラン化合物溶液1,8を用いた比較例1,4と、その他のシラン化合物溶液を用いた実施例1~21との対比より、4官能シラン化合物/3官能シラン化合物の値が3を超えると、成膜時にクラックが発生することが分かった。
また実施例7と、実施例2~6、8~21との対比より、塗布液の粘度が高すぎると塗布安定性が悪くなることが分かった。これはディスペンサの圧損が徐々に小さくなり吐出量が多くなったためと考えられる。
2 LED素子
11、11C、11D 波長変換層
21、21C、21D 反射層
100A、100B、100C、100D LED装置
Claims (12)
- 白色顔料と、シラン化合物と、溶媒と、を含む塗布液であって、
前記シラン化合物総量中の2官能シラン化合物の比率をR2(モル%)、3官能シラン化合物の比率をR3(モル%)、4官能シラン化合物の比率をR4(モル%)、としたときに、下記式1及び式2
0≦R2<20 (式1)
0≦R4/R3≦3 (式2)
の両条件を満たす、塗布液。 - 前記2官能シラン化合物、前記3官能シラン化合物、前記4官能シラン化合物からなる群から選ばれる少なくとも1種が、あらかじめ重合されている、請求項1に記載の塗布液。
- 前記塗布液が、前記白色顔料とは別に、平均粒径5nm以上100nm未満の金属酸化物微粒子、平均粒径100nm以上100μm以下の無機粒子、粘土鉱物粒子、からなる群から選ばれる少なくとも1種をさらに含有する、請求項1または2に記載の塗布液。
- 前記粘土鉱物粒子が、層状ケイ酸塩鉱物、イモゴライト、アロフェン、からなる群から選ばれる少なくとも1種である、請求項3に記載の塗布液。
- 前記塗布液がシランカップリング剤をさらに含有する、請求項1~4のいずれか1項に記載の塗布液。
- 前記塗布液中の溶媒が、1価のアルコールおよび2価以上の多価アルコールの少なくとも一方を含有する、請求項1~5のいずれか1項に記載の塗布液。
- 前記白色顔料が、酸化チタン、酸化アルミニウム、硫酸バリウム、酸化亜鉛、窒化ホウ素からなる群から選ばれる少なくとも1種である、請求項1~6のいずれか1項に記載の塗布液。
- 前記塗布液の粘度が5mPa・sを超え、500mPa・s以下である、請求項1~7のいずれか1項に記載の塗布液。
- 前記塗布液の加熱硬化後の固形分中の白色顔料の濃度が60質量%以上、95質量%以下である、請求項1~8のいずれか1項に記載の塗布液。
- 基板と、前記基板上に配置されたLED素子と、前記基板上の前記LED素子の少なくとも周囲に配置された反射層と、前記LED素子及び前記反射層を覆う波長変換層とを有するLED装置であって、
前記反射層は、白色顔料、シラン化合物、溶媒を含み、かつ前記シラン化合物総量中の2官能シラン化合物の比率をR2(モル%)、3官能シラン化合物の比率をR3(モル%)、4官能シラン化合物の比率をR4(モル%)、としたときに、下記式1及び式2
0≦R2<20 (式1)
0≦R4/R3≦3 (式2)
の両条件を満たす、塗布液を加熱硬化して得られる、LED装置。 - 前記反射層は、前記LED素子の配置領域を除く前記基板上に配置されている、請求項10に記載のLED装置。
- 前記反射層は、前記基板と前記LED素子の間に形成されている、請求項10に記載のLED装置。
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US14/650,785 US20150307717A1 (en) | 2012-12-27 | 2013-12-27 | Coating liquid and led device including reflective layer made of product of curing thereof |
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JP2014141626A (ja) * | 2012-12-28 | 2014-08-07 | Konica Minolta Inc | 塗布液、反射膜、反射シート、太陽電池モジュール、led照明装置および実装用基板 |
WO2016047745A1 (ja) * | 2014-09-26 | 2016-03-31 | コニカミノルタ株式会社 | 塗布液、それを用いたled装置の製造方法およびled装置 |
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JP6459880B2 (ja) | 2015-09-30 | 2019-01-30 | 日亜化学工業株式会社 | 発光装置及びその製造方法 |
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JP2022001630A (ja) * | 2019-09-04 | 2022-01-06 | 株式会社リコー | 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク、組成物収容容器、2次元又は3次元の像の形成方法及び形成装置、硬化物並びに加飾体 |
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