JP2014160713A - Led device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an LED device in which chromaticity of outgoing beams is uniform even when observed from any direction.SOLUTION: An LED device manufacturing method comprises: a process of preparing an LED element in which an LED chip is mounted on a substrate; a process of coating a phosphor dispersion liquid which contains phosphor particles, swelling particles and water and has viscosity of not less than 800 mPas and not more than 500000 mPas on a light-emitting surface and lateral faces of the LED chip by a dispenser and dehydrating the phosphor dispersion liquid; and a process of further coating a composition containing a translucent ceramic material which contains a translucent ceramic material and a solvent on the light-emitting surface and the lateral faces of the LED chip and curing the translucent ceramic material to obtain a wavelength conversion layer in which the phosphor particles and the swelling particles are dispersed in translucent ceramic.

Description

  The present invention relates to a method for manufacturing an LED device.

  In recent years, white LED devices have been developed in which a phosphor such as a YAG phosphor is arranged in the vicinity of a gallium nitride (GaN) blue LED (Light Emitting Diode) chip. In the white LED device, the blue light emitted from the blue LED chip and the yellow light emitted from the phosphor in response to the blue light are mixed to obtain white light. A white LED device in which various phosphors are arranged in the vicinity of the blue LED chip has also been developed. In the white LED device, white light is obtained by mixing blue light emitted from the blue LED chip and red light, green light, or the like emitted from the phosphor upon receiving the blue light. Such white LED devices are widely applied as alternatives to conventional fluorescent lamps and incandescent lamps, and further improvement in light extraction efficiency and longer life are required.

  In a general white LED device, an LED chip and its mounting portion are covered with a wavelength conversion layer in which phosphor particles are dispersed in a transparent resin. However, since the specific gravity of the phosphor particles is higher than the specific gravity of the transparent resin; the phosphor particles settle when the wavelength conversion layer is formed. Therefore, it has been difficult to make the concentration of the phosphor particles uniform in the wavelength conversion layer.

  Therefore, as a method for making the concentration of the phosphor particles in the wavelength conversion layer uniform, it has been proposed to disperse the phosphor particles in a silicone resin having a high viscosity (Patent Document 1). It has also been proposed to add a lipophilic compound obtained by adding an organic cation to a layered clay compound to the composition (Patent Document 2). It has also been proposed to cover the surface of an LED chip with an adhesive transparent resin and to attach phosphor particles to the transparent resin (Patent Document 3).

  According to these methods, the concentration of the phosphor particles can be made uniform to some extent. However, since the LED chip is covered with the resin, there is a possibility that the resin is deteriorated and colored by heat from the LED chip.

  On the other hand, it has also been proposed to disperse phosphor particles in a translucent ceramic (Patent Document 4). In this technique, a metal alkoxide or a ceramic precursor in which phosphor particles are dispersed is applied to the LED chip surface and fired. However, metal alkoxides and translucent ceramic precursors have low viscosity, and phosphor particles tend to settle in the composition. Therefore, the phosphor particles settle in the apparatus for applying the composition, and when a plurality of LED devices are produced, the number of phosphor particles contained in each LED device varies; that is, the light is emitted from each LED device. There was a problem that the chromaticity of the light to be different.

  For such a problem, a method of separately applying phosphor particles and a binder component (such as a translucent ceramic precursor) has been proposed (Patent Document 5).

JP 2002-314142 A JP 2004-153109 A US Pat. No. 7,157,745 Japanese Patent No. 3307316 International Publication No. 2012/023425

  In the method of Patent Document 5, after applying a dispersion of phosphor particles, a binder component (such as a translucent ceramic precursor) is applied. Therefore, it is easy to arrange a desired amount of phosphor particles on the surface of the LED chip; even when a plurality of LED devices are manufactured, the chromaticity of light emitted from each LED device is uniform.

  However, since the fluidity of the phosphor dispersion liquid is high, it is difficult to attach a sufficient amount of phosphor particles to the peripheral portion of the light emitting surface (upper surface) of the LED chip or the side surface of the LED chip. As a result, there is a problem that the chromaticity of the emitted light is likely to be different between when the LED device is observed from the front and when observed from an oblique direction.

  The present invention has been made in view of the above-described problems. That is, an object of the present invention is to provide a method for manufacturing an LED device in which the chromaticity of emitted light is uniform even when observed from any direction.

That is, the first of the present invention relates to the following LED device manufacturing method.
[1] A step of preparing an LED element in which an LED chip is mounted on a substrate, and a phosphor dispersion liquid containing phosphor particles, swellable particles, and water and having a viscosity of 800 mPa · s to 500,000 mPa · s. Applying to the light emitting surface and side surfaces of the LED chip with a dispenser and drying, and further applying a light transmissive ceramic material-containing composition containing a light transmissive ceramic material and a solvent to the light emitting surface and side surfaces of the LED chip. And curing the translucent ceramic material to obtain a wavelength conversion layer in which the phosphor particles and the swellable particles are dispersed in the translucent ceramic.

[2] The phosphor dispersion contains a solvent other than water, and the amount of water contained in the phosphor dispersion is 67% by mass or more based on the total amount of water and solvent contained in the phosphor dispersion. The manufacturing method of the LED device according to [1].
[3] The amount of the swellable particles contained in the phosphor dispersion liquid is 0.3% by mass or more and 70% by mass or less with respect to the total solid content of the phosphor dispersion liquid. 2] The manufacturing method of the LED device of description.
[4] The method for manufacturing an LED device according to any one of [1] to [3], wherein the swellable particles are layered silicate minerals.

[5] The method for manufacturing an LED device according to any one of [1] to [4], wherein the translucent ceramic material is an organic polysiloxane compound.
[6] The method for manufacturing an LED device according to any one of [1] to [5], wherein the translucent ceramic material-containing composition further includes inorganic fine particles.
[7] The method for manufacturing an LED device according to any one of [1] to [6], wherein the solvent of the translucent ceramic material-containing composition contains water.
[8] The method for manufacturing an LED device according to any one of [1] to [7], wherein the translucent ceramic material-containing composition further includes an organometallic compound of a bivalent or higher metal other than Si.

That is, the second of the present invention relates to the following phosphor dispersion liquid for dispensing application.
[9] A phosphor dispersion for dispensing application, comprising phosphor particles, swellable particles, and water, and having a viscosity of 800 mPa · s to 500,000 mPa · s.

  The LED device obtained by the method of the present invention has uniform chromaticity of the emitted light regardless of the angle. Further, according to the method of the present invention, even when a plurality of LED devices are manufactured, the chromaticity of light emitted from each LED device is uniform.

It is a schematic sectional drawing which shows an example of the LED apparatus of this invention. In the manufacturing method of the LED device of this invention, it is the schematic of the dispenser for apply | coating a fluorescent substance dispersion liquid. In the manufacturing method of the LED device of this invention, it is the schematic of the spray apparatus for apply | coating a translucent ceramic material containing composition.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

1. About LED device The structure of the LED device manufactured with the manufacturing method of this invention is shown in the schematic sectional drawing of FIG. An LED device 100 manufactured by the present invention includes an LED element in which an LED chip 3 is mounted on a substrate 1 and a wavelength conversion layer 5.

1-1. LED Element The LED element shown in FIG. 1 includes a substrate (package) 1, a metal part 2, an LED chip 3, and a protruding electrode 4 that connects the metal part 2 and the LED chip 3.

  The substrate 1 can be, for example, a liquid crystal polymer or ceramic, but the material is not particularly limited as long as it has insulating properties and heat resistance. Also, the shape is not particularly limited, and for example, it may be concave as shown in FIG. 1 or may be flat.

  The emission wavelength of the LED chip 3 is not particularly limited. The LED chip 3 may emit blue light (light of about 420 nm to 485 nm) or may emit ultraviolet light, for example.

  The configuration of the LED chip 3 is not particularly limited. When the emission color of the LED chip 3 is blue, the LED chip 3 includes an n-GaN compound semiconductor layer (cladding layer), an InGaN compound semiconductor layer (light emitting layer), and a p-GaN compound semiconductor layer (cladding). Layer) and a transparent electrode layer. The LED chip 3 may have a light emitting surface of 200 to 300 μm × 200 to 300 μm, for example. The height of the LED chip 3 is usually about 50 to 200 μm.

  The metal part 2 can be a wiring made of a metal such as silver. In the LED device 100, the metal part 2 may function as a reflecting plate that reflects light emitted from the LED chip 3. The metal part 2 and the LED chip 3 may be connected via the protruding electrode 4 as shown in FIG. 1 or may be connected via a wire or the like. A mode in which the metal part 2 and the LED chip 3 are connected through the protruding electrodes 4 is referred to as a flip chip type, and a mode in which the metal part 2 and the LED chip 3 are connected through a wire is referred to as a wire bonding type.

  In the LED device 100 shown in FIG. 1, only one LED chip 3 is disposed on the substrate 1; however, a plurality of LED chips 3 may be disposed on the substrate 1.

1-2. Wavelength Conversion Layer The wavelength conversion layer 5 is a layer in which phosphor particles are dispersed in a translucent ceramic, and is a layer formed on at least the light emitting surface (upper surface) and side surfaces of the LED chip 3. The wavelength conversion layer 5 receives light (excitation light) emitted from the LED element (LED chip 3) and emits fluorescence. By mixing the excitation light and the fluorescence, the light from the LED device 100 becomes a desired color. For example, when the light emitted from the LED chip 3 is blue and the fluorescence emitted from the phosphor particles contained in the wavelength conversion layer 5 is yellow, the light from the LED device 100 is white.

  The amount of the phosphor particles contained in the wavelength conversion layer 5 is preferably 10 to 98% by mass, more preferably 30 to 98% by mass, still more preferably 60 to 98% by mass, and more. It is particularly preferably 70 to 98% by mass. The higher the concentration of the phosphor particles contained in the wavelength conversion layer 5, the better. If the concentration of the phosphor particles is high, the strength of the wavelength conversion layer 5 tends to increase. However, if the content ratio of the translucent ceramic is too small, the phosphor particles may not be sufficiently retained.

  The thickness of the wavelength conversion layer 5 formed on the light emitting surface of the LED chip 3 is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 200 μm, and still more preferably 10 to 100 μm. is there. When the thickness of the wavelength conversion layer 5 is less than 5 μm, the amount of phosphor particles is reduced, and there is a possibility that sufficient fluorescence cannot be obtained. On the other hand, if the thickness of the wavelength conversion layer 5 exceeds 200 μm, the concentration of the phosphor particles in the wavelength conversion layer 5 becomes excessively low, so that the concentration of the phosphor particles may not be uniform. The thickness of the wavelength conversion layer 5 formed on the light emitting surface of the LED chip 3 means the maximum thickness of the wavelength conversion layer 5 formed on the light emitting surface of the LED chip 3. The thickness of the wavelength conversion layer 5 formed on the light emitting surface of the LED chip 3 is measured with a laser holo gauge.

  The minimum thickness of the wavelength conversion layer 5 formed on the side surface of the LED chip 3 is preferably 5 μm or more, more preferably 10 μm or more. When the thickness of the wavelength conversion layer formed on the side surface of the LED chip 3 is 5 μm or more, the difference between the chromaticity of light when the LED device is observed from an oblique direction and the light when the LED device is observed from the front. Becomes smaller. The thickness of the wavelength conversion layer 5 formed on the side surface of the LED chip 3 is also measured with a laser holo gauge.

2. Manufacturing method of LED device The manufacturing method of the LED device of the present invention includes the following three steps.
1) Step of preparing an LED element in which an LED chip is mounted on a substrate 2) A phosphor dispersion liquid containing phosphor particles, swellable particles, and water is applied to the top and side surfaces of the LED chip with a dispenser and dried. Step 3) Step of applying a light-transmitting ceramic material-containing composition containing a light-transmitting ceramic material and a solvent to the upper and side surfaces of the LED chip and curing the light-transmitting ceramic material 2) Step and 3) Step Thus, a wavelength conversion layer in which phosphor particles are dispersed in a translucent ceramic is obtained.

  As described above, since the conventional phosphor dispersion liquid has high fluidity, it is difficult to form a sufficiently thick coating on the peripheral portion of the light emitting surface (upper surface) of the LED chip and the side surface of the LED chip. Therefore, the amount of phosphor particles attached in these regions is reduced. As a result, the light emitted from the LED chip and the fluorescence emitted from the phosphor are sufficiently mixed in the front of the LED device to obtain light of desired chromaticity; An amount of fluorescence cannot be obtained, and light with a desired chromaticity cannot be obtained.

  On the other hand, in the present invention, since a phosphor dispersion liquid having a relatively high viscosity is applied, a desired amount of phosphor particles can be adhered to the peripheral edge and the side surface of the upper surface of the LED chip. At this time, since the phosphor dispersion liquid is applied by a dispenser, the phosphor dispersion liquid can be reliably attached to the side surface of the LED chip. Therefore, in the LED device obtained by the present invention, the chromaticity of the emitted light is uniform no matter which direction is observed.

2-1. LED element preparation process In an LED element preparation process, the LED element by which the LED chip was mounted on the board | substrate is prepared. For example, it may be a step of preparing a substrate on which a metal part (wiring) is arranged and mounting an LED chip on the substrate. The LED chip mounting method may be the same as a conventionally known method.

2-2. Phosphor dispersion liquid application process A phosphor dispersion liquid is applied to the light emitting surface and the side surface of the LED chip of the LED element with a dispenser. The phosphor dispersion liquid contains phosphor particles, swellable particles, and water (solvent). The phosphor dispersion liquid may contain a solvent other than water, inorganic particles, or the like, if necessary.

  The viscosity of the phosphor dispersion liquid is preferably 800 mPa · s or more and 500,000 mPa · s, more preferably 850 to 100,000 mPa · s, and further preferably 850 to 50000 mPa · s. When the viscosity of the phosphor dispersion liquid is 800 mPa · s or more, the fluidity of the phosphor dispersion liquid after coating is low, and a layer with a uniform thickness is formed on the side surface of the LED chip and the peripheral edge of the upper surface of the LED chip. It's easy to do. The viscosity of the phosphor dispersion is adjusted by the amount of swellable particles contained in the phosphor dispersion, the amount of water, the type of solvent other than water, and the like. The viscosity of the phosphor dispersion is measured at 25 ° C. with a vibration viscometer.

2-2-1. Phosphor Particles The phosphor particles contained in the phosphor dispersion liquid may be anything that is excited by the light emitted from the LED chip and emits fluorescence having a wavelength different from that of the light emitted from the LED chip. For example, examples of phosphor particles that emit yellow fluorescence include YAG (yttrium, aluminum, garnet) phosphors. The YAG phosphor receives blue light (wavelength 420 nm to 485 nm) emitted from the blue LED chip, and emits yellow fluorescence (wavelength 550 nm to 650 nm).

  The phosphor particles are, for example, 1) A suitable amount of flux (fluoride such as ammonium fluoride) is mixed with a mixed raw material having a predetermined composition and pressed to form a molded body. 2) The obtained molded body 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 mixed raw material having a predetermined composition is obtained by sufficiently mixing oxides such as Y, Gd, Ce, Sm, Al, La, and Ga, or compounds that easily become oxides at high temperatures in a stoichiometric ratio. . Moreover, the mixed raw material which has a predetermined composition mixes the solution which dissolved 1) the rare earth elements of Y, Gd, Ce, and Sm in the acid in stoichiometric ratio, and oxalic acid, and obtains a coprecipitation oxide. 2) It can also be obtained by mixing this coprecipitated oxide with aluminum oxide or gallium oxide.

  The type of the phosphor is not limited to the YAG phosphor, and may be another phosphor such as a non-garnet phosphor that does not contain Ce.

  The average particle diameter of the phosphor particles is preferably 1 μm to 50 μm, and more preferably 10 μm or less. The larger the particle size of the phosphor particles, the higher the light emission efficiency (wavelength conversion efficiency). On the other hand, when the particle diameter of the phosphor particles is too large, a gap generated between the phosphor particles becomes large. Thereby, the intensity | strength of a wavelength conversion layer may fall. The average particle diameter of the phosphor particles can be measured, for example, by a Coulter counter method.

  The amount of the phosphor particles contained in the phosphor dispersion is preferably more than 10% by mass and 99% by mass or less, more preferably 20 to 97% by mass with respect to the total solid content of the phosphor dispersion. . When the concentration of the phosphor particles is less than 10% by mass, the amount of fluorescence obtained from the wavelength conversion layer decreases, and the chromaticity of light emitted from the LED device may not fall within a desired range. On the other hand, when the amount of the phosphor particles exceeds 99% by mass, the amount of the swellable particles is relatively small, and the phosphor particles may settle in the phosphor dispersion liquid.

2-2-2. Swellable particles Swellable particles are contained in the phosphor dispersion. When swellable particles are contained in the phosphor dispersion liquid, the viscosity of the phosphor dispersion liquid increases, and sedimentation of the phosphor particles is suppressed. Furthermore, the strength of the obtained wavelength conversion layer is increased. Examples of swellable particles include layered silicate minerals, imogolite, allophane and the like. Since the layered silicate mineral has a flat plate shape, the film strength of the wavelength conversion layer is increased. The layered silicate mineral is preferably a swellable clay mineral having a mica structure, a kaolinite structure, or a smectite structure, and particularly preferably a swellable clay mineral having a smectite structure rich in swelling properties. Layered silicate minerals that can be swellable particles form a card house structure in the phosphor dispersion. Therefore, the viscosity increases only by being contained in a small amount in the phosphor dispersion.

  Examples of layered silicate minerals include natural or synthetic hectrite, saponite, stevensite, hydelite, montmorillonite, nontrinite, bentonite and other smectite clay minerals, Na-type tetralithic fluoric mica, Li-type tetrasilicate. Examples include swellable mica genus clay minerals such as thick fluorine mica, Na type fluorine teniolite, Li type fluorine teniolite, vermiculite and kaolinite, or a mixture thereof.

  Examples of commercially available swellable 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.), Somasif (synthetic swellable mica manufactured by Coop Chemical Co., Ltd.), SWN (manufactured by Coop Chemical Co., Ltd.) Synthetic smectite), SWF (synthetic smectite manufactured by Coop Chemical Co., Ltd.) and the like.

  The swellable particles may be modified (surface treatment) with a surface ammonium salt or the like. When the surface of the swellable particles is modified, the swellable particles are easily dispersed in the phosphor dispersion liquid.

  The amount of the swellable particles contained in the phosphor dispersion is preferably 0.3 to 70% by mass, more preferably 0.3 to 65% by mass with respect to the total mass of the solid content of the phosphor dispersion. More preferably, it is 0.3-60 mass%, Most preferably, it is 0.3-20 mass%. When the concentration of the swellable particles is less than 0.3% by mass, the viscosity of the phosphor dispersion liquid is not sufficiently increased. On the other hand, when the amount of the swellable particles exceeds 70% by mass, the amount of the phosphor particles is relatively small and sufficient fluorescence may not be obtained. Moreover, when the amount of the swellable particles is excessive, the strength of the obtained wavelength conversion layer may be lowered. Note that the viscosity of the phosphor dispersion does not increase as the proportion of the swellable particles in the phosphor dispersion increases. The viscosity is determined by the content ratio with other components such as the amount of water (solvent) contained in the phosphor dispersion and the amount of phosphor particles.

2-2-3. Water and a solvent other than water The phosphor dispersion liquid contains water, and may contain a solvent other than water as necessary. However, the amount of water is preferably 67% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass with respect to the total amount of water and solvent contained in the phosphor dispersion liquid. % Or more. When 67 mass% or more of water is contained, the above-mentioned swellable particles are sufficiently swollen, so that the viscosity of the phosphor dispersion liquid tends to increase. However, when impurities are contained in water, the swellable particles are difficult to swell. Therefore, the water contained in the phosphor dispersion liquid is preferably pure water.

  The total amount of water and the solvent other than water contained in the phosphor dispersion is usually preferably 5 to 98% by mass, more preferably 10 to 95% by mass with respect to the total amount of the phosphor dispersion. Yes, more preferably 15 to 90% by mass. When the total amount of water and solvent contained in the phosphor dispersion liquid is less than 5% by mass, it becomes difficult to apply the phosphor dispersion liquid from the dispenser. On the other hand, if the total amount of water and solvent exceeds 98% by mass, the amount of phosphor particles is relatively reduced. As a result, in order to obtain a wavelength conversion layer having a desired chromaticity, it is necessary to apply a large amount of the phosphor dispersion liquid, which decreases the manufacturing efficiency of the LED device.

  Solvents other than water are not particularly limited as long as they have excellent compatibility with water, and may be monovalent alcohols, divalent or higher polyhydric alcohols, and the like. Examples of monohydric alcohols include methanol, ethanol, propanol, butanol and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, and the like.

  The boiling point of the solvent is preferably 150 ° C. or higher. When a solvent having a boiling point of 150 ° C. or higher is contained, the storage stability of the phosphor dispersion liquid is improved, and the phosphor dispersion liquid can be stably discharged from the dispenser. On the other hand, the boiling point of the solvent is preferably 250 ° C. or lower from the viewpoint of the drying property of the phosphor dispersion.

2-2-4. Inorganic particles The phosphor dispersion liquid may contain inorganic particles. When inorganic particles are contained in the phosphor dispersion liquid, the viscosity of the phosphor dispersion liquid tends to increase. Further, in the obtained wavelength conversion layer, the gap generated at the interface between the phosphor particles and the swellable particles is filled with inorganic particles, and the strength of the wavelength conversion layer is likely to increase.

  Examples of the inorganic particles include oxide particles such as silicon oxide, titanium oxide, zinc oxide, aluminum oxide, and zirconium oxide. The surface of the inorganic particles may be treated with a silane coupling agent or a titanium coupling agent. The surface treatment increases the adhesion between the inorganic particles and the translucent ceramic. The inorganic particles can be porous inorganic particles having a large specific surface area.

  The particle size distribution of the inorganic particles is not particularly limited. It may be distributed over a wide range or may be distributed over a relatively narrow range. In addition, as for the particle size of an inorganic particle, it is preferable that the center particle size of a primary particle size is 0.001 micrometer or more and 50 micrometers or less, and it is more preferable that it is smaller than the primary particle diameter of fluorescent substance particle. Moreover, it is preferable that the particle diameter of an inorganic particle is the range smaller than the thickness of the wavelength conversion layer to form. The surface smoothness of the wavelength conversion layer is increased. The average particle diameter of the inorganic particles is measured by, for example, a Coulter counter method.

  The amount of inorganic particles contained in the phosphor dispersion is preferably 0.5 to 70% by mass, more preferably 0.5 to 65% by mass, and still more preferably based on the total solid content of the phosphor dispersion. 1.0-60 mass%. The intensity | strength of the wavelength conversion layer obtained as the density | concentration of an inorganic particle is less than 0.5 mass% does not fully increase. Moreover, the handleability at the time of application | coating of a fluorescent substance dispersion liquid deteriorates. On the other hand, if the amount of inorganic particles exceeds 70% by mass, the amount of phosphor particles is relatively small, and sufficient fluorescence cannot be obtained. Furthermore, light is easily scattered by the inorganic particles, and the light extraction efficiency from the LED device is reduced.

  Note that the viscosity does not increase as the proportion of inorganic particles in the phosphor dispersion increases. The viscosity is determined by the content ratio with other components such as the amount of solvent in the phosphor dispersion and the content of phosphor particles.

2-2-5. Method for preparing phosphor dispersion The phosphor dispersion is prepared by mixing and stirring phosphor particles, swellable particles, water, inorganic particles, a solvent, and the like. Stirring is performed by, for example, a stirring mill, a blade kneading stirring device, a thin film swirl type disperser or the like.

  As described above, when the swellable particles are sufficiently swollen with water, the viscosity of the phosphor dispersion liquid tends to increase. Therefore, it is preferable to adjust the viscosity of the phosphor dispersion liquid by adjusting the stirring time, the shear rate during stirring, and the like.

2-2-6. Method of applying phosphor dispersion liquid As described above, the phosphor dispersion liquid is applied to at least the light emitting surface (upper surface) and side surfaces of the LED chip with a dispenser. At this time, the phosphor dispersion liquid may be applied not only to the light emitting surface and the side surface of the LED chip but also to the metal part or the substrate.

  In addition, when the electrode is exposed on the surface of the LED element, if a wavelength conversion layer is formed on the electrode, current may not be supplied. Therefore, the phosphor dispersion liquid may be applied while protecting the electrodes and the like. The method for protecting the electrode is not particularly limited, and for example, a plate mask may be disposed on the electrode. Moreover, you may coat | cover an electrode with resin etc. The resin is removed after the light-transmitting ceramic material is cured in a light-transmitting ceramic material-containing composition application step described later.

  After applying the phosphor dispersion liquid, it is preferable to dry the solvent in the phosphor dispersion liquid. The temperature at which the solvent in the phosphor dispersion liquid is dried is usually 20 to 200 ° C, and preferably 25 to 150 ° C. If the drying temperature is less than 20 ° C., the phosphor dispersion liquid may not be sufficiently dried. On the other hand, if the drying temperature exceeds 200 ° C., the LED chip may be adversely affected. The drying time of the phosphor dispersion liquid is usually 0.1 to 30 minutes, preferably 0.1 to 15 minutes, from the viewpoint of production efficiency.

  The thickness of the coating film after drying the phosphor dispersion liquid is preferably 5 to 200 μm, more preferably 10 to 200 μm, and still more preferably 10 to 100 μm. When the thickness of the coating film containing the phosphor particles is too thin, the thickness of the obtained wavelength conversion layer becomes thin. The thickness of the coating film means the maximum thickness of the film formed on the light emitting surface of the LED chip. The thickness is measured with a laser holo gauge.

  The dispenser for applying the phosphor dispersion liquid may be a conventionally known dispenser. For example, a jet dispenser that does not have a needle (hollow needle) in the discharge part of the phosphor dispersion liquid may be used. However, from the viewpoint of surely applying the phosphor dispersion liquid to a desired region, a needle-type dispenser having a needle (hollow needle) at the discharge portion of the phosphor dispersion liquid is more preferable.

  An example of a needle type dispenser is shown in FIG. The phosphor dispersion liquid 205 is supplied from the coating liquid tank 201 to the valve 203 through the connecting pipe 202. The phosphor dispersion liquid 205 supplied to the bulb 203 is discharged from the needle 204 at the tip of the bulb in accordance with the air pressure or the like applied to the bulb 203 and applied to the object to be applied (light emitting surface or side surface of the LED chip 3). The

  The angle between the needle 204 and the LED element can also be adjusted. When the needle 204 is applied to the side surface of the LED chip 3, as shown in FIG. It is preferable to incline with respect to. The angle of the needle 204 with respect to the substrate 1 is preferably in the range of 0 to 70 ° when the vertical direction from the substrate 1 is 0 °.

  The material of the needle 204 of the needle-type dispenser is not limited as long as it is made of a material that does not corrode with the phosphor dispersion liquid 205. For example, the needle 204 may be made of a metal such as stainless steel or may be made of a resin. The needle 204 is preferably surface-treated with a fluorine compound. When the needle 204 is surface-treated, the phosphor dispersion liquid hardly adheres to the outer peripheral surface of the needle 204, and the amount of the phosphor dispersion liquid discharged from the dispenser 200 tends to be uniform.

  The method for treating the surface of the needle 204 with the fluorine compound is not particularly limited, and may be, for example, a method of immersing the needle 204 in the fluorine compound. At this time, the fluorine compound may be heated. The fluorine compound that surface-treats the needle 204 is preferably incompatible with the phosphor dispersion. Examples of the fluorine compound include a fluorine-based silane coupling agent, a fluororesin, and the like. From the viewpoint of easy treatment, a fluorine-based silane coupling agent is preferable. The inner diameter of the needle 204 is usually preferably 50 to 1000 μm, more preferably 100 to 800 μm.

  The air pressure in the bulb 203 when discharging the phosphor dispersion liquid is preferably 0.02 to 0.5 MPa, more preferably 0.05 to 0.4 MPa. The amount of the phosphor dispersion liquid applied to the LED element is adjusted by the discharge time from the needle 204.

2-3. Translucent ceramic material-containing composition application step After the phosphor dispersion liquid application step described above, the translucent ceramic material-containing composition is further applied to the light emitting surface (upper surface) and side surfaces of the LED chip. Then, the translucent ceramic material is cured to obtain a wavelength conversion layer in which phosphor particles and swellable particles are dispersed in the translucent ceramic. That is, the above-described phosphor particles and swellable particles are bound and fixed with a translucent ceramic.

  The translucent ceramic material-containing composition includes a translucent ceramic material and a solvent, and if necessary, inorganic fine particles, an organometallic compound of a metal having a valence of 2 or more (excluding Si), a silane coupling agent, and the like. included.

2-3-1. About the translucent ceramic material The translucent ceramic material may be a compound that becomes a translucent ceramic (preferably a glass ceramic) by a sol-gel reaction. Examples of the translucent ceramic material include metal alkoxide, metal acetylacetonate, metal carboxylate, polysilazane oligomer and the like, and metal alkoxide is preferable from the viewpoint of good reactivity.

  The metal alkoxide may be an alkoxide of various metals, but is preferably alkoxysilane or aryloxysilane from the viewpoint of the stability of the translucent ceramic obtained and the ease of production.

  The translucent ceramic material, alkoxysilane or aryloxysilane, may be a monomolecular compound (monomer) such as tetraethoxysilane, but is preferably an organic polysiloxane compound (oligomer). The organic polysiloxane compound is a compound in which a silane compound is bonded to a chain or cyclic siloxane. A method for preparing the organic polysiloxane compound will be described later.

  The mass average molecular weight of the organic polysiloxane compound is preferably 1000 to 3000, more preferably 1200 to 2700, and further preferably 1500 to 2000. When the mass average molecular weight of the organic polysiloxane compound is less than 1000, the viscosity of the translucent ceramic material-containing composition is lowered, and the translucent ceramic material-containing composition may be repelled on the LED element. On the other hand, when the mass average molecular weight exceeds 3000, the viscosity of the translucent ceramic material-containing composition increases, and the translucent ceramic material-containing composition may not be uniformly applied. The mass average molecular weight is a value (polystyrene conversion) measured by gel permeation chromatography.

  When the translucent ceramic material is an organic polysiloxane compound, the amount of the organic polysiloxane compound contained in the translucent ceramic material-containing composition is 1 to 40 mass with respect to the total mass of the translucent ceramic material-containing composition. %, And more preferably 2 to 30% by mass. When the amount of the organic polysiloxane compound is less than 1% by mass, the viscosity of the translucent ceramic material-containing composition may become too low. On the other hand, when the amount of the organic polysiloxane compound exceeds 40% by mass, the viscosity of the translucent ceramic material-containing composition becomes excessively high, and the translucent ceramic material-containing composition may not be uniformly applied.

Another preferred example of the translucent ceramic material is a polysilazane oligomer. The polysilazane oligomer is a compound represented by the general formula (I): (R ¹ R ² SiNR ³ ) _n . In general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a vinyl group, or a cycloalkyl group. However, at least one of R ¹ , R ² , and R ³ is a hydrogen atom, and preferably all are hydrogen atoms. In general formula (I), n represents an integer of 1 to 60. The molecular shape of the polysilazane oligomer may be any shape, for example, linear or cyclic.

  When the translucent ceramic material is a polysilazane oligomer, the amount of the polysilazane oligomer contained in the translucent ceramic material-containing composition is preferably large, but when the concentration of the polysilazane oligomer is high, the translucent ceramic material-containing composition The storage stability of may become low. Then, it is preferable that the quantity of a polysilazane oligomer is 5-50 mass% with respect to the translucent ceramic material containing composition total mass.

2-3-2. About a solvent The solvent is contained in the translucent ceramic material containing composition. Any solvent may be used as long as it can dissolve or uniformly disperse the above-described translucent ceramic material. Examples of the solvent 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 glycol, diethylene glycol, Polyhydric alcohols such as 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 mono Propyl ether, diethylene glycol monobutyl ether, propylene glycol mono Monoethers of polyhydric alcohols such as chill ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, or monoacets thereof; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Polyhydric alcohol ethers in which all hydroxyl groups of polyhydric alcohols such as ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether are all alkyl etherified; methyl acetate, ethyl acetate, Such as butyl acetate Ethers; include the like; ketones such as acetone, methyl ethyl ketone and methyl isoamyl ketone. In the translucent ceramic material-containing composition, only one type of solvent may be included, or two or more types of solvents may be included.

  The solvent preferably contains water. It is preferable that the quantity of water is 3-15 mass% with respect to the translucent ceramic material containing composition total mass, More preferably, it is 5-10 mass%. When the translucent ceramic material is an organic polysiloxane compound, the water content is preferably 10 to 120 parts by mass and more preferably 80 to 100 parts by mass with respect to 100 parts by mass of the organic polysiloxane compound. preferable. If the amount of water contained in the translucent ceramic material-containing composition is too small, the organic polysiloxane compound may not be sufficiently hydrolyzed when the translucent ceramic material is cured. On the other hand, if the amount of water contained in the translucent ceramic material-containing composition is excessive, hydrolysis or the like occurs during storage of the translucent ceramic material-containing composition, and the translucent ceramic material-containing composition becomes a gel. There is a risk of becoming.

  It is also preferable that the solvent includes an organic solvent having a boiling point of 150 ° C. or higher (for example, ethylene glycol, propylene glycol, etc.). The translucent ceramic material-containing composition containing an organic solvent having a boiling point of 150 ° C. or higher has high storage stability. In addition, since the solvent hardly evaporates in the coating apparatus, the translucent ceramic material-containing composition can be stably applied from the coating apparatus.

  On the other hand, the boiling point of the solvent contained in the translucent ceramic material-containing composition is preferably 250 ° C. or lower. When the boiling point of the solvent exceeds 250 ° C., it takes time to dry the translucent ceramic material-containing composition.

2-3-3. Inorganic fine particles The light-transmitting ceramic material-containing composition may contain inorganic fine particles. When inorganic fine particles are contained in the translucent ceramic material-containing composition, when the translucent ceramic material-containing composition is cured, stress generated in the film is relaxed, and cracks are hardly generated in the wavelength conversion layer.

The inorganic fine particles are preferably porous particles, and the specific surface area is preferably 200 m ² / g or more. When the inorganic fine particles are porous, the solvent enters the porous voids, and the viscosity of the translucent ceramic material-containing composition increases. However, the viscosity of the translucent ceramic material-containing composition is not simply determined by the amount of inorganic fine particles, but also varies depending on the ratio of the inorganic fine particles and the solvent, the amount of other components, and the like.

  The average primary particle size of the inorganic fine particles is preferably 5 to 100 nm, more preferably 5 to 80 nm, and still more preferably 5 to 50 nm. When the average primary particle size of the inorganic fine particles is within such a range, the above-described crack suppressing effect and refractive index improving effect are easily obtained. The average primary particle size of the inorganic fine particles is measured by a Coulter counter method.

  Examples of the inorganic fine particles include zirconium oxide, titanium oxide, tin oxide, cerium oxide, niobium oxide, and zinc oxide. Among these, since the refractive index is high, the inorganic fine particles are preferably zirconium oxide fine particles. The translucent ceramic material-containing composition may contain only one kind of inorganic fine particles or two or more kinds.

  The inorganic fine particles may have a surface treated with a silane coupling agent or a titanium coupling agent. The surface-treated inorganic fine particles are easily dispersed uniformly in the translucent ceramic material-containing composition.

  The amount of the inorganic fine particles in the translucent ceramic material-containing composition is preferably 10 to 60% by mass, more preferably 15 to 45% by mass, based on the total solid content of the translucent ceramic material-containing composition. More preferably, it is 20-30 mass%. When the amount of the inorganic fine particles is too small, the above-described crack suppressing effect is not enhanced. On the other hand, when the amount of the inorganic fine particles is too large, the amount of the translucent ceramic material (binder) is relatively decreased, and the strength of the wavelength conversion layer may be decreased.

2-3-4. About Metal Compound The translucent ceramic material-containing composition may contain a bivalent or higher metal (excluding Si) organometallic compound. The organometallic compound may be a metal alkoxide or metal chelate of a divalent or higher valent metal element other than Si element. The metal alkoxide or metal chelate forms a metalloxane bond with a translucent ceramic material or a hydroxyl group present on the surface of the LED element when the wavelength conversion layer is formed. The metalloxane bond is very strong. Therefore, when a metal alkoxide or a metal chelate is contained in the translucent ceramic material-containing composition, adhesion between the wavelength conversion layer and the LED element increases.

The metal element contained in the metal alkoxide or metal chelate is preferably a group 4 or group 13 metal element other than the Si element, and a compound represented by the following general formula (II) is preferable.
M ^{m +} X _n Y _m−n (II)
In general formula (II), M represents a group 4 or group 13 metal element, 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.

  In the general formula (II), 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 general LED chip emission wavelength region (especially blue light (wavelength 420 to 485 nm)). The light emitted from the LED chip is difficult to be absorbed.

  In the general formula (II), the hydrolyzable group represented by X may be a group that is hydrolyzed with water to form a hydroxyl group. Preferable examples of 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. In general formula (II), all the groups represented by X may be the same group or different groups.

  The hydrolyzable group represented by X is hydrolyzed and released. Therefore, the group produced after hydrolysis is neutral and is preferably a light boiling group. 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.

  In the general formula (II), the monovalent organic group represented by Y may be a monovalent organic group contained in a general silane coupling agent. Specifically, an aliphatic group, an alicyclic group, an aromatic group, an oil 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. Examples of the substituent 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.

  Specific examples of the metal alkoxide or metal chelate of aluminum represented by the general formula (II) include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide and the like.

  Specific examples of the metal alkoxide or metal chelate of zirconium represented by the general formula (II) 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.

  Specific examples of the metal alkoxide or metal chelate of the titanium element represented by the general formula (II) 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.

  However, the metal alkoxide or metal chelate exemplified above is a part of a commercially available organometallic alkoxide or metal chelate that is easily available. 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 (metal compound) contained in the translucent ceramic material-containing composition is preferably 5 to 100 parts by mass, more preferably 100 parts by mass of the translucent ceramic material. It is 8-40 mass parts, More preferably, it is 10-15 mass parts. When the amount of the metal alkoxide or metal chelate is less than 5 parts by mass, the above-described adhesion improving effect and the like cannot be obtained. On the other hand, when the amount of the metal alkoxide or metal chelate exceeds 100 parts by mass, the preservability of the translucent ceramic material-containing composition decreases.

2-3-5. About a silane coupling agent When a silane coupling agent is contained in a translucent ceramic material containing composition, the adhesiveness of a wavelength conversion layer and an LED element (especially metal part) will increase. The kind of silane coupling agent is not particularly limited, and may be a known silane coupling agent.

  Silane coupling agents include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, and vinyltrichlorosilane; γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4- Epoxy cyclohexyl) Epoxy group-containing silane coupling agents such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and the like Group-containing silane coupling agents; mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; 4-aminobutyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) amino Amino group-containing silane coupling agents such as propyltrimethoxysilane; styryl group-containing silane coupling agents such as styrylethyltrimethoxysilane; cyano group-containing silane coupling agents such as β-cyanoethyltriethoxysilane; , Methyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, trimethylethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane Trimethylchlorosilane, methyltrichlorosilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichloro Silane, dimethyldichlorosilane, trifluoropropyl trimethoxy silane, diphenyl dichlorosilane, and phenyl triacetoxy silane, can be a compound which they are partially condensed.

  It is preferable that 0.01-10 mass% is contained in the solid content of a translucent ceramic material containing composition, and it is preferable that a silane coupling agent is contained 0.1-5.0 mass%. When the silane coupling agent is contained in an amount of 0.01% by mass or more, the adhesion between the wavelength conversion layer and the LED element is likely to increase.

2-3-6. About reaction accelerator The reaction accelerator may be contained in the translucent ceramic material containing composition. The reaction accelerator is particularly preferably contained when the translucent ceramic material is a polysilazane oligomer. The reaction accelerator may be an acid or a base. Specific examples of reaction accelerators include bases such as triethylamine, diethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, and triethylamine; hydrochloric acid, oxalic acid, fumaric acid, sulfonic acid, And acids such as acetic acid; but include, but are not limited to, carboxylates of metals including nickel, iron, palladium, iridium, platinum, titanium, and aluminum. The reaction accelerator is particularly preferably a metal carboxylate. The amount of the reaction accelerator is preferably 0.01 to 5 mol% with respect to the mass of the polysilazane oligomer.

2-3-7. About application | coating and drying of a translucent ceramic material containing composition A translucent ceramic material containing composition is apply | coated to the light emission surface (upper surface) and side surface of an LED chip at least. At this time, you may apply | coat a translucent ceramic material containing composition to area | regions other than the light emission surface (upper surface) and side surface of a LED chip, for example, the surface of a metal part.

  As described above, when the electrode is exposed on the surface of the LED element, if a wavelength conversion layer is formed on the electrode, it may not be energized. A material-containing composition may be applied.

  The application method of the translucent ceramic material-containing composition is not particularly limited. For example, blade coating, spin coating coating, dispenser coating, spray coating, inkjet device coating, etc.

  According to dispenser application, the application amount of the translucent ceramic material-containing composition can be finely controlled. Furthermore, it is easy to apply the translucent ceramic material-containing composition also to the side surface of the LED chip. The dispenser only needs to have a nozzle that does not clog the inorganic fine particles contained in the translucent ceramic material-containing composition, and can be the same as the dispenser used when applying the phosphor dispersion liquid.

  Moreover, the application amount of the translucent ceramic material-containing composition can be finely controlled by application using an ink jet apparatus. It is preferable that the nozzles of the ink jet apparatus are also not clogged with inorganic fine particles contained in the translucent ceramic material-containing composition. Examples of the inkjet device include an inkjet device manufactured by Konica Minolta IJ.

  By spray coating, the coating amount of the translucent ceramic material-containing composition can be reduced. That is, a thin wavelength conversion layer can be formed.

  After application of the translucent ceramic material-containing composition, the coating film is heated to 100 ° C. or higher, preferably 150 to 300 ° C., and the translucent ceramic material-containing composition is dried and cured. When the translucent ceramic material is an organic polysiloxane compound, if the heating temperature is less than 100 ° C., water generated during dehydration condensation cannot be sufficiently removed, and the light resistance of the wavelength conversion layer may be reduced. There is.

  On the other hand, when the translucent ceramic material is a polysilazane oligomer, the coating film is irradiated with VUV radiation (eg, excimer light) containing a wavelength component in the range of 170 to 230 nm, and then cured by heating. It is preferable. The wavelength conversion layer becomes a dense film, and the moisture resistance of the LED device is likely to increase.

  An example of a spray device for applying the translucent ceramic material-containing composition is shown in FIG. 3 (schematic diagram). As shown in FIG. 3, the spray device 200 includes a moving table 280 and a spray device 240 capable of spraying the above-described translucent ceramic material-containing composition 270. The spray device 240 is disposed above the moving table 280. Further, the moving table 280 is configured to be movable up and down, left and right, and front and rear relative to the spray device 240. The substrate 1 on which the LED chip 3 is mounted is disposed on the moving table 280. Thus, the substrate 1 can be moved up and down, left and right, and front and rear relative to the spray device 240.

  The spray device 240 has a nozzle 250 into which air is sent, and an air compressor (not shown) for sending air is connected to the nozzle 250. The hole diameter at the tip of the nozzle 250 is 20 μm to 2 mm, preferably 0.1 to 1.5 mm. The nozzle 250 is movable up and down, left and right, and front and rear relative to the moving table 280.

  As the nozzle 250, for example, Anest Iwata's spray gun W-101-142BPG is used. As the compressor, for example, OFP-071C manufactured by Anest Iwata is used.

  The nozzle 250 can also be adjusted in angle, and can be tilted with respect to the movable table 280 (or the substrate 1 installed thereon). The angle of the nozzle 250 with respect to the injection target (substrate 1) is preferably in the range of 0 to 70 ° when the vertical direction from the injection target is 0 °. In addition, when applying the translucent ceramic material-containing composition to the side surface of the LED chip 3, it is preferable to tilt the nozzle 250 with respect to the substrate 1.

  A tank 210 is connected to the nozzle 250 via a connecting pipe 230. The tank 210 stores a coating material 220 (that is, a translucent ceramic material-containing composition). The tank 210 contains a stirring bar, and the coating material 220 is constantly stirred. By setting it as such a structure, it becomes possible to stir the translucent ceramic material containing composition, and to maintain the state by which inorganic fine particles etc. were disperse | distributed uniformly, for example. An example of the tank 210 is PC-51 manufactured by Anest Iwata.

2-2-8. Preparation method of organic polysiloxane compound The organic polysiloxane compound which is a translucent ceramic material is obtained by polymerizing an alkoxysilane compound or an aryloxysilane compound. The alkoxysilane compound or aryloxysilane compound is represented, for example, by the following general formula (III).
Si (OR) _n Y _4-n (III)

  In general formula (III), n represents the number of alkoxy groups or aryloxy groups (OR), and is an integer of 2 or more and 4 or less. Moreover, R represents an alkyl group or a phenyl group each independently, Preferably it represents a C1-C5 alkyl group or a phenyl group.

  In the general formula (III), Y represents a hydrogen atom or a monovalent organic group. Specific examples of the monovalent organic group represented by Y include an aliphatic group having 1 to 1000 carbon atoms, preferably 500 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 6 or less. An alicyclic group, an aromatic group, and an alicyclic aromatic group are included. These monovalent organic groups 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. Moreover, the monovalent organic group represented by Y may have a substituent. Examples of the substituent include, for example, 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 An organic functional group such as a group, a nitro group, a sulfonic acid group, a carboxy group, a hydroxy group, an acyl group, an alkoxy group, an imino group, and a phenyl group.

  In general formula (III), the group represented by Y is particularly preferably a methyl group. When Y is a methyl group, the light resistance and heat resistance of the wavelength conversion layer are improved.

The alkoxysilane or aryloxysilane represented by the general formula (III) includes the following tetrafunctional silane compounds, trifunctional silane compounds, and bifunctional silane compounds.
Examples of tetrafunctional silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, triethoxymono Methoxysilane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane , Triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Orchid, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane, Examples include tetraalkoxysilanes such as dibutoxymonoethoxymonopropoxysilane and monomethoxymonoethoxymonopropoxymonobutoxysilane, and tetraaryloxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable.

  Examples of 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, monopheny Monohydrosilane compounds such as oxydiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltripentyloxysilane, methylmonomethoxydiethoxysilane, methylmonomethoxydipropoxysilane, methylmonomethoxydipentyloxy Monomethylsilane compounds such as silane, methylmonomethoxydiphenyloxysilane, methylmethoxyethoxypropoxysilane, methylmonomethoxymonoethoxymonobutoxysilane; ethyltrimethoxysilane, ethyltripropoxysilane, ethyltripentyloxysilane, ethyltriphenyloxysilane , Ethyl monomethoxydiethoxysilane, ethyl monomethoxydipropoxysilane, ethyl monomethoxydipentyloxysilane Monoethylsilane compounds such as ethyl, monomethoxydiphenyloxysilane, ethylmonomethoxymonoethoxymonobutoxysilane; propyltrimethoxysilane, propyltriethoxysilane, propyltripentyloxysilane, propyltriphenyloxysilane, propylmonomethoxydi Monopropylsilane compounds such as ethoxysilane, propylmonomethoxydipropoxysilane, propylmonomethoxydipentyloxysilane, propylmonomethoxydiphenyloxysilane, propylmethoxyethoxypropoxysilane, propylmonomethoxymonoethoxymonobutoxysilane; butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltripentyloxysilane, Butyltriphenyloxy Monobutylsilane compounds such as xysilane, butylmonomethoxydiethoxysilane, butylmonomethoxydipropoxysilane, butylmonomethoxydipentyloxysilane, butylmonomethoxydiphenyloxysilane, butylmethoxyethoxypropoxysilane, butylmonomethoxymonoethoxymonobutoxysilane Is included. Among these, methyltrimethoxysilane and methyltriethoxysilane are more preferable, and methyltrimethoxysilane is more preferable.

  Examples of bifunctional silane compounds include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxysilane , Ethoxypentyloxysilane, ethoxyphenyloxysilane, methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylmethoxyphenyloxysilane, ethyldipropoxysilane, ethylmethoxypropoxy Silane, ethyldipentyloxysilane, ethyldiphenyloxysilane, propyldimethoxysilane, propylme Xylethoxysilane, Propylethoxypropoxysilane, Propyldiethoxysilane, Propyldipentyloxysilane, Propyldiphenyloxysilane, Butyldimethoxysilane, Butylmethoxyethoxysilane, Butyldiethoxysilane, Butylethoxypropoxysilane, Butyldipropoxysilane, Butyl Methyldipentyloxysilane, butylmethyldiphenyloxysilane, dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyl Methoxypropoxysilane, diethyldiethoxysilane, diethylethoxy Propoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutylmethoxypentyloxysilane, dibutylmethoxyphenyloxy Silane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylbutyldimethoxysilane, methylbutyldi Ethoxysilane, methylbutyl dipropoxysilane, methylethylethoxypropoxysilane, ethylprop Pyrdimethoxysilane, ethylpropylmethoxyethoxysilane, dipropyldimethoxysilane, dipropylmethoxyethoxysilane, propylbutyldimethoxysilane, propylbutyldiethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutylethoxypropoxysilane, etc. are included . Of these, dimethoxysilane, diethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable.

  The organic polysiloxane compound can be prepared by a method in which the silane compound is hydrolyzed in the presence of an acid catalyst, water, and an organic solvent and subjected to a condensation reaction. The mass average molecular weight of the organic polysiloxane compound is adjusted by reaction conditions (particularly reaction time) and the like.

  At this time, a tetrafunctional silane compound, a trifunctional silane compound, or a bifunctional silane compound may be preliminarily mixed at a desired molar ratio and polymerized at random. Alternatively, a trifunctional silane compound or a bifunctional silane compound may be polymerized to some extent alone to form an oligomer, and then the oligomer may be polymerized with only the tetrafunctional silane compound to form a block copolymer.

The acid catalyst for preparing the organic polysiloxane compound is particularly preferably an organic sulfonic acid represented by the following general formula (IV).
R ⁸ —SO ₃ H (IV)
In the above general formula (IV), the hydrocarbon group represented by R ⁸ is a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, or an anthryl group, preferably a phenyl group. Further, the hydrocarbon group represented by R ⁸ in the general formula (IV) may have a substituent. Examples of the substituent include linear, branched, or cyclic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms; halogen atoms such as fluorine atoms; sulfonic acid groups; carboxyl groups; Amino group; cyano group and the like are included.

  The organic sulfonic acid represented by the general formula (IV) is particularly preferably nonafluorobutanesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, or dodecylbenzenesulfonic acid.

  The amount of the acid catalyst added during the preparation of the organic polysiloxane compound is preferably 1 to 1000 ppm by mass, more preferably 5 to 800 ppm by mass, based on the total amount of the organic polysiloxane compound preparation solution.

  The film quality of the wavelength conversion layer finally obtained varies depending on the amount of water added during the preparation of the organic polysiloxane compound. Therefore, it is preferable to adjust the water addition rate at the time of preparing the organic polysiloxane compound according to the target film quality. The water addition rate is the ratio (%) of the number of moles of water molecules to be added to the number of moles of alkoxy groups or aryloxy groups of the silane compound contained in the organic polysiloxane compound preparation solution. The water addition rate is preferably 50 to 200%, more preferably 75 to 180%. By setting the water addition rate to 50% or more, the film quality of the wavelength conversion layer is stabilized. Moreover, the storage stability of a translucent ceramic material containing composition becomes favorable by setting it as 200% or less.

  Examples of the solvent added when preparing the organic polysiloxane compound include monohydric alcohols such as methanol, ethanol, propanol and n-butanol; alkylcarboxylic acids such as methyl-3-methoxypropionate and ethyl-3-ethoxypropionate. Acid esters; polyhydric alcohols such as ethylene 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 mono Monoethers of polyhydric alcohols such as chill ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, or their monoacetates; methyl acetate, ethyl acetate, butyl acetate, etc. Esters; ketones such as acetone, methyl ethyl ketone, methyl isoamyl ketone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diechi Polyhydric alcohols ethers any polyhydric alcohol hydroxyl group such as glycol methyl ethyl ether and alkyl etherified; and the like. These may be added alone or in combination of two or more.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this.

<Example 1>
An aromatic polyamide circular package 1 (substrate) (opening diameter 3 mm, bottom surface diameter 2 mm, opening wall inclination angle 60 °) having a metal part (silver plating) 2 shown in FIG. 1 was prepared. One blue LED chip 3 (cuboid: 200 μm × 300 μm × 100 μm) was fixed to the center of the opening of the circular package 1 with a die bonding adhesive. In addition, the anode electrode and the cathode electrode of the LED chip 3 were respectively connected to the protruding electrodes 4 on the metal part 2 to obtain LED elements.

  1 g of a phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.), 0.1 g of synthetic mica (ME-100, manufactured by Coop Chemical Co., Ltd.), and 1.5 g of water were mixed. A phosphor dispersion was prepared. The resulting phosphor dispersion had a viscosity of 800 mPa · s. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of synthetic mica relative to the total amount of solids in the phosphor dispersion is 9.1% by mass.

  The phosphor dispersion liquid was filled in a coating liquid tank of a dispenser (manufactured by Musashi Engineering Co., Ltd., SM200DSS-3A). The phosphor dispersion liquid was applied to the light emitting surface and side surfaces of the LED chip and dried at 150 ° C. for 15 minutes. At this time, the air pressure of the dispenser was 0.2 MPa, the vacuum was 0 kPa, and the coating time was 0.02 seconds. The thickness of the obtained layer was 35 μm.

A polysiloxane oligomer dispersion (polysiloxane oligomer (organopolysiloxane compound) 14 mass%, isopropyl alcohol (IPA) 86 mass%; KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 g, and isopropyl alcohol (IPA) 0.3 g By mixing, a translucent ceramic material-containing composition was prepared.
The LED element described above was placed in a spray coating apparatus, and the light-transmitting ceramic material-containing composition was applied onto the LED chip and the metal part. At this time, the spray pressure of the spray coating apparatus was 0.05 MPa, and the relative movement speed between the spray nozzle and the LED element was 150 mm / s. Moreover, the application amount of the translucent ceramic material-containing composition is such that the amount of the cured product (translucent ceramic) of the translucent ceramic material precursor with respect to 100 parts by mass of the phosphor particles contained in the obtained wavelength conversion layer. 1 to 20 parts by mass. Then, it heated and baked at 150 degreeC for 1 hour, and obtained the wavelength conversion layer by which the fluorescent substance particle and the swelling particle | grains were disperse | distributed in the translucent ceramic. The thickness of the wavelength conversion layer was 35 μm.

<Example 2>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.), 0.1 g of synthetic mica (ME-100, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silyl The phosphor dispersion was prepared by mixing 0.1 g of silicic anhydride (manufactured by Nippon Aerosil Co., Ltd.) and 1.5 g of water. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 35 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of synthetic mica relative to the total amount of solids in the phosphor dispersion is 8.3% by mass.

  1 g of polysiloxane oligomer dispersion (polysiloxane oligomer 14% by mass, isopropyl alcohol 86% by mass; KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) and RX300 (average primary particle size: 7 nm, silylated silicic anhydride; Nippon Aerosil Co., Ltd.) (Manufactured) 0.03 g and isopropyl alcohol 0.3 g were mixed to prepare a translucent ceramic material-containing composition. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 35 μm.

<Example 3>
Phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.) 1 g, smectite (Lucentite SWN, manufactured by Corp Chemical Co.) 0.07 g, and water 1.5 g are mixed to phosphor. A dispersion was prepared. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 35 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total solid content of the phosphor dispersion is 6.5% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 35 μm.

<Example 4>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) 0.5 g of treated silicic acid (manufactured by Nippon Aerosil Co., Ltd.) and 1.5 g of water were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 50 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 4.5% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 50 μm.

<Example 5>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), silicia 470 (average particle size of primary particles: 14 μm) (Manufactured by Fuji Silysia) 0.1 g and 1.5 g of water were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 50 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total solid content of the phosphor dispersion is 4.5% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 50 μm.

<Example 6>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) Treated silica (manufactured by Nippon Aerosil Co., Ltd.) (0.1 g), water (1.5 g), and isopropyl alcohol (IPA) (0.1 g) were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 40 μm. It should be noted that the amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 94% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 6.0% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 40 μm.

<Example 7>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) Treated silica (manufactured by Nippon Aerosil Co., Ltd.) (0.1 g), water (1.5 g), and propylene glycol (PG) (0.1 g) were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 40 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 94% by mass; the amount of smectite relative to the total solid content of the phosphor dispersion is 6.0% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 40 μm.

<Example 8>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) (Treatment anhydrous silicic acid; manufactured by Nippon Aerosil Co., Ltd.) 0.1 g, water 1.5 g, and ethylene glycol (EG) 0.1 g were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 40 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 94% by mass; the amount of smectite relative to the total solid content of the phosphor dispersion is 6.0% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 40 μm.

<Example 9>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) (Treatment anhydrous silicic acid; manufactured by Nippon Aerosil Co., Ltd.) 0.1 g, water 1.5 g, and ethylene glycol (EG) 0.1 g were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 40 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 94% by mass; the amount of smectite relative to the total solid content of the phosphor dispersion is 6.0% by mass.

1 g of polysiloxane oligomer dispersion (polysiloxane oligomer 14 mass%, isopropyl alcohol 86 mass%; KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.), zirconia alkoxide solution (tetrabutoxyzirconium (organometallic compound) 70 mass%) and 1-butanol (30% by mass) 0.2 g and 0.3 g of ZrO ₂ slurry dispersion (inorganic fine particles, average particle size: 20 nm) were mixed to prepare a translucent ceramic material-containing composition. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 40 μm.

<Example 10>
1 g of phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co.), 0.07 g of smectite (Lucentite SWN, manufactured by Corp Chemical Co.), RX300 (average primary particle size: 7 nm, silylated) 0.4 g of treated silicic anhydride (manufactured by Nippon Aerosil Co., Ltd.) and 1.5 g of water were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 50 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 4.8% by mass.

A polysilazane oligomer dispersion (NN120-20 (20% by mass of perhydropolysilazane oligomer and 80% by mass of dibutyl ether), manufactured by AZ Electronic Materials) was used as a translucent ceramic material-containing composition. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 50 μm.
<Example 11>
Phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.) 0.5 g, smectite (Lucentite SWN, manufactured by Corp Chemical Co.) 0.1 g, RX300 (average primary particle size: 7 nm, Silica-treated silicic acid anhydride (manufactured by Nippon Aerosil Co., Ltd.) (0.2 g) and water (1.5 g) were mixed to prepare a phosphor dispersion. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 80 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 12.5% by mass.

  A polysilazane oligomer dispersion (NN120-20 (20% by mass of perhydropolysilazane oligomer and 80% by mass of dibutyl ether), manufactured by AZ Electronic Materials) was used as a translucent ceramic material-containing composition. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 80 μm.

<Comparative Example 1>
1 g of polysiloxane oligomer dispersion (polysiloxane oligomer 14 mass%, isopropyl alcohol 86 mass%; KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) and phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.) ) 1g was mixed and the composition for wavelength conversion layers was prepared. The composition for wavelength conversion layers was filled in the same dispenser as Example 1, and it apply | coated to the light emission surface and side surface of the LED chip of an LED element on the same conditions. Then, it heat-baked at 150 degreeC for 1 hour, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer was 40 μm.

<Comparative example 2>
Phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.) (2.1 g), smectite (Lucentite SWN, manufactured by Corp Chemical Co.) (0.005 g), and water (1.5 g) were mixed. A wave phosphor dispersion was prepared. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 30 μm. The amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 100% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 0.2% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 30 μm.

<Comparative Example 3>
Phosphor (YAG 405C205, particle size distribution D50: 20.5 μm, manufactured by Nemoto Special Chemical Co., Ltd.) 1 g, smectite (Lucentite SWN, manufactured by Corp Chemical Co.) 0.07 g, water 1 g, and IPA 1.5 g were mixed, A wave phosphor dispersion was prepared. The phosphor dispersion liquid was filled in the same dispenser as in Example 1, and applied to the light emitting surface and the side surface of the LED chip of the LED element under the same conditions and dried. The thickness of the obtained layer was 35 μm. Note that the amount of water relative to the total amount of water and solvent contained in the phosphor dispersion is 40% by mass; the amount of smectite relative to the total amount of solids in the phosphor dispersion is 6.5% by mass.

  A translucent ceramic material-containing composition was prepared in the same manner as in Example 1. Under the same conditions as in Example 1, the translucent ceramic material-containing composition was applied and baked to obtain a wavelength conversion layer in which phosphor particles and swellable particles were dispersed. The thickness of the wavelength conversion layer was 35 μm.

<Evaluation>
The viscosity of the phosphor dispersion liquid prepared in each example and comparative example, chromaticity variation among a plurality of LED devices prepared in each example and comparative example, and light distribution characteristics of each LED device were evaluated as follows. did.

(viscosity)
The viscosity of each phosphor dispersion at 25 ° C. was measured with a vibration viscometer (VM-10A-L, manufactured by CBC). In addition, when the viscosity was 1000 mPa · s or more, it was measured with a vibration viscometer (VM-10A-MH, manufactured by CBC).

(Chromaticity variation among multiple LED devices)
Five LED devices of each example and comparative example were prepared. The chromaticity of light emitted from the front of each LED device was measured with a spectral radiance meter (CS-1000A, manufactured by Konica Minolta Sensing Co., Ltd.). For chromaticity, the x value and y value of the CIE color system were measured. The z coordinate obtained from the relationship of x + y + z = 1 was omitted.
The standard deviation was calculated | required about chromaticity (x value and y value) of 5 samples of each Example and a comparative example, respectively. And it evaluated by the average value of the standard deviation of x value, and the standard deviation of y value. The evaluation criteria are shown below.
“◎”: The average value of standard deviation is 0.02 or less, and there is no practical problem (applicable to applications where color uniformity is required)
“×”: The average value of the standard deviation is larger than 0.02, which is not preferable for practical use.

(Light distribution characteristics)
5 samples of each LED device of each example and comparative example were produced. And (i) the chromaticity of the emitted light at the front of the LED device, (ii) the chromaticity of the emitted light when tilted 60 ° from the front of the LED device, and (iii) -60 ° ((ii) from the front of the LED device) The chromaticity of the emitted light when tilted 60 ° in the opposite direction was measured. The chromaticity was measured with a spectral radiance meter (CS-1000A, manufactured by Konica Minolta Sensing Co., Ltd.) for the x value and y value of the CIE color system. The z coordinate obtained from the relationship of x + y + z = 1 was omitted.
The standard deviation was determined for each measured chromaticity (x value and y value). And it evaluated by the average value of the standard deviation of x value, and the standard deviation of y value. The evaluation criteria are shown below.
“◎”: The average value of standard deviation is 0.02 or less, and there is no practical problem (applicable to applications where color uniformity is required)
“◯”: The average value of standard deviation is larger than 0.02 and 0.03 or less, and there is no practical problem. “×”: The average value of standard deviation is larger than 0.03, which is practically preferable. Absent

  When the amount of swellable particles contained in the phosphor dispersion liquid is small (Comparative Example 2) and when the amount of water contained in the phosphor dispersion liquid is small (Comparative Example 3), the viscosity of the phosphor dispersion liquid is low. The viscosity of the phosphor dispersion liquid was less than 800 mPa · s. And in the LED device produced using the said phosphor dispersion liquid, the light distribution characteristic became low. That is, chromaticity varied depending on the direction in which the LED device was observed. The viscosity of the phosphor dispersion liquid is low, and it is assumed that the phosphor particles could not be sufficiently adhered to the side surface of the LED chip.

  On the other hand, when the viscosity of the phosphor dispersion was in the range of 800 to 500,000 mPa · s (Examples 1 to 11), the light distribution characteristics were very good. Since the viscosity of the phosphor dispersion liquid is high to some extent, it is presumed that the phosphor particles can be attached to the side surface and the upper surface of the LED chip with a uniform thickness.

  In addition, when the phosphor particles and the translucent ceramic material were applied in one liquid, the chromaticity of light emitted from the plurality of LED devices varied (Comparative Example 1). It is inferred that the phosphor particles settled in the coating device (dispenser), resulting in variations in the concentration of the phosphor particles contained in each wavelength conversion layer. On the other hand, when the phosphor particles and the translucent ceramic material were separately applied, the chromaticity of light emitted from each LED device was uniform even when a plurality of LED devices were produced (Example 1). To 11 and Comparative Examples 2 and 3).

  The LED device manufactured by the manufacturing method of the present invention has a uniform chromaticity of the emitted light even when observed from any direction. Therefore, the present invention can also be applied to an illumination device or the like that requires uniformity of light chromaticity.

1 Substrate (LED package)
2 Metal part 3 LED chip 4 Projection electrode 5 Wavelength conversion layer 100 LED device

Claims (9)

Preparing an LED element having an LED chip mounted on a substrate;
Applying a phosphor dispersion liquid containing phosphor particles, swellable particles, and water and having a viscosity of 800 mPa · s to 500,000 mPa · s with a dispenser on the light emitting surface and side surfaces of the LED chip, and drying ,
A translucent ceramic material-containing composition containing a translucent ceramic material and a solvent is further applied to a light emitting surface and a side surface of the LED chip, and the translucent ceramic material is cured, whereby the phosphor particles and the swelling And a step of obtaining a wavelength conversion layer in which the conductive particles are dispersed in the translucent ceramic. The phosphor dispersion includes a solvent other than water,
The manufacturing method of the LED device of Claim 1 whose quantity of the water contained in the said fluorescent substance dispersion liquid is 67 mass% or more with respect to the total amount of the water and solvent which are contained in the said fluorescent substance dispersion liquid.   The amount of the swellable particles contained in the phosphor dispersion liquid is 0.3% by mass or more and 70% by mass or less based on the total amount of solid content of the phosphor dispersion liquid. Manufacturing method of LED device.   The manufacturing method of the LED device as described in any one of Claims 1-3 whose said swellable particle is a layered silicate mineral.   The manufacturing method of the LED device as described in any one of Claims 1-4 whose said translucent ceramic material is an organic polysiloxane compound.   The manufacturing method of the LED device as described in any one of Claims 1-5 in which the said translucent ceramic material containing composition further contains inorganic particulates.   The manufacturing method of the LED device as described in any one of Claims 1-6 with which the solvent of the said translucent ceramic material containing composition contains water.   The manufacturing method of the LED device as described in any one of Claims 1-7 in which the said translucent ceramic material containing composition further contains the organometallic compound of bivalent or more metals other than Si. A phosphor dispersion for dispensing application, comprising phosphor particles, swellable particles, and water, and having a viscosity of 800 mPa · s to 500,000 mPa · s.

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