JP2017017185A - Phosphor dispersion liquid supply body, method for transporting phosphor dispersion liquid using the same, and method for manufacturing light emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor dispersion liquid supply body hardly causing deterioration in phosphors when a phosphor dispersion liquid is stored, and suppressing phosphor particles from being left in a container.SOLUTION: A phosphor dispersion liquid supply body includes: a plastic syringe including a barrel provided with a nozzle at one end thereof and a plunger inserted from the other end of the barrel and slidable in the barrel; and a phosphor dispersion liquid containing phosphor particles and a solvent and filled inside the plastic syringe. The volume of the phosphor dispersion liquid with respect to the volume of a hollow in the plastic syringe, the hollow being surrounded by an inner wall of the barrel and one end of the plunger, is 90 vol.% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a phosphor dispersion liquid supply body, a method for transporting a phosphor dispersion liquid using the same, and a method for manufacturing a light emitting device.

  In recent years, white LED devices have been put into practical use as alternatives to conventional fluorescent lamps and incandescent lamps. An example of a white LED device is one in which yellow phosphor particles such as YAG are arranged in the vicinity of a gallium nitride (GaN) -based blue LED (Light Emitting Diode) element. In this apparatus, white light is obtained by mixing blue light emitted from a blue LED element and yellow light particles emitted from a phosphor upon receiving blue light.

  Usually, the phosphor particles are arranged in the vicinity of the light emitting element by applying a phosphor dispersion liquid onto the light emitting element (for example, Patent Document 1). In general, such a phosphor dispersion liquid is filled and stored and transported in a metal container, a glass container, a plastic bottle, or the like.

  However, the phosphor particles are very hard. Therefore, when the phosphor dispersion liquid is stored in a metal container or filled and transported, the surface of the metal container is scraped by the phosphor particles, and the metal powder is mixed into the phosphor dispersion liquid. was there. Thus, it has been proposed to store and transport the phosphor dispersion liquid in a resin bag or the like (for example, Patent Document 2).

Japanese Patent Application Laid-Open No. 2014-19844 JP 2014-111363 A

  According to the method of Patent Document 2, metal contamination into the phosphor dispersion liquid can be prevented. However, even if the phosphor dispersion liquid is stored in a glass or resin bag or bottle, the phosphor particles are deteriorated due to vibration during transportation, etc., and the luminous efficiency of light emitted from the light emitting device is reduced. There was a problem to do.

  Further, when the phosphor dispersion liquid was stored in a container such as a bottle or bag, the phosphor particles adhered to the inner wall of the container and easily remained in the container when the phosphor dispersion liquid was taken out. If the phosphor particles remain in the storage container, the concentration of the phosphor particles in the phosphor dispersion liquid taken out from the container may decrease, and the chromaticity of light emitted from the light emitting device may vary. Moreover, since the phosphor particles are expensive, it is desired to reduce the loss of the phosphor particles from the viewpoint of cost.

  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 phosphor dispersion liquid supply body in which the phosphor does not easily deteriorate during storage of the phosphor dispersion liquid, and the phosphor particles hardly remain in the container.

That is, the first of the present invention is the following phosphor dispersion liquid supply body.
[1] A barrel provided with a nozzle at one end, a plastic syringe having a plunger inserted from the other end of the barrel and slidable in the barrel, a phosphor particle and a solvent, and the plastic syringe A volume of the phosphor dispersion liquid with respect to a hollow volume in the plastic syringe surrounded by an inner wall of the barrel and a side end portion of the nozzle of the plunger. However, the phosphor dispersion liquid supply body is 90 volume% or more.

[2] The phosphor dispersion liquid supply body according to [1], wherein the volume of the phosphor dispersion liquid is 95% by volume or more with respect to the hollow volume in the plastic syringe.
[3] The phosphor dispersion liquid supplier according to [1] or [2], wherein the phosphor dispersion has a viscosity at 25 ° C. of 80 to 2000 mPa · s measured by a vibration viscometer.
[4] The phosphor dispersion supply body according to any one of [1] to [3], wherein the phosphor dispersion liquid further includes at least one of inorganic particles and clay minerals.

The second of the present invention relates to the following phosphor dispersion transport method and light emitting device production method.
[5] A method for transporting a phosphor dispersion using the phosphor dispersion supplier according to any one of [1] to [4].
[6] A method for manufacturing a light emitting device comprising a substrate, a light emitting element disposed on the substrate, and a phosphor-containing layer formed on the light emitting element, wherein any one of [1] to [4] Installing the phosphor dispersion liquid supply body according to claim 1 in a coating apparatus, and forming the phosphor-containing layer on the light emitting element by the phosphor liquid discharged from the nozzle of the phosphor dispersion liquid supply body. A method for manufacturing a light emitting device.

  According to the phosphor dispersion liquid supply body of the present invention, the phosphor particles are unlikely to deteriorate during storage or transportation of the phosphor dispersion liquid. Furthermore, the loss of the phosphor particles is small, and the concentration of the phosphor particles in the phosphor dispersion liquid can be kept constant.

It is a schematic sectional drawing which shows an example of the fluorescent substance dispersion liquid supply body of this invention. It is a schematic sectional drawing which shows an example of the LED apparatus obtained with the manufacturing method of the light-emitting device of this invention.

  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. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

1. Phosphor dispersion liquid supply body A schematic cross-sectional view of an example of the phosphor dispersion liquid supply body of the present invention is shown in FIG. The phosphor dispersion liquid supply body of the present invention has a plastic syringe 1 and a phosphor dispersion liquid 2 filled in the plastic syringe 1. The plastic syringe 1 has a barrel 1a having a nozzle 1b at one end and a plunger 1c inserted into the barrel 1a from the other end of the barrel 1a.

  In the phosphor dispersion liquid supply body of the present invention, the inside of the plastic syringe 1 surrounded by the inner wall of the barrel 1a and the end of the plunger 1c on the nozzle 1b side (the surface represented by 1c ′ in the figure). The volume of the phosphor dispersion liquid 2 is 90% by volume or more, preferably 95% by volume or more with respect to the hollow volume. That is, there are few voids in the plastic syringe 1 and the filling rate of the phosphor dispersion liquid 2 is very high.

  As described above, the phosphor dispersion liquid has been conventionally filled in storage containers such as various bottles and bags, and stored and transported. However, in this method, the phosphor particles may be deteriorated during storage and transportation. As a result, there was a problem that the light emission efficiency from the light emitting device manufactured using the phosphor dispersion liquid was lowered. It is assumed that the deterioration of the phosphor particles is caused by the phosphor particles colliding with each other due to the storage of the phosphor dispersion liquid, vibration during transportation, and the like.

  Further, the conventional storage container has a problem that the phosphor particles are likely to remain in the container when the phosphor dispersion liquid is taken out. The phosphor particles are expensive, and it is not preferable from the viewpoint of cost that the phosphor particles remain in the container. Furthermore, if the phosphor particles remain in the container, the concentration of the phosphor particles in the phosphor dispersion liquid after taking out may decrease, and the chromaticity of light from the light emitting device may vary.

  In contrast, in the phosphor dispersion liquid supply body of the present invention, as described above, the phosphor dispersion liquid is filled into the plastic syringe 1 at a high filling rate. For this reason, even if the phosphor dispersion liquid supply body vibrates during storage and transportation of the phosphor dispersion liquid supply body, the phosphor dispersion liquid 2 hardly flows inside the plastic syringe 1. As a result, the phosphor particles hardly collide with each other in the phosphor dispersion liquid 2, and the phosphor dispersion liquid 2 can be maintained in high quality.

  Furthermore, in the phosphor dispersion liquid supply body of the present invention, since the container is the plastic syringe 1, the filling amount of the phosphor dispersion liquid 2 can be freely set depending on the position of the plunger 1c. Further, when the phosphor dispersion liquid is used, the phosphor dispersion liquid is pushed out by sliding the plunger 1c, so that the phosphor dispersion liquid 2 (particularly the phosphor particles) hardly remains in the container (plastic syringe 1). There is little loss of body particles.

  Furthermore, in the phosphor dispersion liquid supply body of the present invention, the hollow volume of the plastic syringe 1 is expanded by sliding the plunger 1c to the side opposite to the nozzle 1a immediately before using the phosphor dispersion liquid 2. The phosphor dispersion liquid 2 can be shaken and stirred together with the plastic syringe 1. Hereinafter, the plastic syringe and the phosphor dispersion liquid in the phosphor dispersion liquid supply body of the present invention will be described in detail.

1-1. Plastic Syringe As described above, a plastic syringe has a barrel having a nozzle at one end and a plunger inserted at the other end of the barrel. The shape of the plastic syringe is not particularly limited as long as the phosphor dispersion liquid can be filled and discharged. For example, you may further have a cap which plugs the discharge port of the nozzle of a plastic syringe and suppresses the leakage of the phosphor dispersion liquid.

  The said barrel should just have a hollow structure which equips one end with a nozzle and can hold | maintain a fluorescent substance dispersion liquid inside. The barrel may be, for example, a structure including a cylindrical barrel body and a nozzle communicating with the barrel body. The nozzle and the barrel main body may be integrally formed, or may be integrally formed by connecting separately formed ones. Moreover, the end of the barrel body opposite to the nozzle (the other end) is normally an open end for inserting the plunger. The barrel main body may be provided with a mechanism for preventing the plunger from falling off on the other end side. Moreover, the flange etc. for hooking a finger may be formed in the outer periphery of the other end side of a barrel main body.

  The maximum capacity of the phosphor dispersion liquid in the plastic syringe is determined by the inner diameter and length of the barrel body. The inner diameter and length are appropriately selected according to the usage form of the phosphor dispersion liquid supply body. Is done. Usually, the maximum capacity of the phosphor dispersion liquid in the plastic syringe is 1 to 50 ml, preferably 2 to 20 ml.

  The shape of the nozzle is not particularly limited as long as the phosphor dispersion liquid can be discharged, and may be cylindrical or tapered. Moreover, you may have the thread groove etc. which can be screwed together with the cap for sealing the nozzle front-end | tip on the outer periphery of a nozzle.

  The material of the barrel (barrel body and nozzle) is not particularly limited as long as it is a material that is not eroded by the solvent contained in the phosphor dispersion liquid, but is preferably a material having low water vapor permeability and excellent impact strength. . Specifically, polyolefin materials such as polypropylene and polyethylene; polystyrene, polyester and the like are preferable.

  On the other hand, the shape of the plunger inserted into the barrel is not particularly limited as long as it is slidable inside the barrel body and can efficiently extrude the phosphor dispersion liquid. It can be similar to a plunger. A gasket may be attached to the nozzle side end of the plunger. When the gasket is attached to the tip of the plunger, the airtightness in the plastic syringe is easily maintained, and the phosphor dispersion liquid can be pushed out more reliably. The shape of the gasket is not particularly limited, and may be the same shape as that of a general plastic syringe gasket. When the gasket is attached to the tip of the plunger, the above-mentioned “hollow volume in the plastic syringe surrounded by the inner wall of the barrel and the end of the plunger on the nozzle side” means “the inner wall of the barrel. And a hollow volume in a plastic syringe surrounded by the nozzle side end of the gasket.

  The material of the plunger is preferably a material excellent in impact strength, and is preferably a polyolefin-based material such as polypropylene or polyethylene; polystyrene, polyester or the like. The material of the plunger may be the same as or different from the barrel. In addition, the material of the gasket is preferably highly flexible from the viewpoint of bringing the gasket into close contact with the inner wall of the barrel, and is preferably vulcanized rubber or thermoplastic elastomer.

  As described above, the plastic syringe may have a cap that seals the nozzle tip. When the plastic syringe has a cap, not only leakage of the phosphor dispersion liquid is suppressed during storage or transportation of the phosphor dispersion liquid, but also volatilization and alteration of the solvent are suppressed. The shape of the cap is not particularly limited as long as it is in close contact with the inner periphery or outer periphery of the nozzle and can suppress the leakage of the phosphor dispersion liquid. In particular, in order to prevent the cap from falling off the nozzle during transportation or storage of the phosphor dispersion liquid supply body, it is particularly preferable to have a structure in which the cap is screwed into a thread groove formed on the outer peripheral surface of the nozzle. The material of the cap is not particularly limited, and may be made of the same material as that of the barrel, for example.

  The plastic syringe may be used after the phosphor dispersion liquid is discharged and refilled with the phosphor dispersion liquid, and is discarded after the phosphor dispersion liquid is discharged. Also good.

1-2. Phosphor dispersion liquid The phosphor dispersion liquid contains phosphor particles and a solvent. The phosphor dispersion liquid may contain inorganic particles or clay mineral as necessary. The phosphor dispersion liquid may further contain a binder component.

  The viscosity at 25 ° C. of the phosphor dispersion is preferably 80 to 2000 mPa · s, more preferably 200 to 1000 mPa · s, and still more preferably 300 to 800 mPa · s. is there. When the viscosity of the phosphor dispersion liquid is 80 mPa · s or more, the flow of the phosphor dispersion liquid in the phosphor dispersion supply body can be moderated. Therefore, it is possible to suppress the phosphor particles from colliding with each other due to vibrations applied during transportation of the phosphor dispersion liquid supply body.

  The viscosity is a value measured 1 minute after the vibrator of a vibration viscometer (for example, VM-10A manufactured by CBC) is immersed in the phosphor dispersion. The viscosity is adjusted by the amount of solvent contained in the phosphor dispersion, the amount of clay mineral particles, the amount of inorganic particles, and the like.

(Phosphor particles)
The phosphor particles only need to be excited by light having a specific wavelength and emit fluorescence having a wavelength different from the specific wavelength. 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) 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.

  The mixed raw material having the above 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. It is done. 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 types of phosphor particles are not limited to YAG phosphors. For example, TAG (terbium, aluminum, garnet) phosphors, sialon (SiAlON) phosphors, and BOS (barium orthosilicate) phosphors. Other phosphors such as a phosphor may be used.

  The average particle diameter of the phosphor particles is preferably 1 μm to 50 μm, and more preferably 20 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, if the particle size of the phosphor particles is too large, in the phosphor-containing layer obtained from the phosphor dispersion liquid, the gap between the phosphor particles and the phosphor particles becomes large, and the strength of the phosphor-containing layer tends to decrease. . The average particle diameter of the phosphor particles refers to the value of D50 measured with a laser diffraction particle size distribution meter. Examples of the laser diffraction particle size distribution measuring device include a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation.

  The amount of the phosphor particles contained in the phosphor dispersion is preferably 2 to 95% by mass, more preferably 10 to 85% by mass with respect to the entire phosphor dispersion. When the amount of the phosphor particles is 10% by mass or more, a sufficient amount of the phosphor particles can be applied by applying the phosphor dispersion liquid. On the other hand, when the amount of the phosphor particles is 85% by mass or less, the fluidity of the phosphor dispersion liquid is improved, and the phosphor dispersion liquid is easily discharged from the plastic syringe.

(solvent)
The phosphor dispersion liquid contains a solvent. The solvent is not particularly limited as long as the phosphor particles can be uniformly dispersed, but a solvent having a boiling point of 250 ° C. or lower is preferable. When the boiling point of the solvent is 250 ° C. or lower, the solvent can be efficiently removed after the phosphor dispersion is applied, and the phosphor dispersion can be dried.

  Examples of the solvent contained in the phosphor dispersion liquid include monoalcohols such as methanol, ethanol, propanol, and butanol; various solvents such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, and 1,4-butanediol. And monohydric alcohols. The phosphor dispersion liquid may contain only one kind of solvent, or two or more kinds.

  Moreover, water may be contained as one of the solvents. When water and a clay mineral described later are contained in the phosphor dispersion liquid, water enters the structure of the clay mineral and the viscosity of the phosphor dispersion liquid is likely to increase.

  The total amount of the solvent contained in the phosphor dispersion liquid is appropriately set according to the desired viscosity of the entire phosphor dispersion liquid. Usually, the total amount of the solvent contained in the phosphor dispersion is 5 to 98% by mass, preferably 15 to 90% by mass with respect to the entire phosphor dispersion.

(Inorganic particles)
The phosphor dispersion liquid may further contain inorganic particles. When inorganic particles are contained in the phosphor dispersion liquid, the viscosity of the phosphor dispersion liquid increases and collision between the phosphor particles is suppressed. Further, in the phosphor-containing layer formed from the phosphor dispersion liquid, the gap between the phosphor particles is filled with inorganic particles, and the strength of the layer is increased.

  Examples of the inorganic particles include oxide fine particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and zinc oxide, fluoride fine particles such as magnesium fluoride, and the like. In the phosphor dispersion liquid, only one kind of inorganic particles may be contained, or two or more kinds thereof may be contained.

  The surface of the inorganic particles may be treated with a silane coupling agent or a titanium coupling agent. When the surface of the inorganic particles is treated, the inorganic particles are easily dispersed uniformly in the phosphor dispersion liquid.

  The average particle diameter of the inorganic particles is preferably 0.001 μm to 50 μm. When the average particle size of the inorganic particles is 50 μm or less, it is easy to obtain a thickening effect of the phosphor dispersion and an effect of improving the strength of the layer. 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 1 to 20% by mass, more preferably 2 to 5% by mass with respect to the total mass of the phosphor dispersion. If the amount of the inorganic particles is 1% by mass or more, the above-described thickening effect and layer strength improvement effect can be sufficiently obtained. On the other hand, when the amount of the inorganic particles is 20% by mass or less, the amount of the phosphor particles is relatively increased, and sufficient fluorescence is easily obtained in the layer obtained from the phosphor dispersion liquid.

(Clay mineral)
When clay mineral is contained in the phosphor dispersion liquid, the viscosity of the phosphor dispersion liquid increases, and collision between the phosphor particles is suppressed. Furthermore, the strength of the layer obtained by applying the phosphor dispersion liquid is increased.

  Examples of clay minerals include layered silicate minerals, imogolite, allophane and the like. The layered silicate mineral is preferably a swellable clay mineral having a mica structure, a kaolinite structure, a smectite structure, or the like, and more preferably a clay mineral having a smectite structure rich in swelling properties.

  Layered clay minerals such as layered silicate minerals form a card house structure in the phosphor dispersion. Therefore, the viscosity of the phosphor dispersion liquid is significantly increased only by containing a small amount of the layered silicate mineral. Further, since the layered silicate mineral has a flat plate shape, the film strength of the layer obtained from the phosphor dispersion liquid is also increased.

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

  Examples of commercial products of clay minerals include Laponite XLG (synthetic hectorite analogues manufactured by LaPorte, UK), Laponite RD (synthetic hectorite analogues manufactured by LaPorte, UK), Thermabis (Synthetic hectorite, Henkel, Germany) Light-like substance), smecton SA-1 (saponite-like substance manufactured by Kunimine Industry Co., Ltd.), Bengel (natural bentonite sold by Hojun Co., Ltd.), Kunipia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), Veegum (USA) , Natural hectorite manufactured by Vanderbilt), 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 surface of the clay mineral may be modified (surface treatment) with an ammonium salt or the like. When the clay mineral is surface-treated, the dispersibility of the clay mineral in the phosphor dispersion liquid increases.

  The amount of the clay mineral contained in the phosphor dispersion liquid is preferably 0.1 to 7% by mass, more preferably 2 to 5% by mass with respect to the total mass of the phosphor dispersion liquid. When the clay mineral content is 0.1% by mass or more, the viscosity of the phosphor dispersion liquid is sufficiently increased. On the other hand, when the amount of the clay mineral is 7% by mass or less, the viscosity of the phosphor dispersion liquid is not excessively increased, and the phosphor dispersion liquid is easily discharged from the plastic syringe.

(Binder component)
The phosphor dispersion liquid may further contain a binder component. When the binder component is contained in the phosphor dispersion liquid, phosphor particles and the like are bound by the binder component in the phosphor-containing layer obtained from the phosphor dispersion liquid. As a result, it is preferable from the viewpoint that the strength of the phosphor-containing layer is increased. On the other hand, when a highly reactive binder component is contained together with the phosphor particles, the storage stability of the phosphor dispersion liquid may be lowered. Therefore, from the viewpoint of storage stability, it is preferable that the phosphor dispersion liquid does not contain a binder component.

  The binder component that can be contained in the phosphor dispersion liquid may be a transparent resin, a precursor thereof, a translucent ceramic precursor, or the like. Examples of the transparent resin that can be a binder component and its precursor include a silicone resin and an epoxy resin.

  On the other hand, the translucent ceramic precursor that may be a binder component may be a known alkoxysilane monomer or an oligomer thereof, a polysilazane oligomer, or the like. These are not particularly limited as long as they are hydrolyzed and polycondensed to form polysiloxane.

  When a binder component is contained in the phosphor dispersion, the amount of the binder component is preferably 10 to 50% by mass, more preferably 20 to 40% by mass with respect to the total amount of the phosphor dispersion. When the amount of the binder component is 10% by mass or more, the phosphor particles and the like are sufficiently bound. On the other hand, when the amount of the binder component is 50% by mass or less, the amount of phosphor particles and the like is relatively large.

-Preparation method of phosphor dispersion liquid The phosphor dispersion liquid is obtained by mixing phosphor particles, clay minerals, inorganic particles, binder components and the like in a solvent and stirring them. Agitation of the mixed liquid can be performed, for example, with an agitation mill, a blade kneading and agitation device, a thin-film swirl disperser, or the like. The viscosity of the phosphor dispersion liquid can also be adjusted by adjusting the stirring conditions.

  A stirrer for producing the phosphor dispersion solution may be a known one. For example, Ultra Thalax (manufactured by IKA Japan), TK auto homomixer (manufactured by Primics), TK pipeline homomixer (manufactured by Primix), TK Philmix (manufactured by Primics), Claremix (manufactured by M Technique) ), Claire SS5 (manufactured by M Technique), Cavitron (manufactured by Eurotech), medialess stirrer such as Fine Flow Mill (manufactured by Taiheiyo Kiko); Viscomill (manufactured by IMEX), Apex Mill (manufactured by Kotobuki Industries) ), Star Mill (Ashizawa, Finetech), DCP Super Flow (Nihon Eirich), MP Mill (Inoue), Spike Mill (Inoue), Mighty Mill (Inoue), SC Mill Media stirrer such as Mitsui Mining Co .; Optimizer (Sugino Machine Ltd.), Nanomizer (manufactured by Yoshida Kikai), and a high-pressure impact type dispersing device such as NANO 3000 (manufactured by Bitsubusha). Examples of the stirring device include a stirrer, a three-one motor, an ultrasonic dispersion device, and the like.

  In addition, since the phosphor particles are very hard particles, it is preferable to avoid wear of a portion where the stirrer and the phosphor dispersion liquid are in contact with each other, and mixing of wear powder associated therewith. Specifically, the material of the portion where the stirrer and the phosphor dispersion are in contact with each other may be ceramic such as titania, zirconia, alumina, or silicone carbide. It is also preferable to coat the wetted part with titanium-based oxide, chromium-based nitride, diamond-like carbon.

1-3. Filling the phosphor dispersion liquid into the plastic syringe The method of filling the phosphor dispersion liquid into the barrel of the plastic syringe is not particularly limited. For example, the tip of the nozzle may be sealed with a cap or the like, and the phosphor dispersion liquid may be injected from the open end side of the barrel body, or may be injected from the nozzle side of the barrel.

  Here, in the phosphor dispersion liquid supply body of the present invention, as described above, the volume of the phosphor dispersion liquid filled in the plastic syringe with respect to the hollow volume surrounded by the barrel and plunger of the plastic syringe. Is 90 volume% or more. In order to achieve the filling rate, it is preferable to push out the air present in the barrel from the nozzle after the injection of the phosphor dispersion liquid.

1-4. Storage and Transport of Phosphor Dispersion Supply Body As described above, in the phosphor dispersion liquid supply body of the present invention, even when the phosphor dispersion liquid supply body vibrates during storage or transportation, the phosphor dispersion liquid is made of plastic. Difficult to flow in syringe. Therefore, the transportation method of the phosphor dispersion liquid supply body is not particularly limited, and any transportation method such as a vehicle, a ship, and an airplane can be supported. Further, even if the phosphor particles are precipitated during storage and transportation, it is possible to expand the volume in the plastic syringe and to shake and agitate by sliding the plunger to the side opposite to the nozzle. Furthermore, since the container is made of plastic, impact resistance is also high. Therefore, the phosphor dispersion liquid supply body of the present invention may be stored and transported in any orientation.

2. Method for producing light-emitting device using phosphor dispersion liquid supply body The phosphor dispersion liquid filled in the phosphor dispersion liquid supply body described above is useful as a composition for forming a phosphor-containing layer of a light-emitting device. Hereinafter, a method for forming a phosphor-containing layer using a phosphor dispersion liquid supply body will be described using a method for manufacturing an LED device as an example, but the present invention is not limited to this method.

An example of the LED device is shown in FIG. The LED device 100 shown in FIG. 2 includes a substrate 10, an LED element 11 disposed on the substrate 10, and a phosphor-containing layer 12 formed so as to cover the LED element 11. And such a manufacturing method of the LED device 100 includes at least the following two steps.
1) Step of preparing a substrate on which an LED element (light emitting element) is arranged 2) The phosphor dispersion liquid supply body described above is installed in a coating apparatus, and directly from a nozzle of a plastic syringe of the phosphor dispersion liquid supply body, Alternatively, the step of discharging the phosphor dispersion liquid onto the LED element (light emitting element) via the coating device and solidifying the phosphor dispersion liquid.

  In addition, the manufacturing method of an LED device may include a step of applying a binder for binding phosphor particles or the like or a precursor thereof on the phosphor-containing layer as necessary.

2-1. Preparation of substrate on which LED elements are arranged First, a substrate on which LED elements are arranged is prepared. In the manufacturing method of the present invention, the substrate on which the LED elements are arranged may be commercially available, but the step of arranging the LED elements on the substrate having metal wiring and electrically connecting them is performed. Also good. A substrate having metal wiring can be obtained by integrally molding a lead frame having a desired shape and a resin.

  The connection method between the metal wiring and the light emitting element is not particularly limited. For example, as shown in FIG. 2, the metal wiring 13 and the light emitting element 11 may be connected via the protruding electrode 14, and the metal wire (not shown) Or the like).

  Here, as shown in FIG. 2, the substrate may have a cavity, but may have a flat plate shape. The substrate can be made of a ceramic resin or a heat resistant resin. Examples of the heat resistant resin include liquid crystal polymer, polyphenylene sulfide, aromatic nylon, epoxy resin, hard silicone resin, polyphthalic acid amide and the like.

  Further, the substrate may contain an inorganic filler. The inorganic filler can be titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, glass fiber, and the like.

  Further, the wavelength of the light emitted from the LED element arranged on the substrate is not particularly limited, and is appropriately selected according to the excitation wavelength of the phosphor. The LED element may be, for example, an element that emits blue light (light of about 420 nm to 485 nm) or an element that emits ultraviolet light. Furthermore, an element that emits green light, red light, or the like may be used.

  The configuration of the LED element is appropriately selected according to the type of the LED element. When the LED element is an element that emits blue light, the LED element includes an n-GaN compound semiconductor layer (cladding layer) and an InGaN compound. A laminate including a semiconductor layer (light emitting layer), a p-GaN-based compound semiconductor layer (cladding layer), and a transparent electrode layer can be used.

  The shape of the LED element is not particularly limited, and may be a rectangular parallelepiped element having a light emitting surface of 200 to 300 μm × 200 to 300 μm, for example. In addition, the height of an LED element is about 50-200 micrometers normally. Further, the LED element may be one in which light is extracted not only from the top surface but also from the side surface and the bottom surface. In the light emitting device 100 shown in FIG. 2, only one LED element 11 is arranged on the substrate 10, but a plurality of LED elements 11 may be arranged on the substrate 10.

2-2. Application of Phosphor-Containing Liquid A phosphor-dispersing liquid is discharged from the above-mentioned phosphor-dispersing liquid supply body so as to cover the above-described LED element, thereby forming a phosphor-containing layer. At this time, the phosphor dispersion liquid supply body may be installed in the coating apparatus, and the phosphor dispersion liquid may be coated directly on the LED element from the nozzle of the phosphor dispersion liquid supply body. Alternatively, the phosphor dispersion liquid may be filled in a coating liquid tank in the coating apparatus, and the phosphor dispersion liquid may be applied using a dispenser, a spray nozzle, an inkjet nozzle, or the like included in the coating apparatus.

  Here, immediately before the phosphor dispersion liquid is discharged, the plunger of the plastic syringe of the phosphor dispersion liquid supply body is moved to the open end side of the barrel, that is, the side opposite to the nozzle, so that the space in the plastic syringe is reduced. An operation of spreading and stirring the phosphor dispersion liquid may be performed.

  Moreover, the coating amount of the phosphor dispersion liquid is appropriately selected according to the type of the LED device, the thickness of the desired phosphor-containing layer, and the like. The thickness of the coating film after drying of the phosphor dispersion is usually preferably about 5 to 200 μm, more preferably 10 to 200 μm, and still more preferably 10 to 100 μm. When the thickness of the phosphor-containing layer containing the phosphor particles is within the above range, the wavelength of light from the LED element can be sufficiently converted by the phosphor particles. The thickness of the phosphor-containing layer means the maximum thickness of the film formed on the light emitting surface of the LED element. The thickness is measured with a laser holo gauge.

  After application of the phosphor dispersion liquid, the solvent in the phosphor-containing liquid is dried. The temperature at which the phosphor dispersion liquid is dried is usually 20 to 200 ° C, and preferably 25 to 150 ° C. If it is lower than 20 ° C., there is a possibility that it cannot be sufficiently dried. On the other hand, if it exceeds 200 ° C., the LED element may be affected. Moreover, drying time is 0.1 minutes-1 hour normally from the surface of manufacturing efficiency, Preferably it is 0.5 minutes-30 minutes. Moreover, when binder components, such as a translucent ceramic precursor, are contained in a fluorescent substance dispersion liquid, this is hardened. For example, when the binder component is an alkoxysilane monomer or an oligomer thereof, the heating temperature is preferably 100 ° C. or higher, more preferably 150 to 300 ° C. If the heating temperature is less than 100 ° C., moisture generated during dehydration condensation of alkoxysilane or the like cannot be sufficiently removed, and the light resistance of the phosphor-containing layer may be lowered.

  On the other hand, when the binder component contained in the phosphor dispersion liquid 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 further cured. It is preferable to perform heat curing. The phosphor-containing layer becomes a dense film, and the moisture resistance of the obtained LED device tends to increase.

  In the above description, the method of applying the phosphor dispersion liquid taken out from the phosphor dispersion supply body directly onto the LED element has been described. However, if necessary, the phosphor dispersion liquid may be diluted with a solvent or other components may be used. It may be applied on the LED element after being mixed.

2-3. Application of Binder or Binder Precursor In the LED device manufacturing method of the present invention, when the phosphor dispersion liquid does not contain a binder component, the phosphor particles in the phosphor-containing layer obtained by applying the phosphor dispersion liquid, etc. You may have the process of apply | coating the binder for binding, or its precursor.

  Specifically, a binder forming composition containing a binder component such as a transparent resin, a precursor thereof, and a translucent ceramic precursor, and a solvent is applied onto the phosphor-containing layer and cured. The phosphor particles can be bound. Examples of the transparent resin that can be a binder component and its precursor include a silicone resin and an epoxy resin.

  On the other hand, the translucent ceramic precursor that may be a binder component may be a known alkoxysilane monomer or an oligomer thereof, a polysilazane oligomer, or the like. These are not particularly limited as long as they are hydrolyzed and polycondensed to form polysiloxane.

  When the binder component is the above-mentioned transparent resin or a precursor thereof, the solvent is hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; propylene glycol monomethyl ether acetate And esters such as ethyl acetate. On the other hand, when the binder component is a translucent ceramic precursor, the solvent may be a monovalent alcohol, a divalent or higher polyhydric alcohol, an ester solvent, and the like.

  The method for applying the binder-forming composition is appropriately selected depending on the type of the binder component, and can be, for example, dispenser application or spray application. Moreover, the composition for binder formation is hardened as needed after application | coating of the composition for binder formation. The curing method and curing conditions of the binder forming composition are appropriately selected depending on the type of resin. An example of the curing method is heat curing.

  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.

[material]
The materials used for preparing the phosphor dispersion are as follows.
-Phosphor particles YAG phosphor: YAG 450C (manufactured by Nemoto Special Chemical Co., Ltd.)
Silicon chlorooxynitride barium strontium-based phosphor: ASK-23 (manufactured by Nemoto Special Chemical Co., Ltd.)
Orthosilicate phosphor: EY4254 (manufactured by Intematix Corporation)
・ Solvent 1-BuOH (1-butanol)
PG (propylene glycol)
・ Clay mineral particles Smecton SA (Saponite, manufactured by Kunimine)
・ Inorganic particles AEROSIL RX300 (silica, manufactured by Nippon Aerosil Co., Ltd.)
・ Binder component KBM13 (Methyltrimethoxysilane, KBM13: Shin-Etsu Chemical Co., Ltd.)

[Preparation of phosphor dispersion]
The materials were mixed at a mass ratio shown in Table 1 below, and dispersed for 15 minutes by an ultrasonic dispersion device to obtain phosphor dispersions A to I. The viscosity of the phosphor dispersion was measured after the vibrator was immersed for 1 minute with a vibration viscometer (manufactured by CBC: VM-10A) at 25 ° C.

[Preparation of phosphor dispersion liquid supply body]
Each phosphor dispersion liquid was filled into a plastic syringe shown in Table 2 below in a specific amount to obtain a phosphor dispersion liquid supply body. The filling rate was calculated from the ratio between the hollow volume formed by the inner wall of the barrel of the plastic syringe and the nozzle side end of the plunger and the volume of the phosphor dispersion filled in the plastic syringe.

The following plastic syringes were used.
・ 2ml plastic syringe: Henke Sass Wolf, trade name HSW NORM-JECT syringe)
-10 ml plastic syringe: Henke Sass Wolf, trade name HSW NORM-JECT syringe)
・ 20ml plastic syringe: Henke Sass Wolf, trade name HSW NORM-JECT syringe)
・ 10ml plastic syringe (with gasket): Terumo ・ 8ml plastic bottle: PS screw tube

[Evaluation]
The amount of residue and the total luminous flux reduction rate of each phosphor dispersion liquid supply body were measured as follows.
(Amount of residue)
Measure the mass of the plastic syringe before filling the phosphor dispersion liquid and the mass of the plastic syringe after discharging the phosphor dispersion liquid, and from these differences, the amount of the phosphor dispersion liquid remaining in the plastic syringe Was calculated. In the case of plastic bottles, the same method was used.

(Total luminous flux reduction rate)
The total luminous flux reduction rate is determined when the LED device is manufactured using the phosphor dispersion liquid immediately after preparation, and when the LED device is prepared using the phosphor dispersion liquid after filling each phosphor dispersion liquid in a container and performing a vibration test. The total luminous flux was compared with the case where it was produced and evaluated. More specifically, the total luminous flux was evaluated by the following method.

[Production of LED device using phosphor dispersion immediately after preparation]
Immediately after preparation, the phosphor dispersion was supplied to a spray coating apparatus. On the other hand, a substrate on which an LED element (emission peak wavelength 450 nm: rectangular parallelepiped; 200 μm × 300 μm × 100 μm) was prepared was prepared, and a phosphor dispersion liquid was spray-coated on the LED element. This board | substrate was heated at 150 degreeC for 1 hour, and fluorescent substance particle was fixed on the LED element. Then, a current of 20 mA was passed through each LED element, and chromaticity was measured. Chromaticity measurement was performed with a spectral radiance meter CS-1000A manufactured by Konica Minolta Sensing. Based on the obtained chromaticity value, the coating conditions of the spray coating apparatus were reset so that the chromaticity x value was 0.33.
Subsequently, a substrate (LED element mounting package) on which a total of 64 LED elements (emission peak wavelength 450 nm: rectangular parallelepiped shape; 200 μm × 300 μm × 100 μm) in 8 rows × 8 columns was prepared. The phosphor dispersion liquid was spray-coated on each LED element of the substrate. This board | substrate was heated at 150 degreeC for 1 hour, the fluorescent substance particle was fixed on the LED element, and the fluorescent substance containing layer was obtained.
Next, 15 parts by mass of tetramethoxysilane (KBM04: manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of methyltrimethoxysilane (KBM13: manufactured by Shin-Etsu Chemical Co., Ltd.), 40 parts by mass of 1-propanol, and 40 parts by mass of ethanol And 2 parts by mass of hydrochloric acid were mixed to obtain a binder forming composition. And the composition for binder formation was apply | coated with the spray apparatus from the fluorescent substance content layer. At this time, the spray pressure was 0.1 MPa, and the moving speed of the nozzle was 100 mm / s. Thereafter, the binder-forming composition was heated at 150 ° C. for 1 hour to obtain a wavelength conversion part in which the phosphor particles were bound with a translucent ceramic. The thickness of the obtained wavelength conversion part was 30 micrometers.
In Example 15, the binder forming composition was not applied.

[Vibration test of phosphor dispersion liquid supply body]
As described above, the phosphor dispersion liquid was filled in each container to prepare a phosphor dispersion liquid supply body. Thereafter, the phosphor dispersion liquid supply body was vibrated for 30 minutes in accordance with a packed cargo-vibration test (JIS Z0232). The vibration test apparatus used was “J230 / SA3M” manufactured by IMV. And the LED apparatus was produced by the method similar to the above.

[Evaluation of total luminous flux reduction rate]
About the apparatus produced using the phosphor dispersion liquid immediately after preparation, one LED element and a wavelength conversion part are regarded as one LED apparatus, and the light from each LED apparatus is manufactured by Konica Minolta Sensing Co., Ltd., respectively. The total luminous flux was measured with CS-1000A. From 64 LED devices, 10 devices having an x value in the range of 0.330 ± 0.005 were selected, and an average value L0 of these total luminous fluxes was obtained.
On the other hand, also about the apparatus produced using the fluorescent substance dispersion liquid after a vibration test, 10 pieces were selected from 64 LED apparatuses by the method similar to the above, and the average value Lx of these total luminous flux was calculated | required. The total luminous flux before and after the vibration test of the corresponding phosphor dispersion liquid was compared.
The total luminous flux reduction rate was calculated from the formula (L0−Lx / L0) × 100.

  As shown in Table 2 above, in the phosphor dispersion liquid supply bodies (Examples 1 to 15 and Comparative Examples 1, 2, and 4) in which a plastic syringe is filled with a phosphor dispersion liquid, the amount of residue is 0.00. It was 25 g or less, which was a very small value. It is inferred that a residue is hardly generated in the plastic syringe by extruding the phosphor dispersion liquid with the plunger. In contrast, in the phosphor dispersion liquid supply body (Comparative Examples 3 and 5) in which the plastic bottle is filled with the phosphor dispersion liquid, the residual amounts are 0.70 g and 0.50 g, and the phosphor particles remain on the inner wall. It was.

  Moreover, when the filling amount (volume) of the phosphor dispersion liquid is 90% by volume or more with respect to the hollow volume formed by the barrel inner wall of the plastic syringe and the nozzle side end of the plunger (Examples 1 to 15), The total luminous flux decrease rate after the vibration test was small. Also by the dispersion test, it is presumed that the phosphor particles hardly collide with each other in the phosphor dispersion liquid and the phosphor particles did not easily deteriorate. In contrast, when the amount of the phosphor dispersion liquid was less than 90% by volume with respect to the hollow volume in the syringe (Comparative Examples 1, 2, and 4), the total luminous flux reduction rate was high. It is inferred that the phosphor particles were partially deteriorated and the wavelength of light from the LED element could not be sufficiently converted.

  In the phosphor dispersion liquid supply body of the present invention, the phosphor dispersion liquid hardly remains in the container, and the phosphor particles can be used without waste. Moreover, in the phosphor dispersion liquid supply body of the present invention, the phosphor particles contained in the phosphor dispersion liquid are hardly deteriorated and high quality can be maintained. Therefore, the phosphor dispersion liquid supplied from the phosphor dispersion liquid supply body of the present invention is very useful as a solution for forming the phosphor-containing layer of various light emitting devices.

DESCRIPTION OF SYMBOLS 1 Plastic syringe 1a Barrel 1b Nozzle 1c Plunger 2 Phosphor dispersion liquid 10 Substrate 11 LED element 12 Phosphor containing layer 13 Metal wiring 14 Projection electrode 100 LED device

Claims (6)

A barrel provided with a nozzle at one end, and a plastic syringe having a plunger inserted from the other end of the barrel and slidable in the barrel;
A phosphor dispersion liquid containing phosphor particles and a solvent and filled in the plastic syringe;
The phosphor dispersion liquid supply, wherein the volume of the phosphor dispersion liquid is 90% by volume or more with respect to the hollow volume in the plastic syringe surrounded by the inner wall of the barrel and the side end of the nozzle of the plunger. body.   The phosphor dispersion liquid supply body according to claim 1, wherein a volume of the phosphor dispersion liquid is 95% by volume or more with respect to a hollow volume in the plastic syringe.   3. The phosphor dispersion liquid supply body according to claim 1, wherein the phosphor dispersion liquid has a viscosity at 25 ° C. of 80 to 2000 mPa · s measured by a vibration viscometer.   The phosphor dispersion liquid supply body according to any one of claims 1 to 3, wherein the phosphor dispersion liquid further contains at least one of inorganic particles and clay minerals.   The transport method of the fluorescent substance dispersion liquid using the fluorescent substance dispersion liquid supply body as described in any one of Claims 1-4. A method for manufacturing a light emitting device comprising a substrate, a light emitting element disposed on the substrate, and a phosphor-containing layer formed on the light emitting element,
The phosphor dispersion liquid supply body according to claim 1 is installed in a coating apparatus, and the phosphor liquid discharged from the nozzle of the phosphor dispersion liquid supply body is placed on the light emitting element. Forming the phosphor-containing layer;
A method for manufacturing a light emitting device, comprising:

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