JP2015153856A - Light emitting device and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light emitting device less in deterioration over time of a reflective layer and also capable of sufficiently extracting light from a side surface of a light emitting element, and a method for manufacturing the light emitting device.SOLUTION: A light emitting device includes: a substrate; a light emitting element mounted on a mounting region of the substrate; a liquid repellent layer formed at a peripheral part of the mounting region of the substrate; and a reflective layer formed on the substrate and the outer circumference of the liquid repellent layer. A method for manufacturing the light emitting device includes the steps of: forming a liquid repellent layer on a surface of a substrate at a peripheral part of a mounting region of a light emitting element; and applying a reflective layer formation composition on the substrate and outside the liquid repellent layer to form a reflective layer.

Description

  The present invention relates to a light emitting device and a method for manufacturing the same.

  In recent years, semiconductor laser devices, LED devices, and the like have been widely applied as alternatives to various light sources, conventional fluorescent lamps, and incandescent lamps. In such a light emitting device, further improvement in light extraction efficiency and longer life are required.

  Therefore, in a general light emitting device, a reflector having a high light reflectance is arranged around the light emitting element. Such a reflector is generally formed of metal plating or the like, and reflects light emitted from the light emitting element toward the light extraction surface.

  However, since the substrate of the light emitting device usually includes wiring such as lead electrodes, a reflector made of metal cannot be formed on the entire surface of the substrate from the viewpoint of preventing electrical conduction. And in the area | region in which the reflector is not formed, light was absorbed by the board | substrate and it was difficult to fully improve light extraction efficiency. Furthermore, the reflector made of metal plating is easily corroded by hydrogen sulfide gas or the like contained in the usage environment of the light emitting device. For this reason, there has been a problem that the light extraction efficiency from the light emitting device decreases with time.

  Therefore, it has been proposed to cover the metal plating with a transparent resin layer (Patent Document 1) or to cover the metal plating with a white resin layer (Patent Document 2).

  On the other hand, in an LED device, it is common to convert light of a specific wavelength emitted from an LED element into light of another specific wavelength by a phosphor. As a manufacturing method of such an LED device, after applying a liquid repellent material to the outer periphery of a flat substrate, a phosphor dispersion liquid is applied on the substrate, thereby forming a wavelength conversion layer only in a desired region. A method has been proposed (Patent Document 3).

JP 2005-136379 A JP 2011-23621 A JP 2012-44048 A

  In the techniques described in Patent Document 1 and Patent Document 2 described above, the resin is easily deteriorated by heat or light. When the resin is deteriorated, the corrosion of the metal plating proceeds. Therefore, with this technology, it has been difficult to sufficiently suppress a decrease in light extraction efficiency from the light emitting device. In particular, in applications where a large amount of light is required, such as in-vehicle headlights, the resin is likely to deteriorate.

  Accordingly, it is conceivable to form a reflective layer made of an inorganic material by applying a composition in which light diffusion particles are dispersed in an inorganic material on a substrate. However, when the composition for obtaining the reflective layer adheres to the light emitting surface of the light emitting element, light cannot be extracted from the light emitting element. Therefore, there is a problem that the light extraction efficiency from the light emitting device cannot be sufficiently increased.

  The present invention has been made in view of the above-described problems. That is, the present invention provides a light-emitting device with little deterioration with time of the reflective layer and sufficient light extraction from the side surface of the light-emitting element, and a method for manufacturing the same.

The present invention provides the following light-emitting device manufacturing method.
[1] A substrate, a light emitting element mounted on a mounting region of the substrate, a liquid repellent layer formed on a peripheral portion of the mounting region of the substrate, and formed on the substrate and on an outer periphery of the liquid repellent layer A method of manufacturing a light-emitting device including a reflective layer, the step of forming a liquid-repellent layer including a liquid-repellent material on a substrate surface at a peripheral portion of a light-emitting element mounting region, on the substrate and from the liquid-repellent layer Applying a reflective layer forming composition to the outside to form a reflective layer.

[2] Manufacture of a light emitting device including a substrate, a light emitting element mounted on the mounting region of the substrate, a liquid repellent layer formed outside the mounting region of the substrate, and a reflective layer covering the liquid repellent layer A method for forming a liquid repellent layer containing a liquid repellent material on a substrate surface outside a mounting region of a light emitting element, and a composition for forming a reflective layer on the substrate so as to cover the liquid repellent layer And a step of forming a reflective layer.

[3] The method for manufacturing a light emitting device according to [2], wherein the liquid repellent layer forming step is a step of forming the liquid repellent layer over the entire substrate surface outside the mounting region.
[4] The method for manufacturing a light emitting device according to [2], wherein the liquid repellent layer forming step is a step of forming the liquid repellent layer in a plurality of lines on a substrate surface outside the mounting region.
[5] The method for manufacturing a light-emitting device according to any one of [2] to [4], wherein the reflective layer forming step is a step of forming a reflective layer whose thickness changes continuously.
[6] The method for manufacturing a light emitting device according to any one of [1] to [5], wherein the liquid repellent layer forming step is a step of forming a liquid repellent layer by a vapor deposition method.

[7] The method for manufacturing a light emitting device according to any one of [1] to [6], wherein the light emitting element is an LED element.
[8] In the above [7], the light emitting device further includes a wavelength conversion layer covering the LED element, and a step of applying a wavelength conversion layer composition containing phosphor particles and a binder on the light emitting element. The manufacturing method of the light-emitting device of description.
[9] The method for manufacturing a light-emitting device according to any one of [1] to [8], wherein the reflective layer forming composition contains a solvent, and the liquid repellent layer has liquid repellency with respect to the solvent. .

The present invention also provides the following light emitting device.
[10] A substrate, a light emitting element mounted on a mounting region of the substrate, a liquid repellent layer formed on a peripheral portion of the mounting region of the substrate, and formed on the substrate and on an outer periphery of the liquid repellent layer A light emitting device having a reflective layer.
[11] A light emitting device comprising: a substrate; a light emitting element mounted on a mounting region of the substrate; a liquid repellent layer formed outside the substrate mounting region; and a reflective layer covering the liquid repellent layer.
[12] The light emitting device according to [11], wherein the thickness of the reflective layer changes continuously.

  In the light emitting device obtained by the method of the present invention, the light emitting surface of the light emitting element is not covered by the reflective layer, and light can be sufficiently extracted from the light emitting surface of the light emitting element. In addition, since the reflective layer hardly deteriorates with time, high light extraction efficiency is maintained over a long period of time.

FIG. 1A is a schematic cross-sectional view showing an example of a light-emitting device obtained by the manufacturing method of the first aspect of the present invention, and FIG. 1B is a top view of the light-emitting device. FIG. 2A is a schematic cross-sectional view showing another example of the light emitting device obtained by the manufacturing method of the first aspect of the present invention, and FIG. 2B is a top view of the light emitting device. It is a schematic sectional drawing which shows the other example of the light-emitting device obtained with the manufacturing method of the 1st aspect of this invention. It is a schematic sectional drawing which shows the other example of the light-emitting device obtained with the manufacturing method of the 1st aspect of this invention. It is an example of the process figure of the 1st aspect of the manufacturing method of the light-emitting device of this invention. It is another example of the process figure of the 1st aspect of the manufacturing method of the light-emitting device of this invention. It is a schematic sectional drawing which shows an example of the light-emitting device obtained with the manufacturing method of the 2nd aspect of this invention. It is a schematic sectional drawing which shows the other example of the light-emitting device obtained with the manufacturing method of the 2nd aspect of this invention. It is a schematic sectional drawing which shows the other example of the light-emitting device obtained with the manufacturing method of the 2nd aspect of this invention. It is an example of the process figure of the 2nd aspect of the manufacturing method of the light-emitting device of this invention. It is explanatory drawing for demonstrating the liquid repellent layer formation process of the 2nd aspect of the manufacturing method of the light-emitting device of this invention, Fig.10 (a) is a schematic sectional drawing, FIG.10 (b) is a top view. is there. It is a schematic sectional drawing which shows an example of the light-emitting device produced in the Example 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 the method of the present invention, a light emitting device is manufactured that includes a substrate, a light emitting element mounted on the substrate, and a reflective layer for reflecting light emitted from the light emitting element toward the light extraction surface. In the present invention, there are the following two modes depending on the method of forming the reflective layer.

1. First Aspect In the first aspect, as shown in FIG. 1, a substrate 1, a light emitting element 2 mounted in a mounting region of the substrate 1, and a repellent formed on a substrate surface at a peripheral portion of the light emitting element 2. The light emitting device 100 having the liquid layer 3 and the reflective layer 4 formed on the outer peripheral substrate surface of the liquid repellent layer 3 is manufactured. Note that in this embodiment, the peripheral portion of the light-emitting element 2 refers to a region around a region where the substrate 1 and the light-emitting element 2 are stacked (hereinafter also referred to as “mounting region”). The substrate surface refers to a surface on which the light emitting element 2 is mounted among the surfaces constituting the substrate 1.

  In this embodiment, as will be described later, the liquid repellent layer 3 is formed on the substrate surface at the peripheral edge of the light emitting element 2 and then the reflective layer 4 is formed. As a result, the liquid repellent layer 3 controls the fluidity and adhesion area of the reflective layer forming composition and suppresses the adhesion of the light emitting element 2 to the light emitting surface. That is, the light emitting surface of the light emitting element 2 is not covered with the reflective layer forming composition, and the light emitted from the light emitting element 2 is sufficiently extracted.

  Here, in the light emitting device 100 obtained by the method of this aspect, the binder of the reflective layer 4 is preferably polysiloxane. In this case, the reflective layer 4 is hardly deteriorated by heat or light, and the light reflectivity of the reflective layer 4 is less likely to deteriorate with time.

  In addition, as shown in FIG. 3, in the light emitting device 100 obtained by the method of this aspect, in addition to the above-described members, light of a specific wavelength emitted from the light emitting element 2 is converted into light of another specific wavelength. A wavelength conversion layer 13 may be further included.

1-1. Members included in light emitting device 1-1-1. Substrate The substrate 1 included in the light emitting device 100 may have a cavity (concave portion) as shown in FIG. The shape of the cavity is not particularly limited. For example, as shown in FIG. 1A, the shape may be a columnar shape, a truncated cone shape, a truncated pyramid shape, a prismatic shape, or the like. Further, the bottom surface of the cavity may be parallel to the mounting surface of the light emitting element 2 as shown in FIG. 1A, but a part of the bottom surface of the cavity is in relation to the mounting surface of the light emitting element 2. May have an angle.

  The substrate 1 preferably has insulating properties and heat resistance, and is preferably 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.

  The substrate 1 may contain an inorganic filler. The inorganic filler can be titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, glass fiber, and the like.

  The substrate 1 usually includes a lead electrode 11 for supplying electricity to the light emitting element 2. The lead electrode 11 is made of a metal such as silver. The substrate 1 having the lead electrode 11 is produced by a general method, and is obtained, for example, by integrally molding a resin and a lead frame.

1-1-2. Light-Emitting Element The light-emitting element 2 included in the light-emitting device 100 can be fixed to the mounting area of the substrate 1 and electrically connected to the lead electrode 11 included in the substrate 1. The kind in particular of the said light emitting element 2 is not restrict | limited, A semiconductor laser element, an LED element, etc. may be sufficient. In the light emitting device 100 illustrated in FIG. 1, only one light emitting element 2 is disposed on the substrate 1, but a plurality of light emitting elements 2 may be disposed on the substrate 1.

  The semiconductor laser element and the LED element are electrically connected to the lead electrode 11 included in the substrate 1 and emit light of a specific wavelength. The wavelength of light emitted from the semiconductor laser element or the LED element is not particularly limited. For example, the LED element can be an element that emits blue light (light of about 420 nm to 485 nm) or an element that emits ultraviolet light.

  When the LED element is an element that emits blue light, the LED element 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). Layer) and a transparent electrode layer. The LED element may have a light emitting surface (upper surface) of, for example, 200 to 300 μm × 200 to 300 μm. Moreover, the height of an LED element is about 50-200 micrometers normally. The light emitting element may extract light from only the upper surface, or may extract light from the upper surface and side surfaces.

  The connection method between the light emitting element 2 and the lead electrode 11 of the substrate 1 is not particularly limited. When the light emitting element 2 is an LED element, for example, as shown in FIG. 1, the LED element and the lead electrode 11 can be connected via a metal wire 12. Further, the LED element 2 can be connected to the lead electrode 11 via the protruding electrode. A mode in which the LED element 2 and the lead electrode 11 are connected through the metal wire 12 is referred to as a wire bonding type, and a mode in which the LED element 2 and the lead electrode 11 are connected through the protruding electrode is a flip chip type. That's it.

1-1-3. Liquid Repellent Layer The liquid repellent layer 3 included in the light emitting device 100 is a layer formed on the substrate surface at the peripheral edge of the mounting region of the light emitting element 2. The contact angle of the reflective layer forming composition with respect to the liquid repellent layer 3 is higher than the contact angle of the reflective layer forming composition with respect to the substrate 1. As a result, the adhesion region and thickness of the reflective layer forming composition are adjusted by the liquid repellent layer, and the adhesion of the reflective layer forming composition to the light emitting surface of the light emitting element 2 is suppressed. The liquid repellent layer 3 not only adjusts the adhesion region of the reflective layer forming composition by liquid repellency, but also physically reflects the adhesion region of the reflective layer forming composition depending on the shape of the liquid repellent layer 3. You may adjust.

  In this aspect, it is preferable that the liquid repellent layer is formed in the peripheral portion of the mounting region of the light emitting element 2, specifically, within a range of 10 μm or less from the outer edge of the mounting region.

  Further, the formation region of the liquid repellent layer 3 is not particularly limited as long as it is a region that can suppress contact between the composition for forming a reflective layer and the light emitting surface of the light emitting device 2, but as shown in FIG. 2 is preferably formed so as to surround the mounting area. On the other hand, the liquid repellent layer 3 may be formed adjacent to the mounting region of the light emitting element 2 as shown in FIG. 1, and as shown in FIGS. 2A and 2B, the light emitting element 2. It may be formed with a gap between the two mounting regions. As shown in FIG. 2B, when the liquid repellent layer 3 is formed with a gap from the mounting region of the light emitting element 2, there is a substrate between the liquid repellent layer 3 and the light emitting element 2. 1 is exposed. Therefore, from the viewpoint of reducing the exposed area of the substrate 1 and suppressing the absorption of light to the substrate 1, the liquid repellent layer 3 is formed on the light emitting element 2 as shown in FIGS. It is preferable that they are formed adjacent to each other.

  The liquid repellent layer 3 may be formed not only on the substrate surface in the mounting region of the light emitting element 2 but also on the upper surface or side surface of the light emitting element 2. The liquid repellent layer 3 may be formed between the substrate 1 and the light emitting element 2.

  The width of the liquid repellent layer 3 is appropriately selected according to the viscosity of the composition for forming the reflective layer, etc., but even if it is very thin, it is possible to suppress adhesion of the composition for forming the reflective layer to the light emitting surface of the light emitting element 2. is there. For example, the width of the liquid repellent layer 3 can be 10 μm or less.

  On the other hand, the thickness of the liquid repellent layer 3 is appropriately selected according to the method of forming the liquid repellent layer 3. For example, when the liquid repellent layer 3 is formed by a vapor deposition method, the liquid repellent layer 3 is not particularly limited. For example, the liquid repellent layer 3 may be a monomolecular film or the like. On the other hand, when the liquid repellent layer 3 is formed by a coating method, it is usually preferably 100 nm or more.

The molecular weight of the liquid repellent material contained in the liquid repellent layer 3 is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. Examples of the liquid repellent material include silicone resin, titanium oxide water repellent, fluorine water repellent, grease, wax and the like. Examples of silicone resins include KER-6020F, KER-6075F, KER-2500 A / B, KER-2600 A / B, KE-109E A / B, KE-1011 A / B, KE-1286T A / B, X-33-197 (primer), SIM-240, KT-1286T A / B, KP-911, X-24-9481 (all manufactured by Shin-Etsu Silicone); OE6370, JCR6101, JCR6125A / B, SH200 (1 mm ² / S), SH200 (10 ⁵ mm ² / s), SH200 (10 ⁶ mm ² / s) (all manufactured by Toray Dow Corning); XE14-3445A / B (made by Momentive Performance); It is.

  Examples of the titanium oxide-based water repellent include NANO INDEX (manufactured by CTC NANOTECHNOROGY).

  Examples of the fluorine-based water repellent include perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkyl ammonium salt, oligomer containing perfluoroalkyl group and hydrophilic group, perfluoroalkyl group and hydrophilic group. Fluorine-containing oligomers containing fluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and new oil groups, urethanes containing perfluoroalkyl groups and hydrophilic groups, perfluoroalkyl esters, perfluoroalkyl phosphate esters, etc. Organic compounds and the like are included. Specific examples of the fluorine-based water repellent include Megafuck F116, Megafuck F120, Megafuck F142D, Megafuck F144D, Megafuck F150, Megafuck F160, Megafuck F171, Megafuck F172, Megafuck F173, and Megafuck F177. , Megafuck F178A, Megafuck F178K, Megafuck F179, Megafuck F183, Megafuck F184, Megafuck F191, Megafuck F812, Megafuck F815, Megafuck F824, Megafuck F833, DEFENSAMCF300, Megafuck MCF310, Megafuck MCF312 , Megafuck MCF323, Megafuck RS304, Megafuck RS202, Megafuck RS201, Megafa CRS102, Megafuck RS101, Megafuck RS105, Megafuck RS401, Megafuck RS402, Megafuck RS501, Megafuck RS502, Megafuck RS301, Megafuck RS303 (all manufactured by Dainippon Ink & Chemicals, Inc.); Florard FC430, Mega Fuck FC431 (all manufactured by Sumitomo 3M); Asahi Guard AG710, Surflon S-382, Megafuck SC-101, Megafuck SC-102, Megafuck SC-103, Megafuck SC-104, Megafuck SC-105, Megafuck SC-106 (all manufactured by Sumitomo 3M); Obtool DAC (manufactured by Daikin Industries), FS-1090, FS-5060 (all manufactured by Fluoro Technology); SFE-G 01, SFE-G008, SFE-X14H (all manufactured by AGC Say Chemical Co., Ltd.), are included.

  Examples of greases include Apolloyl Autolex J-2 (transparent type), Apolloyl Autolex A (light yellowish brown type), Apolloyl Autolex L (light greenish type), Apolloyl Grease reservoir (yellowish brown type), Apolloyl Chassis No. . 0 (brown, dropping point 100 degrees), Apolloyl Chassis No. 000 (light yellow type), Daphne Eponex SR No. 0 (white cap), Daphne Eponex SR No. 2 (blue cap) (all manufactured by Idemitsu Kosan Co., Ltd.); HIVAC-G (manufactured by Shin-Etsu Silicone); Y VAC3 (manufactured by FOMBLIN); high vacuum grease (manufactured by Toray Dow Corning); polybutene HV-1900, polybutene LV-7, Polybden HV-300, Chassis Grease 00, Taflix RB-2 (all manufactured by JX Nippon Oil & Energy), Omega No. 22, Omega No. 33, omega no. 38, omega no. 58, Zeta No. 201 (both manufactured by OMEGA);

  Examples of the wax include Aqua Wax SE442, Aqua Wax SE567, Aqua Wax 50 (all manufactured by Nikka Seiko Co., Ltd.), paraffin wax, micro wax, water-soluble wax (all manufactured by Nippon Seiwa Co., Ltd.); Paraffin wax (JX Manufactured by Nippon Mining & Energy Corporation).

In addition, examples of the liquid repellent material in the case of forming a liquid repellent layer by a vapor deposition method include CF ₄ , SF ₆ , alternative chlorofluorocarbon (HFC), and the like. When a liquid repellent layer is formed with these liquid repellent materials, a layer made of fluoride is formed on the surface of the substrate 1.

1-1-4. Reflective Layer The reflective layer 4 included in the light emitting device 100 of this aspect is a layer formed on the outer peripheral substrate surface of the liquid repellent layer 3 and is formed in contact with the liquid repellent layer 3. The end of the reflective layer 4 on the light emitting element 2 side may cover a part of the liquid repellent layer 3. The reflection layer 4 is a layer that reflects the light emitted from the light emitting element 2 and the fluorescence emitted from the phosphor particles contained in the wavelength conversion layer 13 described later to the light extraction surface side of the light emitting device 100. The light extraction efficiency from the light emitting device 100 is increased by the reflection layer 4 reflecting light.

  The reflective layer 4 is formed so as not to cover the light emitting surface of the light emitting element 2. Here, when light is extracted also from the side surface of the light emitting element 2, a gap is formed between the light emitting element side end of the reflective layer 4 and the side surface of the light emitting element 2, as shown in FIG. It is preferable that The gap is preferably 10 μm or more. At this time, as shown in FIG. 1A, the end of the reflective layer 4 and the side surface of the light emitting element 2 may be in contact with each other on the substrate 1 side of the reflective layer 4.

  The thickness of the reflective layer 4 is preferably 5 to 50 μm, more preferably 5 to 30 μm. If the thickness of the reflective layer 4 is 50 μm or less, cracks are unlikely to occur in the reflective layer 4. On the other hand, when the thickness of the reflective layer 4 is 5 μm or more, the light reflectivity of the reflective layer 4 is likely to be sufficiently increased. The reflective layer 4 may have a constant thickness within the film, but the thickness may change continuously or intermittently.

  The reflective layer 4 preferably contains light diffusing particles and polysiloxane. The light diffusing particles contained in the reflective layer 4 are not particularly limited as long as they have high light diffusibility. The total reflectance of the light diffusing particles is preferably 80% or more, and more preferably 90% or more. The total reflectance can be measured by Hitachi High-Tech, Hitachi spectrophotometer U4100.

  Examples of light diffusing particles include calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, titanium oxide, magnesium oxide, zirconium oxide, zinc sulfide, aluminum hydroxide, boron nitride, aluminum nitride , Potassium titanate, barium titanate, aluminum titanate, strontium titanate, calcium titanate, magnesium titanate, hydroxyapatite, and the like. These particles have a high total reflectance and are easy to handle. The reflective layer 4 may contain only one type of light diffusing particles, or two or more types.

  The average primary particle size of the light diffusing particles is preferably larger than 100 nm and not larger than 20 μm, more preferably larger than 100 nm and not larger than 10 μm, further preferably 200 nm to 2.5 μm. The average primary particle size in the present invention 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 light diffusing particles contained in the reflective layer 4 is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass with respect to the total mass of the reflective layer 4. When the amount of the light diffusing particles is 60% by mass or more, the light reflectivity of the reflective layer 4 is likely to be sufficiently increased. On the other hand, when the amount of the light diffusing particles is 95 mass or less, the amount of the binder is relatively increased, and the strength of the reflective layer 4 is easily increased.

  On the other hand, the polysiloxane that is the binder of the reflective layer 4 may be a cured product of a bifunctional silane compound, a trifunctional silane compound, a tetrafunctional silane compound, or an oligomer thereof. The oligomer of the silane compound is obtained by subjecting a monomer of the silane compound to a condensation reaction.

  The polysiloxane which is the binder of the reflective layer 4 can be, for example, a trifunctional silane compound and a polymer of a tetrafunctional silane compound monomer or oligomer thereof. The polymerization ratio (molar ratio) of the trifunctional silane compound and the tetrafunctional silane compound is preferably 3: 7 to 7: 3, and more preferably 4: 6 to 6: 4. When the polymerization ratio (molar ratio) is in the above range, the degree of crosslinking of the polysiloxane does not increase excessively, and cracks in the reflective layer 4 are suppressed. On the other hand, since the hydroxyl group present on the surface of the substrate 1 or the liquid repellent layer 3 and the silicon in the polysiloxane are sufficiently bonded with siloxane, the adhesion between the reflective layer 4 and the substrate 1 or the liquid repellent layer 3 is increased. Cheap.

  The polysiloxane that is the binder of the reflective layer 4 may be a polymer of a bifunctional silane compound and a trifunctional silane compound monomer or oligomer thereof (polysiloxane). The polymerization ratio (molar ratio) of the bifunctional silane compound and the trifunctional silane compound is preferably 1: 9 to 4: 6, and more preferably 1: 9 to 3: 7. When the polymerization ratio is in the above range, the hydroxyl group present on the surface of the substrate 1 or the liquid repellent layer 3 and the silicon in the polysiloxane are sufficiently siloxane-bonded. Adhesion with 3 is sufficiently enhanced.

  The polysiloxane that is the binder of the reflective layer 4 may be a polymer of a bifunctional silane compound, a trifunctional silane compound, and a monomer or oligomer of a tetrafunctional silane compound. The polymerization ratio of the bifunctional silane compound is preferably 3 to 30 (mol) when the total amount (mol) of the bifunctional silane compound, trifunctional silane compound, and tetrafunctional silane compound is 100. The polymerization ratio of the trifunctional silane compound is preferably 40 to 80 (mol) when the total amount (mol) of the bifunctional silane compound, trifunctional silane compound, and tetrafunctional silane compound is 100. The polymerization ratio of the tetrafunctional silane compound is preferably 10 to 30 (mol) when the total amount (mol) of the bifunctional silane compound, trifunctional silane compound, and tetrafunctional silane compound is 100.

Examples of the tetrafunctional silane compound include a compound represented by the following general formula (II).
Si (OR ⁴ ) ₄ (II)
In said general formula (II), R < ⁴ > represents an alkyl group or a phenyl group each independently, Preferably it represents a C1-C5 alkyl group or a phenyl group.
Specific examples of tetrafunctional silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxymonomethoxy. Silane, trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, Triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Orchid, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dibutoxymonomethoxymonoethoxysilane, Alkoxy silanes such as dibutoxy monoethoxy monopropoxy silane, monomethoxy monoethoxy monopropoxy monobutoxy silane, or aryloxy silane are included. Among these, tetramethoxysilane and tetraethoxysilane are preferable.

Examples of the trifunctional silane compound include a compound represented by the following general formula (III).
R ⁵ Si (OR ⁶ ) ₃ (III)
In the general formula (III), R ⁶ each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group. R ⁵ represents a hydrogen atom or an alkyl group.

  Specific 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, monophenyl Monohydrosilane compounds such as ruoxydiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltripentyloxysilane, methylmonomethoxydiethoxysilane, methylmonomethoxydipropoxysilane, methylmonomethoxydipentyl Monomethylsilane compounds such as oxysilane, methylmonomethoxydiphenyloxysilane, methylmethoxyethoxypropoxysilane, methylmonomethoxymonoethoxymonobutoxysilane; ethyltrimethoxysilane, ethyltripropoxysilane, ethyltripentyloxysilane, ethyltriphenyloxy Silane, ethyl monomethoxydiethoxysilane, ethyl monomethoxydipropoxysilane, ethyl monomethoxydipentyloxy Monoethylsilane compounds such as lan, ethylmonomethoxydiphenyloxysilane, ethylmonomethoxymonoethoxymonobutoxysilane; propyltrimethoxysilane, propyltriethoxysilane, propyltripentyloxysilane, propyltriphenyloxysilane, propylmonomethoxydi Monopropylsilane compounds such as ethoxysilane, propylmonomethoxydipropoxysilane, propylmonomethoxydipentyloxysilane, propylmonomethoxydiphenyloxysilane, propylmethoxyethoxypropoxysilane, propylmonomethoxymonoethoxymonobutoxysilane; butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltripentyloxysilane, Butyltriphenyl Monobutylsilane compounds such as oxysilane, butylmonomethoxydiethoxysilane, butylmonomethoxydipropoxysilane, butylmonomethoxydipentyloxysilane, butylmonomethoxydiphenyloxysilane, butylmethoxyethoxypropoxysilane, butylmonomethoxymonoethoxymonobutoxysilane Is included. Among these, methyltrimethoxysilane and methyltriethoxysilane are preferable, and methyltrimethoxysilane is particularly preferable.

Examples of the bifunctional silane compound include a compound represented by the following general formula (IV).
R ⁷ ₂ Si (OR ⁸ ) ₂ (IV)
In the general formula (IV), R ⁸ each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group. R ⁷ represents a hydrogen atom or an alkyl group.

  Specific examples of the bifunctional silane compound include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxy. Silane, ethoxypentyloxysilane, ethoxyphenyloxysilane, methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, methylmethoxypropoxysilane, methylmethoxypentyloxysilane, methylmethoxyphenyloxysilane, ethyldipropoxysilane, ethylmethoxy Propoxysilane, ethyldipentyloxysilane, ethyldiphenyloxysilane, propyldimethoxysilane, propylene Methoxyethoxysilane, propylethoxypropoxysilane, propyldiethoxysilane, propyldipentyloxysilane, propyldiphenyloxysilane, butyldimethoxysilane, butylmethoxyethoxysilane, butyldiethoxysilane, butylethoxypropoxysilane, butyldipropoxysilane, butyl Methyldipentyloxysilane, butylmethyldiphenyloxysilane, dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyl Methoxypropoxysilane, diethyldiethoxysilane, diethyl ether Xypropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutylmethoxypentyloxysilane, dibutylmethoxyphenyl Oxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylbutyldimethoxysilane, methylbutyl Diethoxysilane, methylbutyldipropoxysilane, methylethylethoxypropoxysilane, ethyl Includes propyldimethoxysilane, ethylpropylmethoxyethoxysilane, dipropyldimethoxysilane, dipropylmethoxyethoxysilane, propylbutyldimethoxysilane, propylbutyldiethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutylethoxypropoxysilane, etc. . Among these, dimethoxysilane, diethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable.

  The amount of polysiloxane contained in the reflective layer 4 is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the total mass of the reflective layer 4. When the amount of polysiloxane is 5% by mass or more, the strength of the reflective layer 4 is likely to be sufficiently increased. On the other hand, when the amount of polysiloxane is 40 mass or less, the amount of light diffusing particles is relatively increased, and the light reflectivity of the reflective layer 4 is likely to increase.

  The reflective layer 4 may include inorganic fine particles, clay mineral particles, and the like in addition to the light diffusing particles and the polysiloxane. If the reflective layer 4 contains inorganic fine particles, the strength of the reflective layer 4 tends to increase. The average primary particle size of the inorganic fine particles is preferably 5 nm to 100 nm, more preferably 5 to 80 nm, still more preferably 5 to 50 nm. When the average primary particle size of the inorganic fine particles is within such a range, the inorganic fine particles enter the gaps between the light diffusing particles, and the strength of the reflective layer 4 tends to increase. The average primary particle size of the inorganic fine particles is measured by a Coulter counter method.

  Examples of the inorganic fine particles include silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide and the like. The surface of the inorganic fine particles may be treated with a silane coupling agent or a titanium coupling agent.

  The amount of the inorganic fine particles contained in the reflective layer 4 is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably based on the total mass of the reflective layer 4. Is 1-10 mass%. When the amount of the inorganic fine particles is less than 0.5% by mass, the strength of the reflective layer 4 is not sufficiently increased. On the other hand, when the amount of inorganic fine particles exceeds 30% by mass, the amount of polysiloxane and light diffusing particles is relatively reduced, and the film strength and light reflectivity may be lowered.

  Moreover, when the clay mineral particles are included in the reflective layer 4, the strength of the reflective layer 4 is likely to increase. Examples of clay mineral particles include layered silicate minerals, allophane, and the like. The layered silicate mineral is preferably a swellable clay mineral having a mica structure, a kaolinite structure, or a smectite structure.

  Examples of layered silicate minerals include natural or synthetic hectorite, saponite, stevensite, hydelite, montmorillonite, nontrite, bentonite, laponite, and other smectite clay minerals, Na-type tetralithic fluoromica, Li-type Non-swelling mica genus clay minerals such as swellable mica genus clay minerals such as tetrasilic fluorinated mica, Na type fluorine teniolite, Li type fluorine teniolite, muscovite, phlogopite, fluorine phlogopite, sericite, potassium tetrasilicon mica , And vermiculite and kaolinite, or mixtures thereof.

  The amount of the clay mineral particles contained in the reflective layer 4 is preferably 0.1 to 5% by mass and more preferably 0.2 to 2% by mass with respect to the total mass of the reflective layer 4.

1-1-5. Wavelength Conversion Layer As described above, in the light emitting device 100 of this aspect, as shown in FIG. 3, the wavelength conversion layer 13 that converts the light of the specific wavelength emitted from the light emitting element 2 into the light of another specific wavelength. May be included. The wavelength conversion layer 13 may be a layer formed so as to cover the light emitting element 2 and the reflective layer 4.

  The thickness of the wavelength conversion layer 13 is preferably about 25 μm to 5 mm. If the wavelength conversion layer 13 is too thick, the concentration of the phosphor particles contained in the wavelength conversion layer 13 may vary. The thickness of the wavelength conversion layer 13 means the maximum thickness of the wavelength conversion layer 13 formed on the light emitting surface of the light emitting element 2. The thickness of the wavelength conversion layer 13 can be measured with a laser holo gauge.

  The wavelength conversion layer 13 includes phosphor particles and a binder. The phosphor particles receive light (excitation light) emitted from the light emitting element 2 and emit fluorescence. By mixing the excitation light and the fluorescence, the color of the light from the light emitting device 100 becomes a desired color. For example, when the light emitted from the light emitting element 2 is blue and the fluorescence emitted from the phosphor included in the wavelength conversion layer 13 is yellow, the light from the light emitting device 100 is white.

  The phosphor particles contained in the wavelength conversion layer 13 may be anything that is excited by light emitted from the light emitting element 2 and emits fluorescence having a wavelength different from that of the light emitted from the light emitting element 2. 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 light emitting element 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. . The mixed raw material having a predetermined composition can be obtained by mixing 1) a solution in which rare earth elements of Y, Gd, Ce, and Sm are dissolved in an acid with a stoichiometric ratio and oxalic acid to obtain a coprecipitated oxide. 2) It can also be obtained by mixing this coprecipitated oxide with aluminum oxide or gallium oxide.

  The 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 at the interface between the phosphor particles and the binder becomes large. Thereby, the intensity | strength of the cured film of a wavelength conversion layer tends to fall. 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 wavelength conversion layer 13 is usually 5 to 15% by mass.

  On the other hand, the binder contained in the wavelength conversion layer 13 may be a transparent resin or the like. The transparent resin can be, for example, a silicone resin and an epoxy resin.

1-2. Modified Example of Configuration of Light-Emitting Device A light-emitting device 100 obtained by the manufacturing method according to this aspect covers a substrate 1, a light-emitting element 2 mounted on the substrate 1, and the light-emitting element 2, as shown in FIG. The configuration also includes a wavelength conversion layer 13 ′, a liquid repellent layer 3 formed on the outer peripheral substrate surface of the wavelength conversion layer 13 ′, and a reflective layer 4 formed on the outer peripheral substrate surface of the liquid repellent layer 3. sell.

  Conventionally, the formation of a reflective layer on the substrate surface outside the wavelength conversion layer has also been studied. In this case, the affinity between the reflective layer forming composition for forming the reflective layer and the wavelength conversion layer is high. The composition easily coats the wavelength conversion layer. On the other hand, in the light emitting device 100 of this embodiment, the liquid repellent layer 3 is formed around the wavelength conversion layer 13 ′, and then the reflective layer 4 is formed. As a result, the liquid repellent layer 3 suppresses the reflective layer forming composition for forming the reflective layer 4 from adhering to the side surface and the top surface of the wavelength conversion layer 13 ′. That is, the coating of the wavelength conversion layer 13 ′ and the like by the reflective layer 4 is suppressed, and light is sufficiently extracted from the light emitting device 100.

  The wavelength conversion layer 13 ′ preferably covers only the light emitting element 2 and its outer periphery. Specifically, the wavelength conversion layer 13 ′ preferably covers the light emitting element 2 and the surrounding area of 10 μm or more, and more preferably covers a region of 30 to 70 μm. When the area of the wavelength conversion layer 13 'is increased, the area of the reflective layer 4 is relatively reduced. Therefore, the light emitted from the light emitting element 2 and the light emitted from the phosphor particles in the wavelength conversion layer 13 ′ are not easily reflected on the light extraction surface side.

  Note that each member included in the light emitting device 100 of this aspect may be the same as described above.

1-3. Method for Manufacturing Light-Emitting Device The manufacturing method according to the first aspect includes the following two steps.
(1) Step of forming a liquid repellent layer on the substrate surface at the peripheral edge of the light emitting element mounting region (2) Applying a reflective layer forming composition to a substrate outside the liquid repellent layer to form a reflective layer The process to perform You may have the process of mounting a light emitting element on a board | substrate as needed, and the process of forming a wavelength change layer on a light emitting element.

  An example of the manufacturing method of this aspect is shown in FIG. In this embodiment, the light emitting element 2 is mounted on the substrate 1 (FIG. 5A), and the liquid repellent layer 3 is formed on the substrate surface at the peripheral portion of the mounting region of the light emitting element 2 (FIG. 5B). Then, a reflective layer forming composition is applied to the substrate surface outside the liquid repellent layer 3 to form a reflective layer (FIGS. 5C and 5D). Further, if necessary, a wavelength conversion layer 13 that covers the light emitting element 2 and the reflective layer 4 is formed (FIG. 5E).

  In the method of this aspect, for example, as shown in FIG. 5C, the liquid repellent layer 3 is formed on the substrate surface at the peripheral portion of the mounting region of the light emitting element 2. Therefore, at the time of applying the reflective layer forming composition, the reflective layer forming composition does not adhere to the light emitting surface of the light emitting element 2 (FIG. 5D), and the light emitting surface of the light emitting element 2 is covered with the reflective layer 4. It becomes difficult.

  In this aspect, the light emitting element mounting step may be performed after the liquid repellent layer forming step. That is, the liquid repellent layer forming step / light emitting element mounting step / reflective layer forming step may be performed in this order.

1-3-1. Light-Emitting Element Mounting Process In the light-emitting element mounting process, the light-emitting element 2 is mounted on the substrate 1 as shown in FIG. The mounting method of the light emitting element 2 may be a method of fixing the light emitting element 2 to the substrate 1 and electrically connecting the electrode of the light emitting element 2 and the lead electrode 11. The method for fixing the light emitting element 2 to the substrate 1 is not particularly limited, and may be a method for fixing by, for example, die bonding. The connection method between the light emitting element 2 and the lead electrode 11 is not particularly limited, and may be a method of connecting via the metal wire 12 or a method of connecting via the protruding electrode as described above.

1-3-2. Liquid-repellent layer forming step In the liquid-repellent layer forming step, a liquid-repellent layer is formed on the substrate surface at the periphery of the mounting region of the light-emitting element 2 as shown in FIG. At this time, a liquid repellent layer may be formed not only on the periphery of the mounting region of the light emitting element 2 but also on the upper surface and side surfaces of the light emitting element 2 as necessary. Further, if necessary, a liquid repellent layer may be formed on the connection portion between the lead electrode 11 and the metal wire 12 of the substrate 1 other than the peripheral portion of the mounting region of the light emitting element 2.

  Moreover, when performing a light emitting element mounting process after a liquid repellent layer formation process as mentioned above, you may form a liquid repellent layer in the mounting area | region of the light emitting element 2 as needed.

  The method for forming the liquid repellent layer is not particularly limited. For example, a spin coating method, a transfer method, a spray method, an electric field spray method, an electric field application dipping method, or the like; or a plasma CVD method, a plasma polymerization method, an ion plating method, It may be a gas phase film forming method such as a plasma assist method or a vapor deposition method.

  When the liquid repellent layer is formed by a coating method, the method for applying the liquid repellent layer forming composition is not particularly limited as long as the liquid repellent layer forming composition can be applied only to a desired region. For example, as shown in FIG. 5B, a mask 21 having an opening is disposed only in the application region of the liquid repellent layer forming composition, and the liquid repellent material is spray applied from the spray device 500 through the mask. Etc. Moreover, the method of apply | coating the liquid repellent layer forming composition only to a desired area | region with a dispenser or an inkjet apparatus may be used.

  The liquid repellent layer forming composition applied in the liquid repellent layer forming step includes the above-described liquid repellent material, and optionally includes a solvent. The kind of the solvent contained in the composition for forming a liquid repellent layer is not particularly limited as long as the above liquid repellent material can be uniformly dispersed or dissolved.

  After the application of the liquid repellent layer forming composition, the liquid repellent layer forming composition is dried as necessary. Examples of the drying method include heat drying.

  On the other hand, when the liquid repellent layer is formed by a vapor deposition method, the liquid repellent material is attached to a desired region through a plate-like mask having an opening only in the region where the liquid repellent layer is formed.

1-3-3. Reflective Layer Forming Step In the reflective layer forming step, as shown in FIG. 5C, the reflective layer forming composition is applied to the substrate surface outside the liquid repellent layer 3. By applying the reflective layer forming composition from the outside of the liquid repellent layer 3, the flow of the reflective layer forming composition is limited by the liquid repellency of the liquid repellent layer 3, and the light emitting element 2 of the reflective layer forming composition. Is suppressed from adhering to the light emitting surface (FIG. 5D).

  The method for applying the reflective layer forming composition is not particularly limited as long as the reflective layer forming composition can be applied to the substrate surface outside the liquid repellent layer 3. For example, as shown in FIG. 5 (c), a method of dropping a reflective layer forming composition from a dispenser 510 at a predetermined position may be used. Moreover, the method of apply | coating the composition for reflective layer formation from an inkjet apparatus may also be used. Furthermore, a plate-like mask or the like that covers the liquid repellent layer 3 or the light-emitting element 2 may be disposed, and spray coating may be performed through the plate-like mask. The application position of the composition for forming a reflective layer is not particularly limited as long as it is outside the liquid repellent layer, but is appropriately selected according to the desired thickness of the liquid repellent layer.

  The composition for forming a reflective layer applied in the reflective layer forming step may be a composition containing the above-described light diffusing particles, the above-described polysiloxane precursor (a monomer of a silane compound or an oligomer thereof), and a solvent. When the reflective layer forming composition contains a solvent, the reflective layer forming composition wets and spreads in a desired region, and the light diffusing particles and the polysiloxane precursor easily adhere to the desired region. The composition for forming a reflective layer may contain the aforementioned inorganic fine particles and the aforementioned clay mineral particles as necessary. When clay mineral particles are contained in the reflective layer forming composition, the viscosity of the reflective layer forming composition tends to increase, and the speed at which the reflective layer forming composition spreads out is easily adjusted.

  The solvent contained in the composition for forming a reflective layer is not particularly limited as long as it can sufficiently dissolve or disperse the light diffusing particles and the polysiloxane precursor, but is preferably a solvent having a boiling point of 250 ° C. or lower. When the boiling point of the solvent is 250 ° C. or lower, the drying rate of the composition for forming a reflective layer tends to increase.

  Examples of the solvent contained in the composition for forming a reflective layer include monoalcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, and 1,4-butanediol. Etc. The reflective layer forming composition may contain only one type of solvent or two or more types of solvents.

  The amount of the solvent contained in the reflective layer forming composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and more preferably 1% to 10% by mass with respect to the total mass of the reflective layer forming composition. Preferably it is 3-10 mass%.

  Here, the liquid repellent layer described above preferably has liquid repellency with respect to the solvent of the reflective layer forming composition. Having liquid repellency means that the contact angle of the substrate 1 with the liquid repellent layer 3 is higher than the contact angle of the reflective layer forming composition with respect to the substrate 1.

  In particular, the difference between the contact angle of the liquid repellent layer 3 with respect to the substrate 1 and the contact angle of the composition for forming a reflective layer with respect to the substrate 1 is preferably 30 to 60 °. When the difference is 30 ° or more, the liquid repellent layer 3 makes it easy to adjust the fluidity of the reflective layer forming composition, and the reflective layer forming composition is prevented from adhering to the light emitting surface of the light emitting element. . The difference in the contact angle is adjusted depending on the liquid repellent material contained in the liquid repellent layer 3 and the type of solvent contained in the reflective layer forming composition.

  The contact angle of the liquid repellent layer 3 with respect to the substrate 1 is determined by forming the liquid repellent layer 3 on a test piece made of the same material as the substrate 1 and measuring the contact angle between the liquid repellent layer 3 and the test piece with a contact angle meter. However, when the contact angle is very small (3 ° or less), the cross section is observed with a microscope to identify the contact angle. Moreover, the contact angle with the test piece which consists of the same material as the board | substrate 1 is similarly measured about the composition for reflective layer formation. Then, the difference is calculated.

  After the application of the reflective layer forming composition, the reflective layer forming composition is dried and cured. The temperature at which the composition for forming a reflective layer is dried and cured is preferably 20 to 200 ° C, more preferably 25 to 150 ° C. If the temperature is lower than 20 ° C., the solvent in the composition for forming a reflective layer may not be sufficiently evaporated. On the other hand, when the temperature exceeds 200 ° C., the substrate 1 and the light emitting element 2 may be affected. The drying / curing time is preferably from 0.1 to 30 minutes, more preferably from 0.1 to 15 minutes, from the viewpoint of production efficiency.

1-3-4. Step for Forming Wavelength Conversion Layer The manufacturing method of this aspect may include a step for forming the wavelength changing layer 13 that covers the light emitting element 2 as shown in FIG. The wavelength conversion layer forming step may be a step of preparing a composition for a wavelength conversion layer containing a binder component and phosphor particles, and applying and curing the composition so as to cover the light emitting element 2 and the reflective layer 4. .

  The method for applying the composition for wavelength conversion layer is not particularly limited as long as it is a method capable of applying the composition for wavelength conversion layer at a desired position, and may be, for example, application from a dispenser or an inkjet device.

  The binder component contained in the wavelength conversion layer composition may be the above-described transparent resin or a precursor thereof. Moreover, a solvent is contained in the composition for wavelength conversion layers as needed. The solvent contained in the composition for wavelength conversion layers is not particularly limited as long as it can dissolve or disperse the binder component. The solvent may be hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; esters such as propylene glycol monomethyl ether acetate and ethyl acetate;

  This is hardened after application | coating of the composition for wavelength conversion layers. The curing method and curing conditions of the wavelength conversion layer composition are appropriately selected depending on the type of binder component. An example of the curing method is heat curing.

1-4. Modification of Manufacturing Method of Light-Emitting Device of First Aspect In the method of this aspect, a wavelength conversion layer forming step may be performed before the liquid repellent layer forming step. Specifically, as shown in FIG. 6, the light emitting element 2 is mounted on the substrate 1 (FIG. 6A), and the wavelength conversion layer 13 ′ is formed so as to cover the light emitting element 2 (FIG. 6). (B)). At this time, the wavelength conversion layer 13 ′ does not cover the entire substrate surface outside the mounting region of the light emitting element 2, but covers only the light emitting element 2 and its outer periphery. Then, the liquid repellent layer 3 is formed on the substrate surface outside the wavelength conversion layer 13 ′ (FIG. 6C), and the reflective layer forming composition is applied to the substrate surface outside the liquid repellent layer 3. The reflective layer 4 is formed (FIG. 6D).

  According to this method, it is difficult for the reflective layer forming composition to adhere to the wavelength conversion layer 13 ′ when the reflective layer forming composition is applied. The mounting method of the light emitting element 2, the method of forming the wavelength conversion layer 13 ', the method of forming the liquid repellent layer 3, and the method of forming the reflective layer 4 in the modification can be the same as those described above.

2. Second Aspect In the method according to the second aspect, as shown in FIG. 7, the substrate 1, the light emitting element 2 mounted on the substrate 1, and the substrate surface outside the mounting region of the light emitting element 2 are formed. The light emitting device 200 having the liquid repellent layer 3 and the reflective layer 4 covering the liquid repellent layer 3 is manufactured.

  In this aspect, as will be described later, after the liquid repellent layer 3 is formed on the substrate surface outside the mounting region of the light emitting element 2, the reflective layer 4 is formed so as to cover the liquid repellent layer 3. As a result, the wet spreading speed and the wet spreading area of the composition for forming the reflective layer 4 are controlled, and the composition does not adhere to the side surface of the light emitting element 2. That is, a gap is generated between the side surface of the light emitting element 2 and the reflective layer 4, and light emitted from the side surface of the light emitting element 2 is sufficiently extracted.

  Furthermore, in the light emitting device 200 obtained by the manufacturing method of this aspect, the binder of the reflective layer 4 is polysiloxane. Therefore, the reflective layer 4 is hardly deteriorated by heat or light, and the light reflectivity of the reflective layer 4 is less likely to deteriorate with time.

  In addition to the above-described members, the light-emitting device 200 of this aspect may further include a wavelength conversion layer 13 that converts light of a specific wavelength emitted from the light-emitting element 2 into light of another specific wavelength. .

2-1. Member included in light-emitting device The substrate 1, the light-emitting element 2, and the wavelength conversion layer included in the light-emitting device 200 of this aspect may be the same as the substrate 1, the light-emitting element 2, and the wavelength conversion layer 13 of the first aspect. .

2-1-1. Liquid Repellent Layer The liquid repellent layer 3 included in the light emitting device 200 of this embodiment is a layer formed on the substrate surface outside the mounting region of the light emitting element 2 as shown in FIG. The contact angle of the reflective layer forming composition with respect to the liquid repellent layer 3 is higher than the contact angle of the reflective layer forming composition with respect to the substrate 1. Since the contact angle of the reflective layer forming composition with respect to the liquid repellent layer 3 is high, the wet spreading speed of the reflective layer forming composition is suppressed, and the wet spreading area of the reflective layer forming composition is controlled. As a result, adhesion of the reflective layer forming composition to the light emitting surface of the light emitting element 2 is suppressed.

  As shown in FIG. 7, the liquid repellent layer 3 of this embodiment may be a layer formed over the entire substrate surface outside the mounting region of the light emitting element 2. When such a liquid repellent layer 3 is formed, it is easy to adjust the wetting and spreading speed of the reflective layer forming composition when applying the reflective layer forming composition for forming the reflective layer 4 described later. As a result, the reflective layer 4 is formed only in a desired region.

  On the other hand, as shown in FIG. 8, the liquid repellent layer 3 of this embodiment may be a plurality of line-shaped layers that multiplexly surround the mounting region of the light emitting element 2. When such a liquid repellent layer 3 is formed, the speed at which the composition for forming a reflective layer wets and spreads is adjusted by the density of the liquid repellent layer 3 when a reflective layer 4 described later is formed. For example, in a region where the liquid repellent layer 3 is densely formed, the reflective layer forming composition is difficult to spread. On the other hand, in the region where the liquid repellent layer is formed sparsely, the reflective layer forming composition is likely to spread out. Therefore, the reflective layer 4 whose thickness continuously changes as shown in FIG. 8 is also formed by the pattern of the liquid repellent layer.

  The line width of the line-shaped liquid repellent layer 3 is appropriately selected according to the desired shape of the wavelength conversion layer 4 and the thickness of the wavelength conversion layer 4. Further, the interval between the plurality of line-like liquid repellent layers 3 is also appropriately selected according to the desired shape of the wavelength conversion layer 4 and the thickness of the wavelength conversion layer 4.

  Also in this embodiment, the liquid repellent layer 3 may be formed not only on the substrate surface in the mounting region of the light emitting element 2 but also on the upper surface or side surface of the light emitting element 2. Further, the liquid repellent layer 3 may be formed between the substrate 1 and the light emitting element 2.

  The thickness of the liquid repellent layer 3 is appropriately selected according to the method for forming the liquid repellent layer. For example, when the liquid repellent layer 3 is formed by a vapor deposition method, the liquid repellent layer 3 may be a monomolecular film or the like. On the other hand, when the liquid repellent layer 3 is formed by a coating method, it is usually 100 nm or more.

The liquid repellent layer 3 includes a liquid repellent material. Examples of the liquid repellent material include silicone resin, titanium oxide water repellent, fluorine water repellent, grease, wax, CF ₄ , SF ₆ , alternative chlorofluorocarbon (HFC), and the like. It may be the same as the liquid repellent material contained in the liquid repellent layer.

2-1-2. Reflective Layer The reflective layer 4 included in the light emitting device 200 of this aspect covers the liquid repellent layer 3 described above. The reflection layer 4 is a layer that reflects light emitted from the light emitting element 2 and fluorescence emitted from phosphor particles contained in the wavelength conversion layer 13 described later to the light extraction surface side of the light emitting device 200. The light extraction efficiency from the light emitting device 200 is increased by the reflection layer 4 reflecting light.

  Also in this embodiment, the reflective layer 4 is formed so as not to cover the light emitting surface of the light emitting element 2. Here, when light is extracted also from the side surface of the light emitting element 2, a gap is formed between the reflective layer 4 and the light emitting surface (for example, the side surface) of the light emitting element 2, as shown in FIG. It is preferable. The gap is preferably 10 μm or more. At this time, as shown in FIG. 7, the end of the reflective layer 4 and the side surface of the light emitting element 2 may be in contact with each other on the substrate 1 side of the reflective layer 4.

  The thickness of the reflective layer 4 is preferably 5 to 50 μm, more preferably 5 to 30 μm. If the thickness of the reflective layer 4 is 50 μm or less, cracks are unlikely to occur in the reflective layer 4. On the other hand, when the thickness of the reflective layer 4 is 5 μm or more, the light reflectivity of the reflective layer 4 is likely to be sufficiently increased. The reflective layer 4 may have a constant thickness within the film, but the thickness may change continuously or intermittently. For example, as shown in FIG. 8, the thickness of the reflective layer 4 increases toward the outer peripheral side of the substrate 1; that is, when the space surrounded by the reflective layer 4 becomes a mortar shape, It becomes easy to be taken out.

  The reflective layer 4 contains light diffusing particles and polysiloxane, and may contain inorganic fine particles and clay mineral particles as necessary. These may be the same as each material included in the reflective layer 4 of the first embodiment.

2-2. Modified Example of Light Emitting Device of Second Aspect As shown in FIG. 9, a light emitting device 200 obtained by the manufacturing method of this aspect includes a substrate 1, a light emitting element 2 mounted on the substrate 1, and the light emitting element 2. A wavelength conversion layer 13 ′ covering the substrate, a liquid repellent layer 3 formed on the outer peripheral substrate surface of the wavelength conversion layer 13 ′, and a reflective layer 4 formed on the outer peripheral substrate surface of the liquid repellent layer 3. But it can be.

  As described above, when the reflective layer is formed on the substrate surface outside the wavelength conversion layer, the affinity for the reflective layer forming composition for forming the reflective layer and the wavelength conversion layer is high, and the composition has a wavelength. Easy to coat the conversion layer. On the other hand, in the light emitting device 200 of this embodiment, the liquid repellent layer 3 is formed around the wavelength conversion layer 13 ′, and then the reflective layer 4 is formed. As a result, the liquid repellent layer 3 suppresses the reflective layer forming composition for forming the reflective layer 4 from adhering to the side surface and the top surface of the wavelength conversion layer 13 ′. That is, the wavelength conversion layer 13 ′ or the like is prevented from being covered with the reflective layer 4, and light is sufficiently extracted from the light emitting device 200.

  The wavelength conversion layer 13 ′ preferably covers only the light emitting element 2 and its outer periphery. Specifically, the wavelength conversion layer 13 ′ preferably covers the light emitting element 2 and the surrounding area of 10 μm or more, and more preferably covers a region of 30 to 70 μm. When the area of the wavelength conversion layer 13 'is increased, the area of the reflective layer 4 is relatively reduced. Therefore, the light emitted from the light emitting element 2 and the light emitted from the phosphor particles in the wavelength conversion layer 13 ′ are not easily reflected on the light extraction surface side.

  Each member included in the light emitting device 200 of this aspect may be the same as described above.

2-3. Manufacturing method of light-emitting device The manufacturing method of the second aspect includes the following two steps.
(1) Step of forming a liquid repellent layer on the substrate surface outside the light emitting element mounting region (2) Step of applying a reflective layer forming composition so as to cover the liquid repellent layer and forming a reflective layer In addition, the method may further include a step of mounting the light emitting element on the mounting region of the substrate and a step of forming the wavelength changing layer on the light emitting element.

  An example of the manufacturing method of this aspect is shown in FIG. In this embodiment, the light emitting element 2 is mounted on the substrate 1 (FIG. 10A), and the liquid repellent layer 3 is formed on the substrate surface outside the mounting region of the light emitting element 2 of the substrate 1 (FIG. 10B). ). And the composition for reflective layer formation is apply | coated so that the liquid repellent layer 3 may be covered, and the reflective layer 4 is formed (FIG.10 (c) and FIG.10 (d)). Further, if necessary, a wavelength conversion layer 13 that covers the light emitting element 2 and the reflective layer 4 is formed (not shown).

  In the method of this aspect, for example, as shown in FIG. 10B, the liquid repellent layer 3 is formed outside the mounting region of the light emitting element 2. Therefore, in the reflective layer forming step, as shown in FIG. 10C, when the reflective layer forming composition is applied from the outer edge side of the substrate 1, the speed at which the reflective layer forming composition spreads out increases the light emitting element 2. It gets slower as you get closer. As a result, the composition for forming the reflective layer does not spread before contacting the light emitting surface of the light emitting element 2, and, for example, between the side surface of the light emitting element 2 and the reflective layer 4 as shown in FIG. A gap can be formed.

  In this aspect, the light emitting element mounting step may be performed after the liquid repellent layer forming step. That is, the liquid repellent layer forming step / light emitting element mounting step / reflective layer forming step may be performed in this order.

  The light emitting element mounting process and the wavelength conversion layer forming process in this aspect may be the same as in the first aspect. Therefore, the liquid repellent layer forming step and the reflective layer forming step will be described below.

2-3-1. Liquid Repellent Layer Forming Step The liquid repellent layer forming step is a step of forming the liquid repellent layer 3 on the substrate surface outside the mounting region of the light emitting element 2 as shown in FIG. The method for forming the liquid repellent layer 3 is not particularly limited. For example, a spin coating method, a transfer method, a spray method, an electric field spray method, an electric field application dipping method or the like; or a plasma CVD method, a plasma polymerization method, an ion plating method Further, it may be a vapor phase film forming method such as a plasma assist method or a vapor deposition method.

  The coating method may be a step of forming the liquid repellent layer 3 by applying the liquid repellent layer forming composition to the entire substrate surface outside the mounting region of the light emitting element 2. At this time, the composition for forming a liquid repellent layer may be applied to the upper surface and side surfaces of the light emitting element 2 as well as the substrate surface at the periphery of the mounting region of the light emitting element 2 as necessary. Moreover, when performing a light emitting element mounting process after a liquid repellent layer formation process, you may apply | coat the composition for liquid repellent layer formation to the board | substrate surface of the mounting area | region of the light emitting element 2 as needed.

  On the other hand, in the liquid repellent layer forming step, as shown in FIG. 11, the liquid repellent layer forming composition is applied in a plurality of lines surrounding the mounting region of the light emitting element 2 to form the liquid repellent layer 3. It can also be a process. In this case, the speed at which the composition for forming a reflecting layer spreads out in the reflecting layer forming step described later is adjusted by the interval between the adjacent liquid repellent layers 3. For example, as shown in FIG. 11, when the liquid repellent layers 3A, 3B, and 3C are formed in three lines, in the region (3A to 3B) where the distance between the liquid repellent layers is narrow, the liquid repellent layer has a repellent property. Due to the liquidity, the composition for forming a reflective layer becomes difficult to spread. On the other hand, in the region (3B to 3C) where the interval between the liquid repellent layers is wide, the composition for forming a reflective layer is easily spread.

  The method for applying the liquid repellent layer forming composition is not particularly limited as long as the liquid repellent layer forming composition can be applied only to a desired region. For example, a method of arranging a mask for protecting the light emitting element 2 and spraying a liquid repellent material from the spray device through the mask may be used. Moreover, the method of apply | coating the composition for liquid repellent layer to a desired area | region with a dispenser or an inkjet apparatus may be used.

  The liquid repellent layer forming composition applied in this embodiment can be the same as the liquid repellent layer forming composition of the first embodiment. After application of the liquid repellent layer forming composition, the liquid repellent layer forming composition is dried as necessary.

  On the other hand, when the liquid repellent layer is formed by a vapor phase film forming method, the liquid repellent layer forming material is attached via a plate-like mask having an opening only in the region where the liquid repellent layer is formed.

2-3-2. Reflective layer forming step In the reflective layer forming step, as shown in FIG. 10C, the reflective layer forming composition is applied so as to cover the liquid repellent layer 3 to form the reflective layer 4. By applying the reflective layer forming composition so as to cover the liquid repellent layer 3, the wetting and spreading speed of the reflective layer forming composition is adjusted, and the thickness and shape of the reflective layer forming composition are adjusted. Furthermore, the contact between the reflective layer 4 and the light emitting surface of the light emitting element is suppressed (FIG. 10D).

  The method for applying the reflective layer forming composition in this embodiment is not particularly limited, but the reflective layer forming composition is dropped from a predetermined position so that the reflective layer forming composition spreads in a desired direction. It is preferable. The position where the composition for forming a reflective layer is dropped is appropriately selected according to the shape of the substrate 1, the pattern of the liquid repellent layer 3, the shape of the desired reflective layer 4, and the like. For example, as shown in FIG. 10C, when the reflective layer forming composition is applied from the wall surface side of the substrate 1 having a cavity, the reflective layer forming composition spreads in the direction of the light emitting element 2. The dropping method of the composition for forming a reflective layer is not particularly limited, and can be dispenser coating, inkjet coating, or the like.

  Also in this embodiment, the liquid repellent layer 3 described above preferably has liquid repellency with respect to the solvent of the reflective layer forming composition. The difference between the contact angle of the liquid repellent layer 3 with respect to the substrate 1 and the contact angle of the reflective layer forming composition with respect to the substrate 1 is preferably 30 to 60 °. When the difference is 30 ° or more, the liquid repellent layer easily adjusts the fluidity of the reflective layer forming composition, and the reflective layer forming composition is suppressed from adhering to the light emitting surface of the light emitting element. The difference in the contact angle is adjusted depending on the liquid repellent material contained in the liquid repellent layer 3 and the type of solvent contained in the reflective layer forming composition. The method for measuring the contact angle may be the same as the method for measuring the contact angle of the first aspect.

  In this aspect, the reflective layer forming composition is sufficiently wetted and spread in a desired region, and then the reflective layer forming composition is dried and cured. The temperature at which the composition for forming a reflective layer is dried and cured is preferably 20 to 200 ° C, more preferably 25 to 150 ° C. If the temperature is lower than 20 ° C., the solvent in the composition for forming a reflective layer may not be sufficiently evaporated. On the other hand, when the temperature exceeds 200 ° C., the substrate 1 and the light emitting element 2 may be affected. The drying / curing time is preferably from 0.1 to 30 minutes, more preferably from 0.1 to 15 minutes, from the viewpoint of production efficiency.

2-4. Modification of Method for Manufacturing Light-Emitting Device of Second Aspect In the method of this aspect as well, the wavelength conversion layer forming step may be performed before the liquid repellent layer forming step. Specifically, the light emitting element 2 is mounted on the substrate 1, and the wavelength conversion layer 13 ′ is formed so as to cover the light emitting element 2. At this time, the wavelength conversion layer 13 ′ does not cover the entire substrate surface outside the mounting region of the light emitting element 2, but covers only the light emitting element 2 and its outer periphery. Then, the liquid repellent layer 3 is formed on the substrate surface outside the wavelength conversion layer 13 ′, and the reflective layer forming composition is applied to the substrate surface outside the liquid repellent layer 3 to form a reflective layer.

  According to this method, at the time of applying the reflective layer forming composition, the reflective layer forming composition hardly adheres to the wavelength conversion layer 13 ′, and the light emitting element side end of the reflective layer 4 and, for example, the wavelength conversion layer 13 ′. A gap is formed between the two. The mounting method of the light emitting element 2, the method of forming the wavelength conversion layer 13 ', the method of forming the liquid repellent layer 3, and the method of forming the reflective layer 4 in the modification can be the same as those described above.

  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]
(Preparation of substrate)
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate is made of polyphthalic amide (PPA) resin, a rectangular parallelepiped having a size of 3.2 mm × 2.8 mm × 1.8 mm, a truncated conical cavity having an opening diameter of 2.4 mm, a wall surface angle of 90 °, and a depth of 0.85 mm. Was formed. A lead electrode and an LED element included in this substrate were connected by a wire to obtain a package. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. Moreover, the peak wavelength of the emitted light of the LED element is 475 nm, and the LED element emits light from the side surface.

(Formation of liquid repellent layer)
A mask having an opening only on the peripheral edge of the LED element mounting area of the above-described package (area having a width of 100 μm from the outer edge of the LED element) was disposed on the package. Then, a composition for forming a liquid repellent layer (fluorine-based liquid repellent material, KP-911: manufactured by Shin-Etsu Chemical Co., Ltd.) was spray applied from above the mask. Thereafter, it was naturally dried for 30 seconds to form a liquid repellent layer. The width of the liquid repellent layer was 100 μm, and the thickness of the liquid repellent layer was 0.592 μm.

(Formation of reflective layer)
A mixture of 7.5% by mass of tetramethoxysilane, 2.5% by mass of methyltrimethoxysilane, 35% by mass of methanol, 35% by mass of acetone, 19.99% by mass of water and 0.01% by mass of nitric acid, Stir at 0 ° C. for 3 hours. Then, it was made to react, stirring at 26 degreeC for 3 days. And the amount of solvent was adjusted so that the solid content value of a polysiloxane precursor (polysiloxane oligomer) might be 10 mass%, and the silane compound solution was obtained.
Thereafter, 58 g of the silane compound solution, 33 g of light diffusing particles (titanium oxide CR-93: manufactured by Ishihara Sangyo Co., Ltd.), 0.5 g of inorganic fine particles (Silicia 470: manufactured by Fuji Silysia Chemical Co., Ltd., average particle size 14 μm), and 1,3- A reflection layer forming composition was obtained by mixing 8.5 g of butanediol. The viscosity of the composition for forming a reflective layer was 20 mPa · s. The viscosity of the composition for forming a reflective layer was measured using a vibration viscometer VISCOMATEMODEL VM-10A (manufactured by Seconic). The measurement temperature was 25 ° C., and the measured value after 1 minute was measured after the vibrator was immersed in the reflective layer forming composition.

  The composition for forming a reflective layer was applied on a substrate outside the liquid repellent layer with a dispenser. After confirming that the composition for forming a reflective layer spread out uniformly on the outer side of the liquid repellent layer, it was baked at 150 ° C. for 1 hour to obtain a reflective layer. The thickness of the obtained reflective layer was 20 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation). The overlapping width of the reflective layer and the liquid repellent layer was 52 μm on average, and the gap between the LED element side end of the reflective layer and the side surface of the LED element was 48 μm on average.

[Example 2]
Implementation was carried out except that the composition at the time of preparing the composition for forming a reflective layer was 50 g of the silane compound solution, 33 g of light diffusing particles (titanium oxide CR-93: manufactured by Ishihara Sangyo Co., Ltd.), and 9 g of 1,3-butanediol. An LED device was obtained in the same manner as in Example 1. The viscosity of the composition for forming a reflective layer was 5 mPa · s.
The thickness of the obtained reflective layer was 20 μm. The thickness of the reflective layer (the thickness of the reflective layer at a position 2 mm away from the center of the LED element) was measured with a laser microscope (manufactured by Keyence Corporation). The overlapping width of the reflective layer and the liquid repellent layer was 52 μm on average, and the gap between the LED element side end of the reflective layer and the side surface of the LED element was 48 μm on average.

[Example 3]
The composition at the time of preparation of the composition for forming a reflective layer was as follows: 58 g of the silane compound solution, 33 g of light diffusing particles (titanium oxide CR-93: manufactured by Ishihara Sangyo Co., Ltd.), inorganic fine particles (Silicia 470: manufactured by Fuji Silysia Chemical Co., Ltd. 14 μm) 1 g, clay mineral particles (micro mica MK-100 (synthetic mica): manufactured by Corp Chemical) 0.4 g, and 1,3-butanediol 7.6 g, the LED device was the same as in Example 1. Obtained. The viscosity of the reflective layer forming composition was 80 mPa · s.
The thickness of the obtained reflective layer was 20 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation). The overlapping width of the reflective layer and the liquid repellent layer was 52 μm on average, and the gap between the end of the reflective layer and the side surface of the LED element was 48 μm on average.

[Comparative Example 1]
An LED device was produced in the same manner as in Example 1 except that the liquid repellent layer was not formed. The thickness of the obtained reflective layer was 20 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation). Moreover, the edge part of the reflective layer was in contact with the side surface of the LED element.

(Evaluation)
The following evaluation was performed about the LED device obtained by each Example and the comparative example, and the composition for reflective layer formation. The results are shown in Table 1.

<Measurement of Contact Angle of Composition for Reflection Layer Formation with Liquid Repellent Layer>
A glass substrate was prepared and thoroughly cleaned. Then, the liquid repellent layer forming composition used in each example was applied to a part of the glass substrate to form a film (liquid repellent film) having the same thickness as the liquid repellent layer. Thereafter, the reflective layer-forming composition prepared in each example was dropped on the liquid-repellent film, and cured by heating at 120 ° C. for 30 minutes. The contact angle between the liquid repellent layer and the glass substrate and the contact angle between the reflective layer forming composition and the glass substrate were measured with a contact angle meter. In addition, when the contact angle was very small, it observed with the microscope. The difference in the contact angle was defined as the contact angle of the reflective layer forming composition with respect to the liquid repellent layer.

<Measurement of light extraction efficiency>
The total luminous flux was measured for the LED devices produced in each example and comparative example. The total luminous flux was measured with a spectral radiance meter (CS-2000, manufactured by Konica Minolta Sensing). The light extraction efficiency was evaluated as a relative value with respect to the total luminous flux, with the total luminous flux of the LED device of Comparative Example 1 being 100.

<Measurement of reflectance>
The reflective layer forming composition was applied to a transparent 1 mm glass plate and cured by a heat treatment at 120 ° C. for 30 minutes to prepare a measurement sample having a reflective layer having a thickness of 20 μm. And the reflectance of each sample was measured with the spectrophotometer V-670 (made by JASCO Corporation).
The evaluation results were judged as follows.
○: Reflectance at a wavelength of 500 nm was 95% or more Δ: Reflectance at a wavelength of 500 nm was 90% or more and less than 95% ×: Reflectance at a wavelength of 500 nm was less than 90%

<Tape peeling experiment>
A reflective layer forming composition was applied on a silver plate and cured by heat treatment at 120 ° C. for 30 minutes to prepare a measurement sample having a reflective layer with a thickness of 20 μm. The work of attaching Nichiban cello tape (registered trademark) (24 mm) to the formed reflective layer and immediately peeling it off was repeated 20 times. And the state of the reflective layer was observed with the microscope for every operation | work, and it judged as follows.
A: No peeling of the reflective layer was observed after 20 operations, and nothing adhered to the surface of the tape. O: No separation was observed after 15 operations, but a slight separation was observed after 20 operations. Δ: Peeling did not occur, but white pigment powder slightly adhered to the surface of the tape after the first work. ×: Peeling of the reflective layer occurred at the time of the 15th work.

  As shown in Table 1 above, when the liquid repellent layer is not formed (Comparative Example 1), the reflective layer covers the side surface of the LED element (a part of the light emitting surface), and the light extraction efficiency from the LED device. Was not enough. On the other hand, when the liquid repellent layer was formed (Examples 1 to 3), a gap was formed between the end of the reflective layer and the side surface of the LED element, and the light extraction efficiency was increased.

[Example 4]
(Formation of liquid repellent layer)
A package similar to that in Example 1 was prepared. A liquid repellent layer forming composition (fluorine-based liquid repellent material, KP-911: manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the entire surface outside the LED element mounting area of the package. Specifically, 20 μl of the liquid repellent layer forming composition was applied in the vicinity of the side surface (4 locations) of the LED element, and further 60 μl was applied at a position 2 mm away from the center of the LED element (4 locations). After confirming that the liquid repellent layer-forming composition spreads over the entire surface of the substrate outside the LED element mounting area, it was naturally dried for 30 seconds to form a liquid repellent layer. The average thickness of the liquid repellent layer was 0.592 μm.

(Formation of reflective layer)
A reflective layer forming composition was prepared in the same manner as in Example 1. The said composition for reflective layer formation was apply | coated with the dispenser from the wall surface side of the cavity of a package. Although the composition for forming a reflective layer gradually wets and spreads to the LED element side, the composition does not move before contacting the LED element. Then, it baked for 30 minutes at 120 degreeC, and obtained the reflective layer. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation).

(Evaluation)
The obtained LED device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

  As shown in Table 2 above, when the liquid repellent layer was not formed (Comparative Example 1), the reflective layer covered the side surface of the LED element, and the light extraction efficiency from the LED device was not sufficient. On the other hand, when the liquid repellent layer is formed on the entire surface outside the LED element mounting region (Example 4), a gap is formed between the edge of the reflective layer and the light emitting surface (side surface) of the LED element. Increased efficiency.

[Example 5]
(Preparation of substrate)
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of polyphthalamide (PPA) resin, and a truncated cone-shaped cavity having an opening diameter of 4.5 mm and an opening depth of 0.7 mm was formed on a rectangular parallelepiped of 5 mm × 5 mm × 1 mm. A lead electrode and an LED element included in this substrate were connected by a wire to obtain a package. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. The peak wavelength of the emitted light from the LED element was 475 nm.

(Formation of liquid repellent layer)
As shown in FIG. 11 (b), 3 liquid repellent layer forming compositions (fluorine-based liquid repellent material, KP-911: manufactured by Shin-Etsu Chemical Co., Ltd.) 3 so as to surround the LED element outside the LED element mounting area. It applied with the dispenser to the shape of a book, and was naturally dried for 30 seconds. The width of each liquid repellent layer was 100 μm. The distance between the liquid repellent layer 3A and the liquid repellent layer 3B was 200 μm, and the distance between the liquid repellent layers 3B and 3C was 500 μm. The average thickness of each liquid repellent layer was 0.592 μm.

(Formation of reflective layer)
A reflective layer forming composition was prepared in the same manner as in Example 1. The composition for forming a reflective layer was applied in a line shape by a dispenser at a position 1000 μm outside from the liquid repellent layer 3A. The application amount of the composition for forming a reflective layer was 30 μL. After confirming that the composition for forming a reflective layer was sufficiently wet and spread, it was baked at 120 ° C. for 30 minutes to obtain a reflective layer. The resulting reflective layer had a continuously changing thickness.

[Example 6]
An LED device was produced in the same manner as in Example 5, except that the amount of the reflective layer forming composition applied was 10 μL.
[Example 7]
An LED device was fabricated in the same manner as in Example 5 except that the liquid repellent layer was formed on the entire surface outside the LED element mounting area.
[Example 8]
An LED device was produced in the same manner as in Example 6 except that the liquid repellent layer was formed on the entire surface outside the LED element mounting area.
[Comparative Example 2]
An LED device was produced in the same manner as in Example 5 except that the liquid repellent layer was not formed.
[Comparative Example 3]
An LED device was produced in the same manner as in Example 6 except that the liquid repellent layer was not formed.

  As shown in Table 3, when the liquid repellent layer was formed in a plurality of lines, a reflective layer having a continuously changing thickness was formed (Examples 5 and 6). On the other hand, when a liquid repellent layer was formed on the entire surface outside the LED element mounting area, a reflective layer having a uniform thickness was obtained (Examples 7 and 8). In either case, the end of the reflective layer did not contact the side surface of the LED element, and the light extraction efficiency was high.

  On the other hand, when the liquid repellent layer was not formed, the reflective layer was in contact with the side surface of the LED element, and the light extraction efficiency was not sufficient.

[Example 9]
(Preparation of substrate)
A substrate having a cavity as shown in FIG. 12 was prepared. The substrate 1 was made of polyphthalic acid amide (PPA) resin, and a truncated cone-shaped cavity having an opening diameter of 4.5 mm and an opening depth of 0.7 mm was formed on a rectangular parallelepiped of 5 mm × 5 mm × 1 mm. In addition, a region having an angle of 45 ° with respect to the mounting surface of the LED element was provided on the wall surface side of the bottom surface of the cavity of the substrate. A lead electrode and an LED element included in this substrate were connected by a wire to obtain a package. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. The peak wavelength of the emitted light from the LED element was 475 nm.

(Formation of liquid repellent layer)
A liquid repellent layer forming composition (fluorine-based liquid repellent material, KP-911: manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the bottom surface of the cavity outside the LED element mounting region with a dispenser and allowed to air dry for 30 seconds.

(Formation of reflective layer)
A reflective layer forming composition was prepared in the same manner as in Example 1. The reflective layer forming composition was applied by 80 μL from the wall surface side of the cavity of the package with a dispenser. Although the reflective layer forming composition gradually wets and spreads toward the LED element side, the composition stopped flowing before the reflective layer forming composition contacted the LED element. Then, it baked for 30 minutes at 120 degreeC, and obtained the reflective layer.

(Evaluation)
When the thickness of the reflective layer of the obtained LED device was measured with a laser holo gauge (manufactured by Mitutoyo Corporation), the thickness of the reflective layer formed on the inclined surface of the substrate was 45 μm. The distance between the LED element side end of the reflective layer and the side surface of the LED element was 200 μm. Furthermore, the angle formed by the surface of the reflective layer and the mounting surface of the LED element on the substrate was 45 °.

[Example 10]
An LED device was produced in the same manner as in Example 9 except that the amount of the reflective layer forming composition applied was 50 μL.

(Evaluation)
When the thickness of the reflection layer of the obtained LED device was measured with a laser holo gauge (manufactured by Mitutoyo Corporation), the thickness of the reflection layer formed on the inclined surface of the substrate was 25 μm. The distance between the LED element side end of the reflective layer and the side surface of the LED element was 350 μm. Furthermore, the angle formed by the surface of the reflective layer and the mounting surface of the LED element on the substrate was 45 °.

[Example 11]
(Preparation of substrate)
A substrate having a cavity similar to that of Example 11 was prepared. A lead electrode and six LED elements included in this substrate were connected with wires, respectively, to obtain a package. The outer shape of the LED element was 200 μm × 80 μm × 100 μm. The peak wavelength of the emitted light from the LED element was 475 nm. Further, the LED elements emit light from the side surfaces, and each LED element was arranged so that the gap between the LED elements was 450 μm.

(Formation of liquid repellent layer)
A mask having an opening only on the peripheral portion (region having a width of 100 μm from the outer edge of the LED element) of the mounting area of each LED element of the package described above was disposed on the package. Then, a composition for forming a liquid repellent layer (fluorine-based liquid repellent material, KP-911: manufactured by Shin-Etsu Chemical Co., Ltd.) was spray applied from above the mask. Thereafter, it was naturally dried for 30 seconds to form a liquid repellent layer. The width of the liquid repellent layer was 100 μm, and the thickness of the liquid repellent layer was 0.592 μm.

(Formation of reflective layer)
A reflective layer forming composition was prepared in the same manner as in Example 1. When the composition for forming a reflective layer was dropped on the outer peripheral side of the cavity of the package, the composition spreaded to the end of each liquid repellent layer. Then, it baked for 30 minutes at 120 degreeC, and obtained the reflective layer.

(Evaluation)
In the obtained LED device, the light emitting surface (upper surface and side surface) of any LED element was not in contact with the reflective layer. Moreover, the light extraction efficiency from each LED element was 70% or more.

[Example 12]
An LED device was produced in the same manner as in Example 11 except that the reflective layer forming composition was dropped onto the center of the cavity of the package.

(Evaluation)
In the obtained LED device, the reflective layer was not in contact with the light emitting surface (upper surface and side surface) of any LED element. Moreover, the light extraction efficiency from each LED element was 70% or more.

[Example 13]
An LED device was produced in the same manner as in Example 1 except that the liquid repellent layer was produced by the following plasma CVD method. A silicone mask having an opening only at the peripheral edge of the LED element mounting area of the above-described package (area having a width of 100 μm from the outer edge of the LED element) was disposed on the package. The liquid repellent layer was plasma polymerized by NIE-200 manufactured by Samco Corporation with 50 sccm of CF ₄ gas at a pressure of 0.6 Pa and 40 W for 40 seconds to produce a film made of fluoride having an average thickness of 1200 nm.

(Evaluation)
In the obtained LED device, the light emitting surface (upper surface and side surface) of the LED element and the reflective layer were not in contact. The light extraction efficiency from each LED element was 85%.

  The light-emitting device obtained by the method of the present invention is excellent in light extraction performance and does not deteriorate in light extraction efficiency over time. Therefore, it is useful for lighting used outdoors or indoors.

1 substrate 2 light emitting element (LED element)
3 Liquid repellent layer 4 Reflective layer 11 Lead electrode 12 Metal wire 13 Wavelength conversion layer 100, 200 Light emitting device (LED device)

Claims (12)

A substrate, a light emitting element mounted on the mounting region of the substrate, a liquid repellent layer formed on a peripheral portion of the mounting region of the substrate, and a reflective layer formed on the substrate and on the outer periphery of the liquid repellent layer; A method of manufacturing a light emitting device including:
Forming a liquid repellent layer containing a liquid repellent material on the substrate surface at the periphery of the mounting region of the light emitting element;
Applying a reflective layer forming composition on the substrate and outside the liquid repellent layer, and forming a reflective layer;
A method for manufacturing a light-emitting device including: A method for manufacturing a light emitting device, comprising: a substrate; a light emitting element mounted on a mounting region of the substrate; a liquid repellent layer formed outside the mounting region of the substrate; and a reflective layer covering the liquid repellent layer. And
Forming a liquid repellent layer containing a liquid repellent material on the substrate surface outside the mounting region of the light emitting element;
Applying a reflective layer forming composition so as to cover the substrate and the liquid repellent layer, and forming a reflective layer;
A method for manufacturing a light-emitting device including:   The method for manufacturing a light emitting device according to claim 2, wherein the liquid repellent layer forming step is a step of forming the liquid repellent layer over the entire substrate surface outside the mounting region.   The method for manufacturing a light emitting device according to claim 2, wherein the liquid repellent layer forming step is a step of forming the liquid repellent layer in a plurality of lines on a substrate surface outside the mounting region.   The manufacturing method of the light-emitting device as described in any one of Claims 2-4 whose said reflection layer formation process is a process of forming the reflection layer from which thickness changes continuously.   The method for manufacturing a light emitting device according to claim 1, wherein the liquid repellent layer forming step is a step of forming a liquid repellent layer by a vapor phase film forming method.   The manufacturing method of the light-emitting device according to claim 1, wherein the light-emitting element is an LED element. The light emitting device further includes a wavelength conversion layer covering the LED element,
The manufacturing method of the light-emitting device of Claim 7 including the process of apply | coating the composition for wavelength conversion layers containing a fluorescent substance particle and a binder on the said light emitting element. The reflective layer forming composition contains a solvent,
The manufacturing method of the light-emitting device according to claim 1, wherein the liquid repellent layer has liquid repellency with respect to the solvent.   A substrate, a light emitting element mounted on the mounting region of the substrate, a liquid repellent layer formed on a peripheral portion of the mounting region of the substrate, and a reflective layer formed on the substrate and on the outer periphery of the liquid repellent layer; A light emitting device.   A light emitting device comprising: a substrate; a light emitting element mounted on a mounting region of the substrate; a liquid repellent layer formed outside the mounting region of the substrate; and a reflective layer covering the liquid repellent layer. The light emitting device according to claim 11, wherein the thickness of the reflective layer varies continuously.

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