JP2014158011A - Method for manufacturing led device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an LED device which is capable of efficiently extracting light for a long period and in which a reflective layer for reflecting an outgoing beam or the like from an LED element is slightly degraded.SOLUTION: A method for manufacturing an LED device comprising a substrate, an LED element mounted on the substrate, a wavelength conversion layer covering the LED element, and a reflective layer formed on the substrate and outside a peripheral part of a mounting region of the LED element comprises the steps of: mounting the LED element on the substrate; applying a composition for reflective layer formation containing a light diffusion particle, an organic silicon compound, and a solvent onto the substrate and forming a reflective layer by hardening the organic silicon compound; and forming a wavelength conversion layer containing a phosphor particle and a binder so as to cover the LED element.

Description

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

  In recent years, a white LED device has been developed in which a phosphor is disposed in the vicinity of an LED element and white light is obtained by exciting the phosphor with light from the LED element. As an example of such an LED device, there is an LED device that obtains white light by combining blue light from a blue LED element and yellow fluorescence emitted from a phosphor upon receiving blue light. There is also an LED device that obtains white light by using an LED element that emits ultraviolet light as a light source and combining blue light, green light, and red light emitted from a phosphor upon receiving the ultraviolet light.

  In the conventional LED device, there is a problem that the substrate on which the LED element is mounted easily absorbs the emitted light of the LED element and the fluorescence emitted by the phosphor, and the light extraction property is not sufficient. Therefore, in a general LED device, a reflector having a high light reflectance is disposed around the LED element. Such a reflector is generally formed of metal plating or the like.

  However, a reflector made of metal plating cannot be formed on the entire surface of the substrate from the viewpoint of preventing electrical conduction. Therefore, there is a problem that light is absorbed by the substrate in the region where the reflector is not formed.

  On the other hand, a reflector in which metal plating is covered with a transparent resin layer (Patent Document 1), and a reflector in which metal plating is covered with a white resin layer have also been proposed (Patent Document 2).

JP 2005-136379 A JP 2011-23621 A

  However, light is scattered multiple times in the vicinity of the reflector. Therefore, as in the techniques of Patent Documents 1 and 2, when the reflector surface made of metal plating is coated with a resin, or when the reflector is made of a resin, the resin is deteriorated by heat or light. As a result, there is a problem that the light reflectivity of the reflective layer decreases with time or electricity is conducted. In particular, in applications where a large amount of light is required, such as in-vehicle headlights, the resin is likely to deteriorate.

  The present invention has been made in view of such a situation. In other words, the present invention provides a method for manufacturing an LED device that can efficiently extract light over a long period of time with little deterioration of a reflective layer for reflecting light emitted from an LED element.

That is, this invention relates to the manufacturing method of the following LED devices.
[1] A substrate, an LED element mounted on the substrate, a wavelength conversion layer covering the LED element, a reflective layer formed on the substrate and outside a peripheral portion of a mounting region of the LED element, A mounting process for mounting the LED element on the substrate, and a reflective layer forming composition containing light diffusing particles, an organosilicon compound, and a solvent is applied on the substrate. A reflective layer forming step of drying and curing the reflective layer forming composition to form the reflective layer; and a wavelength conversion layer composition containing phosphor particles and a binder component so as to cover the LED element. And a wavelength conversion layer forming step of forming the wavelength conversion layer.

[2] The step of forming the reflective layer includes a step of covering the LED element mounting region and its peripheral edge with a plate mask, applying the reflective layer forming composition on the substrate, and forming the reflective layer forming composition. The method for manufacturing an LED device according to [1], further including a step of drying and curing the object in this order.
[3] The reflective layer forming step includes a step of coating a mounting region of the LED element and a peripheral portion thereof with a resist material, applying the reflective layer forming composition onto the substrate, and forming the reflective layer forming composition. The method for manufacturing an LED device according to [1], comprising: a step of drying and curing an object; and a step of removing the resist material and the reflective layer forming composition on the resist material in this order.
[4] In the reflective layer forming step, the LED element mounting region and the peripheral edge thereof are coated with a soluble resin soluble in water or a solvent, and the reflective layer forming composition is applied onto the substrate. A step of drying and curing the reflective layer forming composition, and a step of dissolving the soluble resin in water or a solvent to remove the soluble resin and the reflective layer forming composition on the soluble resin. The manufacturing method of the LED device according to [1], including in this order.
[5] The reflective layer forming step includes a step of applying a liquid repellent to the mounting region of the LED element and a peripheral portion thereof, and the reflective layer forming composition is applied onto the substrate. The method for manufacturing an LED device according to [1], further including a step of drying and curing the object in this order.

[6] The wavelength conversion layer forming step, the wavelength conversion layer forming step, and the reflective layer forming step are performed in this order, and the wavelength conversion layer forming step covers the mounting region of the LED element and the peripheral portion thereof. A step of forming a conversion layer, wherein the reflection layer formation step has a height higher than the upper surface of the wavelength conversion layer covering the LED element on the substrate and outside the peripheral portion of the LED element mounting region. The method for manufacturing an LED device according to [1], which is a step of forming a low reflective layer.
[7] The LED device according to [6], wherein the wavelength conversion layer forming step includes a step of placing the light emitting surface of the LED element of the substrate facing vertically downward and curing the composition for wavelength conversion layer. Manufacturing method.
[8] In the above [6] or [7], the wavelength conversion layer forming step includes a step of arranging the light emitting surface of the LED element of the substrate facing vertically downward and applying the wavelength conversion layer composition. The manufacturing method of the LED device of description.

[9] The method further includes a light-transmitting layer forming step of forming a light-transmitting layer that covers the LED element, the mounting step, the light-transmitting layer forming step, the reflecting layer forming step, and the wavelength conversion layer forming step. The light-transmitting layer forming step is performed in sequence, and the light-transmitting layer composition including the light-transmitting material is applied so as to cover the LED element mounting region and the peripheral portion thereof, thereby forming the light-transmitting layer. The reflective layer forming step forms a reflective layer having a height lower than the upper surface of the translucent layer covering the LED element on the substrate and outside the peripheral portion of the LED element mounting region. The manufacturing method of the LED device as described in [1] which is a process to perform.
[10] The LED device according to [9], wherein the translucent layer forming step includes a step of placing the light emitting surface of the LED element of the substrate facing vertically downward to cure the translucent layer composition. Manufacturing method.
[11] In the above [9] or [10], the translucent layer forming step includes a step of arranging the light emitting surface of the LED element of the substrate facing vertically downward and applying the translucent layer composition. The manufacturing method of the LED device of description.

[12] The reflective layer forming step includes a step of forming a partition wall that surrounds a peripheral portion of the LED element mounting region, and a step of forming a reflective layer having a height lower than the partition wall outside the partition wall. The manufacturing method of the LED device as described in [1].
[13] The method for manufacturing an LED device according to [1], wherein the substrate has a groove portion surrounding a peripheral portion of a mounting region of the LED element.

[14] The LED device manufacturing method according to [1], wherein the substrate has a mounting area surface of the LED element protruding from the reflective layer forming surface.
[15] In the reflective layer forming step, the step of applying the reflective layer forming composition to a partial area A outside the peripheral edge of the LED element mounting area, and the LED element separated from the area A Applying the reflective layer forming composition to a part of the region B outside the peripheral edge of the mounting region, and applying the reflective layer forming composition to the gap between the region A and the region B; The manufacturing method of the LED device as described in [1].
[16] In the reflective layer forming step, the light emitting surface of the LED element of the substrate is disposed vertically downward, and the reflective layer forming composition is applied while relatively moving the substrate and the coating apparatus. The manufacturing method of the LED device as described in [1] including the step to do.

  In the LED device obtained by the manufacturing method of the present invention, the reflective layer is hardly deteriorated by heat or light. Therefore, good light extraction efficiency can be maintained over a long period of time.

It is a schematic sectional drawing which shows an example of the LED device obtained by the manufacturing method of this invention. It is a schematic sectional drawing which shows the other example of the LED device obtained by the manufacturing method of this invention. It is a schematic sectional drawing which shows the other example of the LED device obtained by the manufacturing method of this invention. It is a schematic sectional drawing which shows the other example of the LED device obtained by the manufacturing method of this invention. It is a schematic sectional drawing which shows the other example of the LED device obtained by the manufacturing method of this invention. It is a schematic sectional drawing which shows the other example of the LED device obtained by the manufacturing method of this invention. It is process drawing which shows an example of the manufacturing method of the LED apparatus of this invention. FIG. 8A is a top view showing an example of a plate-like mask that protects the LED element mounting region and its peripheral edge in the LED device manufacturing method of the present invention, and FIG. It is explanatory drawing of the method of arrange | positioning a mask and apply | coating the composition for reflective layer formation. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is a top view which shows the position of the partition formed with the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention. It is process drawing which shows the other example of the manufacturing method of the LED device of this invention.

1. LED Device The LED device obtained by the method of the present invention has a reflective layer that reflects the emitted light or the like of the LED element to the light extraction surface side. Examples of the structure of the LED device of the present invention are shown in the schematic sectional views of FIGS. As shown in FIGS. 1 to 6, the LED device 100 is formed on the substrate 1, the LED element 2 mounted on the substrate 1, and on the substrate 1 and outside the peripheral portion of the mounting region of the LED element 2. The reflective layer 21 and the wavelength conversion layer 11 that covers the LED element 2 are included. The wavelength conversion layer 11 is a layer that contains phosphor particles and converts light of a specific wavelength emitted from the LED element 2 into light of another wavelength. The reflective layer 21 is a layer that reflects the light emitted from the LED element 2 and the fluorescence emitted from the phosphor particles to the light extraction surface side of the LED device 100.

  As described above, when the reflective layer is made of a resin, there is a problem that the reflective layer is deteriorated by heat or light, and the light reflectivity of the reflective layer is lowered with time. On the other hand, in the LED device 100 obtained by the method of the present invention, the binder of the reflective layer 21 is a cured product of an organosilicon compound; that is, a translucent ceramic. Therefore, it is hard to deteriorate with heat and light, and the light reflectivity of the reflective layer 21 does not decrease with time.

1-1. Substrate The substrate 1 may have a cavity (concave portion) as shown in FIGS. 1 to 6 or may have a flat plate shape. The shape of the cavity is not particularly limited. For example, as shown in FIG. 1 or the like, a truncated cone shape, a truncated pyramid shape, a columnar shape, a prismatic shape, or the like may be used.
Further, as shown in the schematic cross-sectional view of FIG. 15A, the groove portion 10 may be provided so as to surround the mounting region of the LED element 2 and the peripheral portion thereof. Furthermore, as shown in the schematic cross-sectional view of FIG. 16A, the mounting surface 1 a of the LED element 2 may protrude from the formation surface 1 b of the reflective layer 3.

  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 metal part 3 is usually disposed on the substrate 1. The metal part 3 is made of a metal such as silver. The metal part 3 may be a pair of metal electrode parts that electrically connect an external power source (not shown) and the LED element 2. As shown in FIGS. 2 and 4, the metal portion 3 can also be a metal reflection film that reflects light from the LED element 2 toward the light extraction surface of the LED device 100.

  The board | substrate 1 and the metal part 3 are produced by a general method, for example, are obtained by integrally molding resin and a metal plate.

1-2. LED Element The LED element 2 is electrically connected to a metal part (metal wiring) 3 disposed on the substrate 1 and emits light of a specific wavelength. The wavelength of the light emitted from the LED element 2 is not particularly limited. The LED element 2 may be, for example, an element that emits blue light (light of about 420 nm to 485 nm) or an element that emits ultraviolet light.

  The configuration of the LED element 2 is not particularly limited. When the LED element 2 is an element that emits blue light, the LED element 2 includes an n-GaN compound semiconductor layer (cladding layer), an InGaN compound semiconductor layer (light emitting layer), and a p-GaN compound semiconductor layer. It may be a laminate of (cladding layer) and a transparent electrode layer. The LED element 2 may have a light emitting surface of 200 to 300 μm × 200 to 300 μm, for example. Moreover, the height of the LED element 2 is about 50-200 micrometers normally. In the LED device 100 shown in FIGS. 1 to 6, only one LED element 2 is disposed on the substrate 1, but a plurality of LED elements 2 may be disposed on the substrate 1.

  The connection method between the LED element 2 and the metal part (metal electrode part) 3 disposed on the substrate 1 is not particularly limited. For example, as shown in FIG. 1, the LED element 2 and the metal part 3 may be connected via a wire 4. Further, as shown in FIG. 3, the LED element 2 and the metal portion 3 may be connected via the protruding electrode 5. An aspect in which the LED element 2 and the metal part 3 are connected via the wire 4 is referred to as a wire bonding type, and an aspect in which the LED element 2 and the metal part 3 are connected via the protruding electrode 5 is a flip chip type. That's it.

1-3. Reflective Layer The reflective layer 21 is a layer that reflects the light emitted from the LED element 2 and the fluorescence emitted from the phosphor particles contained in the wavelength conversion layer 11 to the light extraction surface side of the LED device 100. By disposing the reflective layer 21, the amount of light extracted from the LED device 100 increases.

  The reflective layer 21 is formed on the substrate 1 and outside the peripheral edge of the LED element 2 mounting area. The mounting area of the LED element 2 refers to a light emitting surface of the LED element 2 and a connection part between the LED element 2 and the metal part 3. The peripheral portion of the mounting region of the LED element 2 refers to a region from the outer edge of the mounting region to the outside of the width of 1 μm. That is, the reflective layer 21 is formed in a region that does not hinder the light emission of the LED element 2 and the connection between the LED element 2 and the metal part (metal electrode part) 3.

  As shown in FIG. 1, when the substrate 1 has a cavity, the reflective layer 21 may be formed only on the bottom surface of the cavity. As shown in FIG. 2, the reflective layer 21 is formed on the side surface 6 and the bottom surface of the cavity. It may be formed. When the reflective layer 21 is formed on the cavity inner wall surface 6, the light traveling in the horizontal direction on the surface of the wavelength conversion layer 11 can be reflected by the reflective layer 21 and extracted.

  As shown in FIGS. 2 and 4, the reflective layer 21 may be formed so as not to cover the metal portion 3. In this case, light from the LED element 2 and the like is reflected by the metal portion 3 and the reflective layer 21.

  The reflective layer 21 is obtained by curing a composition for forming a reflective layer, which will be described later, and is a layer in which light diffusion particles are dispersed in a translucent ceramic (cured product of an organosilicon compound). The thickness of the reflective layer 21 is preferably 5 to 50 μm, more preferably 5 to 30 μm. If the thickness of the reflective layer 21 exceeds 50 μm, cracks are likely to occur in the reflective layer 21. On the other hand, when the thickness of the reflective layer 21 is less than 5 μm, the light reflectivity of the reflective layer 21 is not sufficient, and the light extraction efficiency from the LED device 100 may not be increased.

1-4. Wavelength Conversion Layer The wavelength conversion layer 11 includes phosphor particles and a binder. The phosphor particles receive light (excitation light) emitted from the LED element 2 and emit fluorescence. By mixing the excitation light and the fluorescence, the color of the light from the LED device 100 becomes a desired color. For example, when the light from the LED element 2 is blue and the fluorescence emitted from the phosphor included in the wavelength conversion layer 11 is yellow, the light from the LED device 100 is white.

  The wavelength conversion layer 11 should just coat | cover the LED element 2, for example, as FIG. 1-4 and FIG. 6 show, you may coat | cover the reflective layer 21 and the metal part 3 with LED element 2. FIG. For example, as shown in FIG. 5, only the LED element 2 may be covered.

  The phosphor particles included in the wavelength conversion layer 11 may be anything that is excited by light emitted from the LED element 2 and emits fluorescence having a wavelength different from that of the emitted light from the LED 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 LED 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 binder contained in the wavelength conversion layer 11 can be a transparent resin or a translucent ceramic. The transparent resin can be, for example, a silicone resin and an epoxy resin. When the binder is a transparent resin, the wavelength conversion layer 11 preferably has a thickness of about 25 μm to 5 mm. If the wavelength conversion layer 11 is too thick, the concentration of the phosphor particles becomes excessively low, and the phosphor particles may not be uniformly dispersed. The thickness of the wavelength conversion layer 11 means the maximum thickness of the wavelength conversion layer 11 formed on the light emitting surface of the LED element 2. The thickness of the wavelength conversion layer 11 can be measured with a laser holo gauge. When the binder is a transparent resin, the amount of phosphor particles contained in the wavelength conversion layer 11 is generally 5 to 15% by mass.

  On the other hand, the translucent ceramic may be the same as the translucent ceramic included in the reflective layer. That is, it can be a cured product of an organosilicon compound (polysiloxane or the like). When the binder is a translucent ceramic, the thickness of the wavelength conversion layer 11 is preferably 5 to 200 μm. When the binder is a translucent ceramic, if the wavelength conversion layer 11 is excessively thick, cracks or the like are likely to occur in the wavelength conversion layer 11. Even when the binder is a translucent ceramic, the thickness of the wavelength conversion layer 11 means the maximum thickness of the wavelength conversion layer 11 formed on the light emitting surface of the LED element 2. The thickness of the wavelength conversion layer 11 can be measured with a laser holo gauge.

  Moreover, when a binder is a translucent ceramic, it is preferable that the quantity of the fluorescent substance particle contained in the wavelength conversion layer 11 is 60-95 mass%. The higher the concentration of the phosphor particles contained in the wavelength conversion layer 11, the better. If the concentration of the phosphor particles is high, the strength of the wavelength conversion layer 11 tends to increase. However, if the content ratio of the translucent ceramic is too small, the phosphor particles may not be sufficiently retained.

1-5. Translucent Layer As shown in FIG. 5 or FIG. 6, the LED device 100 may include a translucent layer 31. The light transmissive layer 31 functions to protect the LED element 2 from external impacts, gases, and the like. The light transmissive layer 31 includes a light transmissive material. The translucent material may be a transparent resin or a translucent ceramic.

  When the translucent material is a transparent resin, the transparent resin can be, for example, a silicone resin and an epoxy resin. In this case, the thickness of the translucent layer 31 is usually preferably 25 μm to 5 mm, more preferably 1 to 3 mm. In general, it is difficult to make the thickness of the translucent layer 31 containing the transparent resin 25 μm or less. On the other hand, from the viewpoint of miniaturization of the LED device, the thickness of the translucent layer 31 is preferably 5 mm or less. The thickness of the light transmissive layer 31 means the maximum thickness of the light transmissive layer 31 formed on the light emitting surface of the LED element 2. The thickness of the translucent layer 31 can be measured with a laser holo gauge.

  On the other hand, when the translucent material is a translucent ceramic, the translucent ceramic may be the same as the translucent ceramic included in the reflective layer 21. That is, it can be a cured product of an organosilicon compound (polysiloxane or the like). In this case, it is preferable that the translucent layer 31 has a thickness of 0.5 to 10 μm. When the thickness of the light transmissive layer 31 is less than 0.5 μm, the effect of protecting the LED element 2 from an external impact, gas, or the like may not be sufficiently obtained. On the other hand, when the thickness of the light transmitting layer 31 exceeds 10 μm, the light transmitting layer 31 may be cracked. Even when the translucent material is ceramic, the thickness of the translucent layer 31 means the maximum thickness of the translucent layer 31 formed on the light emitting surface of the LED element 2. The thickness of the translucent layer 31 is measured with a laser holo gauge.

2. Reflective Layer Forming Composition The reflective layer described above is obtained by applying a reflective layer forming composition containing an organosilicon compound, light diffusing particles, and a solvent, and drying and curing the composition. The composition for forming a reflective layer may contain metal oxide fine particles, inorganic particles, clay mineral particles, metal alkoxide or metal chelate, silane coupling agent, reaction accelerator and the like, if necessary.

2-1. Organosilicon Compound The organosilicon compound can be (i) a polysilazane oligomer and (ii) a monomer of a silane compound or an oligomer thereof.

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

  (Ii) The monomer or oligomer of the silane compound may be a bifunctional silane compound, a trifunctional silane compound, or a tetrafunctional silane compound, or an oligomer thereof. As will be described later, the oligomer of the silane compound is obtained by subjecting a monomer of the silane compound to a condensation reaction.

  The oligomer of the silane compound is preferably a monomer of a trifunctional silane compound and a tetrafunctional silane compound or an oligomer thereof. The polymerization 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 of the tetrafunctional silane compound is excessive, the degree of crosslinking of the cured product increases. Therefore, cracks are likely to occur in the resulting reflective layer. On the other hand, when the polymerization ratio of the trifunctional silane compound is excessive, a large amount of organic groups derived from the trifunctional silane compound remain in the polysiloxane. Therefore, the obtained reflective layer tends to repel the composition for wavelength conversion layer described later, and the adhesion between the obtained reflective layer and the wavelength conversion layer tends to be lowered.

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 ⁵ is each independently represent an alkyl group or a phenyl group, preferably an alkyl group or a phenyl group, having 1 to 5 carbon atoms. R ⁶ 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.

When R ⁵ represented by the general formula (III) of these trifunctional silane compounds is a methyl group, the hydrophobicity of the reflective layer surface becomes low. As a result, when the wavelength conversion layer is formed on the reflective layer, the composition for the wavelength conversion layer is easily wetted and spreads, and the adhesion between the obtained reflective layer and the wavelength conversion layer is increased. Examples of the trifunctional silane compound in which R ⁵ represented by the general formula (III) is a methyl group include methyltrimethoxysilane and methyltriethoxysilane, and methyltrimethoxysilane is particularly preferable.

  When the organosilicon compound contained in the composition for forming a reflective layer is (i) a polysilazane oligomer, the concentration of the polysilazane oligomer in the composition for forming a reflective layer is preferably higher. However, when these concentrations are too high, the storage stability of the composition for forming a reflective layer is lowered. Therefore, it is preferable that the quantity of a polysilazane oligomer is 5-50 mass% with respect to the total mass of the composition for reflection layer formation.

  When the organosilicon compound contained in the reflective layer forming composition is (ii) a monomer or oligomer of a silane compound, the amount of the silane compound monomer or oligomer contained in the reflective layer forming composition is also reflected. It is preferable that it is 5-50 mass% with respect to the total mass of the composition for layer formation.

(Method for preparing oligomer of silane compound)
The silane compound oligomer (polysiloxane oligomer) contained in the above-mentioned reflective layer forming composition is prepared by the following method. The monomer of the silane compound is hydrolyzed in the presence of an acid catalyst, water, and an organic solvent to cause a condensation reaction. The mass average molecular weight of the oligomer of the silane compound is adjusted by reaction conditions (particularly reaction time).

  The mass average molecular weight of the oligomer of the silane compound contained in the composition for forming a reflective layer is preferably 1000 to 3000, more preferably 1200 to 2700, and further preferably 1500 to 2000. When the mass average molecular weight of the oligomer of the silane compound contained in the composition for forming a reflective layer is less than 1000, the viscosity of the composition for forming a reflective layer is low, and liquid repellency or the like is likely to occur when the reflective layer is formed. On the other hand, if the mass average molecular weight of the oligomer of the silane compound contained in the composition for forming a reflective layer exceeds 3000, the composition for forming a reflective layer increases in viscosity, and it may be difficult to form a uniform film. The mass average molecular weight is a value (polystyrene conversion) measured by gel permeation chromatography.

  The acid catalyst for preparing the oligomer of the silane compound only needs to act as a catalyst during hydrolysis of the silane compound, and may be either an organic acid or an inorganic acid. Examples of inorganic acids include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, with phosphoric acid and nitric acid being particularly preferred. Examples of organic acids include compounds having a carboxylic acid residue such as formic acid, oxalic acid, fumaric acid, maleic acid, glacial acetic acid, acetic anhydride, propionic acid, and n-butyric acid; organic sulfonic acid, and organic sulfone A compound having a sulfur-containing acid residue, such as an acid esterified product (organic sulfate ester or organic sulfite ester), is included.

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

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

  The amount of the acid catalyst added at the time of preparing the oligomer of the silane compound is preferably 1 to 1000 ppm by mass, more preferably 5 to 800 ppm by mass with respect to the total amount of the oligomer preparation solution.

  The film quality of the resulting polysiloxane varies depending on the amount of water added during preparation of the oligomer of the silane compound. Therefore, it is preferable to adjust the water addition rate during oligomer preparation according to the target film quality. The water addition rate is the ratio (%) of the number of moles of water molecules to be added to the number of moles of alkoxy groups or aryloxy groups of the silane compound contained in the oligomer preparation solution. The water addition rate is preferably 50 to 200%, more preferably 75 to 180%. By setting the water addition rate to 50% or more, the film quality of the resulting reflective layer is stabilized. Moreover, the storage stability of the composition for reflective layer formation becomes favorable by setting it as 200% or less.

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

2-2. Light Diffusing Particle The light diffusing particle contained in the composition for forming a reflective layer is not particularly limited as long as it has 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 zinc oxide (ZnO), barium titanate (BaTiO ₃ ), barium sulfate (BaSO ₄ ), titanium dioxide (TiO ₂ ), boron nitride (BrN), magnesium oxide (MgO), calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), barium oxide (BaO), zirconium oxide (ZrO ₂ ) and the like are included. Among these, the light diffusing particles are preferably titanium dioxide, barium sulfate, barium titanate, boron nitride, zinc oxide, and aluminum oxide. These particles have a high total reflectance and are easy to handle. The reflective layer forming composition may contain only one type of light diffusing particles, or may contain 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 composition for forming a reflective layer is 60 to 95% by mass, more preferably based on the total solid content (total amount of components other than the solvent) of the composition for forming a reflective layer. It is 70-90 mass%. If the amount of the light diffusing particles is less than 60% by mass, the resulting reflective layer may have insufficient light reflectivity. On the other hand, when the amount of the light diffusing particles exceeds 95% by mass, the amount of the binder in the resulting reflective layer is relatively small, and the strength of the reflective layer may be lowered.

2-3. Metal oxide fine particles The composition for forming a reflective layer may contain metal oxide fine particles having an average primary particle size of 5 to 100 nm. When metal oxide fine particles are contained in the reflective layer forming composition, minute irregularities are generated on the surface of the resulting reflective layer. Due to the unevenness, an anchor effect is generated between the obtained reflective layer and the wavelength conversion layer, and adhesion between the reflective layer and the wavelength conversion layer is increased. Moreover, since the gap between the light diffusion particles is filled in the obtained reflective layer, the strength of the reflective layer is increased, and cracks are hardly generated in the reflective layer.

  The type of the metal oxide fine particles is not particularly limited, but is preferably at least one selected from the group consisting of zirconium oxide, titanium oxide, cerium oxide, niobium oxide, and zinc oxide. In particular, from the viewpoint of increasing the film strength, zirconium oxide fine particles are preferably contained. The reflective layer may contain only one kind of metal oxide fine particles, or two or more kinds.

  The metal oxide fine particles may have a surface treated with a silane coupling agent or a titanium coupling agent. When the surface of the metal oxide fine particles is treated, the metal oxide fine particles are easily dispersed uniformly in the reflective layer forming composition.

  The average primary particle size of the metal oxide fine particles is 5 to 100 nm, preferably 5 to 80 nm, more preferably 5 to 50 nm. When the average primary particle size of the metal oxide fine particles is 100 nm or less, the metal oxide fine particles easily enter the gaps between the light diffusing particles, and the strength of the resulting reflective layer is likely to increase. Further, when the average primary particle size of the metal oxide fine particles is 5 nm or more, appropriate irregularities are easily formed on the surface of the reflective layer, and the above-described anchor effect is easily obtained.

  The amount of the metal oxide fine particles contained in the reflective layer forming composition is 0.5 to 30% by mass with respect to the total solid content of the reflective layer forming composition (total amount of components other than the solvent). Is preferable, more preferably 0.5 to 20% by mass, still more preferably 1 to 10% by mass, and particularly preferably 2 to 10% by mass. When the content of the metal oxide fine particles is less than 0.5% by mass, the anchor effect at the interface between the obtained reflective layer and the wavelength conversion layer and the strength of the film are not sufficiently increased. On the other hand, when the content of the metal oxide fine particles exceeds 30% by mass, the amount of the organosilicon compound is relatively decreased, and the film strength may be lowered.

2-4. Inorganic particles The reflective layer forming composition may contain inorganic particles having an average particle diameter of 100 nm or more and 100 μm or less. When inorganic particles are contained in the reflective layer forming composition, the viscosity of the reflective layer forming composition tends to increase. Furthermore, the strength of the resulting reflective layer is likely to increase. The inorganic particles can be oxide particles such as silicon oxide, fluoride particles such as magnesium fluoride, and a mixture thereof. Of these, silicon oxide is particularly preferable. The surface of the inorganic particles may be treated with a silane coupling agent or a titanium coupling agent. By the surface treatment, the compatibility between the inorganic particles and the organosilicon compound or the solvent is increased.

  The amount of the inorganic particles contained in the reflective layer forming composition is preferably 0.1 to 10% by mass, and preferably 0.2 to 5% by mass with respect to the total mass of the reflective layer forming composition. It is more preferable. If the amount of the inorganic particles exceeds 10% by mass, cracks are likely to occur during the formation of the reflective layer. On the other hand, when the amount of the inorganic particles is less than 0.1%, the thickening effect of the composition for forming a reflective layer is lowered.

  The average particle diameter of the inorganic particles is preferably 100 nm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less from the viewpoint that the strength of the resulting reflective layer is increased. The average particle diameter of the inorganic particles can be measured, for example, by a Coulter counter method.

  The shape of the inorganic particles is not particularly limited, and may be a needle shape or a flat plate shape, or may be a hollow structure.

2-5. Clay mineral particles The composition for reflection layer formation may contain clay mineral particles. When clay mineral particles are contained in the reflective layer forming composition, the viscosity of the reflective layer forming composition is increased, and sedimentation of the light diffusing particles is suppressed.

  Examples of clay mineral particles include layered silicate minerals, imogolite, allophane and the like. The layered silicate mineral is preferably a clay mineral having a mica structure, a kaolinite structure, or a smectite structure.

  Layered silicate mineral particles tend to form a card house structure when the reflective layer-forming composition is allowed to stand. When the layered silicate mineral particles form a card house structure, the viscosity of the reflective layer forming composition is greatly increased. On the other hand, the card house structure is apt to collapse by applying a certain pressure, thereby reducing the viscosity of the composition for forming a reflective layer. That is, when the layered silicate mineral particles are included in the reflective layer forming solution, the viscosity of the reflective layer forming composition increases in a stationary state, and when a certain pressure is applied, the reflective layer forming composition The viscosity of the product is lowered.

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

  Examples of commercial products of clay mineral particles include Laponite XLG (synthetic hectorite analogue manufactured by LaPorte, UK), Laponite RD (Synthetic hectorite analogue produced by LaPorte, UK), Thermabis (Synthetic product, Henkel, Germany) Hectorite-like substance), smecton SA-1 (saponite-like substance manufactured by Kunimine Industry Co., Ltd.), Bengel (natural bentonite sold by Hojun Co., Ltd.), Kunivia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), bee gum ( Natural hectorite manufactured by Vanderbilt, USA, Daimonite (synthetic swellable mica manufactured by Topy Industries, Ltd.), Micromica (synthetic non-swellable mica, manufactured by Coop Chemical Co., Ltd.), Somasifu (Coop Chemical Co., Ltd.) ) Synthetic swelling mica), SWN (synthetic smectite manufactured by Corp Chemical Co.), SWF ( Synthetic smectite manufactured by Top Chemical Co., Ltd.), M-XF (white mica manufactured by Repco), S-XF (metal mica manufactured by Repco), PDM-800 (fluorine manufactured by Topy Industries, Ltd.) Phlogopite), sericite OC-100R (sericite manufactured by Oakem Tsusho Co., Ltd.), PDM-K (G) 325 (potassium tetrasilicon mica manufactured by Topy Industries, Ltd.), and the like.

  The clay mineral particles are preferably at least one selected from the group consisting of layered silicate minerals, imogolite, and allophane. These particles have a very large surface area, and a small amount tends to increase the viscosity of the composition for forming a reflective layer.

  The content of the clay mineral particles 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 composition for forming a reflective layer. When the content of the clay mineral particles is low, the viscosity of the reflective layer forming composition is difficult to increase, and the light diffusing particles are likely to settle. On the other hand, when the content of clay mineral particles is excessive, the viscosity of the reflective layer forming composition becomes excessively high, and the reflective layer forming composition may not be uniformly discharged from the coating apparatus.

  The surface of the clay mineral particles may be modified (surface treatment) with an ammonium salt or the like in consideration of compatibility with the solvent in the composition for forming a reflective layer.

2-6. Metal alkoxide or metal chelate The reflective layer forming composition may contain a metal alkoxide or metal chelate of a divalent or higher metal element other than Si element. When the metal alkoxide or the metal chelate is contained in the reflective layer forming composition, the adhesion between the resulting reflective layer and the substrate is enhanced. Since the metal contained in the metal alkoxide or metal chelate forms a metalloxane bond with the hydroxyl group on the surface of the substrate, the adhesion between the reflective layer and the substrate is enhanced.

The type of metal element contained in the metal alkoxide or metal chelate is not particularly limited as long as it is a bivalent or higher-valent metal element (excluding Si), but is preferably a group 4 or group 13 element. That is, specifically, the metal alkoxide or metal chelate is preferably a compound represented by the following general formula (V).
M ^{m +} X _n Y _m−n (V)
In general formula (V), M represents a Group 4 or Group 13 metal element, and m represents the valence (3 or 4) of M. X represents a hydrolyzable group, and n represents the number of X groups (an integer of 2 or more and 4 or less). However, m ≧ n. Y represents a monovalent organic group.

  In the general formula (V), the group 4 or group 13 metal element represented by M is preferably aluminum, zirconium, or titanium, and particularly preferably zirconium. A cured product of an alkoxide or chelate containing a zirconium element does not have an absorption wavelength in an emission wavelength region of a general LED element (particularly blue light (wavelength: 420 to 485 nm)). The light from the LED element 2 is hardly absorbed.

  In the general formula (V), the hydrolyzable group represented by X may be a group that is hydrolyzed with water to form a hydroxyl group. Preferable examples of the hydrolyzable group include a lower alkoxy group having 1 to 5 carbon atoms, an acetoxy group, a butanoxime group, a chloro group and the like. In general formula (V), all the groups represented by X may be the same group or different groups.

  As described above, the hydrolyzable group represented by X is hydrolyzed when the metal element forms a metalloxane bond with a hydroxyl group or the like on the surface of the substrate. Therefore, the compound produced after hydrolysis is preferably neutral and light boiling. Therefore, the group represented by X is preferably a lower alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group or an ethoxy group.

  In the general formula (V), the monovalent organic group represented by Y may be a monovalent organic group contained in a general silane coupling agent. Specifically, an aliphatic group, an alicyclic group, an aromatic group, an oil having 1 to 1000 carbon atoms, preferably 500 or less, more preferably 100 or less, further preferably 40 or less, and particularly preferably 6 or less. It may be a ring aromatic group. The organic group represented by Y may be an aliphatic group, an alicyclic group, an aromatic group, or a group in which an alicyclic aromatic group is bonded via a linking group. The linking group may be an atom such as O, N, or S, or an atomic group containing these.

  The organic group represented by Y may have a substituent. Examples of the substituent include halogen atoms such as F, Cl, Br, and I; vinyl group, methacryloxy group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, Organic groups such as nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group and phenyl group are included.

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

  Specific examples of the metal alkoxide or metal chelate containing a zirconium element represented by the general formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium. Examples include tetra n-butoxide, zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide, dibutoxyzirconium bis (ethylacetoacetate), and the like.

  Specific examples of the metal alkoxide or metal chelate containing the titanium element represented by the general formula (V) include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium. Examples include tetramethoxypropoxide, titanium tetra n-propoxide, titanium tetraethoxide, titanium lactate, titanium bis (ethylhexoxy) bis (2-ethyl-3-hydroxyhexoxide), titanium acetylacetonate, and the like.

  However, the metal alkoxide or metal chelate exemplified above is a part of a commercially available organometallic alkoxide or metal chelate that is easily available. The metal alkoxides or metal chelates shown in the list of coupling agents and related products in Chapter 9 “Optimum Utilization Technology of Coupling Agents” published by Science and Technology Research Institute are also applied to the composition for forming a reflective layer.

  The amount of the metal alkoxide or metal chelate contained in the composition for forming a reflective layer is 1 to 30% by mass relative to the total mass of the solid content of the composition for forming a reflective layer (total amount of components other than the solvent). Preferably, it is 5-20 mass%, More preferably, it is 5-15 mass%. When the amount of the metal alkoxide or metal chelate is less than 1% by mass, it is difficult to increase the adhesion between the resulting reflective layer and the substrate. On the other hand, when the amount of the metal alkoxide or metal chelate exceeds 30% by mass, the amount of the binder component is relatively decreased in the obtained reflective layer, and the strength may be decreased.

  Further, the amount of metal element derived from metal alkoxide or metal chelate (excluding Si element) contained in the obtained reflective layer is 0.5% relative to the number of moles of Si element contained in the composition for forming a reflective layer. It is preferable that it is -20 mol%, More preferably, it is 1-10 mol%. When the amount of the metal element is less than 0.5 mol%, the adhesion between the resulting reflective layer and the substrate does not increase. On the other hand, when the amount of metal alkoxide or metal chelate increases, the amount of light diffusing particles relatively decreases, and thus the light reflectivity of the reflective layer may be reduced. The amount of the metal element and the amount of the Si element can be calculated by energy dispersive X-ray spectroscopy (EDX).

2-7. Silane Coupling Agent The reflective layer forming composition may further contain a silane coupling agent. When the silane coupling agent is included in the reflective layer forming composition, the adhesion between the resulting reflective layer and the substrate, the reflective layer and the wavelength conversion layer are increased, and the durability of the LED device is improved.

  Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-Ami Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) ) -2-Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like are included. In the composition for forming a reflective layer, these may be contained alone or in combination of two or more.

  The amount of the silane coupling agent contained in the reflective layer forming composition is preferably 1 to 10% by mass with respect to the total mass (total amount of components other than the solvent) of the solid content of the reflective layer forming composition. 3 to 7% by mass is more preferable. If the amount of the silane coupling agent is too small, the adhesion between the resulting reflective layer and the substrate and the adhesion between the reflective layer and the wavelength conversion layer are not sufficiently enhanced. If the amount is too large, the heat resistance of the resulting reflective layer is reduced. There is a fear.

2-8. Solvent The solvent contained in the reflective layer forming composition is not particularly limited as long as it can dissolve or disperse the organosilicon compound. For example, it may be an aqueous solvent having excellent compatibility with water, or may be a non-aqueous solvent having low compatibility with water.

  When the organosilicon compound contained in the composition for forming a reflective layer is a polysilazane oligomer, the solvent can be an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogen hydrocarbon, an ether, or an ester. Specific examples include methyl ethyl ketone, tetrahydrofuran, benzene, toluene, xylene, dimethyl fluoride, chloroform, carbon tetrachloride, ethyl ether, isopropyl ether, dibutyl ether, and ethyl butyl ether.

  On the other hand, when the organosilicon compound contained in the composition for forming a reflective layer is a silane compound monomer or oligomer thereof, the solvent is not particularly limited, but alcohols are preferable, and polyhydric alcohols are particularly preferable. When alcohol is contained in the composition for forming a reflective layer, the viscosity of the composition for forming a reflective layer increases, and precipitation of light diffusing particles is suppressed. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, and the like, particularly ethylene glycol, propylene glycol, 1,3-butanediol, Alternatively, 1,4-butanediol is preferable.

  Whatever the organosilicon compound contained in the reflective layer-forming composition, the solvent contained in the reflective layer-forming composition preferably has a boiling point of 250 ° C. or lower. When the boiling point of the solvent is too high, drying of the composition for forming a reflective layer is delayed.

  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%.

2-9. Reaction accelerator The composition for forming a reflection layer may contain a reaction accelerator together with an organosilicon compound (particularly a polysilazane oligomer). The reaction accelerator may be either acid or base. Examples of reaction accelerators include amines such as triethylamine, diethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, and triethylamine; hydrochloric acid, oxalic acid, fumaric acid, sulfonic acid, and Acids such as acetic acid; metal carboxylates including nickel, iron, palladium, iridium, platinum, titanium, and aluminum are included. The reaction accelerator is particularly preferably a metal carboxylate. The amount of the reaction accelerator contained in the reflective layer forming composition is preferably 0.01 to 5 mol% with respect to the mass of the polysilazane oligomer.

3. Method for Manufacturing LED Device The above-described method for manufacturing an LED device includes at least the following three steps.
a) Mounting step of mounting LED elements on a substrate b) Reflective layer forming step of applying the above-mentioned reflective layer forming composition and drying and curing the reflective layer forming composition to form a reflective layer c) LED A wavelength conversion layer forming step of applying a wavelength conversion layer composition containing phosphor particles and a binder component so as to cover an element, and forming a wavelength conversion layer. In the method of the present invention, d) LED as necessary. A translucent layer forming step of forming a translucent layer so as to cover the element.

The manufacturing method of the LED device of the present invention may have the following four modes depending on the order in which the above steps are performed.
(1) 1st aspect performed in order of mounting process, reflective layer formation process, and wavelength conversion layer formation process (2) 2nd aspect performed in order of reflective layer formation process, mounting process, and wavelength conversion layer formation process (3) ) Third embodiment performed in order of mounting process, wavelength conversion layer forming process, and reflective layer forming process (4) Fourth process performed in order of mounting process, translucent layer forming process, reflective layer forming process, and wavelength converting layer forming process Aspect of

3-1) First Aspect In the first aspect, for example, as shown in FIG. 7, a mounting step for mounting the LED element 2 on the substrate 1 (FIG. 7A), the periphery of the mounting region of the LED element 2 A reflective layer forming step (FIG. 7B) for forming the reflective layer 21 on the outside of the portion, and a wavelength conversion layer forming step for forming the wavelength conversion layer 11 so as to cover the LED element 2 and the reflective layer 21 (FIG. 7 ( c)).

3-1-1) Mounting Step In the mounting step of the first aspect, the substrate 1 on which the metal part 3 (metal wiring) is formed is prepared. And the LED element 2 is fixed to the said board | substrate 1, and the LED element 2 and the metal part 3 of the board | substrate 1 are electrically connected. The method for fixing the LED element 2 to the substrate 1 is not particularly limited, and may be a method for fixing the LED element 2 by, for example, die bonding. Moreover, the connection method of the LED element 2 and the metal part 3 is not particularly limited. For example, as shown in FIG. 7A, a method of connecting via the protruding electrodes 5 can be used. Moreover, the method of connecting the LED element 2 and the metal part 3 via a wire etc. may be sufficient.

3-1-2) Reflective Layer Forming Process In the reflective layer forming process of the first aspect, the LED element 2 mounting region (the light emitting surface of the LED element 2 mounted in the mounting process described above, the LED element 2 and the metal part 3). The composition for forming a reflective layer is applied and cured so that the composition for forming a reflective layer does not adhere to the peripheral portion thereof.

  The method for forming the reflective layer 21 only in a desired region includes (i) a method in which a region where the reflective layer is not formed is covered with another member and the reflective layer is formed in a specific region; A method of forming a reflective layer in a specific region depending on the shape of a member to which the composition is applied (that is, a substrate on which an LED element is mounted); (iii) a method of applying the composition for forming a reflective layer, There is a method of forming in a specific region.

  (I) In the method of covering the region where the reflective layer is not formed with another member and forming the reflective layer in a specific region, the mounting region of the LED element 2 and its peripheral portion (region where the reflective layer is not formed) are protected. By applying the step, applying and curing the reflective layer forming composition 21 ', and removing the member that protects the mounting region of the LED element 2 and its peripheral portion as necessary, only the desired region is performed. The reflective layer 21 can be formed.

  In the method (i), the method for protecting the mounting region of the LED element 2 and the peripheral portion thereof is not particularly limited. For example, as shown in the top view of FIG. 8A and the cross-sectional view of FIG. 8B, a method of covering the mounting region of the LED element 2 and its peripheral portion with the plate-like mask 110 may be used. The shape of the plate-like mask 110 is appropriately selected according to the mounting area of the LED element 2 and the shape of the peripheral edge thereof. The material of the mask 110 is not particularly limited as long as it does not transmit the reflective layer forming composition, and may be resin, metal, ceramic, or the like.

  In the method (i), another example of a method for protecting the mounting region of the LED element 2 and the peripheral portion thereof is as follows. As shown in FIG. It can be a method of covering the periphery. Specifically, as shown in FIG. 9A, the substrate 1 and the LED element 2 are covered with a resist material 120. Then, as shown in FIG. 9B, the resist material 120 is exposed while shielding the mounting area of the LED element 2 and its peripheral edge with a light shielding mask 121 or the like. Thereafter, as shown in FIG. 9C, the resist material is developed; that is, the resist material 120 in the region where the reflective layer is formed is removed. Thereby, the mounting area | region of LED element 2 and its peripheral part are protected with the resist material 120. FIG.

  The positive resist material 120 has been described above as an example, but the resist material 120 may be a negative type. Examples of the resist material include a positive photosensitive material such as a general naphthoquinone diazide compound, a negative photosensitive material such as a bisazide compound, and the like.

  The method for applying the resist material 120 is not particularly limited, and may be, for example, spray application or dispenser application. The curing method of the resist material 120 is appropriately selected according to the type of the resist material, and may be irradiation with light having a specific wavelength, heat treatment, or the like. The developing method of the resist material may be a method of dissolving and removing with a resist developer or the like.

  In addition, you may protect the mounting area | region of LED element 2, and its peripheral part with the resist material 120, without performing the said exposure and image development. For example, the mounting region and the peripheral portion thereof can be covered with the resist material 120 by applying the resist material 120 only to the mounting region of the LED element 2 and the peripheral portion thereof and curing it. The application method of the resist material 120 may be any method that can apply the resist material 120 only to a desired region, and may be dispenser application, inkjet application, or the like. At this time, a region where the resist material 120 is not applied may be protected with a plate mask or the like.

  Further, in the method (i), another example of the method for protecting the mounting region of the LED element 2 and the peripheral portion thereof is to use a soluble resin soluble in water or a solvent only in the mounting region of the LED element 2 and the peripheral portion thereof. It can also be a method of applying to and curing.

  The soluble resin is not particularly limited as long as it is soluble in water or a solvent and can be removed after forming the reflective layer. Examples of the availability resin include acrylic resin and polycarbonate resin that are soluble in polyvinyl alcohol, tetrahydrofuran (THF), and dichloromethane.

  The method for applying the soluble resin may be any method that can apply the soluble resin only to a desired region, and may be dispenser application, inkjet application, or the like. At this time, the region where the soluble resin is not applied may be protected with a plate mask or the like.

  In addition, in the method (i), still another example of the method for protecting the mounting region of the LED element 2 and the peripheral portion thereof is to apply a liquid repellent only to the mounting region of the LED element 2 and the peripheral portion thereof and to dry. It can also be a method.

  The liquid repellent is not particularly limited as long as the composition can prevent the composition from adhering to the mounting region of the LED element 2 and the peripheral portion thereof when the composition for forming a reflective layer is applied. Examples of the liquid repellent include fluorine-based coating agents (for example, KP-911 and X-24-9481 manufactured by Shin-Etsu Chemical Co., Ltd., FS-1090 and FS-5060 manufactured by Fluoro Technology Co., Ltd., and Opt-Ace manufactured by Daikin Co., Ltd.) Silicone-based coating agents (for example, KS-702 and KS-725 manufactured by Shin-Etsu Chemical Co., Ltd.); titanium oxide-based coating agents (for example, NANO INDENT, manufactured by CTC Nanotechnology, Inc.).

  The application method of the liquid repellent may be any method that can apply the liquid repellent only to a desired region, and may be dispenser application, ink jet application, or the like. At this time, the region where the liquid repellent agent is not applied may be protected with a plate mask or the like.

  In the method (i), the region where the reflective layer is not formed is protected with another member (a plate-like mask, a resist mask, a soluble resin, a liquid repellent, etc.), and then shown in FIG. 8B or FIG. 9D. As shown, the reflective layer forming composition 21 ′ is applied onto the substrate 1.

  The application method of the reflective layer forming composition 21 ′ is not particularly limited, and can be dispenser application or spray application. When the composition for forming a reflective layer is applied by spray coating, the thickness of the reflective layer 21 can be easily reduced. Further, when the substrate 1 has a cavity, it is easy to apply the reflective layer forming composition to the inner wall surface 6 of the cavity.

  After the reflective layer forming composition 21 ′ is applied to the substrate 1, the reflective layer forming composition is dried and cured. The temperature at which the reflective layer forming composition 21 ′ 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 may not be sufficiently evaporated. On the other hand, if the temperature exceeds 200 ° C., the LED element 2 may be adversely 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. When the organosilicon compound contained in the reflective layer forming composition 21 ′ is a polysilazane oligomer, the coating film is further irradiated with UVU radiation (eg, excimer light) in the wavelength range of 170 to 230 nm, and then further cured. By performing heat curing, a denser film is formed.

  In the method (i), after curing of the reflective layer forming composition 21 ′, the mounting region of the LED element 2 and its peripheral portion, such as a plate mask, a resist material, and a soluble resin, were protected as necessary. Remove the protective member. When removing the resist material 120 and the soluble resin, as shown in FIG. 9 (e), the reflective layer forming composition 21 'laminated thereon is also removed. Thereby, the reflective layer 21 is formed only in a desired region. The plate mask may be removed before the reflection layer forming composition 21 'is cured.

  The method for removing the protective member is appropriately selected depending on the type of the protective member. The plate-like mask may be removed from the substrate 1. The resist material 120 is removed by a general dry etching method or a wet etching method. The soluble resin is removed by washing the substrate 1 with water or a solvent.

(Ii) A method of forming a reflective layer in a specific region depending on the shape of a member (that is, a substrate on which an LED element is mounted) to which a composition for forming a reflective layer is applied is shown in FIG. A step (FIG. 13A) of forming the partition wall 200 around the periphery of the mounting region of the element 2 (a region where no reflective layer is formed), and a reflection lower in height than the partition wall 200 in a region outside the partition wall 200 And the step of forming the layer 21 (FIG. 13B).

  In this method, as shown in FIG. 13 (b), the reflective layer forming composition 21 ′ is dammed up by the partition walls 200 formed around the LED elements 2, so that the reflective layer forming composition 21 ′ is It does not adhere to the LED element mounting area and its peripheral edge.

  For example, as shown in the top view of FIG. 14, the partition wall 200 is preferably formed so as to surround the peripheral portion of the mounting region of the LED element 2. Moreover, it is preferable that the partition wall 200 is a member with high transparency with respect to visible light, or a white member from the viewpoint of the light extraction property of the LED device 100.

  The height of the partition wall 200 to be formed may be higher than the coating thickness of the reflective layer forming composition 21 ′; it is preferably 5 to 200 μm, more preferably 20 to 100 μm. On the other hand, the width of the partition wall is usually preferably 10 to 1000 μm, more preferably 50 to 500 μm.

  The method for forming the partition wall 200 is not particularly limited, and may be a method in which a frame member made of resin or ceramic formed by a known method is disposed so as to surround the peripheral portion of the mounting region; LED element 2 Alternatively, the partition wall forming composition may be applied and cured so as to surround the periphery of the mounting region.

  The partition forming composition is not particularly limited as long as it is a material capable of forming a transparent or white partition, and may be, for example, the same composition as the reflective layer forming composition.

  The method for applying the partition wall forming composition is not particularly limited as long as the partition wall forming composition can be applied only to a desired region, and can be dispenser coating, jet dispenser coating, inkjet coating, or the like. Moreover, the hardening method of the composition for partition formation is suitably selected according to the component contained in the composition for partition formation. An example of the curing method is heat curing.

  In this method, after the partition wall 200 is formed, the reflective layer forming composition 21 ′ is applied to a region outside the partition wall 200. At this time, the coating amount of the reflective layer forming composition is adjusted so that the thickness of the reflective layer forming composition 21 ′ does not exceed the height of the partition wall 200. The application method of the reflective layer forming composition 21 ′ is not particularly limited, and may be dispenser application, jet dispenser application, inkjet application, or the like. The curing method of the reflective layer forming composition 21 ′ can be the same as the curing method of the reflective layer forming composition 21 ′ in the method (i).

  On the other hand, (ii) another example of a method for forming a reflective layer in a specific region depending on the shape of a member to which the reflective layer forming composition 21 ′ is applied (that is, a substrate on which an LED element is mounted) As shown in FIG. 15, the wavelength conversion layer composition 21 ′ may be applied to the substrate 1 having the groove 10 so as to surround the mounting region of the LED element 2 and the peripheral portion thereof, and cured.

  In this method, as shown in FIG. 15B, when the reflective layer forming composition 21 ′ is applied, the reflective layer forming composition 21 ′ flows into the groove 10 in the vicinity of the mounting region of the LED element 2. . As a result, the reflective layer forming composition 21 ′ does not adhere to the mounting region of the LED element 2 and the peripheral portion thereof, and the reflective layer 21 is formed only in a desired region.

  The depth of the groove 10 provided on the substrate may be a depth that can sufficiently store the composition for forming a reflective layer to be applied, and is preferably 50 to 1000 μm, and more preferably 100 to 500 μm. On the other hand, the width of the groove is usually preferably 50 to 1000 μm, more preferably 100 to 500 μm. The groove 10 is preferably formed when the substrate 1 is manufactured.

  The application method of the reflective layer forming composition 21 ′ is not particularly limited, and may be dispenser application, inkjet application, or the like. At this time, it is preferable to apply the reflective layer forming composition 21 ′ from a region outside the groove 10. Further, the coating amount of the reflective layer forming composition 21 ′ is adjusted so that the reflective layer forming composition 21 ′ does not overflow from the groove 10. The method for curing the reflective layer forming composition 21 ′ may be the same as the method for curing the reflective layer forming composition 21 ′ in the method (i).

  Further, (ii) another example of a method for forming a reflective layer in a specific region depending on the shape of a member (that is, a substrate on which an LED element is mounted) to which the reflective layer forming composition 21 ′ is applied is shown in FIG. 16, the LED element mounting surface 1a of the substrate 1 may be a method in which the reflective layer forming composition 21 ′ is applied and cured on the substrate 1 protruding from the reflective layer forming surface 1b.

  In this method, there is a step between the mounting surface 1a of the LED element 2 and the reflective layer forming surface 1b. Therefore, when the reflective layer forming composition 21 ′ is applied, the reflective layer forming composition 21 ′ does not adhere to the mounting region of the LED element 2 and the peripheral portion thereof, and the reflective layer 21 is formed only in a desired region. A film is formed.

  The difference in height (step) between the LED element mounting surface 1a and the reflective layer forming surface 1b may be larger than the coating thickness of the reflective layer forming composition 21 ′; preferably 5 to 500 μm, More preferably, it is 20-100 micrometers. The step is preferably formed when the substrate 1 is manufactured.

  The method for applying the reflective layer forming composition 21 ′ is not particularly limited as long as the reflective layer forming composition 21 ′ can be applied only to the reflective layer forming surface. It is possible. The curing method of the reflective layer forming composition 21 ′ can be the same as the curing method of the reflective layer forming composition 21 ′ in the method (i).

(Iii) The method of forming the reflective layer only in a specific region by the method of applying the composition for forming the reflective layer is as shown in FIG. After applying the reflective layer forming composition 21′A to the region A (FIG. 17A); applying the reflective layer forming composition 21′B to the region B separated from the region A (FIG. 17 ( b)); Further, the reflective layer forming composition may be applied to a region between the region A and the region B (FIG. 17C).

  When the reflective layer forming composition is continuously applied around the LED element mounting area by a general method, the reflective layer forming composition easily flows; the reflective layer forming composition wets and spreads over the entire substrate. Cheap. As a result, the composition for forming a reflective layer tends to adhere to the LED element mounting region and its peripheral portion. On the other hand, when the reflective layer forming composition 21 ′ is applied to regions (regions A and B) that are separated little by little, the reflective layer forming composition 21 ′ is formed by the surface tension of the reflective layer forming composition 21 ′. Difficult to spread wet. When the reflective layer forming composition 21 ′ is applied little by little so as to fill the gap between the region A and the region B, the reflective layer forming composition is increased even when the coating area of the reflective layer forming composition 21 ′ is increased. The object 21 'is difficult to flow. Therefore, according to the method, the reflective layer forming composition 21 ′ can be applied only to a desired region.

  The areas of the region A and the region B and the amount of the reflective layer forming composition 21 ′ applied to each region are appropriately selected according to the size of the LED device 100 to be manufactured. In the example shown in FIG. 17, the reflective layer forming composition 21 ′ is applied to the two regions A and B that are opposed to each other with the LED element 2 interposed therebetween, and then the reflective layer forming composition is interposed in the gap. 21 ′ is applied; the reflective layer forming composition 21 ′ may be applied to three or more places separated from each other, and then the reflective layer forming composition 21 ′ may be applied to the gaps.

  The method for applying the reflective layer forming composition 21 ′ is not particularly limited as long as a desired amount of the reflective layer forming composition can be applied to a desired region. For example, dispenser application or inkjet application is possible. sell. The curing method of the reflective layer forming composition 21 ′ can be the same as the curing method of the reflective layer forming composition 21 ′ in the method (i).

  (Iii) Another example of the method of forming the reflective layer only in a specific region by the method of applying the composition for forming the reflective layer is as follows. As shown in FIG. A method of applying and curing the reflective layer forming composition 21 ′ in a desired region while relatively moving the coating device 110 of the reflective layer forming composition 21 ′ and the substrate 1. It can be.

  In this method, the reflective layer forming composition 21 ′ applied to the substrate 1 is difficult to move in the horizontal direction. Accordingly, the wetting and spreading of the reflective layer forming composition 21 ′ can be suppressed, and the reflective layer forming composition 21 ′ can be applied only to a desired region.

  The method for applying the reflective layer forming composition 21 ′ is not particularly limited as long as a desired amount of the reflective layer forming composition can be applied to a desired region. For example, dispenser application or inkjet application is possible. sell. The curing method of the reflective layer forming composition 21 ′ can be the same as the curing method of the reflective layer forming composition 21 ′ in the method (i). The curing of the reflective layer forming composition 21 ′ is preferably performed while the light emitting surface 2 a of the LED element of the substrate 1 is directed vertically downward.

3-1-3) Wavelength Conversion Layer Formation Step In the wavelength conversion layer formation step of the first aspect, the wavelength conversion layer 11 is formed on the substrate 1 on which the reflective layer 21 is formed (FIG. 9 (f)). The wavelength conversion layer 11 is formed by preparing a wavelength conversion layer composition containing a binder component and phosphor particles, applying the composition to cover the LED element 2 and the reflective layer 21, and curing the composition. It is possible.

  The binder component contained in the wavelength conversion layer composition may be the above-described transparent resin or a precursor thereof, or an organosilicon compound. 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. When the binder component is the aforementioned transparent resin or a precursor thereof, the solvent is a hydrocarbon such as toluene or xylene; a ketone such as acetone or methyl ethyl ketone; an ether such as diethyl ether or tetrahydrofuran; propylene glycol monomethyl ether acetate, ethyl It may be an ester such as acetate. On the other hand, when the binder component is an organosilicon compound, the solvent may be the same as the solvent contained in the reflective layer forming composition.

  Mixing of the composition for wavelength conversion layer can be performed by, for example, a stirring mill, a blade kneading stirring device, a thin-film swirling disperser, or the like. By adjusting the stirring conditions, the precipitation of the phosphor particles in the wavelength conversion layer composition is suppressed.

  The coating method of the composition for wavelength conversion layers is suitably selected according to the kind of binder component. When the binder component is a transparent resin or a precursor thereof, it can be dispenser application or the like. On the other hand, when the binder component is an organosilicon compound, it can be dispenser coating, spray coating, or the like.

  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.

3-2) Second Aspect In the second aspect, for example, as shown in FIG. 10, a reflective layer forming step (FIG. 10A) for forming a projecting layer outside the peripheral portion of the mounting area of the LED element 2. ), The step of mounting the LED element 2 on the substrate 1 (and the wavelength conversion layer forming step of forming the wavelength conversion layer 11 so as to cover the LED element 2 (FIG. 7C)).

3-2-1) Reflective layer forming step In the reflective layer forming step of the second aspect, a composition for forming a reflective layer is formed in the connection region 2 '(mounting region) between the metal part 3 and the LED element 2 and the peripheral portion thereof. The composition for forming a reflective layer is applied and cured so that no sticking occurs.

  The method for forming the reflective layer only in a desired region includes (i) a method in which a region where the reflective layer is not formed is covered with another member and the reflective layer is formed only in a specific region; (ii) for forming the reflective layer A method of forming a reflective layer only in a specific region depending on the shape of a member to which the composition is applied (that is, a substrate on which an LED element is mounted); (iii) a method of applying a composition for forming a reflective layer, Is formed only in a specific region. Any method may be the same as each method of the first aspect described above.

3-2-2) Mounting Step In the mounting step of the second aspect, as shown in FIG. 10B, the LED element 2 is fixed on the substrate 1 on which the reflective layer 21 is formed, and the LED element 2 And the metal part 3 are electrically connected. The mounting method of the LED element is the same as the mounting method of the first aspect.

3-2-3) Wavelength Conversion Layer Formation Step In the wavelength conversion layer formation step of the second aspect, as shown in FIG. 10C, the wavelength conversion layer 11 is formed on the substrate 1 on which the reflective layer 21 is formed. Form. The wavelength conversion layer 11 is formed by preparing a wavelength conversion layer composition containing a binder component and phosphor particles, applying the composition to cover the LED element 2 and the reflective layer 21, and curing the composition. It is possible. The composition for wavelength conversion layer and its application / curing method are the same as the composition for wavelength conversion layer and the application / curing method of the first embodiment.

3-3) Third Aspect In the third aspect, as shown in FIG. 11, a mounting step (FIG. 11 (a)) for mounting the LED element 2, a mounting region of the LED element 2, and a peripheral portion thereof are covered. As shown in FIG. 11C, the wavelength conversion layer forming step for forming the wavelength conversion layer (FIG. 11B), the reflection layer forming step for forming the reflection layer 21 outside the peripheral edge of the mounting region of the LED element 2 (FIG. 11C). )). In the third aspect, after the wavelength conversion layer 11 protects the mounting region of the LED element 2 and its peripheral portion (FIG. 11B), the reflective layer 21 is formed (FIG. 11C). Therefore, the reflective layer forming composition for forming the reflective layer 21 does not adhere to the mounting region of the LED element 2 and its peripheral portion.

3-3-1) Mounting Step In the mounting step of the third aspect, as shown in FIG. 11A, the LED element 2 is fixed on the substrate 1, and the LED element 2 and the metal part 3 are electrically connected. Connect. The mounting method of the LED element is the same as the mounting method of the first aspect. In this aspect, as shown in FIG. 11A, it is more preferable to connect the LED element 2 and the metal part 3 via the protruding electrode 5. When the LED element 2 and the metal part 3 are connected via the protruding electrode 5, in the wavelength conversion layer forming step described later, the mounting area of the LED element 2 and its peripheral part can be easily covered with the wavelength conversion layer composition. .

3-3-2) Wavelength conversion layer formation step In the wavelength conversion layer formation step of the third aspect, the LED element 2 mounting region and its peripheral portion; that is, the LED element 2 and the connection region between the LED element 2 and the metal portion 3 And the wavelength conversion layer 11 is formed so that the peripheral part may be covered at least. At this time, the wavelength conversion layer 11 may be formed so as to cover only the mounting region of the LED element 2 and its peripheral edge.

  Further, the wavelength conversion layer 11 may be formed so as to cover the substrate 1 outside the peripheral portion of the mounting region of the LED element 2. However, when the wavelength conversion layer 11 is also formed outside the peripheral portion of the mounting region of the LED element 2, the thickness of the wavelength conversion layer 11 is formed to be thinner than the LED element 2. When the LED element 2 is buried in the wavelength conversion layer 11, the reflective layer forming composition is likely to adhere to the mounting region of the LED element 2 and the peripheral portion thereof in a reflective layer forming step described later.

  For example, as illustrated in FIG. 11B, the wavelength conversion layer 11 is preferably formed not only on the upper surface of the LED element 2 but also on the side surface. If the wavelength conversion layer 11 is also formed on the side surface of the LED element 2, light emitted from the side surface of the LED element 2 can also be extracted, and the light extraction efficiency of the LED device 100 is increased.

  The wavelength conversion layer 11 is formed by preparing a composition for a wavelength conversion layer containing a binder component and phosphor particles, and applying the composition so as to cover the mounting region of the LED element 2 and its peripheral portion, It can be a method of curing. The coating method of the composition for wavelength conversion layers is suitably selected according to the binder component contained in the composition for wavelength conversion layers. For example, when the binder component is a resin or a precursor thereof, it can be dispenser application or the like. When the binder component is an organosilicon compound, it can be dispenser application, spray application, or the like.

  The application of the wavelength conversion layer composition may be performed with the light emitting surface of the LED element 2 directed vertically upward as shown in FIG. 11 (a). As shown in FIG. The light emitting surface 2a of the element 2 may be directed vertically downward. As shown in FIG. 11A, when the composition for wavelength conversion layer is applied to the mounting region of LED element 2 and its peripheral portion with the light emitting surface of LED element 2 facing vertically upward, for wavelength conversion layer It is preferable to apply the wavelength conversion layer composition while protecting a region where the composition is not applied. The composition for wavelength conversion layer wets and spreads, and the composition for wavelength conversion layer may adhere besides a desired area | region. The method for protecting the region where the composition for wavelength conversion layer is not applied can be the same as the method for protecting the mounting region of LED element 2 and its peripheral portion in the reflective layer forming step of the first aspect.

  On the other hand, as shown in FIG. 19A, when the wavelength conversion layer composition is applied with the light emitting surface 2a of the LED element 2 facing vertically downward, the wavelength conversion layer composition hardly spreads in the horizontal direction. Therefore, in this case, it is not necessary to protect the area where the wavelength conversion layer composition is not applied.

  After application of the wavelength conversion layer composition, the wavelength conversion layer composition is cured. Curing of the composition for wavelength conversion layer may be performed with the light emitting surface of the LED element 2 directed vertically upward as shown in FIG. 11 (b). As shown in FIG. The light emitting surface 2a of the element 2 may be directed vertically downward. As shown in FIG. 19 (b), when the light emitting surface 2a of the LED element 2 is directed vertically downward, the wavelength conversion layer composition is difficult to spread in the horizontal direction, so that the wavelength conversion layer 11 is formed only in a desired region. Easy to form a film.

  In addition, the composition for wavelength conversion layers and its hardening method are the same as the composition for wavelength conversion layers of a 1st aspect, and the application | coating and hardening method.

3-3-3) Reflective Layer Forming Step In the reflective layer forming step of the third aspect, the reflective layer forming composition is applied only outside the peripheral edge of the mounting area of the LED element 2 to form the reflective layer 21. . At this time, the reflective layer 21 is formed so that the height of the reflective layer 21 does not exceed the upper surface of the wavelength conversion layer 11 covering the LED element 2. Since the laminated region of the LED element 2 and the wavelength conversion layer 11 has a certain thickness, the reflective layer 21 can be formed by applying the reflective layer forming composition so as not to exceed the upper surface of the wavelength conversion layer 11 covering the LED element 2. Is formed only outside the peripheral edge of the mounting area of the LED element 2.

  As a method of applying the reflective layer forming composition only to the outside of the peripheral edge of the mounting area of the LED element 2, it is possible to apply a dispenser or the like. The reflective layer forming composition and the method for curing the reflective layer forming composition are the same as the reflective layer forming composition of the first aspect and the curing method thereof.

3-4. Fourth Aspect In the fourth aspect, as shown in FIG. 12, the mounting step (FIG. 12 (a)) for mounting the LED element 2, the mounting region of the LED element 2 and the peripheral portion thereof are covered. A translucent layer forming step for forming the translucent layer 31 (FIG. 12B), a step of forming the reflective layer 21 outside the peripheral edge of the mounting region of the LED element 2 (FIG. 12C), and the LED element The wavelength conversion layer forming step for forming the wavelength conversion layer 11 covering 2 (FIG. 12D) is performed in this order. In the fourth embodiment, the light-transmitting layer 31 protects the mounting area of the LED element 2 and its peripheral portion (FIG. 12B), and then the reflective layer 21 is formed (FIG. 11C). Therefore, the reflective layer forming composition for forming the reflective layer 21 is difficult to adhere to the mounting region of the LED element 2 and the peripheral portion thereof, and the reflective layer 21 can be easily formed.

3-4-1) Mounting Step In the mounting step of the fourth aspect, as shown in FIG. 12A, the LED element 2 is fixed on the substrate 1, and the LED element 2 and the metal part 3 are electrically connected. Connect. The mounting method of the LED element is the same as the mounting method of the first aspect. In this aspect, as shown in FIG. 13A, it is more preferable to connect the LED element 2 and the metal part 3 via the protruding electrode 5. When the LED element 2 and the metal part 3 are connected via the protruding electrode 5, in the wavelength conversion layer forming step described later, the mounting area of the LED element 2 and its peripheral part can be easily covered with the wavelength conversion layer composition. .

3-4-2) Translucent layer forming step In the translucent layer forming step of the fourth aspect, the LED element 2 mounting region and its peripheral portion; that is, the LED element 2 and the connection region between the LED element 2 and the metal portion 3 And the translucent layer 31 is formed so that the peripheral part may be covered at least (FIG.12 (b)). At this time, the translucent layer 31 may be formed so as to cover only the mounting region of the LED element 2. Moreover, you may form the translucent layer 31 so that the board | substrate 1 outside the peripheral part of the mounting area | region of an LED element may also be covered. However, when the light transmissive layer 31 is also formed outside the peripheral portion of the mounting region of the LED element 2, the light transmissive layer 31 is formed so that the thickness of the light transmissive layer 31 is smaller than the thickness of the LED element 2. When the LED element 2 is buried in the light-transmitting layer 31, the reflective layer forming composition easily adheres to the mounting region of the LED element 2 and the peripheral portion thereof in a reflective layer forming process described later.

  For example, as shown in FIG. 12B, the light transmissive layer 31 is preferably formed not only on the upper surface of the LED element 2 but also on the side surface. If the translucent layer 31 is also formed on the side surface of the LED element 2, light emitted from the side surface of the LED element 2 can also be extracted, and the light extraction efficiency of the LED device 100 is increased.

  The method for forming the light-transmitting layer 31 is a method of preparing a light-transmitting layer composition containing a light-transmitting material, and applying and curing the composition so as to cover the mounting region of the LED element 2 and its peripheral edge. It can be.

  The translucent material contained in the composition for translucent layer may be the aforementioned transparent resin or a precursor thereof, or an organosilicon compound. The composition for light transmissive layer may contain a solvent. The solvent contained in the composition for light transmissive layer is not particularly limited as long as it can dissolve or disperse the light transmissive material. When the translucent material is the above-mentioned transparent resin or a precursor thereof, the solvent is hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; propylene glycol monomethyl ether acetate And esters such as ethyl acetate. On the other hand, when the translucent material is an organosilicon compound, the solvent may be the same as the solvent contained in the reflective layer forming composition.

  The method for applying the light transmissive layer composition is not particularly limited, and is appropriately selected depending on the light transmissive material contained in the light transmissive layer composition. For example, when the translucent material is a resin or a precursor thereof, it may be dispenser application or the like. Further, when the translucent material is an organosilicon compound, it can be dispenser coating, spray coating, or the like.

  Application of the composition for the light transmissive layer may be performed with the light emitting surface of the LED element 2 directed vertically upward as shown in FIG. 12 (a). As shown in FIG. The light emitting surface of the element 2 may be directed vertically downward. When the light emitting surface of the LED element 2 is directed vertically upward and the composition for the light transmissive layer is applied only on the mounting area of the LED element 2 and the peripheral portion thereof, the area where the composition for the light transmissive layer is not applied is protected. However, it is preferable to apply the light-transmitting layer composition. The composition for light transmissive layer is wet and spreads, and the composition for light transmissive layer may adhere in addition to a desired region. The method for protecting the region where the light transmitting composition is not applied may be the same as the method for protecting the mounting region of LED element 2 and its peripheral portion in the reflective layer forming step of the first aspect.

  On the other hand, as shown in FIG. 20A, when the light-transmitting layer composition is applied with the light emitting surface 2a of the LED element 2 facing vertically downward, the light-transmitting layer composition is difficult to spread in the horizontal direction. Therefore, in this case, it is not necessary to protect the area where the composition for light transmissive layer is not applied.

  After application of the light transmissive layer composition, the light transmissive layer composition is cured. Curing of the composition for light transmissive layer may be performed with the light emitting surface of the LED element 2 directed vertically upward as shown in FIG. 12 (b). As shown in FIG. The light emitting surface of the element 2 may be directed vertically downward. As shown in FIG. 20B, when the light emitting surface of the LED element 2 is directed vertically downward, the composition for the light transmissive layer is difficult to spread in the horizontal direction. Therefore, it is easy to form the translucent layer 31 only in a desired region.

  The curing method and curing conditions of the light transmissive layer composition are appropriately selected depending on the type of the binder component. An example of the curing method is heat curing.

3-4-3) Reflective layer forming step In the reflective layer forming step of the fourth aspect, the reflective layer forming composition is applied only outside the peripheral edge of the mounting region of the LED element 2 to form the reflective layer 21. (FIG. 12 (c)). At this time, the reflective layer 21 is formed so that the height of the reflective layer 21 does not exceed the upper surface of the light transmissive layer 31 covering the LED element 2. Since the laminated region of the LED element 2 and the translucent layer 31 has a certain thickness, the reflective layer 21 is formed by applying the reflective layer forming composition so as not to exceed the upper surface of the translucent layer 31 covering the LED element 2. Is formed only outside the peripheral edge of the mounting area of the LED element 2.

  As a method of applying the reflective layer forming composition only to the outside of the peripheral edge of the mounting area of the LED element 2, it is possible to apply a dispenser or the like. The reflective layer forming composition and the method for curing the reflective layer forming composition can be the same as the reflective layer forming composition of the first aspect and the curing method thereof.

3-4-4) Wavelength Conversion Layer Formation Step In the wavelength conversion layer formation step of the fourth aspect, the wavelength conversion layer 11 is formed on the substrate 1 on which the reflection layer 21 and the light transmission layer 31 are formed (FIG. 12). (D)). The wavelength conversion layer 11 is formed by preparing a composition for a wavelength conversion layer containing a binder component and phosphor particles, and applying the composition so as to cover the LED element 2, the translucent layer 31, and the reflective layer 21. And can be cured. The wavelength conversion layer composition and the coating / curing method thereof may be the same as the wavelength conversion layer composition and coating / curing method of the first embodiment.

  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.

(1) Preparation of wavelength conversion layer composition (wavelength conversion layer composition A)
A silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KER2600) and a yellow phosphor (manufactured by Nemoto Special Chemical Co., Ltd., YAG 450C205 (volume average particle size particle size D50 20.5 μm)) were mixed to obtain a wavelength conversion layer composition. . The density | concentration of the yellow fluorescent substance in the composition for wavelength conversion layers was 5 mass%.

(Composition B for wavelength conversion layer)
3.25 g of tetramethoxysilane, 4.00 g of methanol, and 4.00 g of acetone were mixed and stirred. Further, 5.46 g of water and 4.7 μL of 60% nitric acid were added to this mixed solution and stirred for 3 hours to obtain a polysiloxane solution. Subsequently, 6.5 g of a yellow phosphor (manufactured by Nemoto Special Chemical Co., YAG 450C205 (volume average particle diameter D50 20.5 μm))) was mixed with the polysiloxane solution to obtain a wavelength conversion layer composition B.

(2) Preparation of composition for forming reflective layer 2.10 g of methyltrimethoxysilane, 0.98 g of tetramethoxysilane, 4.00 g of methanol, and 4.00 g of acetone were mixed and stirred. To this mixture, 5.46 g of water and 4.7 μL of an aqueous nitric acid solution having a concentration of 60% by mass were added. This mixed solution was further stirred for 3 hours to obtain a polysiloxane oligomer solution containing a polysiloxane oligomer of trifunctional component: tetrafunctional component (polymerization ratio) = 7: 3. Subsequently, 12.0 g of titanium oxide (Fuji Titanium Industry TA-100, particle size 600 nm) and 1 g of 1,3-butanediol were mixed into the polysiloxane oligomer solution to obtain a composition for forming a reflective layer.

(3) Production of LED device [Example 1]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A metal part arranged on the substrate and the LED element 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.

  A plate-like mask shown in FIG. 8 was arranged so as to cover the light emitting surface of the LED element, the connection part between the LED element and the metal part, and the peripheral part thereof. From the upper part of the package, the above-described composition for forming a reflective layer was applied by spraying. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray coating, the plate mask was removed and baked at 150 ° C. for 1 hour to form a reflective layer. The thickness of the obtained reflection layer was 15 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation).

  The composition for wavelength conversion layer A was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 2]
A substrate having a cavity as shown in FIG. 3 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A metal part arranged on the substrate and the LED element were connected by a protruding electrode 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.

  A positive resist material (OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied so as to cover the LED element. The package was heated at 110 ° C. for 30 minutes in a nitrogen atmosphere. Then, a light-shielding mask that shields the LED element mounting region and its peripheral portion was placed on the package, and UV light was irradiated through the light-shielding mask. Thereafter, the resist material was removed with an alkaline developer, and a film (resist film) made of the resist material was formed only on the LED element mounting region and its peripheral portion. The package was further washed with pure water.

  Thereafter, the above-mentioned composition for forming a reflective layer was spray-coated inside the package. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the moving speed of the nozzle was 100 mm / s. After spray coating, it was baked at 150 ° C. for 1 hour. The thickness of the obtained reflection layer was 15 μm.

  The package on which the reflective layer was formed was washed with tetrahydrofuran (THF), and the resist film and the reflective layer formed on the resist film were removed. Further, the wavelength conversion layer composition A was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 3]
Similar to Example 2, a package in which a metal part and an LED element were connected by a protruding electrode was prepared. PVA aqueous solution was prepared by dissolving polyvinyl alcohol (PVA) JC-25, manufactured by Nippon Vinegar Poval, in water at a concentration of 10% by weight. The prepared PVA aqueous solution was potted on the LED element and its peripheral portion with a dispenser and dried at 80 ° C. for 1 hour to form a film (PVA film) made of a soluble resin. The thickness of the film made of the obtained soluble resin was 200 μm.

  Thereafter, the above-mentioned composition for forming a reflective layer was spray-coated inside the package. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray coating, it was baked at 150 ° C. for 1 hour. The thickness of the obtained reflection layer was 15 μm. The package in which the reflective layer was formed was washed in water to remove the soluble resin and the reflective layer formed on the soluble resin.

  The wavelength conversion layer composition A described above was potted with a dispenser on the package having the reflective layer formed thereon, heated at 100 ° C. for 1 hour, and then cured by heating at 150 ° C. for 2 hours to form a wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 4]
Similar to Example 2, a package in which a metal part and an LED element were connected by a protruding electrode was prepared. A plate-shaped mask having openings only in the LED element mounting region of the package and the peripheral edge thereof was disposed. From above the mask, the above-described composition B for wavelength conversion layer was spray-coated. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray application, the plate mask was removed and baked at 150 ° C. for 1 hour to form a wavelength conversion layer only in the LED element mounting region and its peripheral portion. The thickness of the obtained wavelength conversion layer (the thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 50 μm.

  The above-mentioned composition for forming a reflective layer was poured from the cavity side of the package with a dispenser. The composition for forming a reflective layer was baked at 150 ° C. for 1 hour to form a reflective layer on the outside of the peripheral edge of the LED element mounting region. The thickness of the obtained reflection layer was 15 μm.

  Thereafter, a silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KER2600) was potted with a dispenser. The silicone resin was heated at 100 ° C. for 1 hour and then heated at 150 ° C. for 2 hours to form a sealing layer. The thickness of the sealing layer (the thickness of the sealing layer formed on the upper surface of the LED element) was 700 μm.

[Example 5]
Similar to Example 2, a package in which a metal part and an LED element were connected by a protruding electrode was prepared. Silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KER2600) was potted with a dispenser so as to cover the LED element (mounting region) of the package and the peripheral edge thereof. The silicone resin was heated at 100 ° C. for 1 hour and then heated at 150 ° C. for 2 hours to obtain a light-transmitting layer. The thickness of the obtained light transmissive layer (thickness of the light transmissive layer formed on the upper surface of the LED element) was 50 μm.

  From the cavity side of the package, the above-described composition for forming a reflective layer was poured from a dispenser. The said composition for reflective layer formation was baked at 150 degreeC for 1 hour, and the reflective layer was formed in the outer side of the peripheral part of the mounting area | region of an LED element. The thickness of the obtained reflection layer was 15 μm.

  Further, the wavelength conversion layer composition A was potted with a dispenser. The wavelength conversion layer composition A was heated at 100 ° C. for 1 hour and then heated at 150 ° C. for 2 hours to form a wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 6]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed.

  A plate-shaped mask was arranged so as to cover the mounting area of the LED element of the package and the peripheral edge thereof; that is, the area where the LED element is placed and the area where the LED element and the metal part are connected. From the upper part of the package, the above-described composition for forming a reflective layer was applied by spraying. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray coating, the plate mask was removed and baked at 150 ° C. for 1 hour to form a reflective layer. The thickness of the obtained reflection layer was 15 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation).

  The metal part of the package in which the reflective layer was formed and the LED element were connected by a wire. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. The emission peak wavelength of the LED element was 475 nm.

  The composition for wavelength conversion layer A was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 7]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed.

  The LED element mounting area and its peripheral part in the package; that is, the area where the LED element is placed, the area where the LED element and the metal part are connected, and the positive resist material (Tokyo Ohka) Industrial-made OFPR-800LB) was applied with a dispenser. The package was heated at 110 ° C. for 30 minutes in a nitrogen atmosphere. Then, a light-shielding mask that shields only the LED element mounting region and its peripheral portion was placed on the package, and UV light was irradiated through the light-shielding mask. Thereafter, the resist film was removed with an alkali developer, and a film (resist film) made of a resist material was formed only on the LED element mounting region and its peripheral portion. The package was washed with pure water.

  From the upper part of the package, the above-described composition for forming a reflective layer was applied by spraying. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray coating, the plate mask was removed and baked at 150 ° C. for 1 hour to form a reflective layer. The thickness of the obtained reflection layer was 15 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation).

  The package on which the reflective layer was formed was washed with tetrahydrofuran (THF), and the resist film and the reflective layer formed on the resist film were removed. Then, the metal part of the package in which the reflective layer was formed and the LED element were connected with a wire. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. The emission peak wavelength of the LED element was 475 nm.

  The composition for wavelength conversion layer A was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 8]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed.

  The LED element mounting region and its peripheral portion in the package; that is, the region for mounting the LED element, the region for connecting the LED element and the metal portion, and the PVA aqueous solution as in Example 3 so as to cover the peripheral portion. Was applied with a dispenser. The said coating film was dried at 80 degreeC for 1 hour, and the film | membrane (PVA film) which consists of soluble resin was formed. The thickness of the film made of the obtained soluble resin was 200 μm.

  From the upper part of the package, the above-described composition for forming a reflective layer was spray-coated. The spray conditions at this time were such that the distance from the nozzle tip to the package was 60 mm, the discharge pressure was 0.1 MPa, and the nozzle moving speed was 100 mm / s. After spray coating, the reflective layer was formed by baking at 150 ° C. for 1 hour. The thickness of the obtained reflection layer was 15 μm. The thickness of the reflective layer was measured with a laser holo gauge (manufactured by Mitutoyo Corporation).

  The package in which the reflective layer was formed was immersed in water, and the soluble resin and the reflective layer formed on the soluble resin were removed. Then, the metal part of the package in which the reflective layer was formed and the LED element were connected with a wire. The outer shape of the LED element was 305 μm × 330 μm × 100 μm. The peak wavelength of the LED element was 475 nm.

  The composition for wavelength conversion layer A was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 9]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A metal part arranged on the substrate and the LED element 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.

  Meanwhile, a partition wall forming composition was prepared. Specifically, 10 g of 1,3-butanediol and 2 g of silica (RX300, manufactured by Nippon Aerosil Co., Ltd.) are mixed with 10 g of the reflective layer forming composition described above, and the homogenizer (Primics Co., Ltd.) is used until the viscosity becomes 250 mPa · s. The product was dispersed with a mini mixer.

The partition wall forming composition was applied by a jet dispenser so as to surround the peripheral portion of the LED element mounting region of the package. Thereafter, the partition wall forming composition was fired at 150 ° C. for 1 hour to obtain partition walls. The partition wall had a width of 250 μm and a thickness of 100 μm, and the distance between the inner periphery of the partition wall and the outer periphery of the LED element was 100 μm.
Subsequently, the composition for forming a reflective layer was potted with a dispenser so as to cover the entire region outside the region surrounded by the partition walls (bottom surface of the cavity). At this time, the composition for forming the reflective layer was potted from one point without moving the dispenser, but the composition for forming the reflective layer did not penetrate into the region surrounded by the partition walls and adhered to the side surface of the LED element. I did not. The reflective layer forming composition was fired at 150 ° C. for 1 hour to form a reflective layer on the outside of the partition wall. The thickness of the reflective layer was 50 μm.

  The above-mentioned composition A for wavelength conversion layer was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 10]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A metal part arranged on the substrate and the LED element were connected by a wire to obtain a package. The outer shape of the LED element was 305 μm × 330 μm × 100 μm, and the peak wavelength of the emitted light from the LED element was 475 nm. In the substrate, grooves were formed by machining so as to surround the outer periphery of the LED element mounting region. The width of the groove was 500 μm and the depth was 100 μm, and the distance between the inner periphery of the groove and the outer periphery of the LED element was 100 μm.

  Subsequently, the above-described composition for forming a reflective layer was potted with a dispenser so as to cover the groove and the entire region outside the groove (bottom surface of the cavity). At this time, the composition for forming the reflective layer was potted from one point without moving the dispenser, but the composition for forming the reflective layer did not penetrate inside the groove, and the composition for forming the reflective layer on the side surface of the LED element. The thing did not adhere. The reflective layer forming composition was baked at 150 ° C. for 1 hour to form a reflective layer. The thickness of the reflective layer was 30 μm.

  The above-mentioned composition A for wavelength conversion layer was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 11]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A 400 μm × 400 μm × 100 μm copper plate was bonded to the LED element mounting region of this substrate. And the LED element was mounted on the said copper plate, the metal part and the LED element were connected with the wire, and the package was obtained. The outer shape of the LED element was 305 μm × 330 μm × 100 μm, and the peak wavelength of the emitted light from the LED element was 475 nm.

  The above-described composition for forming a reflective layer was potted with a dispenser so as to cover the entire outer region (bottom surface of the cavity) of the copper plate. At this time, the reflecting layer forming composition was potted from one point without moving the dispenser, but the reflecting layer forming composition did not adhere to the side surface of the LED element. The reflective layer forming composition was baked at 150 ° C. for 1 hour to form a reflective layer. The thickness of the reflective layer was 30 μm.

  The above-mentioned composition A for wavelength conversion layer was potted on the package with a dispenser. And after heating the composition A for wavelength conversion layers at 100 degreeC for 1 hour, it heated at 150 degreeC for 2 hours, and obtained the wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

[Example 12]
A substrate having a cavity as shown in FIG. 1 was prepared. The substrate was made of a polyphthalamide (PPA) resin. The substrate was a rectangular parallelepiped of 3.2 mm × 2.8 mm × 1.8 mm, and a truncated cone-shaped cavity having an opening diameter of 2.4 mm, a wall surface angle of 45 °, and a depth of 0.85 mm was formed. A metal part arranged on the substrate and the LED element 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.

  This package was turned upside down, and the LED element was placed with its light emitting surface facing vertically downward. And the above-mentioned composition A for wavelength conversion layers was filled into the syringe, the plunger was loaded into the syringe, and then the air adapter was mounted. The needle of the syringe was fixed upward, the clearance between the needle tip and the light emitting surface of the LED element was set to 50 μm, and the wavelength conversion layer composition A was applied to the LED element and its peripheral part. The coating conditions were adjusted as appropriate so that the entire LED element and its peripheral edge were covered.

The package coated with the wavelength conversion layer composition A was heated at 100 ° C. for 1 hour with the light emitting surface of the LED element directed vertically downward, and further heated at 150 ° C. for 2 hours to obtain a wavelength conversion layer. Thereafter, the package was turned upside down, and the light emitting surface of the LED element was installed vertically upward. And the above-mentioned composition for reflective layer formation was potted with the dispenser around the wavelength conversion layer so that all the area | regions (bottom surface of a cavity) outside the wavelength conversion layer might be covered. The composition for forming a reflective layer was baked at 150 ° C. for 1 hour to form a reflective layer on the outside of the peripheral edge of the LED element mounting region. The thickness of the obtained reflective layer was 30 μm.
Thereafter, a silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KER2600) was potted with a dispenser. The silicone resin was heated at 100 ° C. for 1 hour and then heated at 150 ° C. for 2 hours to form a sealing layer. The thickness of the sealing layer (the thickness of the sealing layer formed on the upper surface of the LED element) was 700 μm.

[Example 13]
Similar to Example 2, a package in which a metal part and an LED element were connected by a protruding electrode was prepared. A fluorosilicone coating agent (manufactured by Shin-Etsu Chemical Co., Ltd., KP-911) was potted with a dispenser so as to cover the LED element (mounting region) and the peripheral edge of the package. The said fluorosilicone coating agent was dried at normal temperature, and the mounting area | region of LED element and its peripheral part were protected with the liquid repellent.

  The above-mentioned composition for forming a reflective layer was potted with a dispenser so as to cover the entire area outside the LED element mounting area (bottom surface of the cavity). At this time, the reflecting layer forming composition was potted from one point without moving the dispenser, but the reflecting layer forming composition did not adhere to the side surface of the LED element. The said composition for reflective layer formation was baked at 150 degreeC for 1 hour, and the reflective layer was formed in the outer side of the peripheral part of the mounting area | region of an LED element. The thickness of the obtained reflective layer was 25 μm.

  Subsequently, the composition A for wavelength conversion layer was potted with a dispenser. The wavelength conversion layer composition A was heated at 100 ° C. for 1 hour and then heated at 150 ° C. for 2 hours to form a wavelength conversion layer. The thickness of the obtained wavelength conversion layer (thickness of the wavelength conversion layer formed on the upper surface of the LED element) was 750 μm.

  In the LED device obtained by the method of the present invention, the reflective layer does not deteriorate over time. Therefore, the light extraction efficiency from the LED device is good over a long period of time. Therefore, it is suitable for various lighting devices used indoors and outdoors, including automotive headlights that require a large amount of light.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 LED element 3 Metal part 4 Wire 5 Projection electrode 6 Cavity inner wall surface 11 Wavelength conversion layer 21 Reflective layer 31 Translucent layer 100 LED device

Claims (16)

An LED having a substrate, an LED element mounted on the substrate, a wavelength conversion layer covering the LED element, and a reflective layer formed on the substrate and outside the peripheral portion of the mounting region of the LED element A device manufacturing method comprising:
A mounting step of mounting the LED element on the substrate;
A reflective layer forming step of forming a reflective layer by applying a reflective layer forming composition containing light diffusing particles, an organosilicon compound, and a solvent on the substrate, and drying and curing the reflective layer forming composition. When,
A wavelength conversion layer forming step of coating the wavelength conversion layer containing phosphor particles and a binder component so as to cover the LED element, and forming the wavelength conversion layer;
The manufacturing method of the LED device containing this. The reflective layer forming step includes
Covering the LED element mounting region and its peripheral edge with a plate mask;
The method for manufacturing an LED device according to claim 1, comprising: applying the reflective layer forming composition on the substrate, and drying and curing the reflective layer forming composition in this order. The reflective layer forming step includes
Coating the LED element mounting region and its peripheral edge with a resist material;
Applying the reflective layer forming composition on the substrate and drying and curing the reflective layer forming composition;
Removing the resist material and the reflective layer forming composition on the resist material;
The manufacturing method of the LED device of Claim 1 which contains these in this order. The reflective layer forming step includes
Coating the LED element mounting region and its peripheral edge with water or a soluble resin soluble in a solvent;
Applying the reflective layer forming composition on the substrate and drying and curing the reflective layer forming composition;
Dissolving the soluble resin in water or a solvent to remove the soluble resin and the reflective layer forming composition on the soluble resin;
The manufacturing method of the LED device of Claim 1 which contains these in this order. The reflective layer forming step includes
Applying a liquid repellent to the mounting area of the LED element and its peripheral edge; and
Applying the reflective layer forming composition on the substrate and drying and curing the reflective layer forming composition;
The manufacturing method of the LED device of Claim 1 which contains these in this order. It is performed in the order of the mounting step, the wavelength conversion layer forming step, and the reflective layer forming step,
The wavelength conversion layer forming step is a step of forming the wavelength conversion layer so as to cover a mounting region of the LED element and a peripheral portion thereof.
The reflective layer forming step is a step of forming a reflective layer having a height lower than the upper surface of the wavelength conversion layer covering the LED element on the substrate and outside the peripheral edge of the LED element mounting region. The manufacturing method of the LED device of Claim 1.   The said wavelength conversion layer formation process arrange | positions the light emission surface of the LED element of the said board | substrate toward the perpendicular downward direction, and the process of manufacturing the said composition for wavelength conversion layers of Claim 6 is included. .   The LED device according to claim 6 or 7, wherein the wavelength conversion layer forming step includes a step of arranging the light emitting surface of the LED element of the substrate facing vertically downward and applying the composition for wavelength conversion layer. Production method. A light-transmitting layer forming step of forming a light-transmitting layer covering the LED element;
The mounting step, the translucent layer forming step, the reflective layer forming step, and the wavelength conversion layer forming step are performed in this order,
The translucent layer forming step is a step of forming a translucent layer by applying a translucent layer composition containing a translucent material so as to cover the mounting region of the LED element and its peripheral portion.
The reflective layer forming step is a step of forming a reflective layer having a height lower than the upper surface of the light-transmitting layer covering the LED element on the substrate and outside the peripheral edge of the LED element mounting region. The manufacturing method of the LED device of Claim 1.   The method for manufacturing an LED device according to claim 9, wherein the translucent layer forming step includes a step of placing the light emitting surface of the LED element of the substrate facing vertically downward and curing the translucent layer composition. .   11. The LED device according to claim 9, wherein the translucent layer forming step includes a step of arranging the light emitting surface of the LED element of the substrate facing vertically downward and applying the translucent layer composition. Production method. The reflective layer forming step includes
Forming a partition wall that surrounds a peripheral edge of the LED element mounting region;
Forming a reflective layer having a height lower than that of the partition wall outside the partition wall;
The manufacturing method of the LED device of Claim 1 containing this.   The manufacturing method of the LED device of Claim 1 with which the said board | substrate has the groove part surrounding the peripheral part of the mounting area | region of the said LED element.   The manufacturing method of the LED device according to claim 1, wherein a mounting area surface of the LED element protrudes from the reflective layer forming surface of the substrate. The step of forming the reflective layer comprises applying the composition for forming a reflective layer to a partial region A outside a peripheral edge of a mounting region of the LED element;
Applying the reflective layer forming composition to a partial region B outside the peripheral edge of the mounting region of the LED element separated from the region A;
Applying the reflective layer forming composition to the gap between the region A and the region B;
The manufacturing method of the LED device of Claim 1 containing this. The reflective layer forming step includes
The light emitting surface of the LED element of the said board | substrate is arrange | positioned toward the vertically downward direction, The process for apply | coating the said composition for reflective layer formation is included, moving the said board | substrate and a coating device relatively. Of manufacturing the LED device.

Images