JP2015089898A - Inorganic phosphor powder, curable resin composition using inorganic phosphor powder, wavelength conversion member, and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide phosphor powder capable of improving light extraction efficiency of an optical semiconductor device more easily.SOLUTION: In inorganic phosphor powder, inorganic oxide fine particles having average particle diameter of 1 nm-10 μm are adhered to a surface of an inorganic phosphor particle used for wavelength conversion. The inorganic oxide fine particles are within a range of 0.1-10 pts.mass based on 100 pts.mass of the inorganic phosphor particle.

Description

  The present invention relates to an inorganic phosphor powder, a curable resin composition containing the inorganic phosphor powder, a wavelength conversion member made of a cured product of the curable resin composition, and an optical semiconductor device including the cured product.

  Since an optical semiconductor element such as a light emitting diode (LED) has an excellent characteristic of low power consumption, it is increasingly applied to an optical semiconductor device for outdoor lighting or automobile use. Such an optical semiconductor device generally emits light emitted from a semiconductor light emitting element that emits blue light, near ultraviolet light, or ultraviolet light by using a phosphor that is a wavelength conversion material to obtain a pseudo white light. This device is capable of emitting light in any color according to the purpose of use, such as light bulb color and white, and is used in a wide range of products. As phosphors suitable for such a light emitting device, various oxide and sulfide phosphors are known to be used.

  For the purpose of further improving the light extraction efficiency of the optical semiconductor device, the light emission efficiency of the optical semiconductor element and the characteristics of the peripheral members are improved. In the field of phosphors that are wavelength conversion materials, wavelength conversion is also performed. Improvements in efficiency, reliability such as heat resistance and moisture resistance have also been made.

  As an example of improving the wavelength conversion efficiency, Patent Document 1 proposes a method of coating phosphor particles with a transparent metal, transition metal, or metalloid oxide. However, the method of Patent Document 1 is not industrial because of complicated processes, and the reliability of the obtained coated phosphor particles is not sufficient.

  Patent Document 2 proposes a method in which a light extraction structure such as a microlens array is provided on the surface of a thin film phosphor layer using a polymer containing at least one fluorescent powder as a binder. However, the method of Patent Document 2 has a problem that the manufacturing process of the light extraction structure is complicated and not industrial, and may not be used depending on the device structure or the manufacturing process.

  On the other hand, further improvement of the light extraction efficiency of the optical semiconductor device is still required, and further improvement is required.

Special table 2011-503266 gazette Special table 2012-508986 gazette

  An object of this invention is to provide the fluorescent substance powder which improves the light extraction efficiency of an optical semiconductor device more simply. Another object of the present invention is to provide a curable resin composition containing the phosphor powder, a wavelength conversion member made of a cured product of the curable resin composition, and an optical semiconductor device including the cured product.

The present invention has been made in order to solve the above-described problems, and is an inorganic phosphor powder, in which inorganic oxide fine particles adhere to the surface of an inorganic phosphor particle used for wavelength conversion, Inorganic phosphor powder characterized in that oxide fine particles have an average particle diameter of 1 nm or more and 10 μm or less and in a range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic phosphor particles. I will provide a.
Inorganic phosphor powder with inorganic oxide fine particles attached to the surface of such inorganic phosphor particles can be easily manufactured and also improves the wavelength conversion efficiency of light emitted from the optical semiconductor element, and the optical semiconductor using the same The light extraction efficiency of the apparatus can be improved.

In this case, the inorganic oxide fine particles are preferably silica or alumina.
With such inorganic oxide fine particles, there are few volatile components and high transparency can be obtained.

The inorganic oxide fine particles are hydrophobic silica, and the hydrophobic silica fine particles are formed on the surface of hydrophilic silica fine particles composed of SiO ₂ units on the surface of R ¹ SiO _3/2 units (R ¹ is a substitution). Or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and an R ² ₃ SiO _1/2 unit (wherein R ² is independently a substituted or unsubstituted monovalent group having 1 to 6 carbon atoms). Hydrophobized by introducing a hydrocarbon group).
With such inorganic oxide fine particles, the light extraction efficiency of the optical semiconductor device can be further improved.

The fine particles of the hydrophobic silica have a particle size of 0.005 μm or more and 1.00 μm or less, a particle size distribution D ₉₀ / D ₁₀ value of 3 or less, and an average circularity of 0.8 or more and 1 or less. It is preferable that.
With such silica fine particles, the fluidity of the inorganic phosphor particles can be easily controlled.

Further, in the present invention, a curable resin composition used for an optical semiconductor device, which is one or more selected from an epoxy resin, a silicone resin, an organically modified silicone resin, and an acrylic resin, and any one of the above inorganic Provided is a curable resin composition comprising phosphor powder.
If it is such a curable resin composition, the cured | curing material excellent in the characteristic of transparency, heat resistance, and light resistance can be given easily.

Furthermore, in this invention, the wavelength conversion member which consists of hardened | cured material of curable resin composition is provided. Moreover, in this invention, an optical semiconductor device provided with an optical semiconductor element and the hardened | cured material of the said curable resin composition as a wavelength conversion member is provided.
Such a wavelength conversion member and an optical semiconductor device can easily increase the wavelength conversion efficiency of light emitted from the optical semiconductor element and improve the light extraction efficiency of the optical semiconductor device using the same.

  The inorganic phosphor powder obtained by the present invention in which inorganic oxide fine particles are adhered to the surface of the inorganic phosphor particles can be industrially manufactured and has a simple configuration, while converting the wavelength of light emitted from the optical semiconductor element. The efficiency is improved, and an optical semiconductor device using the same improves the light extraction efficiency.

The electron micrograph of the inorganic fluorescent substance powder composition which made the spherical hydrophobic silica fine particle manufactured by the synthesis example of the preparation example 1 adhere to the inorganic fluorescent substance powder surface is shown. The electron micrograph of the inorganic fluorescent substance composition which made the fine alumina particle of the preparation example 2 adhere to the inorganic fluorescent substance powder surface is shown. The electron micrograph of the untreated inorganic fluorescent substance of the preparation example 4 is shown. An example of the figure of the optical semiconductor device using inorganic fluorescent substance powder is shown.

  As described above, improvement of the light extraction efficiency of the optical semiconductor device is demanded by a simpler method. Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained an inorganic phosphor powder having an average particle diameter of 1 nm or more and 10 μm or less on the surface of the inorganic phosphor particles used for wavelength conversion. By using the inorganic phosphor powder, wherein the inorganic oxide fine particles are a powder adhered in a range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic phosphor particles. And found that the above-mentioned problems can be achieved. And an inorganic phosphor powder having inorganic oxide fine particles on a surface suitable as a wavelength conversion material for LED elements, a curable resin composition containing the inorganic phosphor powder, a cured product of the curable resin composition, and the cured product It came to complete the optical semiconductor device provided with the wavelength conversion member which consists of, and the said hardened | cured material.

  The inorganic phosphor powder having the inorganic oxide fine particles attached to the surface of the inorganic phosphor particles in the present invention increases the wavelength conversion efficiency of the light emitted from the optical semiconductor element. Therefore, the inorganic phosphor powder is used. In the optical semiconductor device, the light extraction efficiency is improved.

That is, the present invention provides an inorganic phosphor powder having inorganic oxide fine particles on the surface of inorganic phosphor particles, a curable resin composition containing the inorganic phosphor powder, and a wavelength conversion comprising a cured product of the curable resin composition. An optical semiconductor device using the member and the cured product is provided.
Hereinafter, the present invention will be described in more detail, but the present invention is not limited thereto.

  First, the present invention is an inorganic phosphor powder in which inorganic oxide fine particles are adhered to the surface of inorganic phosphor particles used for wavelength conversion by physical adsorption or the like, and has a shape as illustrated in FIGS. 1 and 2. It is characterized by having.

  Inorganic phosphor particles generally have a smooth surface as illustrated in FIG. 3. In an optical semiconductor device typified by an LED, inorganic phosphor particles for performing such wavelength conversion are used. Is irradiated with blue light, and the wavelength-converted wavelength light is emitted from the phosphor, and the blue light and the wavelength-converted wavelength light are combined into a pseudo white color.

  However, as illustrated in FIG. 3, since the inorganic phosphor particles have a smooth surface close to a mirror surface, the wavelength of light is not efficiently converted due to the total reflection phenomenon. That is, due to the total reflection phenomenon, it is difficult for blue light to enter the inside of the inorganic phosphor, and light having a wavelength converted wavelength is not easily extracted outside the phosphor due to the total reflection phenomenon. As a result, the wavelength conversion efficiency is reduced.

  On the other hand, as understood with reference to FIGS. 1 and 2, in the structure in which the inorganic oxide fine particles are attached on the surface of the inorganic phosphor particles of the present invention, the surface of the inorganic phosphor is simulated, so-called photo. A structure similar to a nick crystal structure and a low reflection structure (antireflection structure) is provided. For this reason, the total reflection phenomenon is alleviated, blue light easily enters the inside of the inorganic phosphor, and light having a wavelength converted wavelength is easily extracted outside the phosphor. For this reason, the wavelength conversion efficiency increases, and the light extraction efficiency of the optical semiconductor device can be improved.

(Inorganic phosphor particles)
The inorganic phosphor particles to be subjected to the surface treatment method of the present invention (hereinafter sometimes referred to as “phosphors” as appropriate) are not particularly limited. For example, from a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer. In which the light is absorbed and converted into light of a different wavelength. Nitride-based phosphor particles mainly activated by lanthanoid-based elements such as Eu and Ce, oxynitride-based phosphor particles, lanthanoid-based particles such as Eu, and alkalis mainly activated by transition metal-based elements such as Mn Earth metal halogen apatite phosphor particles, alkaline earth metal halogen borate phosphor particles, alkaline earth metal aluminate phosphor particles, alkaline earth metal silicate phosphor particles, alkaline earth metal sulfide phosphor particles Particles, alkaline earth metal thiogallate phosphor particles, alkaline earth metal silicon nitride phosphor particles, germanate phosphor particles, or rare earth aluminate phosphor particles mainly activated with a lanthanoid element such as Ce, Organic and organic complex phosphor particles mainly activated with rare earth silicate phosphor particles or lanthanoid elements such as Eu, Ca—Al—Si—O—N based oxy Is preferably at least any one or more selected from a nitride glass phosphor particles. As specific examples, the following phosphor particles can be used, but are not limited thereto.

Nitride-based phosphor particles mainly activated by lanthanoid elements such as Eu and Ce are M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) There is). In addition _{MSi 7 N 10: Eu, M} 1.8 Si 5 O 0.2 N 8: Eu, M 0.9 Si 7 O 0.1 N 10: Eu (M is the same) is like also.

Examples of the oxynitride phosphor particles mainly activated by lanthanoid elements such as Eu and Ce include MSi ₂ O ₂ N ₂ : Eu (M is the same as described above).

M ₅ (PO ₄ ) ₃ X: R (M is the same as described above) for alkaline earth halogen apatite phosphor particles mainly activated by lanthanoid-based elements such as Eu and transition metal-based elements such as Mn. , X is at least one selected from F, Cl, Br, and I. R is any one or more of Eu and Mn).

The alkaline earth metal borate halogen phosphor particles include M ₂ B ₅ O ₉ X: R (M is the same as described above, and X is at least one selected from F, Cl, Br, and I). R is one or more of Eu and Mn).

Alkaline earth metal aluminate phosphor particles include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, BaMgAl ₁₀ O ₁₇ : R (R is one or more of Eu and Mn).

Examples of the alkaline earth metal sulfide phosphor particles include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

The rare earth aluminate phosphor particles mainly activated with a lanthanoid element such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce, (Y, Gd) ₃ (Al, Ga) ₅ O _{12 and} other YAG phosphor particles represented by the composition formula. Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphor particles include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is And at least one selected from F, Cl, Br, and I).

  The phosphor particles described above contain one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti instead of Eu or in addition to Eu as desired. It can also be made.

  Further, phosphor particles other than the above-described phosphor particles and having the same performance and effect can also be used.

The Ca—Al—Si—O—N-based oxynitride glass phosphor particles are expressed in terms of mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, and Al ₂ O ₃ is 0 to 30 mol. %, SiO is 25 to 60 mol%, AlN is 5 to 50 mol%, rare earth oxide or transition metal oxide is 0.1 to 20 mol%, and the total of the five components is 100 mol%. Is a phosphor particle using as a base material. In addition, in the phosphor particles using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to the rare earth oxide ions are rare earth oxides. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

There is no particular limitation on the particle size of the phosphors used in the phosphor of the present invention, the median particle diameter (D ₅₀₎ in a conventional 0.1μm or more, preferably 2μm or more, more preferably 10μm or more. Moreover, it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 25 micrometers or less. If D ₅₀ is too small, and the luminance decreases, there is a possibility that phosphor particles tend to aggregate. On the other hand, when D ₅₀ is too large, there is a possibility that clogging of such coating unevenness or dispenser may occur.

(Other phosphor particles)
In addition to the above phosphors, other phosphors can be used depending on the purpose, such as improved durability and improved dispersibility.

There are no particular restrictions on the composition of the other phosphors, but metal oxides typified by Y ₂ O ₃ , Zn ₂ SiO _4, etc., which are crystal bases, metal nitrides typified by Sr ₂ Si ₅ N _8, etc. , Phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, and sulfides typified by ZnS, SrS, CaS, etc., Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, A combination of rare earth metal ions such as Er, Tm and Yb and metal ions such as Ag, Cu, Au, Al, Mn and Sb as activators or coactivators is preferred.

(Inorganic oxide fine particles)
Examples of the inorganic oxide fine particles in the present invention are listed below, but are not limited thereto. The inorganic oxide fine particles are metal, transition metal or metalloid oxide fine particles, and are made of, for example, an oxide of a metal selected from one or more of Si, Ti, Al, Zr, Mg, Ge, Y and the like. It is characterized by being. In order to obtain the effect of improving the wavelength conversion efficiency of phosphors having various shapes and specific gravities in the target product, it may be selected so as to obtain a moderately attached state on the phosphor surface. An inorganic oxide fine particle having a corresponding refractive index may be used. A wavelength conversion function may be imparted to the inorganic oxide fine particles. In any case, it is convenient to use a commercially available product.

  Preferable examples of the inorganic oxide fine particles include silica, alumina, magnesium oxide, zirconium oxide, titanium oxide and other antimony oxides, aluminum hydroxide, barium sulfate, magnesium carbonate, and barium carbonate. In particular, silica and alumina, which have few volatile components and can provide high transparency, are preferably used.

For example, in the case of silica, silica produced by a dry method such as fumed silica or fused silica, or silica produced by a wet method such as colloidal silica, sol-gel silica, or precipitated silica can be used. In particular, fumed silica is preferable from the viewpoint of easy adhesion. Examples of the fumed silica include AEROSIL (R) 90, AEROSIL (R) 130, AEROSIL (R) 150, AEROSIL (R) 200, AEROSIL (R) manufactured by Nippon Aerosil Co., Ltd. ) 300, AEROSIL (R) 380, AEROSIL (R) OX50, AEROSIL (R) EG50, AEROSIL (R) TT600, Leorosil QS-09, QS-10L, QS-10, QS-102, manufactured by Tokuyama Corporation CP-102, QS-20L, QS-20, QS-25C, QS-30, QS-30C, QS-40, etc. are mentioned. In addition, as hydrophobic fumed silica, AEROSIL (R) R972, AEROSIL (R) R974, AEROSIL (R) R104, AEROSIL (R) R106, AEROSIL (R) R202, AEROSIL (R) manufactured by Nippon Aerosil Co., Ltd. R805
, AEROSIL (R) R812, AEROSIL (R) R816, AEROSIL (R) R7200, AEROSIL (R) R8200, AEROSIL (R) R9200, AEROSIL (R) RY50, AEROSIL (R) NY50, AEROSIL (R) RY200, AEROSIL (R) RY200S, AEROSIL (R) RX50, AEROSIL (R) NAX50, AEROSIL (R) RX200, AEROSIL (R) RX300, AEROSIL (R) R504, AEROSIL (R) DT4, Leorosil MT- manufactured by Tokuyama Corporation 10, MT-10C, DM-10, DM-10C, DM-20S, DM-30, DM-30S, KS-20S, KS-20SC, HM-20L, HM-30S, PM-2 L, and the like. Moreover, you may use the silicone powder which consists of polyorganosilsesquioxane resin, the silicone powder which has polyorganosilsesquioxane resin in part or all of the surface, and the hydrophobic spherical silica fine particle described below. These may be used alone or in combination of two or more.

  Alumina generally has an α-phase crystal structure, but may contain intermediate phases such as θ-phase, γ-phase, and δ-phase. From the viewpoint of the stability of alumina, α-alumina is preferably used. Specific examples of alumina include A30 series, AN series, A40 series, MM series, LS series, AHP series, manufactured by Nippon Light Metal Co., Ltd., “Admafine Alumina” (trade name) AO-5 type, AO-8 type , Nippon Bikosky CR series, Taimei Chemical Co., Ltd., Tymicron, Aldrich 10 μm 2 diameter alumina powder, Showa Denko A-42 series, A-43 series, A-50 series, AS series, AL- 43 series, AL-47 series, AL-160SG series, A-170 series, AL-170 series, Sumitomo Chemical AM series, AL series, AMS series, AES series, AKP series, AA series etc. Not as long.

  The particle diameter of the inorganic oxide fine particles is 1 nm or more and 10 μm or less, more preferably 50 nm or more and 5 μm or less. Aggregation tends to occur with fine particles of less than 1 nm, and the individual particles of the inorganic oxide fine particles cannot maintain the primary particle diameter, which may deteriorate the ability to impart fluidity to the inorganic phosphor particles. If fine particles with a particle size exceeding 10 μm are added, a structure similar to a so-called photonic crystal structure or low reflection structure (antireflection structure) that improves wavelength conversion efficiency cannot be obtained, and causes nozzle clogging during the dispensing process. There is a fear. The addition amount of the inorganic oxide fine particles is in a range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the particle inorganic phosphor because an effect of improving the wavelength conversion efficiency may be obtained. More preferably, it is 5 parts by mass or less. In order to acquire the addition effect, 0.1 mass part or more is required. If the amount added is too large, it may cause nozzle clogging during the dispensing process. Moreover, when this addition amount exceeds 10 mass parts, it is not preferable in terms of cost.

  The inorganic oxide fine particles may be surface-treated with a silane coupling agent for the purpose of maintaining the state in which the inorganic oxide fine particles are adhered to the surface of the inorganic phosphor particles. By treating the surface of the inorganic phosphor particles with the inorganic oxide fine particles attached to the surface, the inorganic oxide fine particles attached by physical adsorption can be obtained as chemically attached particles. It can be selected so that characteristics such as brightness and color coordinates in the target optical semiconductor device can be obtained satisfactorily. As the silane coupling agent, an alkyl group-containing silane coupling agent, an alkenyl group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth) acryl group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, Examples include known isocyanurate group-containing silane coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, and the like.

  There is no particular limitation on the method for attaching the inorganic oxide fine particles to the surface of the inorganic phosphor particles. In accordance with a known mixing method, using a Henschel mixer, a V-type blender, a ribbon blender, a raking machine, a kneader mixer, a butterfly mixer, or a mixer of various types such as a normal propeller stirrer, or a mixing with a revolving stirrer A predetermined amount of each component may be mixed uniformly. During the stirring, the inside of the stirring system may be evacuated for the purpose of improving the adhesion rate of the inorganic fine particles. By using the above method, the inorganic oxide fine particles can be easily attached to the surface of the inorganic phosphor particles.

(Hydrophobic spherical silica fine particles)
Hydrophobic silica fine particles are R ¹ SiO _3/2 units (R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) on the surface of hydrophilic silica fine particles composed of SiO ₂ units. And R ² ₃ SiO _1/2 units (R ² is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms). Preferably there is.

The fine particles of the hydrophobic silica have a particle size of 0.005 μm or more and 1.00 μm or less, a particle size distribution D ₉₀ / D ₁₀ value of 3 or less, and an average circularity of 0.8 or more and 1 or less. It is preferable that.

The characteristics of the hydrophobic spherical silica fine particles mixed with the inorganic phosphor powder will be described in more detail.
The hydrophobic spherical silica fine particles used in the present invention are
(A1) obtaining a hydrophilic spherical silica fine particle substantially consisting of SiO ₂ units by hydrolyzing and condensing a tetrafunctional silane compound, a partial hydrolysis-condensation product thereof, or a combination thereof;
(A2) R ¹ SiO _3/2 units (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) are introduced onto the surface of the hydrophilic spherical silica fine particles. Process,
(A3) introducing a R ² ₃ SiO _1/2 unit (wherein each R ² is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms). Manufactured by the method,
Hydrophobic spherical silica fine particles (1) having a particle size in the range of 0.005 to 1.0 μm, a particle size distribution D ₉₀ / D ₁₀ of 3 or less and an average circularity of 0.8 to 1. is there.

  The hydrophobic spherical silica fine particles have a particle size of 0.005 μm to 1.00 μm, preferably 0.01 μm to 0.30 μm, particularly preferably 0.03 μm to 0.20 μm. If the particle diameter is 0.005 μm or more, the inorganic phosphor particles can be taken out well without vigorous aggregation of the inorganic phosphor particles. Moreover, favorable fluidity | liquidity and a filling property can be provided to inorganic fluorescent substance particle as it is 1.00 micrometer or less.

The value of D ₉₀ / D ₁₀ that is an index of the particle size distribution of the hydrophobic spherical silica fine particles is 3 or less. Here, D ₁₀ and D ₉₀ are values obtained by measuring the particle size distribution. When the particle size distribution of the powder is measured, the particle size that becomes 10% cumulative from the smaller side is called D ₁₀ , and the particle size that becomes 90% cumulative from the smaller side is called D ₉₀ . Since this D ₉₀ / D ₁₀ is 3 or less, the particle size distribution of the hydrophobic spherical silica fine particles in the present invention is sharp. Thus, it is preferable that the particles have a sharp particle size distribution because it is easy to control the fluidity of the inorganic phosphor particles. The D ₉₀ / D ₁₀ is more preferably 2.9 or less.

  In the present invention, the particle size distribution of the fine particles is measured by a dynamic light scattering method / laser Doppler nanotrack particle size distribution measuring apparatus (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter is determined. The particle diameter was taken. The median diameter is a particle diameter corresponding to 50% cumulative when the particle size distribution is expressed as a cumulative distribution.

  Further, the average circularity of the hydrophobic spherical silica fine particles is preferably 0.82 to 1 because it is excellent in the effect of preventing aggregation of the silica fine particles and the effect of imparting fluidity to the inorganic phosphor particles, and is preferably 0.92-1. More preferred. Here, “spherical” includes not only a true sphere but also a slightly distorted sphere. Such a “spherical” shape refers to a particle having a circularity in the range of 0.8 to 1 when evaluated by the circularity when the particles are projected two-dimensionally. Here, the circularity is (peripheral length of a circle equal to the particle area) / (peripheral length of particle). This circularity can be measured by image analysis of a particle image obtained with an electron microscope or the like.

In the above, the hydrophilic spherical silica particles and "consisting essentially SiO ₂ units", although microparticles basically is composed of SiO ₂ units, than is composed of only SiO ₂ units It means having a large number of silanol groups at least on the surface as is generally known. In some cases, the hydrolyzable group (hydrocarbyloxy group) derived from the tetrafunctional silane compound as a raw material and / or its partial hydrolysis-condensation product is not partially converted into a silanol group, but a slight amount of fine particles as it is. It means that it may remain on the surface or inside.

  As described above, in the present invention, a small particle size sol-gel silica obtained by hydrolysis of tetraalkoxysilane is used as a silica base (silica before hydrophobization treatment). By performing a specific surface treatment on this, the particle diameter after the hydrophobization treatment is maintained as the primary particle diameter of the silica base when obtained as a powder, but is a small particle diameter that is not agglomerated, Hydrophobic silica fine particles that can impart good fluidity to the inorganic phosphor particles are obtained.

  Use of tetraalkoxysilane having a small number of carbon atoms in the alkoxy group as a silica particle having a small particle diameter, use of an alcohol having a small number of carbon atoms as a solvent, increasing the hydrolysis temperature, during hydrolysis of tetraalkoxysilane By changing the reaction conditions such as lowering the concentration of the catalyst and lowering the concentration of the hydrolysis catalyst, a silica raw material having an arbitrary particle size can be obtained.

  As described above and as will be described in more detail below, the silica particle having a small particle diameter is subjected to a specific surface treatment to obtain desired hydrophobic silica fine particles.

(Method for producing hydrophobic spherical silica fine particles (1))
Next, one method for producing the hydrophobic spherical silica fine particles will be described in detail below.
The hydrophobic spherical silica fine particles of the present invention are
Step (A1): Step of synthesizing hydrophilic spherical silica fine particles Step (A2): Surface treatment step with trifunctional silane compound Step (A3): Obtained by a surface treatment step with a functional silane compound. Hereinafter, each process is demonstrated one by one.

(Step (A1): Step of synthesizing hydrophilic spherical silica fine particles)
Formula (I): Si (OR ³ ) ₄ (I)
(Wherein each R ³ is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms), a tetrafunctional silane compound, a partial hydrolysis product thereof, or a mixture thereof, Hydrolysis and condensation in a mixed liquid of a hydrophilic organic solvent containing a hydrophilic substance and water can provide a mixed solvent dispersion of hydrophilic spherical silica fine particles.

In the general formula (I), R ³ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. . Examples of the monovalent hydrocarbon group represented by R ³ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and an aryl group such as a phenyl group, preferably a methyl group, An ethyl group, a propyl group, or a butyl group, particularly preferably a methyl group or an ethyl group.

  Examples of the tetrafunctional silane compound represented by the general formula (I) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; and tetraphenoxysilane, preferably , Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, particularly preferably tetramethoxysilane and tetraethoxysilane. Examples of the partial hydrolysis-condensation product of the tetrafunctional silane compound represented by the general formula (I) include alkyl silicates such as methyl silicate and ethyl silicate.

The hydrophilic organic solvent is not particularly limited as long as it dissolves the tetrafunctional silane compound represented by the general formula (I), the partial hydrolysis-condensation product, and water. For example, alcohols ; Cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran, and the like, preferably alcohols and cellosolves, particularly preferably Examples include alcohols. Examples of the alcohol include general formula (V): R ⁵ OH (V)
(Wherein R ⁵ is a monovalent hydrocarbon group having 1 to 6 carbon atoms).

In the general formula (V), R ⁵ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1-2. Examples of the monovalent hydrocarbon group represented by R ⁵ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, preferably methyl group, ethyl group, propyl group and isopropyl group. Preferably a methyl group and an ethyl group are mentioned. Examples of the alcohol represented by the general formula (V) include methanol, ethanol, propanol, isopropanol, butanol and the like, preferably methanol and ethanol. As the number of carbon atoms in the alcohol increases, the particle size of the spherical silica fine particles to be generated increases. Therefore, methanol is preferable in order to obtain silica particles having a desired small particle diameter.

  Examples of the basic substance include ammonia, dimethylamine, diethylamine and the like, preferably ammonia, diethylamine, and particularly preferably ammonia. These basic substances may be dissolved in water in a required amount, and the obtained aqueous solution (basic) may be mixed with the hydrophilic organic solvent.

  The basic substance is used in an amount of 0.01 to 2 mol with respect to a total of 1 mol of the hydrocarbyloxy group of the tetrafunctional silane compound represented by the general formula (I) and / or its partial hydrolysis-condensation product. It is preferable that it is 0.02-0.5 mol, and it is especially preferable that it is 0.04-0.12 mol. At this time, the smaller the amount of the basic substance, the desired small particle size silica fine particles.

  The amount of water used in the hydrolysis and condensation is 0.000 per 1 mol in total of the hydrocarbyloxy groups of the tetrafunctional silane compound represented by the general formula (I) and / or the partial hydrolysis condensation product thereof. It is preferably 5 to 5 mol, more preferably 0.6 to 2 mol, and particularly preferably 0.7 to 1 mol. The ratio of the hydrophilic organic solvent to water (hydrophilic organic solvent: water) is preferably 0.5 to 10 in terms of mass ratio, more preferably 3 to 9, and more preferably 5 to 8. Particularly preferred. As the amount of the hydrophilic organic solvent increases, silica particles having a desired small particle diameter can be obtained.

  Hydrolysis and condensation of the tetrafunctional silane compound represented by the general formula (I) can be carried out by a well-known method, that is, in a mixture of a hydrophilic organic solvent containing a basic substance and water in the general formula (I). It is performed by adding a tetrafunctional silane compound or the like shown.

  The concentration of silica fine particles in the mixed solvent dispersion of hydrophilic spherical silica fine particles obtained in this step (A1) is generally 3 to 15% by mass, preferably 5 to 10% by mass.

(Step (A2): Surface treatment step with trifunctional silane compound)
In the mixed solvent dispersion of the hydrophilic spherical silica fine particles obtained in the step (A1), the general formula (II):
R ¹ Si (OR ⁴ ) ₃ (II)
(Wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and each R ⁴ is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms) The surface of the hydrophilic spherical silica fine particle is treated by adding the trifunctional silane compound represented by the formula (1) or a partial hydrolysis product thereof, or a mixture thereof, and treating the surface of the hydrophilic spherical silica fine particle thereby. R ¹ SiO _3/2 units (where R ¹ is as described above) are introduced into to obtain a mixed solvent dispersion of the first hydrophobic spherical silica fine particles.

  This step (A2) is indispensable for suppressing the aggregation of silica fine particles in the subsequent concentration step (A3). If the aggregation cannot be suppressed, the individual particles of the obtained silica-based powder cannot maintain the primary particle diameter, and the fluidity imparting ability is deteriorated.

In the general formula (II), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms. It is a hydrogen group. Examples of the monovalent hydrocarbon group represented by R ¹ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, preferably methyl group, ethyl group, n -A propyl group or an isopropyl group, particularly preferably a methyl group or an ethyl group. Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, preferably fluorine atom.

In the general formula (II), R ⁴ is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 monovalent hydrocarbon groups. It is a group. Examples of the monovalent hydrocarbon group represented by R ⁴ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group. Or an ethyl group is mentioned.

  Examples of the trifunctional silane compound represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxy. Unsubstituted or halogen-substituted trisilane such as silane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane Alkoxysilane, etc., preferably methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane, more preferably methyltrimethoxysilane Emissions and methyltriethoxysilane, or they partially hydrolyzed condensation products thereof.

  The addition amount of the trifunctional silane compound represented by the general formula (II) is 0.001 to 1 mol, preferably 0.01 to 0.1 mol, per mol of Si atom in the used hydrophilic spherical silica fine particles. Most preferably, it is 0.01-0.05 mol. When the added amount is 0.001 mol or more, the resulting hydrophobic spherical silica fine particles have good dispersibility. Therefore, the effect of imparting fluidity to the inorganic phosphor particles appears, and if it is 1 mol or less, the silica fine particles Aggregation does not occur.

  The concentration of the silica fine particles in the mixed solvent dispersion of the first hydrophobic spherical silica fine particles obtained in this step (A2) is usually 3% by mass or more and less than 15% by mass, preferably 5 to 10% by mass. When the concentration is within this range, productivity is improved and silica fine particles are not aggregated.

(Concentration process)
A part of the hydrophilic organic solvent and water is removed from the mixed solvent dispersion liquid of the first hydrophobic spherical silica fine particles thus obtained and concentrated to mix the first hydrophobic spherical silica fine particles. A solvent-concentrated dispersion is obtained. At this time, a hydrophobic organic solvent may be added in advance (before the concentration step) or during the concentration step. In this case, the hydrophobic solvent used is preferably a hydrocarbon or ketone solvent. Specific examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and the like, and methyl isobutyl ketone is preferable. Examples of the method for removing a part of the hydrophilic organic solvent and water include distillation and distillation under reduced pressure. The resulting concentrated dispersion preferably has a silica fine particle concentration of 15 to 40% by mass, more preferably 20 to 35% by mass, and particularly preferably 25 to 30% by mass. When the amount is 15% by mass or more, the surface treatment of the subsequent process proceeds smoothly, and when the amount is 40% by mass or less, the aggregation of silica fine particles does not occur.

  In the concentration step, the silazane compound represented by the general formula (III) and the monofunctional silane compound represented by the general formula (IV) used as the surface treatment agent in the next step (A3) are mixed with alcohol or water. Significance of suppressing problems such that the surface treatment is insufficient due to reaction, aggregation occurs when drying is performed thereafter, and the resulting silica powder cannot maintain the primary particle size and the fluidity imparting ability deteriorates. There is also.

(Step (A3): Surface treatment step with a functional silane compound)
In the mixed solvent dispersion of the first hydrophobic spherical silica fine particles obtained in the step (A2), the general formula (III):
R ² ₃ SiNHSiR ² ₃ (III)
(In the formula, each R ² is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms)
Or a silazane compound represented by formula (IV):
R ² ₃ SiX (IV)
(Wherein R ² is as defined in the general formula (III) and X is an OH group or a hydrolyzable group), and a monofunctional silane compound or a mixture thereof is added, whereby By treating the surface of the first hydrophobic spherical silica fine particles and introducing R ² ₃ SiO _1/2 units (where R ² is as defined in the general formula (III)) to the surface of the fine particles, Two hydrophobic spherical silica fine particles are obtained. By the treatment in this step, R ² ₃ SiO _1/2 units are introduced to the surface in a form of triorganosilylation of silanol groups remaining on the surface of the first hydrophobic spherical silica fine particles.

In the above general formulas (III) and (IV), R ² is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, Preferably it is a 1-2 monovalent hydrocarbon group. The monovalent hydrocarbon group represented by R ² is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, preferably a methyl group, an ethyl group or a propyl group, particularly preferably , Methyl group or ethyl group. Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, preferably fluorine atom.

  Examples of the hydrolyzable group represented by X include a chlorine atom, an alkoxy group, an amino group, and an acyloxy group, preferably an alkoxy group or an amino group, and particularly preferably an alkoxy group.

  Examples of the silazane compound represented by the general formula (III) include hexamethyldisilazane and hexaethyldisilazane, preferably hexamethyldisilazane. Examples of the monofunctional silane compound represented by the general formula (IV) include monosilanol compounds such as trimethylsilanol and triethylsilanol; monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane; monoalkoxy such as trimethylmethoxysilane and trimethylethoxysilane. Silane; monoaminosilane such as trimethylsilyldimethylamine and trimethylsilyldiethylamine; monoacyloxysilane such as trimethylacetoxysilane, preferably trimethylsilanol, trimethylmethoxysilane or trimethylsilyldiethylamine, particularly preferably trimethylsilanol or trimethylmethoxysilane It is done.

The amount of the silazane compound and / or functional silane compound used is 0.1 to 0.5 mol, preferably 0.2 to 0.4 mol, based on 1 mol of Si atoms of the hydrophilic spherical silica fine particles used. Most preferably, it is 0.25-0.35 mol. If the amount used is 0.1 mol or more, the dispersibility of the resulting hydrophobic silica fine particles will be improved, so that an effect of imparting fluidity to the inorganic phosphor particles appears. When the amount used is 0.5 mol or less, it is economically advantageous.
The hydrophobic spherical silica fine particles can be obtained as a powder by a conventional method such as atmospheric drying or reduced pressure drying.

(Curable resin composition)
The present invention can be made into a curable resin composition by mixing and dispersing a powder in which inorganic oxide fine particles adhere to the surface of inorganic phosphor particles used for wavelength conversion in a curable resin composition.

  The curable resin composition of the present invention is a curable resin composition used for an optical semiconductor device, and one or more selected from an epoxy resin, a silicone resin, an organically modified silicone resin, and an acrylic resin, and the above Inorganic phosphor powder is included.

  The curable resin composition is at least one selected from an epoxy resin, a silicone resin, an organically modified silicone resin, an acrylic resin, and a modified epoxy resin, and has a viscosity at room temperature of 100 mPa · s to 10,000 mPa · s. Preferably they are 100 mPa * s or more and 5000 mPa * s or less. The curable resin composition of the present invention is more preferably a silicone resin or an organically modified silicone resin from the viewpoints of transparency, heat resistance, and light resistance.

  The curable resin composition of the present invention is useful as an optical coating material such as a light-emitting diode and an LED element sealing material, and a wavelength conversion member. If the curable resin composition is used, a commercially available product may be used. it can. Curing conditions may follow the specified conditions of each curable resin composition. If it is a silicone resin, for example, KER-2500 (manufactured by Shin-Etsu Chemical Co., Ltd.), KER6110 (manufactured by Shin-Etsu Chemical Co., Ltd.), SCR1012 (manufactured by Shin-Etsu Chemical Co., Ltd.) if it is a modified silicone resin, STYCAST2017M4 (manufactured by Shin-Etsu Chemical Co., Ltd.) Henkel Japan Co., Ltd.), W0922 (Daicel Chemical Industries Co., Ltd.), and the like, but are not limited thereto.

(Wavelength conversion member and optical semiconductor device)
In this invention, the wavelength conversion member which consists of hardened | cured material of curable resin composition is provided. Moreover, in this invention, an optical semiconductor device provided with an optical semiconductor element and the hardened | cured material of the said curable resin composition as a wavelength conversion member is provided.

  Such a wavelength conversion member and an optical semiconductor device can improve the wavelength conversion efficiency of the light emitted from the optical semiconductor element, and can improve the light extraction efficiency of the wavelength conversion member and the optical semiconductor device using the same. Moreover, since phosphor powder can be industrially produced and provided relatively easily, a wavelength conversion member and an optical semiconductor device using the phosphor powder can be made low-cost and high-quality.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The following examples do not limit the present invention.
(Synthesis example of hydrophobic spherical silica fine particles)
(Step (A1): Step of synthesizing hydrophilic spherical silica fine particles)
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel, and a thermometer, 989.5 g of methanol, 135.5 g of water, and 66.5 g of 28% aqueous ammonia were mixed. This solution was prepared to 35 ° C., and 436.5 g (2.87 mol) of tetramethoxysilane was added dropwise over 6 hours while stirring. Even after the completion of the dropwise addition, the suspension was further stirred for 0.5 hours for hydrolysis to obtain a suspension of hydrophilic spherical silica fine particles.

(Step (A2): Surface treatment step with trifunctional silane compound)
To the suspension obtained in step (A1), 4.4 g (0.03 mol) of methyltrimethoxysilane was added dropwise at room temperature over 0.5 hours, and stirring was continued for 12 hours after the addition. Was subjected to a hydrophobic treatment to obtain a dispersion of hydrophobic spherical silica fine particles.

  Next, an ester adapter and a condenser tube were attached to a glass reactor, and the resulting dispersion was heated to 60 to 70 ° C. to distill off 1021 g of a mixture of methanol and water, and concentrated in a mixed solvent of hydrophobic spherical silica fine particles. A dispersion was obtained. At this time, the content of the hydrophobic spherical silica fine particles in the concentrated dispersion was 28% by mass.

(Step (A3): Surface treatment step with a functional silane compound)
After adding 138.4 g (0.86 mol) of hexamethyldisilazane to the concentrated dispersion obtained in the step (A2) at room temperature, the dispersion is heated to 50 to 60 ° C. and reacted for 9 hours. As a result, the silica fine particles in the dispersion were trimethylsilylated. Next, the solvent in this dispersion was distilled off at 130 ° C. under reduced pressure (6650 Pa) to obtain 186 g of hydrophobic spherical silica fine particles (1).

  The hydrophilic spherical silica fine particles obtained in the step (A1) were measured according to the following measuring method 1. Moreover, it measured according to the following measuring methods 2-3 about the hydrophobic spherical silica fine particle obtained through each step of said process (A1)-(A3).

(Measurement method 1: Measurement of particle diameter of hydrophilic spherical silica fine particles obtained in step (A1))
Silica fine particle suspension was added to methanol so that the silica fine particle might be 0.5 mass%, and the fine particle was dispersed by applying ultrasonic waves for 10 minutes. The particle size distribution of the fine particles treated in this way is measured with a dynamic light scattering method / laser Doppler nanotrack particle size distribution measuring device (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter is measured as particles. The diameter. The median diameter is a particle diameter corresponding to 50% cumulative when the particle size distribution is expressed as a cumulative distribution.

(Measurement method 2: Measurement of particle diameter and measurement of particle size distribution D ₉₀ / D ₁₀ of hydrophobic spherical silica fine particles obtained in step (A3))
Silica fine particles were added to methanol so as to be 0.5% by mass, and the fine particles were dispersed by applying ultrasonic waves for 10 minutes. The particle size distribution of the fine particles treated in this way is measured with a dynamic light scattering method / laser Doppler nanotrack particle size distribution measuring device (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter is measured as particles. The diameter. The particle size distribution D ₉₀ / D ₁₀ is measured by setting D _{10 as} the particle diameter at which accumulation is 10% from the smaller side and D _{90 at} 90% from the smaller side in the distribution when the particle diameter is measured. D ₉₀ / D ₁₀ was calculated from the measured values.

(Measurement method 3: Shape measurement of hydrophobic spherical silica fine particles)
The shape was confirmed by observation with an electron microscope (manufactured by Hitachi, trade name: S-4700 type, magnification: 100,000 times). The term “spherical” includes not only a true sphere but also a slightly distorted sphere. Note that the shape of such particles is evaluated by the circularity when the particles are projected two-dimensionally, and the circularity is in the range of 0.8 to 1. Here, the circularity is (peripheral length of a circle equal to the particle area) / (peripheral length of particle).

The particle diameter of the hydrophobic silica fine particles finally obtained in the synthesis example of the hydrophobic spherical silica fine particles according to the above is 52 nm, the particle size distribution D ₉₀ / D ₁₀ is 2.21, the shape is spherical, and the circularity is 0.86.

(Preparation of powder with inorganic oxide fine particles attached to the surface of inorganic phosphor particles)
As an inorganic phosphor used in the preparation examples, product name: 81003 manufactured by Nemoto Special Chemical Industry Co., Ltd. was used.
(Preparation Example 1)
To 100 parts by mass of the inorganic phosphor particles, 2 parts by mass of hydrophobic spherical silica fine particles (average particle size 52 nm) synthesized as inorganic oxide fine particles (method for producing hydrophobic spherical silica fine particles (I)) were mixed with a self-revolving stirrer. (Product name: ARV-310, manufactured by Shinky Co., Ltd.) was used and uniformly mixed at 800 rpm for 3 minutes without using a vacuum degassing mechanism to obtain phosphor (1).

(Preparation Example 2)
100 parts by mass of inorganic phosphor particles and 2 parts by mass of alumina (trade name: Aeroxide AluC805, made by Aerosil Co., Ltd., primary particle size: 15 nm) as inorganic oxide fine particles were mixed with a self-revolving stirrer (product name: ARV-310, manufactured by Shinky Corporation). ) And using a vacuum degassing mechanism, the mixture was uniformly mixed at 800 rpm for 3 minutes to obtain a phosphor (2).

(Preparation Example 3)
To 100 parts by mass of inorganic phosphor particles, 2 parts by mass of fumed silica (trade name: Reosirol DM-30S, primary particle size 7 nm, manufactured by Tokuyama Co., Ltd.) as inorganic oxide fine particles was added to a self-revolving stirrer (Sinky Corp., product name). : ARV-310), without using a vacuum degassing mechanism, and uniformly mixed at 800 rpm for 3 minutes to obtain a phosphor (3).

(Preparation Example 4)
A phosphor (4) was obtained by using 100 parts by mass of the inorganic phosphor particles without treatment.

(Formulation of curable resin composition including powder having inorganic oxide fine particles attached to the surface of inorganic phosphor particles)
In the following Examples and Comparative Examples, 2 parts by weight were weighed as the weight of the inorganic phosphor without the inorganic oxide fine particles attached to 100 parts by weight of the curable resin composition (in the case of Preparation Example 1, 2 parts). 0.04 parts by mass, and 2.00 parts by mass in the case of Preparation Example 4. That is, the phosphor content in the sealing material was set to the same volume%). After this was uniformly mixed using a self-revolving stirrer equipped with a vacuum degassing mechanism (product name: ARV-310, manufactured by Shinky Corp.), immediately the amount of 5 CC was transferred to a 10 CC syringe for dispensing. Then, a predetermined amount was applied to the SMD5050 package without waiting time, and the coating was continuously applied to one lead frame (120 packages), and immediately heated and cured at 150 degrees for 4 hours to obtain an optical semiconductor package. . Ten optical semiconductor packages thus obtained were sampled arbitrarily.

Example 1
A curable resin composition (1) was prepared by using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (1) as the phosphor.

(Example 2)
A curable resin composition (2) was prepared using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (2) as the phosphor.

(Example 3)
A curable resin composition (3) was prepared by using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (3) as the phosphor.

Example 4
A curable resin composition (4) was prepared by using SCR 1012 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the organically modified silicone resin composition and phosphor (1) as the phosphor.

(Example 5)
As an epoxy resin composition, diglycidyl ether compound of hydrogenated bisphenol A (trade name: HBPADGE, manufactured by Maruzen Petrochemical Co., Ltd.) is used with Ricacid MH (methylhexahydrophthalic anhydride: manufactured by Shin Nippon Rika Co., Ltd.) The ratio of acid anhydride equivalent is 1: 1 and mixed well. Further, tetra-n-butylphosphonium o, o′-diethyl phosphorodithionate (PX-4ET: Nippon Chemical Industry Co., Ltd.) is used as a curing accelerator. Product) was added and mixed well. A curable resin composition (5) was prepared by using the phosphor (1) as a phosphor.

(Comparative Example 1)
A curable resin composition (6) was prepared by using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (4) as the phosphor.

(Comparative Example 2)
Prepared according to the above using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (4) as the phosphor, and further, as inorganic oxide fine particles (method for producing hydrophobic spherical silica fine particles (I)) 0.04 parts by mass of the hydrophobic spherical silica fine particles synthesized in (1) were simply added to the composition and prepared in the same manner as a curable resin composition (7).

  Evaluation in curable resin composition (1)-(7) prepared by the said Example and comparative example was performed in the following way. The results are shown in Table 1.

(Production of optical semiconductor package)
As shown in FIG. 4, as the optical semiconductor element 2, an LED chip having a light emitting layer made of InGaN and having a main light emission peak of 450 nm is formed in an SMD5050 package (I-CHIUN PRECISION INDUSTRY CO., Ltd., resin part PPA). The optical semiconductor device 8 was manufactured by mounting on the substrate and wire bonding.
That is, the optical semiconductor element 2 was fixed to the resin 6 having the pair of lead electrodes 3 and 4 by using the die bond material 7. After the optical semiconductor element 2 and the lead electrodes 3 and 4 were connected by the gold wire 5, the phosphor-containing sealing material 1 was potted and cured by heating at 150 ° C. for 4 hours to produce an optical semiconductor device 8. .

(Measurement of total luminous flux (Lm), color coordinates (x), total radiant flux (mW))
Ten optical semiconductor devices obtained in the above process were measured using a total luminous flux measurement system HM-9100 (manufactured by Otsuka Electronics Co., Ltd.), total luminous flux value (Lm), color coordinates (x), total radiant flux (mW). Was measured (applied current IF = 50 mA), and the average value was determined.

  As shown in the above table, in Examples 1 to 5, an LED device was prepared by mixing powder in which inorganic oxide fine particles adhered to the surface of inorganic phosphor particles used for wavelength conversion in a sealing material. As compared with Comparative Example 1 in which the present invention is not used, the total luminous flux value is high, the color coordinate value is large, and the total radiant flux is small.

  An increase in the total luminous flux value compared with the same phosphor content means that the light extraction efficiency of the LED device is increased.

  A larger color coordinate value compared with the same phosphor content means that the wavelength-converted light has increased, that is, more light has been extracted from the phosphor.

  The smaller total radiant flux compared to the same phosphor content means a decrease in the wavelength region with high energy, and the blue light is reduced by wavelength conversion, that is, more light is emitted to the phosphor. Means that wavelength conversion has been performed.

  As understood from the above, in Examples 1 to 5 using the present invention, they can be manufactured industrially, both increase the wavelength conversion efficiency of the phosphor, and further, the light extraction efficiency of the LED device. I was able to increase.

  On the other hand, Comparative Example 2 which was a composition equivalent to Example 1 but did not perform the step of attaching inorganic oxide fine particles was the same result as Comparative Example 1, and increased the wavelength conversion efficiency of the phosphor. Furthermore, the light extraction efficiency of the LED device could not be increased.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

DESCRIPTION OF SYMBOLS 1 ... Phosphor containing sealing material, 2 ... Optical semiconductor element, 3 ... 1st lead electrode,
4 ... 2nd lead electrode, 5 ... Gold wire, 6 ... Resin, 7 ... Die bond material,
8: Optical semiconductor device.

(Preparation of powder with inorganic oxide fine particles attached to the surface of inorganic phosphor particles)
As an inorganic phosphor used in the preparation examples, product name: 81003 manufactured by Nemoto Special Chemical Industry Co., Ltd. was used.
(Preparation Example 1)
To 100 parts by mass of the inorganic phosphor particles, 2 parts by mass of hydrophobic spherical silica fine particles (average particle size 52 nm) synthesized as inorganic oxide fine particles ( an example of synthesis of hydrophobic spherical silica fine particles) were mixed with a self-revolving stirrer ((stock) ) Product name: ARV-310) manufactured by Shinky Co., Ltd. was uniformly mixed at 800 rpm for 3 minutes without using a vacuum degassing mechanism to obtain a phosphor (1).

(Comparative Example 2)
Prepared as described above using KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silicone resin composition and phosphor (4) as the phosphor, and further synthesized as inorganic oxide fine particles ( Synthesis example of hydrophobic spherical silica fine particles). 0.04 parts by mass of the hydrophobic spherical silica fine particles were simply added to the composition and prepared in the same manner as a curable resin composition (7).

Claims (7)

An inorganic phosphor powder,
On the surface of the inorganic phosphor particles used for wavelength conversion, inorganic oxide fine particles having an average particle diameter of 1 nm or more and 10 μm or less are 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic phosphor particles. An inorganic phosphor powder characterized by being a powder adhered in a range.   The inorganic phosphor powder according to claim 1, wherein the inorganic oxide fine particles are silica or alumina. The inorganic oxide fine particles are hydrophobic silica,
The hydrophobic silica fine particles have R ¹ SiO _3/2 units (R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) on the surface of hydrophilic silica fine particles composed of SiO ₂ units. And R ² ₃ SiO _1/2 units (R ² is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms). The inorganic phosphor powder according to claim 1 or 2, wherein: The hydrophobic silica fine particles have a particle size of 0.005 μm or more and 1.00 μm or less, a particle size distribution D ₉₀ / D ₁₀ value of 3 or less, and an average circularity of 0.8 or more and 1 or less. The inorganic phosphor powder according to claim 3, wherein: A curable resin composition used in an optical semiconductor device,
One type or two or more types selected from an epoxy resin, a silicone resin, an organically modified silicone resin, and an acrylic resin, and the inorganic phosphor powder according to any one of claims 1 to 4, A curable resin composition.   The wavelength conversion member which consists of hardened | cured material of the curable resin composition of Claim 5.   An optical semiconductor device comprising an optical semiconductor element and a cured product of the curable resin composition according to claim 5 as a wavelength conversion member.

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