TWI557950B - An inorganic phosphor powder, a hardened resin composition using an inorganic phosphor powder, a wavelength conversion member, and a semiconductor device - Google Patents
An inorganic phosphor powder, a hardened resin composition using an inorganic phosphor powder, a wavelength conversion member, and a semiconductor device Download PDFInfo
- Publication number
- TWI557950B TWI557950B TW103138033A TW103138033A TWI557950B TW I557950 B TWI557950 B TW I557950B TW 103138033 A TW103138033 A TW 103138033A TW 103138033 A TW103138033 A TW 103138033A TW I557950 B TWI557950 B TW I557950B
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- TW
- Taiwan
- Prior art keywords
- inorganic phosphor
- inorganic
- cerium oxide
- fine particles
- resin composition
- Prior art date
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 165
- 239000004065 semiconductor Substances 0.000 title claims description 53
- 238000006243 chemical reaction Methods 0.000 title claims description 44
- 239000000843 powder Substances 0.000 title claims description 41
- 239000011342 resin composition Substances 0.000 title claims description 41
- 239000002245 particle Substances 0.000 claims description 149
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 95
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 95
- 239000010419 fine particle Substances 0.000 claims description 74
- 239000011859 microparticle Substances 0.000 claims description 59
- 230000002209 hydrophobic effect Effects 0.000 claims description 49
- 230000003287 optical effect Effects 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 41
- 238000009826 distribution Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
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- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229920002675 Polyoxyl Polymers 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 claims 1
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- -1 rare earth metal ion Chemical class 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 28
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- 238000000034 method Methods 0.000 description 19
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- 239000000047 product Substances 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 15
- 238000000605 extraction Methods 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
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- 239000007859 condensation product Substances 0.000 description 7
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- 229910052725 zinc Inorganic materials 0.000 description 3
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
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- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- Microelectronics & Electronic Packaging (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Led Device Packages (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Luminescent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係關於無機螢光體粉末、包含無機螢光體粉末的硬化性樹脂組成物、由硬化性樹脂組成物之硬化物所成之波長變換構件及具備硬化物之光半導體裝置。 The present invention relates to an inorganic phosphor powder, a curable resin composition containing an inorganic phosphor powder, a wavelength conversion member formed of a cured product of a curable resin composition, and an optical semiconductor device including a cured product.
發光二極體(LED)等之光半導體元件由於具有耗電量少之優異特性，故對於屋外照明用途或汽車用途之光半導體裝置之應用增加。此種光半導體裝置一般係藉由波長轉換材料的螢光體，使自發出藍色光、近紫外光或紫外光之半導體發光元件發出之光進行波長轉換而獲得疑似白光之發光裝置，係可根據燈泡色、白色等使用目的以任意色發光，已利用於廣泛製品。適於此種發光裝置之螢光體已知有使用各式各樣之氧化物或硫化物之螢光體。 Since an optical semiconductor element such as a light-emitting diode (LED) has excellent characteristics of low power consumption, application to an optical semiconductor device for outdoor lighting use or automotive use has increased. Such an optical semiconductor device is generally a light-emitting device that converts light emitted from a semiconductor light-emitting element that emits blue light, near-ultraviolet light, or ultraviolet light by a phosphor of a wavelength conversion material to obtain a light-emitting device suspected of white light. The color of the bulb, white, etc. are illuminated in any color for the purpose of use, and have been utilized in a wide range of products. Phosphors suitable for such light-emitting devices are known to use phosphors of various oxides or sulfides.
以進一步提高光半導體裝置之光取出效率為目的，已朝光半導體元件之發光效率之提高、周邊構件之特性提高等進展，另一方面即使是波長轉換材料的螢光體領域，亦進行波長轉換效率之提高、耐熱及耐濕等之信賴 性提高。 In order to further improve the light extraction efficiency of the optical semiconductor device, the luminous efficiency of the optical semiconductor element is improved, and the characteristics of the peripheral member are improved. On the other hand, wavelength conversion is performed even in the field of the phosphor of the wavelength conversion material. Increased efficiency, heat resistance and moisture resistance Sexual improvement.
作為波長轉換效率提高之例，專利文獻1中已提案以透明金屬、過渡金屬或半金屬之氧化物被覆螢光體粒子之方法。然而，專利文獻1之方法由於步驟複雜而無法工業化，所得被覆螢光體粒子之信賴性亦不足。 As an example of improvement in wavelength conversion efficiency, Patent Document 1 proposes a method of coating phosphor particles with an oxide of a transparent metal, a transition metal or a semimetal. However, the method of Patent Document 1 cannot be industrialized due to complicated steps, and the reliability of the obtained coated phosphor particles is also insufficient.
又，專利文獻2中提案有在以包含至少一種螢光粉體之高分子作為黏結劑之薄膜螢光體層之表面上設置微透鏡陣列等之光取出構造之方式。然而，專利文獻2之方法亦有光取出構造之製造步驟複雜而無法工業化，因裝置構造或製造步驟而有無法利用之情況等之課題。 Further, Patent Document 2 proposes a method of providing a light extraction structure such as a microlens array on the surface of a thin film phosphor layer containing a polymer containing at least one phosphor powder as a binder. However, the method of Patent Document 2 also has a problem that the manufacturing steps of the light extraction structure are complicated and cannot be industrialized, and there is a problem that it cannot be utilized due to the device structure or the manufacturing steps.
另一方面，依然有需要進一步提高光半導體裝置之光取出效率，而要求進一步改善。 On the other hand, there is still a need to further improve the light extraction efficiency of the optical semiconductor device, and further improvement is required.
[專利文獻1]日本特表2011-503266號公報 [Patent Document 1] Japanese Patent Publication No. 2011-503266
[專利文獻2]日本特表2012-508986號公報 [Patent Document 2] Japanese Patent Publication No. 2012-508986
本發明之目的係提供一種更簡便地提高光半導體裝置之光取出效率之螢光體粉末。且，本發明之目的係提供包含該螢光體粉末之硬化性樹脂組成物、由該硬化性樹脂組成物之硬化物所成之波長轉換構件、及具備前述 硬化物之光半導體裝置。 SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphor powder which more easily improves the light extraction efficiency of an optical semiconductor device. Further, an object of the present invention is to provide a curable resin composition containing the phosphor powder, a wavelength conversion member formed of a cured product of the curable resin composition, and the foregoing A thin semiconductor device for hardening.
本發明係為解決上述課題而完成者，係提供一種無機螢光體粉末，其特徵係使無機氧化物微粒子附著於波長轉換所用之無機螢光體粒子之表面上而成之粉末，前述無機氧化物微粒子之平均粒徑為1nm以上且10μm以下，且相對於前述無機螢光體粒子100質量份為0.1質量份以上10質量份以下之範圍。 In order to solve the above problems, the present invention provides an inorganic phosphor powder characterized in that inorganic oxide fine particles are attached to a surface of an inorganic phosphor particle for wavelength conversion, and the inorganic oxidation is performed. The average particle diameter of the fine particles is 1 nm or more and 10 μm or less, and is in the range of 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the inorganic phosphor particles.
於此種無機螢光體粒子表面附著有無機氧化物微粒子之無機螢光體粉末可容易製造，且可提高自光半導體元件發出之光的波長轉換效率，可提高使用其之光半導體裝置之光取出效率。 The inorganic phosphor powder having inorganic oxide fine particles adhered to the surface of such inorganic phosphor particles can be easily produced, and the wavelength conversion efficiency of light emitted from the optical semiconductor element can be improved, and the light of the optical semiconductor device using the same can be improved. Take out the efficiency.
該情況下，前述無機氧化物微粒子較好為二氧化矽或氧化鋁。 In this case, the inorganic oxide fine particles are preferably cerium oxide or aluminum oxide.
若為此種無機氧化物微粒子，則揮發成分少，可獲得高透明性。 When such an inorganic oxide fine particle is used, a volatile component is few, and high transparency can be obtained.
此外，前述無機氧化物微粒子較好為疏水性二氧化矽，該疏水性二氧化矽之微粒子係藉由在由SiO2單位所成之親水性二氧化矽微粒子表面導入R1SiO3/2單位(R1為經取代或未經取代之碳原子數1~20之1價烴基)及R2 3SiO1/2單位(R2獨立為經取代或未經取代之碳原子數1~6之1價烴基)而疏水化者。 In addition, the inorganic oxide fine particles is preferably hydrophobic silicon dioxide, based fine particles of the hydrophobic silicon dioxide fine particles introduced into the surface by R 1 SiO 3/2 units of SiO 2 units to the hydrophilic silicon dioxide (R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and R 2 3 SiO 1/2 unit (R 2 is independently a substituted or unsubstituted carbon atom number 1 to 6) A monovalent hydrocarbon group) and a hydrophobized one.
若為此種無機氧化物微粒子，則可進一步提高光半導 體裝置之光取出效率。 If it is such inorganic oxide fine particles, the light semiconducting can be further improved. Light extraction efficiency of the body device.
且，前述疏水性二氧化矽微粒子較好係粒徑為0.005μm以上且1.00μm以下，粒度分佈D90/D10之值為3以下，且平均圓形度為0.8以上且1以下者。 Further, the hydrophobic cerium oxide fine particles preferably have a particle diameter of 0.005 μm or more and 1.00 μm or less, a particle size distribution D 90 /D 10 of 3 or less, and an average circularity of 0.8 or more and 1 or less.
若為此種二氧化矽微粒子，則容易控制前述無機螢光體粒子之流動性。 If it is such a cerium oxide microparticle, it is easy to control the fluidity of the said inorganic phosphor particle.
進而本發明提供一種硬化性樹脂組成物，其係光半導體裝置所用之硬化性樹脂組成物，其特徵係包含自環氧樹脂、聚矽氧樹脂、有機改質聚矽氧樹脂及丙烯酸樹脂選出之一種或兩種以上，以及上述之任一種無機螢光體粉末者。 Further, the present invention provides a curable resin composition which is a curable resin composition for use in an optical semiconductor device, which is characterized by comprising an epoxy resin, a polyoxyxylene resin, an organically modified polyoxyl resin, and an acrylic resin. One or two or more, and any one of the above inorganic phosphor powders.
若為此種硬化性樹脂組成物，則可簡單地獲得透明性、耐熱性、耐光性之特性優異之硬化物。 When it is such a curable resin composition, a cured product excellent in transparency, heat resistance, and light resistance can be easily obtained.
進而本發明提供一種由硬化性樹脂組成物之硬化物所成之波長變換構件。且，本發明提供一種光半導體裝置，其具備光半導體元件、作為波長變換構件之前述硬化性樹脂組成物之硬化物。 Further, the present invention provides a wavelength conversion member made of a cured product of a curable resin composition. Furthermore, the present invention provides an optical semiconductor device including an optical semiconductor element and a cured product of the curable resin composition as a wavelength conversion member.
此種波長轉換構件及光半導體裝置可簡單地提高自光半導體元件發出之光的波長轉換效率，且可提高使用其光半導體裝置之光取出效率。 Such a wavelength conversion member and an optical semiconductor device can easily improve the wavelength conversion efficiency of light emitted from the optical semiconductor element, and can improve the light extraction efficiency of the optical semiconductor device using the same.
依據本發明所得之使無機氧化物微粒子附著於無機螢光體粒子表面而成之無機螢光體粉末係一方面可 工業化製造且簡單構成，一方面可提高自光半導體元件發出之光之波長轉換效率，且可提高使用其之光半導體裝置之光取出效率者。 The inorganic phosphor powder obtained by adhering the inorganic oxide fine particles to the surface of the inorganic phosphor particles obtained according to the present invention may be Industrialized manufacturing and simple configuration can improve the wavelength conversion efficiency of light emitted from the optical semiconductor element, and can improve the light extraction efficiency of the optical semiconductor device using the same.
1‧‧‧加有螢光體之密封材 1‧‧‧Fluorescent sealant
2‧‧‧光半導體元件 2‧‧‧Optical semiconductor components
3‧‧‧第1導線電極 3‧‧‧1st wire electrode
4‧‧‧第2導線電極 4‧‧‧2nd wire electrode
5‧‧‧金線 5‧‧‧ Gold wire
6‧‧‧樹脂 6‧‧‧Resin
7‧‧‧黏晶材 7‧‧‧Mack crystal
8‧‧‧光半導體裝置 8‧‧‧Optical semiconductor devices
圖1係顯示調製例1之使合成例所製造之球狀疏水性二氧化矽微粒子附著於無機螢光體粉末表面而成之無機螢光體粉末組成物之電子顯微鏡照片。 Fig. 1 is an electron micrograph showing the composition of the inorganic phosphor powder obtained by attaching the spherical hydrophobic ceria particles produced in the synthesis example to the surface of the inorganic phosphor powder in the preparation example 1.
圖2係顯示調製例2之使氧化鋁微粒子附著於無機螢光體粉末表面而成之無機螢光體組成物之電子顯微鏡照片。 2 is an electron micrograph showing an inorganic phosphor composition in which alumina fine particles are attached to the surface of the inorganic phosphor powder in Preparation Example 2.
圖3係顯示調製例4之未處理之無機螢光體的電子顯微鏡照片。 Fig. 3 is an electron micrograph showing an untreated inorganic phosphor of Preparation Example 4.
圖4係顯示利用無機螢光體粉末之光半導體裝置之圖之一例。 Fig. 4 is a view showing an example of a photo-semiconductor device using an inorganic phosphor powder.
如上述，要求藉更簡便方法提高光半導體裝置之光取出效率。因此，本發明人等為解決上述課題而進行積極檢討之結果，發現藉由使用如下之無機螢光體粉末可達成上述課題，該無機螢光體粉末之特徵係使平均粒徑1nm以上且10μm以下之無機氧化物微粒子以相對於前述無機螢光體粒子100質量份為0.1質量份以上10質量份 以下之範圍附著於波長變換所用之無機螢光體粒子表面而成之粉末。因此，最終完成在作為LED元件用波長轉換材料等之適宜表面上具有無機氧化物微粒子之無機螢光體粉末、包含前述無機螢光體粉末之硬化性樹脂組成物、硬化性樹脂組成物之硬化物、由前述硬化物所成之波長轉換構件及具備前述硬化物之光半導體裝置。 As described above, it is required to improve the light extraction efficiency of the optical semiconductor device by a simpler method. Therefore, the inventors of the present invention have found that the above problems can be attained by using an inorganic phosphor powder having an average particle diameter of 1 nm or more and 10 μm. The following inorganic oxide fine particles are 0.1 parts by mass or more and 10 parts by mass based on 100 parts by mass of the inorganic phosphor particles. The following range is attached to the powder of the surface of the inorganic phosphor particles used for wavelength conversion. Therefore, the inorganic phosphor powder having inorganic oxide fine particles on the suitable surface of the wavelength conversion material for LED elements or the like, the curable resin composition containing the inorganic phosphor powder, and the hardening resin composition are hardened. A wavelength conversion member made of the cured product and an optical semiconductor device including the cured product.
如此本發明之使無機氧化物微粒子附著於無機螢光體粒子表面而成之無機螢光體粉末係可提高自光半導體元件發出之光的波長轉換效率，因此對於使用前述無機螢光體粉末之光半導體裝置可提高光取出效率者。 Thus, the inorganic phosphor powder obtained by adhering the inorganic oxide fine particles to the surface of the inorganic phosphor particles of the present invention can improve the wavelength conversion efficiency of light emitted from the optical semiconductor element, and therefore, the use of the inorganic phosphor powder described above is used. The optical semiconductor device can improve the light extraction efficiency.
亦即，本發明係提供於無機螢光體粒子之表面具有無機氧化物微粒子之無機螢光體粉末、包含前述無機螢光體粉末之硬化性樹脂組成物、由前述硬化性樹脂組成物之硬化物所成之波長轉換構件及使用前述硬化物之光半導體裝置者。 In other words, the present invention provides an inorganic phosphor powder having inorganic oxide fine particles on the surface of the inorganic phosphor particles, a curable resin composition containing the inorganic phosphor powder, and a hardening of the curable resin composition. A wavelength conversion member formed of the material and an optical semiconductor device using the cured material.
以下，更詳細說明本發明，但本發明並不受限於該等。 Hereinafter, the present invention will be described in more detail, but the present invention is not limited thereto.
首先，本發明之特徵係藉由物理吸附等使無機氧化物微粒子附著於波長轉換所用之無機螢光體粒子之表面上而成之無機螢光體粉末，且具有圖1及圖2所例示之形狀。 First, the present invention is characterized in that the inorganic oxide fine particles are adhered to the surface of the inorganic phosphor particles for wavelength conversion by physical adsorption or the like, and have the exemplified in FIGS. 1 and 2 . shape.
無機螢光體粒子一般係如圖3所例示般之表面為光滑之狀態，以LED為代表之光半導體裝置而言，係對用於進行此種波長轉換之無機螢光體粒子照射藍光， 且發出由螢光體進行波長轉換後之波長的光，結合藍光與經波長轉換之波長的光而成為疑似白光。 The inorganic phosphor particles are generally in a state in which the surface is smooth as illustrated in FIG. 3. In the case of an optical semiconductor device represented by an LED, the inorganic phosphor particles for performing such wavelength conversion are irradiated with blue light. And the light of the wavelength after the wavelength conversion by the phosphor is combined with the blue light and the wavelength-converted light to become a suspected white light.
然而，如圖3所例示，無機螢光體粒子由於具有光滑且接近鏡面之狀態之表面，故光因全反射現象而無法有效地進行波長轉換。亦即，因全反射現象，使藍光不易侵入到無機螢光體內部，且經波長轉換之波長之光因全反射現象而不易取出至螢光體外部。因此，成為波長轉換效率降低之狀態。 However, as illustrated in Fig. 3, since the inorganic phosphor particles have a surface that is smooth and close to the mirror surface, the light cannot be efficiently wavelength-converted due to the total reflection phenomenon. That is, due to the phenomenon of total reflection, blue light is less likely to intrude into the interior of the inorganic phosphor, and the wavelength-converted wavelength light is not easily taken out to the outside of the phosphor due to total reflection. Therefore, the wavelength conversion efficiency is lowered.
另一方面，如觀察圖1及圖2所理解，本發明之無機螢光體粒子之表面上附著無機氧化物微粒子之構造中，無機螢光體表面設有類似於疑似所謂光子結晶(photonic crystal)構造、低反射構造(抗反射構造)之構造。因此，緩和了全反射現象，使藍光容易侵入到無機螢光體內部，且使經波長轉換之波長之光容易取出至螢光體外部。因此，波長轉換效率上升，且可提高光半導體裝置之光取出效率。 On the other hand, as understood from the observation of Fig. 1 and Fig. 2, in the structure in which the inorganic oxide fine particles are attached to the surface of the inorganic phosphor particles of the present invention, the surface of the inorganic phosphor is provided with a photon crystal similar to the photonic crystal. Structure of a low-reflection structure (anti-reflection structure). Therefore, the total reflection phenomenon is alleviated, so that the blue light easily intrudes into the inside of the inorganic phosphor, and the wavelength-converted light is easily taken out to the outside of the phosphor. Therefore, the wavelength conversion efficiency is increased, and the light extraction efficiency of the optical semiconductor device can be improved.
(無機螢光體粒子) (Inorganic phosphor particles)
成為本發明之表面處理方法對象之無機螢光體粒子(以下有時適當稱為「螢光體」)並無特別限制，但列舉為例如吸收來自以氮化物系半導體作為發光層之半導體發光二極體之光並經波長轉換成不同波長之光者。較好為由主要以Eu、Ce等鑭系元素賦活之氮化物系螢光體粒子、氧氮化物系螢光體粒子、主要以Eu等鑭系、Mn等過渡金 屬系之元素賦活之鹼土類鹵磷灰石螢光體粒子、鹼土類金屬硼酸鹵螢光體粒子、鹼土類金屬鋁酸鹽螢光體粒子、鹼土類金屬矽酸鹽螢光體粒子、鹼土類金屬硫化物螢光體粒子、鹼土類硫代鎵酸鹽(thiogallate)螢光體粒子、鹼土類金屬氮化矽螢光體粒子、鍺酸鹽螢光體粒子、或主要以Ce等鑭矽元素賦活之稀土類鋁酸鹽螢光體粒子、稀土類矽酸鹽螢光體粒子或主要以Eu等鑭系元素賦活之有機及有機錯合物螢光體粒子、Ca-Al-Si-O-N系氧氮化物玻璃螢光體粒子等選出之至少任一種以上。具體例可使用下述之螢光體例子，但並不限於該等。 The inorganic phosphor particles to be subjected to the surface treatment method of the present invention (hereinafter sometimes referred to as "fluorescent body" as appropriate) are not particularly limited, but are exemplified by, for example, absorbing semiconductor light-emitting light from a nitride-based semiconductor as a light-emitting layer. The light of the polar body is converted into light of different wavelengths by wavelength. It is preferred that the nitride-based phosphor particles, the oxynitride-based phosphor particles, which are mainly activated by lanthanoid elements such as Eu or Ce, and the transition metal such as lanthanum or Mn such as Eu Alkaline earth haloaluminate phosphor particles, alkaline earth metal borate halogen phosphor particles, alkaline earth metal aluminate phosphor particles, alkaline earth metal silicate phosphor particles, alkaline earth metals Sulfide phosphor particles, alkaline earth thiogallate phosphor particles, alkaline earth metal lanthanum nitride phosphor particles, phthalate phosphor particles, or mainly enthalpy elements such as Ce Rare earth aluminate phosphor particles, rare earth silicate phosphor particles or organic and organic complex phosphor particles mainly activated by lanthanides such as Eu, Ca-Al-Si-ON oxygen At least one or more selected from the group consisting of nitride glass phosphor particles and the like. As a specific example, the following examples of the phosphors can be used, but are not limited thereto.
主要以Eu、Ce等鑭系元素賦活之氮化物系螢光體粒子有M2Si5N8：Eu(M為由Sr、Ca、Ba、Mg、Zn選出之至少一種)等。除此外亦有MSi7N10：Eu、M1.8Si5O0.2N8：Eu、M0.9Si7O0.1N10：Eu(M與前述相同)等。 The nitride-based phosphor particles mainly excited by lanthanoid elements such as Eu or Ce have M 2 Si 5 N 8 :Eu (M is at least one selected from Sr, Ca, Ba, Mg, and Zn). In addition, there are also 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 as described above) and the like.
主要以Eu、Ce等鑭系元素賦活之氧氮化物系螢光體粒子有MSi2O2N2：Eu(M與前述相同)等。 The oxynitride-based phosphor particles mainly excited by lanthanoid elements such as Eu or Ce have MSi 2 O 2 N 2 :Eu (M is the same as described above).
主要以Eu等鑭系、Mn等過渡金屬系之元素賦活之鹼土類鹵磷灰石螢光體粒子有M5(PO4)3X：R(M與前述相同，X為由F、Cl、Br、I選出之至少一種，R為Eu、Mn之任一種以上)等。 The alkaline earth haloapatite phosphor particles mainly activated by elements such as Eu and the transition metal system such as Mn have M 5 (PO 4 ) 3 X:R (M is the same as the above, and X is F, Cl, Br, At least one selected from I, R is at least one of Eu and Mn, and the like.
鹼土類金屬硼酸鹵螢光體粒子有由M2B5O9X：R(M與前述相同，X為由F、Cl、Br、I選出之至少一種，R為Eu、Mn之任一種以上)等。 The alkaline earth metal borate halogen phosphor particles are composed of M 2 B 5 O 9 X:R (M is the same as described above, X is at least one selected from F, Cl, Br, and I, and R is any one of Eu and Mn. )Wait.
鹼土類金屬鋁酸鹽螢光體粒子有SrAl2O4：R、Sr4Al14O25：R、CaAl2O4：R、BaMg2Al16O27：R、BaMg2Al16O12：R、BaMgAl10O17：R(R為Eu、Mn之任一種以上)等。 The alkaline earth metal aluminate phosphor particles are 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 any one or more of Eu and Mn).
鹼土類金屬硫化物螢光體粒子有La2O2S：Eu、Y2O2S：Eu、Gd2O2S：Eu等。 The alkaline earth metal sulfide phosphor particles are La 2 O 2 S:Eu, Y 2 O 2 S:Eu, Gd 2 O 2 S:Eu or the like.
主要以Ce等鑭系元素賦活之稀土類鋁酸鹽螢光體粒子有以Y3Al5O12：Ce、(Y0.8Gd0.2)3Al5O12：Ce、Y3(Al0.8Ga0.2)5O12：Ce、(Y,Gd)3(Al,Ga)5O12之組成式表示之YAG系螢光體粒子。另外，亦有以Tb、Lu等取代Y之一部分或全部之Tb3Al5O12：Ce、Lu3Al5O12：Ce等。 The rare earth aluminate phosphor particles mainly activated by lanthanides such as Ce have Y 3 Al 5 O 12 :Ce, (Y 0.8 Gd 0.2 ) 3 Al 5 O 12 :Ce, Y3 (Al 0.8 Ga 0.2 ) 5 O 12: Ce, (Y , Gd) 3 (Al, Ga) denotes the YAG-based phosphor particles consisting of formula 5 O 12. Further, Tb 3 Al 5 O 12 :Ce, Lu 3 Al 5 O 12 :Ce or the like in which one or all of Y is replaced by Tb, Lu or the like may be used.
其他螢光體粒子有由ZnS：Eu、Zn2GeO4：Mn、MGa2S4：Eu(M為由Sr、Ca、Ba、Mg、Zn選出之至少一種。X為由F、Cl、Br、I選出之至少一種)等。 The other phosphor particles are 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 from F, Cl, Br , at least one of I selected, etc.
上述螢光體粒子亦可視需要替代Eu或除Eu以外又含有由Tb、Cu、Ag、Au、Cr、Nd、Dy、Co、Ni、Ti選出之一種以上。 The above-mentioned phosphor particles may be one or more selected from the group consisting of Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti, in addition to Eu or in addition to Eu.
又，亦可使用上述螢光體粒子以外之螢光體粒子且具有同樣性能、效果之螢光體粒子。 Further, it is also possible to use phosphor particles having the same properties and effects as the phosphor particles other than the above-described phosphor particles.
又，所謂Ca-Al-Si-O-N系氧氮化物玻璃螢光體粒子係以莫耳%表示，含有以CaO換算為20~50莫耳%之CaCO3、0~30莫耳%之Al2O3、25~60莫耳%之SiO、5~50莫耳%之AlN、0.1~20莫耳%之稀土類氧化物或過渡金屬氧化物，且5成分合計為100莫耳%之氧氮化物玻璃 作為母體材料之螢光體粒子。又，以氧氮化物玻璃作為母體材料之螢光體粒子，其氮含量較好為15wt%以下，較好稀土類氧化物離子以外之成為增感劑之其他稀土類元素離子作為稀土類氧化物而於螢光玻璃中以0.1~10莫耳%範圍之含量作為共賦活劑而含有。 In addition, the Ca-Al-Si-ON oxynitride glass phosphor particles are represented by mol%, and contain CaCO 3 in an amount of 20 to 50 mol% in terms of CaO, and Al 2 in an amount of 0 to 30 mol%. O 3 , 25 to 60 mol% of SiO, 5 to 50 mol% of AlN, 0.1 to 20 mol% of rare earth oxide or transition metal oxide, and 5 components totaling 100 mol% of oxygen and nitrogen Phosphate glass is used as the phosphor particles of the parent material. Further, the phosphor particles having the oxynitride glass as a matrix material preferably have a nitrogen content of 15% by weight or less, and preferably other rare earth element ions which are sensitizers other than the rare earth oxide ions are used as the rare earth oxide. In the fluorescent glass, the content is in the range of 0.1 to 10 mol% as a co-activator.
本發明之螢光體所使用之螢光體之粒徑並無特別限制，以中央粒徑(D50)計通常為0.1μm以上，較好為2μm以上，更好為10μm以上。且，通常為100μm以下，較好為50μm以下，更好為25μm以下。D50太小時，會有亮度降低，螢光體粒子凝聚之虞。另一方面，D50太大時，會有發生塗佈不均或佈膠機等阻塞之虞。 The particle diameter of the phosphor used in the phosphor of the present invention is not particularly limited, and is usually 0.1 μm or more, preferably 2 μm or more, and more preferably 10 μm or more in terms of the central particle diameter (D 50 ). Further, it is usually 100 μm or less, preferably 50 μm or less, more preferably 25 μm or less. When D 50 is too small, there is a decrease in brightness and agglomeration of phosphor particles. On the other hand, when D 50 is too large, there will occur unevenness in coating or plastic cloth, etc. blocking risk.
(其他螢光體粒子) (other phosphor particles)
此外，除上述螢光體外，依據提高耐久性、提高分散性等目的亦可使用其他螢光體。 Further, in addition to the above-mentioned fluorescent body, other phosphors may be used for the purpose of improving durability and improving dispersibility.
其他螢光體之組成並無特別限制，較好於以結晶母體Y2O3、Zn2SiO4等為代表之金屬氧化物、以Sr2Si5N8等為代表之金屬氮化物、以Ca5(PO4)3Cl等為代表之磷酸鹽及以ZnS、SrS、CaS等為代表之硫化物中，組合Ce、Pr、Nd、Pm、Sm、Eu、Tb、Dy、Ho、Er、Tm、Yb等稀土類金屬之離子或Ag、Cu、Au、Al、Mn、Sb等金屬離子作為賦活元素或共賦活元素者。 The composition of the other phosphor is not particularly limited, and is preferably a metal oxide typified by a crystal precursor such as Y 2 O 3 or Zn 2 SiO 4 or a metal nitride represented by Sr 2 Si 5 N 8 or the like. Ca 5 (PO 4 ) 3 Cl or the like is a representative phosphate and a sulfide represented by ZnS, SrS, CaS or the like, and is combined with Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, A rare earth metal ion such as Tm or Yb or a metal ion such as Ag, Cu, Au, Al, Mn or Sb is used as an active element or a coactive element.
(無機氧化物微粒子) (inorganic oxide microparticles)
本發明之上述無機氧化物微粒子之例列舉於下，但並不限於該等。無機氧化物微粒子為金屬、過渡金屬或半金屬之氧化物微粒子，為例如特徵係由Si、Ti、Al、Zr、Mg、Ge、Y等選出之一種以上之金屬之氧化物所成者。只要選擇為成為目的之製品中獲得具有各種形狀及比重之螢光體之波長轉換效率提高效果，能獲得適度附著於螢光體表面之狀態即可，再者，只要使用依據目的之折射率的無機氧化物微粒子即可。亦可對無機氧化物微粒子賦予波長轉換功能。可簡便地使用任何市售者。 Examples of the above inorganic oxide fine particles of the present invention are listed below, but are not limited thereto. The inorganic oxide fine particles are oxide fine particles of a metal, a transition metal or a semimetal, and are, for example, those having an oxide of one or more selected from the group consisting of Si, Ti, Al, Zr, Mg, Ge, Y, and the like. It is only necessary to select a state in which the wavelength conversion efficiency of the phosphor having various shapes and specific gravities is obtained in the desired product, and it is possible to obtain a state in which the phosphor is appropriately attached to the surface of the phosphor, and further, a refractive index according to the purpose is used. The inorganic oxide fine particles are sufficient. It is also possible to impart a wavelength conversion function to the inorganic oxide fine particles. Any commercially available person can be easily used.
至於無機氧化物微粒子，較佳之例列舉為二氧化矽、氧化鋁、氧化鎂、氧化鋯、氧化鈦或其他氧化銻、氫氧化鋁、硫酸鋇、碳酸鎂、碳酸鋇等。尤其較好使用揮發成分少、獲得高透明性之二氧化矽或氧化鋁。 As the inorganic oxide fine particles, preferred examples are ceria, alumina, magnesia, zirconia, titania or other cerium oxide, aluminum hydroxide, barium sulfate, magnesium carbonate, barium carbonate and the like. It is particularly preferable to use cerium oxide or aluminum oxide having a small amount of volatile components and obtaining high transparency.
例如，若為二氧化矽，則列舉為發煙二氧化矽、熔融二氧化矽等之以乾式法製造之二氧化矽，或膠體二氧化矽、溶凝膠二氧化矽、沉澱二氧化矽等之以濕式法製造之二氧化矽。尤其基於容易附著之觀點，以發煙二氧化矽較佳。發煙二氧化矽於作為例如親水性發煙二氧化矽時列舉為日本AEROSIL(股)製之AEROSIL(R)90、AEROSIL(R)130、AEROSIL(R)150、AEROSIL(R)200、AEROSIL(R)300、AEROSIL(R)380、AEROSIL(R)OX50、AEROSIL(R)EG50、AEROSIL(R)TT600、TOKUYAMA(股)製之REOLOSIL QS-09、QS-10L、QS-10、QS-102、CP-102、QS-20L、QS-20、QS- 25C、QS-30、QS-30C、QS-40等。且，作為疏水性發煙二氧化矽列舉為日本AEROSIL(股)製之AEROSIL(R)R972、AEROSIL(R)R974、AEROSIL(R)R104、AEROSIL(R)R106、AEROSIL(R)R202、AEROSIL(R)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、TOKUYAMA(股)製之REOLOSIL MT-10、MT-10C、DM-10、DM-10C、DM-20S、DM-30、DM-30S；KS-20S、KS-20SC、HM-20L、HM-30S、PM-20L等。且，亦可使用由聚有機倍半矽氧烷樹脂所成之聚矽氧粉末、或表面之一部分或全部具有聚有機倍半矽氧烷樹脂之聚矽氧粉末、或以下所述之疏水性球狀二氧化矽微粒子。該等可單獨使用，亦可混合2種以上使用。 For example, in the case of cerium oxide, cerium oxide produced by a dry method such as fumed cerium oxide or molten cerium oxide, or colloidal cerium oxide, lyotropic cerium oxide, precipitated cerium oxide, or the like is exemplified. The cerium oxide produced by the wet method. Especially for the viewpoint of easy adhesion, it is preferred to use fumed cerium oxide. The fumed cerium oxide is exemplified by AEROSIL (R) 90, AEROSIL (R) 130, AEROSIL (R) 150, AEROSIL (R) 200, AEROSIL manufactured by AEROSIL Co., Ltd., for example, as hydrophilic fuming ceria. (R)300, AEROSIL(R)380, AEROSIL(R)OX50, AEROSIL(R)EG50, AEROSIL(R)TT600, TOKUYAMA(s) REOLOSIL QS-09, QS-10L, QS-10, QS- 102, CP-102, QS-20L, QS-20, QS- 25C, QS-30, QS-30C, QS-40, etc. Further, as the hydrophobic fuming ceria, AEROSIL(R)R972, AEROSIL(R)R974, AEROSIL(R)R104, AEROSIL(R)R106, AEROSIL(R)R202, AEROSIL manufactured by Japan AEROSIL Co., Ltd. are listed. (R) 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, TOKUYAMA REOLOSIL MT-10, MT-10C, DM-10, DM-10C, DM-20S, DM-30, DM-30S; KS-20S, KS-20SC, HM-20L, HM-30S, PM-20L, etc. . Further, a polyfluorene oxide powder obtained from a polyorganosilsesquioxane resin, or a polyfluorene oxide powder partially or wholly having a polyorganosilsesquioxane resin, or a hydrophobicity as described below may be used. Spherical cerium oxide microparticles. These may be used singly or in combination of two or more.
氧化鋁一般使用α相之結晶構造者，但亦可包含θ相、γ相、δ相等中間相。就氧化鋁之安定性之觀點等而言以使用α氧化鋁較佳。氧化鋁之具體例列舉為日本輕金屬公司製之A30系列、AN系列、A40系列、MM系列、LS系列、AHP系列，ADAMTECH公司製之「Admafine Alumina」(商品名)AO-5型、AO-8型，日 本BAIKOWSKI公司製之CR系列、大明化學工業公司製之TAIMICRON、Aldrich公司製之10μm 2徑氧化鋁粉末、昭和電工公司製之A-42系列、A-43系列、A-50系列、AS系列、AL-43系列、AL-47系列、AL-160SG系列、A-170系列、AL-170系列、住友化學公司製之AM系列、AL系列、AMS系列、AES系列、AKP系列、AA系列等，但並不限於此。 Alumina generally uses a crystal structure of an α phase, but may also include an intermediate phase of θ phase, γ phase, and δ. From the viewpoint of the stability of alumina and the like, it is preferred to use α-alumina. Specific examples of the alumina are A30 series, AN series, A40 series, MM series, LS series, and AHP series manufactured by Nippon Light Metal Co., Ltd., and "Admafine Alumina" (trade name) AO-5 type and AO-8 manufactured by ADAMTECH. Type, day CR series manufactured by BAIKOWSKI Co., Ltd., TAIMICRON manufactured by Daming Chemical Industry Co., Ltd., 10 μm 2 diameter alumina powder manufactured by Aldrich Co., Ltd., A-42 series, A-43 series, A-50 series, AS series manufactured by Showa Denko Co., Ltd. AL-43 series, AL-47 series, AL-160SG series, A-170 series, AL-170 series, AM series, AL series, AMS series, AES series, AKP series, AA series, etc. by Sumitomo Chemical Co., Ltd. Not limited to this.
無機氧化物微粒子之粒徑係平均粒徑1nm以上且10μm以下，更好為50nm以上且5μm以下。未達1nm之微粒子有容易引起凝聚，該無機氧化物微粒子之各個粒子因無法維持一次粒徑而有對該無機螢光體粒子之流動性賦予能變差之虞。添加超過10μm粒徑之微粒子時，會有無法獲得提高波長轉換效率之類似所謂光子結晶構造、低反射構造(抗反射構造)之構造，且有成為佈膠步驟中之噴嘴阻塞原因之虞。基於能良好獲得提高波長轉換效率之效果，無機氧化物微粒子之添加量相對於粒子無機螢光體100質量份為0.1質量份以上且10質量份以下之範圍。更好為5質量份以下。為了獲得添加效果，必須為0.1質量份以上。添加量過多時會有成為佈膠步驟中之噴嘴阻塞原因之虞。且該添加量超過10質量份時，成本而言較不佳。 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. The fine particles of less than 1 nm are likely to cause aggregation, and the respective particles of the inorganic oxide fine particles are incapable of maintaining the primary particle diameter, and the fluidity of the inorganic phosphor particles is deteriorated. When fine particles having a particle diameter of more than 10 μm are added, a structure similar to a so-called photonic crystal structure and a low-reflection structure (anti-reflection structure) which improves the wavelength conversion efficiency cannot be obtained, and the nozzle may be blocked in the step of laminating. The amount of the inorganic oxide fine particles to be added is in the range of 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the particulate inorganic phosphor, based on the effect of improving the wavelength conversion efficiency. More preferably 5 parts by mass or less. In order to obtain an additive effect, it must be 0.1 parts by mass or more. When the amount of addition is too large, there is a possibility that the nozzle is blocked in the step of laminating. When the amount added exceeds 10 parts by mass, the cost is not preferable.
作為維持無機氧化物微粒子附著於無機螢光體粒子表面之狀態目的，上述無機氧化物微粒子亦可藉矽烷偶合劑進行表面處理。只要藉由使無機氧化物微粒子附 著於無機螢光體粒子表面而成之粒子表面經表面處理，能使以物理吸附而附著之無機氧化物微粒子以藉化學性強固附著之粒子獲得，在成為目的之光半導體裝置中良好地獲得明亮、色座標等特性之方式選擇即可。至於矽烷偶合劑例示為含烷基之矽烷偶合劑、含烯基之矽烷偶合劑、含環氧基之矽烷偶合劑、含(甲基)丙烯醯基之矽烷偶合劑、含異氰酸酯基之矽烷偶合劑、含異氰尿酸酯基之矽烷偶合劑、含胺基之矽烷偶合劑、含巰基之矽烷偶合劑等習知者。 The inorganic oxide fine particles may be surface-treated with a decane coupling agent for the purpose of maintaining the state in which the inorganic oxide fine particles adhere to the surface of the inorganic phosphor particles. As long as the inorganic oxide particles are attached The surface of the particles formed on the surface of the inorganic phosphor particles is surface-treated, and the inorganic oxide fine particles adhered by physical adsorption can be obtained by chemically adhering particles, and are well obtained in the intended optical semiconductor device. You can choose the characteristics such as brightness and color coordinates. The decane coupling agent is exemplified by an alkyl group-containing decane coupling agent, an alkenyl group-containing decane coupling agent, an epoxy group-containing decane coupling agent, a (meth) acrylonitrile group-containing decane coupling agent, and an isocyanate group-containing decane coupler. Mixtures, isocyanurate-containing decane coupling agents, amine-containing decane coupling agents, fluorenyl-containing decane coupling agents, and the like.
使無機氧化物微粒子附著於無機螢光體粒子表面之方法並無特別限制。只要依據習知之混合方法，使用以亨歇爾混練機、V型摻合機、帶型摻合機(ribbon blender)、擂潰機、捏合混練機、蝶型攪拌機、或通常之葉片式攪拌子等各種形式之混練機進行之混合、以自公轉式攪拌機進行之混合，均勻混合各成分之特定量即可。攪拌時，以提高無機微粒子附著率為目的，亦可將攪拌系內設為真空。若使用上述方法則可簡單地使無機氧化物微粒子附著於無機螢光體粒子表面。 The method of attaching the inorganic oxide fine particles to the surface of the inorganic phosphor particles is not particularly limited. As long as according to the conventional mixing method, a Henschel mixer, a V-type blender, a ribbon blender, a kneading machine, a kneading mixer, a butterfly mixer, or a conventional blade stirrer is used. Mixing with various types of kneading machines, mixing with a revolving mixer, and uniformly mixing a specific amount of each component. When stirring, it is also possible to set the inside of the stirring system to a vacuum for the purpose of increasing the adhesion rate of the inorganic fine particles. When the above method is used, the inorganic oxide fine particles can be easily attached to the surface of the inorganic phosphor particles.
(疏水性球狀二氧化矽微粒子) (hydrophobic spherical cerium oxide microparticles)
疏水性二氧化矽微粒子較好係藉由將R1SiO3/2單位(R1為經取代或未經取代之碳原子數1~20之1價烴基)及R2 3SiO1/2單位(R2獨立為經取代或未經取代之碳原子數1~6之1價烴基)導入由SiO2單位所成之親水性二氧 化矽微粒子之表面而疏水化者。 The hydrophobic cerium oxide microparticles are preferably obtained by using R 1 SiO 3/2 units (R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and R 2 3 SiO 1/2 unit. (R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and is introduced into the surface of the hydrophilic ceria microparticles formed of SiO 2 units to be hydrophobized.
且，前述疏水性二氧化矽微粒子較好係粒徑為0.005μm以上且1.00μm以下，粒度分佈D90/D10之值為3以下，且平均圓形度為0.8以上且1以下者。 Further, the hydrophobic cerium oxide fine particles preferably have a particle diameter of 0.005 μm or more and 1.00 μm or less, a particle size distribution D 90 /D 10 of 3 or less, and an average circularity of 0.8 or more and 1 or less.
針對上述無機螢光體粉末中混合之疏水性球狀二氧化矽微粒子之特徵更詳細加以說明。 The characteristics of the hydrophobic spherical cerium oxide microparticles mixed in the above inorganic phosphor powder will be described in more detail.
本發明所使用之疏水性球狀二氧化矽微粒子係以包含下列步驟之方法製造，且粒徑為0.005~1.0μm之範圍，粒度分佈D90/D10之值為3以下，且平均圓形度為0.8~1之疏水性球狀二氧化矽微粒子(1)：(A1)藉由使4官能性矽烷化合物、其部分水解縮合產物或該等之組合經水解及縮合而獲得實質上由SiO2單位所成之親水性球狀二氧化矽微粒子之步驟，(A2)將R1SiO3/2單位(式中，R1為經取代或未經取代之碳原子數1~20之1價烴基)導入該親水性球狀二氧化矽微粒子表面之步驟，與(A3)導入R2 3SiO1/2單位(式中，各R2係相同或不同，為經取代或未經取代之碳原子數1~6之1價烴基)之步驟。 The hydrophobic spherical cerium oxide microparticles used in the present invention are produced by a method comprising the following steps, and have a particle diameter of 0.005 to 1.0 μm, a particle size distribution D 90 /D 10 of 3 or less, and an average circular shape. Hydrophobic spherical cerium oxide microparticles (1) having a degree of 0.8 to 1 (A1) obtained by substantially hydrolyzing and condensing a tetrafunctional decane compound, a partially hydrolyzed condensation product thereof, or a combination thereof 2 units of hydrophilic spherical cerium oxide microparticles, (A2) will be R 1 SiO 3/2 units (wherein R 1 is a substituted or unsubstituted carbon atom number of 1 to 20 hydrocarbon) is introduced into the hydrophilic silicon dioxide fine particles spherical surface of the step, and (A3) introducing R 2 3 SiO 1/2 units (wherein, each R 2 is the same or different system, a substituted or non-substituted carbon The step of a monovalent hydrocarbon group having an atomic number of 1 to 6.
上述疏水性球狀二氧化矽微粒子之粒徑為0.005μm~1.00μm，較好為0.01μm~0.30μm，最好為0.03μm~0.20μm。該粒徑若為0.005μm以上，則不會發生無機螢光體粒子之劇烈凝聚，可良好地取出該無機螢光體粒子。且為1.00μm以下時，可對無機螢光體粒子賦予良 好流動性或填充性。 The hydrophobic spherical cerium oxide microparticles have a particle diameter of 0.005 μm to 1.00 μm, preferably 0.01 μm to 0.30 μm, preferably 0.03 μm to 0.20 μm. When the particle diameter is 0.005 μm or more, the inorganic phosphor particles are not strongly aggregated, and the inorganic phosphor particles can be favorably taken out. When it is 1.00 μm or less, it is possible to impart good properties to inorganic phosphor particles. Good fluidity or filling.
上述疏水性球狀二氧化矽微粒子之粒度分佈指標之D90/D10之值為3以下。此處，D10及D90分別為藉由測定粒徑分佈獲得之值。測定粉體之粒徑分佈時，將自粒徑小的側起累積10%之粒徑設為D10，自粒徑小的側起累積90%之粒徑設為D90。由於該D90/D10為3以下，故本發明之疏水性球狀二氧化矽微粒子之粒度分佈之特徵為陡峭。若為此粒度分佈陡峭之粒子，就容易控制無機螢光體粒子之流動性方面而言係較佳。上述D90/D10更好為2.9以下。 The particle size distribution index of the above hydrophobic spherical cerium oxide microparticles has a value of D 90 /D 10 of 3 or less. Here, D 10 and D 90 are values obtained by measuring the particle size distribution, respectively. When the particle size distribution of the powder is measured, the particle diameter at which 10% is accumulated from the side having a small particle diameter is D 10 , and the particle diameter at which 90% is accumulated from the side where the particle diameter is small is D 90 . Since the D 90 /D 10 is 3 or less, the particle size distribution of the hydrophobic spherical cerium oxide microparticles of the present invention is steep. If the particle having a steep particle size distribution is used, it is preferable to control the fluidity of the inorganic phosphor particles. The above D 90 /D 10 is more preferably 2.9 or less.
又，本發明中，微粒子之粒度分佈係以動態光散射法/雷射都卜勒法Nanotrack粒度分佈測定裝置(日機裝股份有限公司製，商品名：UPA-EX150)測定，以其體積基準中值徑作為粒徑。又，所謂中值徑係相當於以粒度分佈作為累積分佈表示時累積50%之粒徑。 Further, 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 (manufactured by Nikkiso Co., Ltd., trade name: UPA-EX150), based on the volume basis. The median diameter is taken as the particle size. Further, the median diameter system corresponds to a particle diameter which is accumulated by 50% when the particle size distribution is expressed as a cumulative distribution.
又上述疏水性球狀二氧化矽微粒子之平均圓形度於0.8~1時，由於二氧化矽微粒子之凝聚防止效果及對無機螢光體粒子之流動性賦予效果優異而較佳，更好為0.92~1。此處所謂「球狀」不僅為真球狀，亦包含稍變形之球。所謂此「球狀」之形狀係以將粒子投影成二次元時之圓形度予以評價，且指圓形度落於0.8~1之範圍者。此處所謂圓形度係(與粒子面積相等之圓之圓周長)/(粒子周圍長)。該圓形度可藉由以電子顯微鏡等獲得之粒子像進行影像解析而測定。 Further, when the average circularity of the hydrophobic spherical cerium oxide fine particles is from 0.8 to 1, the effect of preventing aggregation of the cerium oxide fine particles and the effect of imparting fluidity to the inorganic phosphor particles are preferable, and more preferably 0.92~1. Here, the "spherical shape" is not only a true spherical shape but also a slightly deformed ball. The shape of the "spherical shape" is evaluated by the circularity when the particles are projected into a quadratic element, and the circularity falls within the range of 0.8 to 1. Here, the circularity system (the circumference of a circle equal to the particle area) / (the circumference around the particle). The circularity can be measured by image analysis using a particle image obtained by an electron microscope or the like.
上述中，所謂親水性球狀二氧化矽微粒子係「實質上由SiO2單位所成」意指該微粒子基本上由SiO2單位構成，但並非僅由SiO2單位構成者，而係至少表面具有多數個如通常已知之矽烷醇基。且，視情況，亦可使源自原料之4官能性矽烷化合物及/或其部分水解縮合產物之水解性基(烴氧基(hydrocarbyloxy))不被轉化成一部分矽烷醇基而少量直接殘留在微粒子表面或內部。 In the above, the hydrophilic spherical cerium oxide microparticles "substantially formed of SiO 2 units" means that the microparticles are substantially composed of SiO 2 units, but are not composed of only SiO 2 units, but have at least a surface. Most are stanol groups which are generally known. Further, as the case may be, the hydrolyzable group (hydrocarbyloxy) derived from the starting material of the tetrafunctional decane compound and/or its partial hydrolysis condensation product may not be converted into a part of the stanol group and may be directly retained in a small amount. Microparticle surface or interior.
如上述，本發明中將藉由四烷氧基矽烷之水解所得之小粒徑溶凝膠法二氧化矽作為二氧化矽原體(疏水化處理前之二氧化矽)。使之進行特定之表面處理，而以粉體獲得時疏水化處理後之粒徑雖維持二氧化矽原體之一次粒徑，但為未凝聚之小粒徑，獲得可對無機螢光體粒子賦予良好流動性之疏水性二氧化矽微粒子。 As described above, in the present invention, the small particle size lyotropic cerium oxide obtained by hydrolysis of tetraalkoxy decane is used as the cerium oxide precursor (cerium oxide before the hydrophobization treatment). The specific surface treatment is carried out, and the particle size after the hydrophobization treatment is maintained as the primary particle diameter of the cerium oxide precursor, but the small particle size which is not condensed, and the inorganic phosphor particles can be obtained. Hydrophobic cerium oxide microparticles that impart good fluidity.
使用烷氧基之碳原子數小的四烷氧基矽烷作為小粒徑之二氧化矽原體時，藉由使用碳原子數小的醇作為溶劑、提高水解溫度、降低四烷氧基矽烷之水解時濃度、降低水解觸媒之濃度等之變更反應條件，可獲得任意粒徑之二氧化矽原體。 When a tetraalkoxy decane having a small number of carbon atoms of an alkoxy group is used as the ceria precursor having a small particle diameter, by using an alcohol having a small carbon number as a solvent, the hydrolysis temperature is lowered, and the tetraalkoxy decane is lowered. The cerium oxide having an arbitrary particle diameter can be obtained by changing the reaction conditions such as the concentration at the time of hydrolysis and the concentration of the hydrolysis catalyst.
藉由對該小粒徑之二氧化矽原體以如前述般而且更詳細敘述於下之方式，進行特定之表面處理，而獲得期望之疏水性二氧化矽微粒子。 The desired hydrophobicity of the ceria particles is obtained by subjecting the small-sized ceria precursor to a specific surface treatment as described above and in more detail.
(疏水性球狀二氧化矽微粒子(1)之製造方法) (Method for producing hydrophobic spherical cerium oxide microparticles (1))
接著，針對上述疏水性球狀二氧化矽微粒子之製造方 法之一詳細說明於下。 Next, the manufacturer of the above hydrophobic spherical cerium oxide microparticles One of the laws is detailed below.
本發明之疏水性球狀二氧化矽微粒子係藉由下述步驟獲得： The hydrophobic spherical cerium oxide microparticles of the present invention are obtained by the following steps:
步驟(A1)：親水性球狀二氧化矽微粒子之合成步驟 Step (A1): Synthesis step of hydrophilic spherical cerium oxide microparticles
步驟(A2)：藉由3官能性矽烷化合物之表面處理步驟 Step (A2): surface treatment step by trifunctional decane compound
步驟(A3)：藉由1官能性矽烷化合物之表面處理步驟。 Step (A3): a surface treatment step by a monofunctional decane compound.
以下，依序說明各步驟。 Hereinafter, each step will be described in order.
(步驟(A1)：親水性球狀二氧化矽微粒子之合成步驟) (Step (A1): Synthesis step of hydrophilic spherical cerium oxide microparticles)
藉由使以下述通式(I)表示之4官能性矽烷化合物、其部分水解物、或該等之混合物在含鹼性物質之親水性有機溶劑與水之混合液中水解及縮合，而獲得親水性球狀二氧化矽微粒子之混合溶劑分散液：通式(I)：Si(OR3)4 (I) By subjecting a tetrafunctional decane compound represented by the following formula (I), a partially hydrolyzate thereof, or a mixture thereof to hydrolysis and condensation in a mixture of a hydrophilic organic solvent containing a basic substance and water, Mixed solvent dispersion of hydrophilic spherical cerium oxide microparticles: general formula (I): Si(OR 3 ) 4 (I)
(式中，各R3為相同或不同之碳原子數1~6之一價烴基)。 (Wherein, each R 3 is the same or different from one to 6 carbon atoms, a monovalent hydrocarbon group).
上述通式(I)中，R3為碳原子數1~6之一價烴基，較好為碳原子數1~4，最好為1~2之一價烴基。以R3表示之一價烴基列舉為例如甲基、乙基、丙基、丁基之烷基；如苯基之芳基，較好列舉為甲基、乙基、丙基或丁基，最好為甲基或乙基。 In the above formula (I), R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon atom number of 1 to 4, preferably 1 to 2 carbon atoms. The monovalent hydrocarbon group represented by R 3 is exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group or 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; Good is methyl or ethyl.
以上述通式(I)表示之4官能性矽烷化合物 列舉為例如四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷等四烷氧基矽烷；及四苯氧基矽烷，較好列舉為四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷及四丁氧基矽烷，最好列舉為四甲氧基矽烷及四乙氧基矽烷。此外，作為以通式(I)表示之4官能性矽烷化合物之部分水解縮合產物列舉為例如矽酸甲酯、矽酸乙酯等矽酸烷酯。 a tetrafunctional decane compound represented by the above formula (I) For example, tetraalkoxynonane such as tetramethoxynonane, tetraethoxysilane, tetrapropoxydecane or tetrabutoxydecane; and tetraphenoxydecane, preferably tetramethoxynonane, is exemplified. Tetraethoxydecane, tetrapropoxydecane and tetrabutoxydecane are preferably exemplified by tetramethoxynonane and tetraethoxydecane. Further, the partially hydrolyzed condensation product of the tetrafunctional decane compound represented by the general formula (I) is exemplified by an alkyl phthalate such as methyl decanoate or ethyl decanoate.
前述親水性有機溶劑只要是能使以通式(I)表示之4官能性矽烷化合物、其部分水解縮合產物與水溶解者及無特別限制，列舉為例如醇類；甲基溶纖素、乙基溶纖素、丁基溶纖素、乙酸溶纖素等溶纖素類；丙酮、甲基乙基酮等酮類；二噁烷、四氫呋喃等醚類等，較好列舉為醇類、溶纖素類，最好列舉為醇類。該醇類列舉為以通式(V)表示之醇：R5OH (V) The hydrophilic organic solvent is not particularly limited as long as it can dissolve the tetrafunctional decane compound represented by the formula (I), the partially hydrolyzed condensation product thereof and water, and is, for example, an alcohol; methyl cellosolve, B. Cellulite, butyl cellosolve, cellosolve such as cellulase; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran, preferably listed as alcohols and cellosolve Classes, preferably listed as alcohols. The alcohol is exemplified by the alcohol represented by the general formula (V): R 5 OH (V)
(式中，R5為碳原子數1~6之一價烴基)。 (wherein R 5 is a one-valent hydrocarbon group having 1 to 6 carbon atoms).
上述通式(V)中，R5為碳原子數1~6之一價烴基，較好為碳原子數1~4，最好為1~2之一價烴基。以R5表示之一價烴基列舉為例如甲基、乙基、丙基、異丙基、丁基等烷基，較好列舉為甲基、乙基、丙基及異丙基，更好列舉為甲基及乙基。以通式(V)表示之醇列舉為例如甲醇、乙醇、丙醇、異丙醇、丁醇等，較好列舉為甲醇、乙醇。醇之碳原子數增加時，生成之球狀二氧化矽微粒子之粒徑變大。因此，為了獲得目標之小粒徑之二氧 化矽微粒子，以甲醇較佳。 In the above formula (V), R 5 is a one-valent hydrocarbon group having 1 to 6 carbon atoms, preferably a carbon number of 1 to 4, preferably 1 to 2, a monovalent hydrocarbon group. The monovalent hydrocarbon group represented by R 5 is exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and a methyl group, an ethyl group, a propyl group and an isopropyl group are preferred, and more preferably It is a methyl group and an ethyl group. The alcohol represented by the formula (V) is exemplified by methanol, ethanol, propanol, isopropanol, butanol, and the like, and methanol or ethanol is preferred. When the number of carbon atoms of the alcohol increases, the particle diameter of the formed spherical cerium oxide microparticles becomes large. Therefore, in order to obtain the target small-sized cerium oxide fine particles, methanol is preferred.
且，上述鹼性物質列舉為氨、二甲胺、二乙胺等，較好為氨、二乙胺，最好為氨。該等鹼性物質只要將所需量溶解於水中後，使所得水溶液(鹼性)與前述親水性有機溶劑混合即可。 Further, the above basic substance is exemplified by ammonia, dimethylamine, diethylamine or the like, preferably ammonia or diethylamine, and most preferably ammonia. These alkaline substances may be prepared by dissolving the required amount in water and then mixing the obtained aqueous solution (basic) with the hydrophilic organic solvent.
該鹼性物質之使用量相對於以通式(I)表示之4官能性矽烷化合物及/或其部分水解縮合產物之烴基氧基之合計1莫耳較好為0.01~2莫耳，更好為0.02~0.5莫耳，最好為0.04~0.12莫耳。此時，鹼性物質之量愈少則愈可成為期望之小粒徑二氧化矽微粒子。 The amount of the basic substance used is preferably from 0.01 to 2 mol, more preferably from 0.01 to 2 mol, based on the total of the hydrocarbyloxy group of the tetrafunctional decane compound represented by the formula (I) and/or its partial hydrolysis condensation product. It is 0.02~0.5 m, preferably 0.04~0.12 mol. At this time, the smaller the amount of the alkaline substance, the more the desired small-sized cerium oxide fine particles.
上述水解及縮合所使用之水量相對於以通式(I)表示之4官能性矽烷化合物及/或其部分水解縮合產物之烴氧基之合計1莫耳較好為0.5~5莫耳，更好為0.6~2莫耳，最好為0.7~1莫耳。上述親水性有機溶劑相對於水之比率(親水性有機溶劑：水)以質量比計，較好為0.5~10，更好為3~9，最好為5~8。親水性有機溶劑之量愈多愈可獲得期望之小粒徑二氧化矽微粒子。 The amount of water used for the hydrolysis and condensation is preferably from 0.5 to 5 moles per 1 mole of the total of the alkoxy groups of the tetrafunctional decane compound represented by the formula (I) and/or its partial hydrolysis condensation product. Good for 0.6~2 moles, preferably 0.7~1 moles. The ratio of the hydrophilic organic solvent to water (hydrophilic organic solvent: water) is preferably from 0.5 to 10, more preferably from 3 to 9, more preferably from 5 to 8, in terms of mass ratio. The more the amount of the hydrophilic organic solvent, the more the desired small particle size cerium oxide microparticles can be obtained.
以通式(I)表示之4官能性矽烷化合物等之水解及縮合係藉由習知方法，亦即，將以通式(I)表示之4官能性矽烷化合物等添加於含鹼性物質之親水性有機溶劑與水之混合物中而進行。 The hydrolysis and condensation of the tetrafunctional decane compound represented by the formula (I) are carried out by a conventional method, that is, a tetrafunctional decane compound represented by the formula (I) is added to the basic substance-containing substance. It is carried out in a mixture of a hydrophilic organic solvent and water.
該步驟(A1)中獲得之親水性球狀二氧化矽微粒子之混合溶劑分散液中之二氧化矽微粒子濃度一般為3~15質量%，較好為5~10質量%。 The concentration of the cerium oxide fine particles in the mixed solvent dispersion of the hydrophilic spherical cerium oxide fine particles obtained in the step (A1) is usually from 3 to 15% by mass, preferably from 5 to 10% by mass.
(步驟(A2)：藉由3官能性矽烷化合物之表面處理步驟) (Step (A2): surface treatment step by trifunctional decane compound)
於步驟(A1)中獲得之親水性球狀二氧化矽微粒子之混合溶劑分散液中添加以下述通式(II)表示之3官能性矽烷化合物、或其部分水解物、或其等之混合物，藉此處理該親水性球狀二氧化矽微粒子之表面，而將R1SiO3/2單位(R1係如前述)導入前述親水性球狀二氧化矽微粒子表面，獲得第一疏水性球狀二氧化矽微粒子之混合溶劑分散液：R1Si(OR4)3 (II) a trifunctional decane compound represented by the following formula (II), or a partial hydrolyzate thereof, or a mixture thereof, is added to the mixed solvent dispersion of the hydrophilic spherical cerium oxide microparticles obtained in the step (A1). By treating the surface of the hydrophilic spherical cerium oxide microparticles, R 1 SiO 3/2 units (R 1 as described above) are introduced into the surface of the hydrophilic spherical cerium oxide microparticles to obtain a first hydrophobic spherical shape. Mixed solvent dispersion of cerium oxide microparticles: R 1 Si(OR 4 ) 3 (II)
(式中，R1為經取代或未經取代之碳原子數1~20之一價烴基，各R4為相同或不同之碳原子數1~6之一價烴基)。 (wherein R 1 is a substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms, and each R 4 is the same or different one or more carbon atoms having 1 to 6 carbon atoms).
本步驟(A2)係在下一步驟之濃縮步驟(A3)中抑制二氧化矽微粒子凝聚所不可或缺。若無法抑制凝聚，則所得二氧化矽粉體之各個粒子無法維持一次粒徑，故流動性賦予能變差。 This step (A2) is indispensable for suppressing the coagulation of cerium oxide microparticles in the concentration step (A3) of the next step. If the aggregation cannot be suppressed, the particles of the obtained cerium oxide powder cannot maintain the primary particle diameter, so that the fluidity imparting ability is deteriorated.
上述通式(II)中，R1為經取代或未經取代之碳原子數1~20之一價烴基，較好為碳原子數1~3，最好為1~2之一價烴基。以R1表示之一價烴基列舉為例如甲基、乙基、正丙基、異丙基、丁基、己基等烷基，較好列舉為甲基、乙基、正丙基或異丙基，最好列舉為甲基或乙基。且，該等一價烴基之氫原子之一部分或全部亦可經 氟原子、氯原子、溴原子等鹵原子，較好經氟原子取代。 In the above formula (II), R 1 is a substituted or unsubstituted hydrocarbon having 1 to 20 carbon atoms, preferably a hydrocarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. The monovalent hydrocarbon group represented by R 1 is exemplified by an alkyl group such as methyl, ethyl, n-propyl, isopropyl, butyl or hexyl, preferably methyl, ethyl, n-propyl or isopropyl. Preferably, it is methyl or ethyl. Further, part or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, preferably by a fluorine atom.
上述通式(II)中，R4為相同或不同之碳原子數1~6之一價烴基，較好為碳原子數1~3，最好為1~2之一價烴基。以R4表示之一價烴基列舉為例如甲基、乙基、丙基、丁基等烷基，較好為甲基、乙基或丙基，最好為甲基或乙基。 In the above formula (II), R 4 is the same or different one-valent hydrocarbon group having 1 to 6 carbon atoms, preferably a carbon number of 1 to 3, preferably 1 to 2 of a monovalent hydrocarbon group. The monovalent hydrocarbon group represented by R 4 is exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group, an ethyl group or a propyl group, preferably a methyl group or an ethyl group.
以通式(II)表示之3官能性矽烷化合物列舉為例如甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、異丙基三甲氧基矽烷、異丙基三乙氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、己基三甲氧基矽烷、三氟丙基三甲氧基矽烷、十七氟癸基三甲氧基矽烷等未經取代或經鹵素取代之三烷氧基矽烷等，較好為甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷及乙基三乙氧基矽烷，更好為甲基三甲氧基矽烷及甲基三乙氧基矽烷，或該等之部分水解縮合產物。 The trifunctional decane compound represented by the formula (II) is exemplified by, for example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethyl Oxy decane, n-propyl triethoxy decane, isopropyl trimethoxy decane, isopropyl triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, hexyl trimethoxy decane An unsubstituted or halogen-substituted trialkoxy decane such as trifluoropropyltrimethoxydecane or heptadecafluorodecyltrimethoxydecane, preferably methyltrimethoxydecane or methyltriethoxy More preferably, decane, ethyltrimethoxydecane and ethyltriethoxydecane are methyltrimethoxydecane and methyltriethoxydecane, or a partially hydrolyzed condensation product thereof.
以通式(II)表示之3官能性矽烷化合物之添加量為所使用之親水性球狀二氧化矽微粒子之Si原子每1莫耳為0.001~1莫耳，較好為0.01~0.1莫耳，最好為0.01~0.05莫耳。添加量為0.001莫耳以上時，由於所得疏水性球狀二氧化矽微粒子之分散性良好，故展現對無機螢光體粒子之流動性化賦予效果，若為1莫耳以下則不會發生二氧化矽微粒子之凝聚。 The amount of the trifunctional decane compound represented by the formula (II) is such that the Si atom of the hydrophilic spherical cerium oxide microparticle used is 0.001 to 1 mol per 1 mol, preferably 0.01 to 0.1 mol. It is preferably 0.01~0.05 m. When the amount of addition is 0.001 mol or more, since the dispersibility of the obtained hydrophobic spherical cerium oxide fine particles is good, it exhibits an effect of imparting fluidity to the inorganic phosphor particles, and if it is 1 mol or less, it does not occur. Coagulation of cerium oxide microparticles.
該步驟(A2)中獲得之第一疏水性球狀二氧 化矽微粒子之混合溶劑分散液中之該二氧化矽微粒子濃度通常為3質量%以上且未達15質量%，較好為5~10質量%。若為該濃度之範圍內則生產性提高，亦不會發生二氧化矽微粒子之凝聚。 The first hydrophobic spherical dioxygen obtained in the step (A2) The concentration of the cerium oxide microparticles in the mixed solvent dispersion of the cerium microparticles is usually 3% by mass or more and less than 15% by mass, preferably 5 to 10% by mass. If it is within the range of the concentration, the productivity is improved, and the aggregation of the cerium oxide microparticles does not occur.
(濃縮步驟) (concentration step)
自如此獲得之第一疏水性球狀二氧化矽微粒子之混合溶劑分散液去除前述親水性有機溶劑與水之一部分並濃縮，而獲得第一疏水性球狀二氧化矽微粒子之混合溶劑濃縮分散液。此時，可預先(濃縮步驟前)或於濃縮步驟中添加疏水性有機溶劑。此時，作為使用之疏水性溶劑較好為烴系或酮系溶劑。具體而言作為該溶劑列舉為甲苯、二甲苯、甲基乙基酮、甲基異丁基酮等，以甲基異丁基酮較佳。去除前述親水性有機溶劑與水之一部分之方法列舉為例如餾除、減壓餾除等。所得濃縮分散液之二氧化矽微粒子濃度較好為15~40質量%，更好為20~35質量%，最好為25~30質量%。若為15質量%以上則可順利進行後步驟之表面處理，若為40質量%以下則不會發生二氧化矽微粒子之凝聚。 The mixed solvent dispersion of the first hydrophobic spherical cerium oxide microparticles thus obtained is removed from a part of the hydrophilic organic solvent and water, and concentrated to obtain a mixed solvent concentrated dispersion of the first hydrophobic spherical cerium oxide microparticles. . At this time, a hydrophobic organic solvent may be added in advance (before the concentration step) or in the concentration step. In this case, the hydrophobic solvent to be used is preferably a hydrocarbon-based or ketone-based solvent. Specifically, the solvent is exemplified by toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone or the like, and methyl isobutyl ketone is preferred. The method of removing a part of the hydrophilic organic solvent and water is exemplified by, for example, distillation, vacuum distillation, and the like. The concentration of the cerium oxide microparticles in the obtained concentrated dispersion is preferably from 15 to 40% by mass, more preferably from 20 to 35% by mass, most preferably from 25 to 30% by mass. When it is 15% by mass or more, the surface treatment of the subsequent step can be smoothly performed, and if it is 40% by mass or less, aggregation of the cerium oxide microparticles does not occur.
濃縮步驟亦具有之意義係抑制下述缺點：於下一步驟(A3)中作為表面處理劑使用之以通式(III)表示之矽氮烷化合物及以通式(IV)表示之單官能性矽烷化合物與醇或水反應而使表面處理變不充分，於隨後進行乾燥時產生凝聚，使所得二氧化矽粉體無法維持一次粒 徑，且使流動性賦予能變差。 The concentration step also has the meaning of suppressing the following disadvantages: the decazane compound represented by the formula (III) and the monofunctionality represented by the formula (IV) used as a surface treating agent in the next step (A3) The decane compound reacts with an alcohol or water to make the surface treatment insufficient, and coagulation occurs in the subsequent drying, so that the obtained cerium oxide powder cannot maintain the primary granules. The diameter and the ability to impart fluidity deteriorate.
(步驟(A3)：藉由單官能性矽烷化合物之表面處理步驟) (Step (A3): Surface treatment step by monofunctional decane compound)
於步驟(A2)中獲得之第一疏水性球狀二氧化矽微粒子之混合溶劑分散液中添加以下述通式(III)表示之矽氮烷化合物，或以下述通式(IV)表示之單官能性矽烷化合物或該等之混合物：R2 3SiNHSiR2 3 (III) To the mixed solvent dispersion of the first hydrophobic spherical cerium oxide fine particles obtained in the step (A2), a decazane compound represented by the following formula (III) or a single one represented by the following formula (IV) is added. a functional decane compound or a mixture of these: R 2 3 SiNHSiR 2 3 (III)
(式中，各R2為相同或不同之經取代或未經取代之碳原子數1~6之一價烴基)，R2 3SiX (IV) (wherein each R 2 is the same or different substituted or unsubstituted hydrocarbon atom having 1 to 6 carbon atoms), R 2 3 SiX (IV)
(式中，R2係如通式(III)中之定義，X為OH基或水解性基)，藉此處理前述第一疏水性球狀二氧化矽微粒子之表面，且將R2 3SiO1/2單位(但，R2係如通式(III)中之定義)導入該微粒子表面，而獲得第二疏水性球狀二氧化矽微粒子。藉由該步驟之處理，使殘存於第一疏水性球狀二氧化矽微粒子表面之矽烷醇基經三有機矽烷基化之形態將R2 3SiO1/2導入該表面。 (wherein R 2 is as defined in the formula (III), X is an OH group or a hydrolyzable group), whereby the surface of the first hydrophobic spherical cerium oxide microparticles is treated, and R 2 3 SiO is used. 1/2 unit (however, R 2 is as defined in the formula (III)) is introduced into the surface of the fine particles to obtain second hydrophobic spherical cerium oxide fine particles. By the treatment of this step, R 2 3 SiO 1/2 is introduced into the surface in a form in which the decyl alcohol group remaining on the surface of the first hydrophobic spherical cerium oxide microparticles is alkylated by triorganoindole.
上述通式(III)及(IV)中，R2為相同或不同之經取代或未經取代之碳原子數1~6之一價烴基，較好為碳原子數1~4，最好1~2之一價烴基。以R2表示之一價烴基列舉為例如甲基、乙基、丙基、異丙基、丁基等烷基，較好為甲基、乙基或丙基，最好為甲基或乙基。且該 等一價烴基之氫原子之一部分或全部亦可經氟原子、氯原子、溴原子等鹵原子，較好經氟原子取代。 In the above formulae (III) and (IV), R 2 is the same or different substituted or unsubstituted hydrocarbon having 1 to 6 carbon atoms, preferably 1 to 4, preferably 1 ~2 one-valent hydrocarbon group. The monovalent hydrocarbon group represented by R 2 is exemplified by 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, preferably a methyl group or an ethyl group. . Further, part or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, preferably by a fluorine atom.
以X表示之水解性基列舉為氯原子、烷氧基、胺基、醯氧基，較好為烷氧基或胺基，最好為烷氧基。 The hydrolyzable group represented by X is exemplified by a chlorine atom, an alkoxy group, an amine group or a decyloxy group, preferably an alkoxy group or an amine group, and more preferably an alkoxy group.
以通式(III)表示之矽氮烷化合物列舉為例如六甲基二矽氮烷、六乙基二矽氮烷等，較好為六甲基二矽氮烷。以通式(IV)表示之單官能性矽烷化合物列舉為例如三甲基矽烷醇、三乙基矽烷醇等單矽烷醇化合物；三甲基氯矽烷、三乙基氯矽烷等單氯矽烷；三甲基甲氧基矽烷、三甲基乙氧基矽烷等單烷氧基矽烷；三甲基矽烷基二甲基胺、三甲基矽烷基二乙基胺等單胺基矽烷；三甲基乙醯氧基矽烷等單乙醯氧基矽烷，較好為三甲基矽烷醇、三甲基甲氧基矽烷或三甲基矽烷基二乙基胺，最好為三甲基矽烷醇或三甲基甲氧基矽烷。 The nonazepine compound represented by the formula (III) is exemplified by, for example, hexamethyldiazepine or hexaethyldioxane, and preferably hexamethyldioxane. The monofunctional decane compound represented by the formula (IV) is exemplified by a monostanol compound such as trimethyl stanol or triethyl decyl alcohol; monochloro decane such as trimethyl chlorodecane or triethyl chlorodecane; a monoalkoxydecane such as methyl methoxy decane or trimethyl ethoxy decane; monoamino decane such as trimethyl decyl dimethylamine or trimethyl decyl diethylamine; trimethyl ethane Monoethoxy decane, such as decyloxydecane, preferably trimethylstanol, trimethylmethoxydecane or trimethyldecyldiethylamine, preferably trimethylstanol or trimethyl Methoxy decane.
前述矽胺烷化合物及/或官能性矽烷化合物之使用量相對於使用之親水性球狀二氧化矽微粒子之Si原子1莫耳為0.1~0.5莫耳，較好為0.2~0.4莫耳，最好為0.25~0.35莫耳。使用量若為0.1莫耳以上，則所得疏水性二氧化矽微粒子之分散性良好，故展現對無機螢光體粒子之流動性賦予效果。若使用量為0.5莫耳以下，則經濟上有利。 The amount of the sulfamethoxane compound and/or the functional decane compound used is 0.1 to 0.5 mol, preferably 0.2 to 0.4 mol, relative to the Si atom of the hydrophilic spherical cerium oxide microparticle used. Good for 0.25~0.35 Mo. When the amount used is 0.1 mol or more, the obtained hydrophobic cerium oxide fine particles have good dispersibility, and thus exhibit an effect of imparting fluidity to the inorganic phosphor particles. It is economically advantageous if the amount used is less than 0.5 mol.
上述疏水性球狀二氧化矽微粒子藉由常壓乾燥、減壓乾燥等常用方法可以粉體獲得。 The above hydrophobic spherical cerium oxide fine particles can be obtained by a usual method such as drying under normal pressure and drying under reduced pressure.
(硬化性樹脂組成物) (curable resin composition)
本發明將使無機氧化物微粒子附著於波長轉換所用之無機螢光體粒子之表面而成之粉末混合、分散於硬化性樹脂組成物中，可作成硬化性樹脂組成物。 In the present invention, a powder obtained by adhering inorganic oxide fine particles to the surface of the inorganic phosphor particles for wavelength conversion is mixed and dispersed in a curable resin composition, and can be used as a curable resin composition.
本發明之硬化性樹脂組成物為光半導體裝置所用之硬化性樹脂組成物，其特徵係包含由環氧樹脂、聚矽氧樹脂、有機改質聚矽氧樹脂及丙烯酸樹脂選出之一種或兩種以上、以及前述無機螢光體粉末者。 The curable resin composition of the present invention is a curable resin composition for an optical semiconductor device, and is characterized by comprising one or two selected from the group consisting of epoxy resin, polyoxynoxy resin, organic modified polyoxyl resin, and acrylic resin. The above and the above inorganic phosphor powder.
前述硬化性樹脂組成物係由環氧樹脂、聚矽氧樹脂、有機改質聚矽氧樹脂、丙烯酸樹脂及改質環氧樹脂中選出之至少一種，在室溫下之黏度為100mPa．s以上且10000mPa．s以下，更好為100mPa．s以上且5000mPa．s以下。本發明之硬化性樹脂組成物就透明性、耐熱性、耐光性之觀點而言，更好為聚矽氧樹脂、有機改質聚矽氧樹脂。 The curable resin composition is at least one selected from the group consisting of epoxy resin, polyoxynoxy resin, organic modified polyoxyl resin, acrylic resin and modified epoxy resin, and has a viscosity of 100 mPa at room temperature. Above s and 10000mPa. s below, better for 100mPa. Above s and 5000mPa. s below. The curable resin composition of the present invention is more preferably a polyoxyxylene resin or an organically modified polyfluorene oxide from the viewpoint of transparency, heat resistance and light resistance.
本發明之硬化性樹脂組成物可使用作為發光二極體、LED元件密封材料等之光學塗佈材料、波長轉換用構件，若為前述硬化性樹脂組成物則可使用市售品。硬化條件只要根據各硬化性樹脂組成物之指定條件即可。若為聚矽氧樹脂，則列舉為例如KER-2500(信越化學工業公司製)、KER6110(信越化學工業公司製)，若為改質聚矽氧樹脂則為SCR1012(信越化學工業公司製)，若為環氧樹脂則為STYCAST2017M4(日本HENKEL公司 製)、W0922(Daicel化學工業公司製)等，但並不限於此。 As the curable resin composition of the present invention, an optical coating material such as a light-emitting diode or an LED element sealing material, or a wavelength conversion member can be used, and a commercially available product can be used as the curable resin composition. The curing conditions may be determined according to the conditions specified for each of the curable resin compositions. For example, KER-2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and KER610 (manufactured by Shin-Etsu Chemical Co., Ltd.), and SCR1012 (manufactured by Shin-Etsu Chemical Co., Ltd.), If it is epoxy resin, it is STYCAST2017M4 (Japan HENKEL company System, W0922 (made by Daicel Chemical Industry Co., Ltd.), etc., but it is not limited to this.
(波長轉換構件及光半導體裝置) (wavelength conversion member and optical semiconductor device)
本發明提供由硬化性樹脂組成物之硬化物所成之波長轉換構件。又，本發明提供具備光半導體元件、作為波長轉換構件之前述硬化性樹脂組成物之硬化物的光半導體裝置。 The present invention provides a wavelength conversion member made of a cured product of a curable resin composition. Moreover, the present invention provides an optical semiconductor device including an optical semiconductor element and a cured product of the curable resin composition as a wavelength conversion member.
此等波長轉換構件及光半導體裝置可提高由光半導體元件發出之光的波長轉換效率，且提高使用其之波長轉換構件或光半導體裝置之光取出效率。且，由於可較簡單地工業生產螢光體粉末而提供，故使用其之波長轉換構件或光半導體裝置亦可為低成本且高品質者。 The wavelength conversion member and the optical semiconductor device can improve the wavelength conversion efficiency of light emitted from the optical semiconductor element, and improve the light extraction efficiency of the wavelength conversion member or the optical semiconductor device using the same. Further, since it can be provided by industrially producing a phosphor powder relatively easily, a wavelength conversion member or an optical semiconductor device using the same can be low cost and high quality.
以下，使用實施例及比較例具體說明本發明。又下述實施例絕不用以限制本發明。 Hereinafter, the present invention will be specifically described using examples and comparative examples. The following examples are in no way intended to limit the invention.
(疏水性球狀二氧化矽微粒子之合成例) (Synthesis example of hydrophobic spherical cerium oxide microparticles)
(步驟(A1)：親水性球狀二氧化矽微粒子之合成步驟) (Step (A1): Synthesis step of hydrophilic spherical cerium oxide microparticles)
將甲醇989.5g、水135.5g、與28%氨水66.5g饋入具備攪拌機、滴加漏斗與溫度計之3升玻璃製反應器中並混合。將該溶液調製成35℃，邊攪拌邊於6小時內滴加四甲氧基矽烷436.5g(2.87莫耳)。該滴加結束後，再持續 攪拌0.5小時進行水解，藉此獲得親水性球狀二氧化矽微粒子之懸浮液。 989.5 g of methanol, 135.5 g of water, and 66.5 g of 28% aqueous ammonia were fed into a 3 liter glass reactor equipped with a stirrer, a dropping funnel, and a thermometer, and mixed. This solution was adjusted to 35 ° C, and 436.5 g (2.87 mol) of tetramethoxy decane was added dropwise over 6 hours while stirring. After the drop is over, continue Hydrolysis was carried out for 0.5 hour while stirring, whereby a suspension of hydrophilic spherical cerium oxide microparticles was obtained.
(步驟(A2)：藉由3官能性矽烷化合物之表面處理步驟) (Step (A2): surface treatment step by trifunctional decane compound)
在室溫下於0.5小時內將甲基三甲氧基矽烷4.4g(0.03莫耳)滴加於步驟(A1)中獲得之懸浮液中，滴加後再持續攪拌12小時，藉由對二氧化矽微粒子表面進行疏水化處理，獲得疏水性球狀二氧化矽微粒子之分散液。 4.4 g (0.03 mol) of methyltrimethoxydecane was added dropwise to the suspension obtained in the step (A1) at room temperature over 0.5 hours, and stirring was continued for 12 hours after the dropwise addition, by oxidizing The surface of the fine particles is hydrophobized to obtain a dispersion of hydrophobic spherical cerium oxide fine particles.
接著，於玻璃製反應器上安裝酯轉接器與冷卻管，將所得分散液加熱至60~70℃餾除甲醇與水之混合物1021g，獲得疏水性球狀二氧化矽微粒子之混合溶劑濃縮分散液。此時，濃縮分散液中之疏水性球狀二氧化矽微粒子之含量為28質量%。 Next, an ester adapter and a cooling tube were installed on the glass reactor, and the obtained dispersion was heated to 60 to 70 ° C to distill 1021 g of a mixture of methanol and water to obtain a mixed solvent of hydrophobic spherical cerium oxide microparticles. liquid. At this time, the content of the hydrophobic spherical cerium oxide fine particles in the concentrated dispersion was 28% by mass.
(步驟(A3)：藉由單官能性矽烷化合物之表面處理步驟) (Step (A3): Surface treatment step by monofunctional decane compound)
在室溫下將六甲基二矽氮烷138.4g(0.86莫耳)添加於步驟(A2)中獲得之濃縮分散液中後，將該分散液加熱至50~60℃，反應9小時，藉此使該分散液中之二氧化矽微粒子三甲基矽烷基化。接著，在130℃、減壓下(6650Pa)餾除該分散液中之溶劑，獲得疏水性球狀二氧化矽微粒子(1)186g。 After adding 138.4 g (0.86 mol) of hexamethyldioxane to the concentrated dispersion obtained in the step (A2) at room temperature, the dispersion was heated to 50 to 60 ° C for 9 hours. This alkylates the cerium oxide microparticles trimethyl hydrazine in the dispersion. Next, the solvent in the dispersion was distilled off at 130 ° C under reduced pressure (6650 Pa) to obtain 186 g of hydrophobic spherical cerium oxide microparticles (1).
針對步驟(A1)中獲得之親水性球狀二氧化矽微粒子，根據下述測定方法1進行測定。且，針對經過上述步驟(A1)~(A3)之各階段獲得之疏水性球狀二氧化矽微粒子，依據下述測定方法2~3進行測定。 The hydrophilic spherical cerium oxide fine particles obtained in the step (A1) were measured according to the following measurement method 1. Further, the hydrophobic spherical cerium oxide fine particles obtained in the respective stages of the above steps (A1) to (A3) were measured in accordance with the following measurement methods 2 to 3.
(測定方法1：步驟(A1)中獲得之親水性球狀二氧化矽微粒子之粒徑測定) (Measurement Method 1: Determination of Particle Size of Hydrophilic Spherical Cerium Oxide Particles Obtained in Step (A1))
以使二氧化矽微粒子成為0.5質量%之方式將二氧化矽微粒子懸浮液添加於甲醇中，施以超音波10分鐘，藉此使該微粒子分散。以動態光散射法/雷射都卜勒Nanotech粒度分佈測定裝置(日機裝股份有限公司製，商品名：UPA-EX150)測定經此處理之微粒子之粒度分佈，以其體積基準中值徑作為粒徑。又，所謂中值徑係相當於以累積分佈表示粒度分佈時累積50%之粒徑。 The cerium oxide fine particle suspension was added to methanol so that the cerium oxide fine particles were 0.5% by mass, and ultrasonic waves were applied for 10 minutes to disperse the fine particles. The particle size distribution of the microparticles thus treated was measured by a dynamic light scattering method/laser Doppler Nanotech particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., trade name: UPA-EX150), and the volume-based median diameter was used as the volume-based diameter. Particle size. Further, the median diameter system corresponds to a particle diameter which is accumulated by 50% when the particle size distribution is expressed by a cumulative distribution.
(測定方法2：步驟(A3)中獲得之疏水性球狀二氧化矽微粒子之粒徑測定及粒度分佈D90/D10之測定) (Measurement Method 2: Particle size measurement of hydrophobic spherical cerium oxide microparticles obtained in the step (A3) and measurement of particle size distribution D 90 /D 10 )
以成為0.5質量%之方式將二氧化矽微粒子添加於甲醇中，施以超音波10分鐘，藉此使該微粒子分散。以動態光散射法/雷射都卜勒Nanotech粒度分佈測定裝置(日機裝股份有限公司製，商品名：UPA-EX150)測定經此處理之微粒子之粒度分佈，以其體積基準中值徑作為粒徑。粒度分佈D90/D10之測定係將上述粒徑測定時之分佈中自粒徑較小側起累積10%之粒徑設為D10，自粒徑較小側起 累積90%之粒徑設為D90，由測定之值計算D90/D10。 The cerium oxide fine particles were added to methanol so as to be 0.5% by mass, and ultrasonic waves were applied for 10 minutes to disperse the fine particles. The particle size distribution of the microparticles thus treated was measured by a dynamic light scattering method/laser Doppler Nanotech particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., trade name: UPA-EX150), and the volume-based median diameter was used as the volume-based diameter. Particle size. The particle size distribution D 90 /D 10 is determined by setting the particle diameter of 10% from the smaller particle diameter side to D 10 in the distribution of the above particle diameter measurement, and accumulating 90% of the particle diameter from the smaller particle diameter side. Set to D 90 and calculate D 90 /D 10 from the measured value.
(測定方法3：疏水性球狀二氧化矽微粒子之形狀測定) (Measurement Method 3: Determination of the shape of hydrophobic spherical cerium oxide microparticles)
以電子顯微鏡(日立製作所製，商品名：S-4700型，倍率：10萬倍)進行觀察，確認形狀。所謂「球狀」不僅為真球狀，亦包含稍變形之球。又此種粒子之形狀係以將粒子投影成二次元時之圓形度予以評價，且指圓形度為0.8~1之範圍者。此處所謂圓形度為(與粒子面積相等之圓之圓周長)/(粒子周圍長)。 The shape was observed by an electron microscope (manufactured by Hitachi, Ltd., trade name: S-4700, magnification: 100,000 times). The so-called "spherical shape" is not only a true spherical shape, but also a slightly deformed ball. Further, the shape of the particles is evaluated by the degree of circularity when the particles are projected into a quadratic element, and the circularity is in the range of 0.8 to 1. Here, the circularity is (the circumference of a circle equal to the particle area) / (the circumference around the particle).
依據上述之於疏水性球狀二氧化矽微粒子之合成例最終獲得之疏水性二氧化矽微粒子之粒徑為52nm，粒度分佈D90/D10為2.21，形狀為球狀，圓形度為0.86。 The hydrophobic cerium oxide microparticles finally obtained according to the above synthesis example of the hydrophobic spherical cerium oxide microparticles have a particle diameter of 52 nm, a particle size distribution D 90 /D 10 of 2.21, a spherical shape, and a circularity of 0.86. .
(無機螢光體粒子表面附著有無機氧化物微粒子之粉末之調製) (Preparation of powder of inorganic oxide fine particles adhered to the surface of inorganic phosphor particles)
使用根本特殊化學工業公司製之商品名：81003作為調製例中使用之無機螢光體。 The product name: 81003, manufactured by the company, is used as an inorganic phosphor used in the preparation example.
(調製例1) (Modulation example 1)
使用自公轉式攪拌機(THINKY(股)製 製品名：ARV-310)，不使用真空脫氣機構，以800rpm將作為無機氧化物微粒子之於(疏水性球狀二氧化矽微粒子(I)之製造方法)中合成之疏水性球狀二氧化矽微粒子(平均 粒徑52nm)2質量份均勻混合於無機螢光體粒子100質量份中歷時3分鐘，作成螢光體(1)。 Using a self-propelled mixer (product name: ARV-310), without using a vacuum degassing mechanism, as an inorganic oxide fine particle at 800 rpm (manufacture of hydrophobic spherical cerium oxide microparticles (I)) Method for synthesizing hydrophobic spherical cerium oxide microparticles (average 2 parts by mass of the particle diameter of 52 nm) was uniformly mixed in 100 parts by mass of the inorganic phosphor particles for 3 minutes to prepare a phosphor (1).
(調製例2) (Modulation example 2)
使用自公轉式攪拌機(THINKY(股)製 製品名：ARV-310)，不使用真空脫氣機構，以800rpm將作為無機氧化物微粒子之氧化鋁(商品名：Aeroxide AluC805 AEROSIL公司製 一次粒徑15nm)2質量份均勻混合於無機螢光體粒子100質量份中歷時3分鐘，作成螢光體(2)。 Using a self-revolving mixer (product name: ARV-310), using a vacuum degassing mechanism, alumina as an inorganic oxide fine particle at 800 rpm (trade name: Aeroxide AluC805 AEROSIL) primary particle size 15 nm 2 parts by mass were uniformly mixed in 100 parts by mass of the inorganic phosphor particles for 3 minutes to prepare a phosphor (2).
(調製例3) (Modulation Example 3)
使用自公轉式攪拌機(THINKY(股)製 製品名：ARV-310)，不使用真空脫氣機構，以800rpm將作為無機氧化物微粒子之發煙二氧化矽(商品名：REOLOSIL DM-30S TOKUYAMA公司製 一次粒徑7nm)2質量份均勻混合於無機螢光體粒子100質量份中歷時3分鐘，作成螢光體(3)。 Using a self-revolving mixer (product name: ARV-310), using a vacuum degassing mechanism, a fumed cerium oxide as an inorganic oxide fine particle at 800 rpm (trade name: REOLOSIL DM-30S TOKUYAMA) 2 parts by mass of a primary particle diameter of 7 nm) was uniformly mixed in 100 parts by mass of the inorganic phosphor particles for 3 minutes to prepare a phosphor (3).
(調製例4) (Modulation Example 4)
無機螢光體粒子100質量份未經處理直接使用，作成螢光體(4)。 100 parts by mass of the inorganic phosphor particles were used without being treated, and a phosphor (4) was produced.
(包含無機螢光體粒子之表面附著有無機氧化物微粒子之 粉末之硬化性樹脂組成物之調配) (Inorganic oxide particles are attached to the surface of the inorganic phosphor particles) Preparation of powdered curable resin composition)
以下之實施例、比較例中，相對於硬化性樹脂組成物100質量份，以未附著無機氧化物微粒子之狀態之無機螢光體之重量計量2質量份(調製例1時為2.04質量份，調製例4時為2.00質量份，亦即，密封材中之螢光體含量成為相同體積%)。使用具備真空脫氣機構之自公轉式攪拌機(THINKY(股)製 製品名：ARV-310)將其均勻混合後，立刻以佈膠用之10CC針筒移液成為5CC之量，不設置待機時間對前述SMD5050封裝進行規定量塗佈，在1片導線架(120個封裝)上持續進行塗佈，隨後立即進行150度、4小時之加熱硬化，成為光半導體封裝。任意取樣10個如此獲得之各光半導體封裝。 In the following examples and comparative examples, the amount of the inorganic phosphor in the state in which the inorganic oxide fine particles were not adhered was 2 parts by mass based on 100 parts by mass of the curable resin composition (2.04 parts by mass in the case of preparation example 1). In the case of Preparation Example 4, it was 2.00 parts by mass, that is, the content of the phosphor in the sealing material became the same volume%). After using a self-revolving mixer (THINKY (product name: ARV-310) with a vacuum degassing mechanism, it is uniformly mixed, and immediately pipetting to a 10CC syringe for 5CC, no standby time is set. The SMD5050 package was coated in a predetermined amount, and was continuously applied on one lead frame (120 packages), and then immediately subjected to heat curing at 150 degrees and 4 hours to become an optical semiconductor package. Ten of the optical semiconductor packages thus obtained were randomly sampled.
(實施例1) (Example 1)
使用作為聚矽氧樹脂組成物之KER2500(信越化學工業公司製)與作為螢光體之螢光體(1)，依據上述調製，作成硬化性樹脂組成物(1)。 KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (1) as a phosphor are used as the composition of the polyoxyxylene resin, and the curable resin composition (1) is prepared in accordance with the above preparation.
(實施例2) (Example 2)
使用作為聚矽氧樹脂組成物之KER2500(信越化學工業公司製)與作為螢光體之螢光體(2)，依據上述調製，作成硬化性樹脂組成物(2)。 KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (2) as a phosphor are used as the composition of the polyoxyxylene resin, and the curable resin composition (2) is prepared in accordance with the above preparation.
(實施例3) (Example 3)
使用作為聚矽氧樹脂組成物之KER2500(信越化學工業公司製)與作為螢光體之螢光體(3)，依據上述調製，作成硬化性樹脂組成物(3)。 KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (3) as a phosphor are used as the composition of the polyoxyxylene resin, and a curable resin composition (3) is prepared in accordance with the above preparation.
(實施例4) (Example 4)
使用作為有機改質聚矽氧樹脂組成物之SCR1012(信越化學工業公司製)與作為螢光體之螢光體(1)，依據上述調製，作成硬化性樹脂組成物(4)。 SCR1012 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (1) as a phosphor are used as the composition of the organically modified polysiloxane composition, and a curable resin composition (4) is produced in accordance with the above preparation.
(實施例5) (Example 5)
使用RIKACID MH(甲基六氫鄰苯二甲酸酐：新日本理化公司製)，以使環氧當量與酸酐當量之比=1：1之方式添加作為環氧樹脂組成物氫化雙酚A之二縮水甘油醚化合物(商品名：HBPADGE丸善石油化學公司製)並充分混合，再添加整體之0.5質量份之作為硬化促進劑之四正丁基鏻o,o’-二乙基二硫代磷酸鹽(PX-4ET：日本化學工業公司製)並充分混合。對其使用螢光體(1)作為螢光體且根據上述調製，作成硬化性樹脂組成物(5)。 RIKACID MH (methylhexahydrophthalic anhydride: manufactured by Nippon Chemical Co., Ltd.) was added as a resin composition hydrogenated bisphenol A as a ratio of epoxy equivalent to anhydride equivalent = 1:1. Glycidyl ether compound (trade name: manufactured by HBPADGE Maruzen Petrochemical Co., Ltd.) and thoroughly mixed, and further added 0.5 parts by mass of tetra-n-butyl fluorene, o'-diethyldithiophosphate as a hardening accelerator (PX-4ET: manufactured by Nippon Chemical Industry Co., Ltd.) and thoroughly mixed. The phosphor (1) is used as a phosphor, and a curable resin composition (5) is prepared according to the above-described preparation.
(比較例1) (Comparative Example 1)
使用作為聚矽氧樹脂組成物之KER2500(信越化學工業公司製)與作為螢光體之螢光體(4)，依據上述調製，作成硬化性樹脂組成物(6)。 KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (4) as a phosphor are used as a composition of a polyoxyxylene resin, and a curable resin composition (6) is produced in accordance with the above preparation.
(比較例2) (Comparative Example 2)
使用作為聚矽氧樹脂組成物之KER2500(信越化學工業公司製)與作為螢光體之螢光體(4)，依據上述調製，進而簡單將作為無機氧化物微粒子之於(疏水性球狀二氧化矽微粒子(I)之製造方法)中合成之疏水性球狀二氧化矽微粒子0.04質量份添加於組成物中同樣調製，作成硬化性樹脂組成物(7)。 KER2500 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a phosphor (4) as a phosphor are used as the composition of the polymer, and further, as the inorganic oxide fine particles (hydrophobic spherical shape) 0.04 parts by mass of the hydrophobic spherical cerium oxide fine particles synthesized in the method of producing cerium oxide fine particles (I) was added to the composition to prepare a curable resin composition (7).
以下述要領進行上述實施例及比較例調製之硬化性樹脂組成物(1)~(7)之評價。其結果示於表1。 The evaluation of the curable resin compositions (1) to (7) prepared in the above examples and comparative examples was carried out in the following manner. The results are shown in Table 1.
(光半導體封裝之製作) (production of optical semiconductor package)
如圖4所示，將作為光半導體元件2之具有由InGaN所成之發光層且主發光波峰為450nm之LED晶片搭載於SMD5050封裝(I-CHIUN PRECISION INDUSTRY CO.，公司製，樹脂部PPA)上且經打線接合，製作光半導體裝置8。 As shown in FIG. 4, an LED chip having a light-emitting layer made of InGaN and having a main light-emitting peak of 450 nm is mounted on an SMD5050 package (I-CHIUN PRECISION INDUSTRY CO., Ltd., resin part PPA). The optical semiconductor device 8 is fabricated by bonding and bonding.
亦即，使用黏晶材7將光半導體元件2固定於具有一對導線電極3、4之樹脂6上。以金線5連接光半導體元件2與導線電極3、4後，灌入加有螢光體之密封材1，在150℃加熱4小時予以硬化，製作光半導體裝置8。 That is, the optical semiconductor element 2 is fixed to the resin 6 having the pair of lead electrodes 3, 4 by using the adhesive material 7. After the optical semiconductor element 2 and the lead electrodes 3 and 4 were connected by the gold wire 5, the sealing material 1 to which the phosphor was applied was poured, and the film was heated at 150 ° C for 4 hours to be cured, thereby producing an optical semiconductor device 8.
(全光束(Lm)、色座標(x)、全放射束(mW)之測定) (Measurement of full beam (Lm), color coordinates (x), total radiation beam (mW))
使用全光束測定系統HM-9100(大塚電子(股)製)測定10個以上述步驟獲得之光半導體裝置之全光束值(Lm)、色座標(x)、全放射束(mW)(施加電流IF=50mA)，求出平均值。 The total beam value (Lm), the color coordinate (x), and the total radiation beam (mW) of the optical semiconductor device obtained by the above steps were measured using a full beam measuring system HM-9100 (manufactured by Otsuka Electronics Co., Ltd.) (applying current) IF = 50 mA), and the average value was obtained.
如上述表所示，實施例1~實施例5係將使無機氧化物微粒子附著於波長轉換所用之無機螢光體粒子表面而成之粉末混合於密封材中作成LED裝置之例，與未使用本發明之比較例1比較，所有之全光束值均提高，色座標值變大，且全放射束為較小之值。 As shown in the above table, Examples 1 to 5 are examples in which a powder obtained by adhering inorganic oxide fine particles to the surface of the inorganic phosphor particles for wavelength conversion is mixed in a sealing material to form an LED device, and is not used. In Comparative Example 1 of the present invention, all of the total beam values were increased, the color coordinate value was increased, and the total radiation beam was a small value.
以相同之螢光體含量予以比較時，全光束值變高意指LED裝置之光取出效率變高。 When the same phosphor content is compared, the increase in the total beam value means that the light extraction efficiency of the LED device becomes high.
以相同之螢光體含量予以比較時，色座標值變大意指經波長轉換之光變多，亦即自更多螢光體取出 光。 When comparing the same phosphor content, the color coordinate value becomes larger, meaning that the wavelength-converted light becomes more, that is, it is taken out from more phosphors. Light.
以相同之螢光體含量予以比較時，全放射束變小意指具有高能量之波長區域減少，且意味著經波長轉換之藍光減少，亦即，光進入到更多螢光體並經波長轉換。 When compared with the same phosphor content, the reduction of the total radiation beam means that the wavelength region with high energy is reduced, and that the wavelength-converted blue light is reduced, that is, the light enters more phosphors and passes through the wavelength. Conversion.
如由上述所理解，使用本發明之實施例1~實施例5可工業上製造，且螢光體之波長轉換效率均高，再者，可提高LED裝置之光取出效率。 As understood from the above, the first to fifth embodiments of the present invention can be industrially manufactured, and the wavelength conversion efficiency of the phosphor is high, and further, the light extraction efficiency of the LED device can be improved.
另一方面，為與實施例1相同之組成物並且未進行附著無機氧化物微粒子之步驟之比較例2係與比較例1相同之結果，無法提高螢光體之波長轉換效率，進而無法提高LED裝置之光取出效率。 On the other hand, Comparative Example 2, which is the same composition as that of Example 1, and in which the inorganic oxide fine particles were not attached, was the same as Comparative Example 1, and the wavelength conversion efficiency of the phosphor could not be improved, and the LED could not be improved. Light extraction efficiency of the device.
又，本發明並不限於上述實施形態。上述實施形態為例示，具有與本發明之申請專利範圍所記載之技術思想實質相同之構成，且發揮相同作用效果者不管何者均包含於本發明之技術範圍中。 Further, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and have substantially the same configuration as the technical idea described in the patent application scope of the present invention, and the same effects and effects are included in the technical scope of the present invention.
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