KR20240055739A - Covered KSF phosphor, method for producing this phosphor, curable silicone composition containing this phosphor, and optical semiconductor device - Google Patents
Covered KSF phosphor, method for producing this phosphor, curable silicone composition containing this phosphor, and optical semiconductor device Download PDFInfo
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- KR20240055739A KR20240055739A KR1020247006786A KR20247006786A KR20240055739A KR 20240055739 A KR20240055739 A KR 20240055739A KR 1020247006786 A KR1020247006786 A KR 1020247006786A KR 20247006786 A KR20247006786 A KR 20247006786A KR 20240055739 A KR20240055739 A KR 20240055739A
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- South Korea
- Prior art keywords
- ksf phosphor
- polymer
- phosphor particles
- ksf
- coated
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 21
- 230000003287 optical effect Effects 0.000 title claims description 20
- 239000004065 semiconductor Substances 0.000 title claims description 19
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- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
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- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XKFIQZCHJUUSBA-UHFFFAOYSA-N perisoxal Chemical compound C1=C(C=2C=CC=CC=2)ON=C1C(O)CN1CCCCC1 XKFIQZCHJUUSBA-UHFFFAOYSA-N 0.000 description 1
- 229950005491 perisoxal Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- H01L33/56—
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/852—Encapsulations
- H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Led Device Packages (AREA)
Abstract
본 발명은, 피복 KSF 형광체입자로서, 상기 피복 KSF 형광체입자는 폴리머에 의한 표면코팅을 갖고, 상기 폴리머가, (메트)아크릴산에스테르 중합체이고, 상기 폴리머의 비율이, 상기 피복 KSF 형광체입자 전체의 0.1~20질량%의 범위인 것을 특징으로 하는 피복 KSF 형광체입자이다. 이에 따라, 고온조건하에 있어서도 산성 물질의 발생이 억제된 KSF 형광체입자, 및, 이 형광체입자를 함유하는 경화성 실리콘 조성물을 제공한다.The present invention relates to coated KSF phosphor particles, wherein the coated KSF phosphor particles have a surface coating made of a polymer, the polymer is a (meth)acrylic acid ester polymer, and the ratio of the polymer is 0.1 of the total of the coated KSF phosphor particles. It is a coated KSF phosphor particle characterized in that it is in the range of ~20% by mass. Accordingly, KSF phosphor particles in which generation of acidic substances is suppressed even under high temperature conditions, and a curable silicone composition containing these phosphor particles are provided.
Description
본 발명은 폴리머에 의한 표면코팅을 갖는 KSF 형광체(망간 부활 규복불화물 형광체(マンガン賦活ケイ複フッ化物螢光體, manganese-activated silicon complex fluoride phosphor))입자, 및, 이 폴리머에 의한 표면코팅을 갖는 형광체입자를 함유하는 경화성 실리콘 조성물, 및 이 경화성 실리콘 조성물의 경화물로 봉지한 광반도체 장치에 관한 것이다.The present invention relates to KSF phosphor (manganese-activated silicon complex fluoride phosphor) particles having a surface coating made of a polymer, and having a surface coating made of this polymer. It relates to a curable silicone composition containing phosphor particles and an optical semiconductor device sealed with a cured product of the curable silicone composition.
현재, 청색발광 다이오드와 다양한 형광체를 조합함으로써 백색을 발광하는 광반도체 장치(LED)가 실용화되고 있으며, 화상표시장치나 조명장치 등에 응용되고 있다.Currently, optical semiconductor devices (LEDs) that emit white light by combining blue light-emitting diodes and various phosphors are being put into practical use, and are being applied to image display devices, lighting devices, etc.
최근, 형광체 중에서 적색의 형광을 발하는 형광체로서 KSF 형광체가 사용되고 있으며(특허문헌 1, 2), 높은 발광효율과 연색성을 양립할 수 있는 재료로서 주목받고 있다. KSF 형광체의 특징의 하나로서, 적색발광 영역의 반값폭이 좁은 것을 들 수 있고, 화상표시장치에 유효하게 사용되기 시작하고 있다.Recently, among phosphors, KSF phosphor has been used as a phosphor that emits red fluorescence (Patent Documents 1 and 2), and is attracting attention as a material capable of achieving both high luminous efficiency and color rendering properties. One of the characteristics of KSF phosphors is that the half width of the red light emission region is narrow, and they are beginning to be effectively used in image display devices.
한편, LED용 봉지재로는, 각종 형광체를 분산시킨 경화성 실리콘 수지가 널리 사용되고 있다. 그러나, KSF 형광체를 경화성 실리콘에 분산시킨 봉지재를 고출력의 LED 용도로 사용한 경우, 고온환경하에 있어서 KSF 형광체로부터 산성 물질이 발생하여, 실리콘을 분해하는 문제가 있었다.Meanwhile, curable silicone resins in which various phosphors are dispersed are widely used as encapsulants for LEDs. However, when an encapsulant in which KSF phosphor is dispersed in curable silicone is used for high-output LED purposes, there is a problem that acidic substances are generated from the KSF phosphor in a high temperature environment and decompose the silicone.
본 발명은, 상기 사정을 감안하여 이루어진 것으로서, 고온조건하에 있어서도 산성 물질의 발생이 억제된 KSF 형광체입자, 및, 이 형광체입자를 함유하는 경화성 실리콘 조성물을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above circumstances, and its purpose is to provide KSF phosphor particles in which generation of acidic substances is suppressed even under high temperature conditions, and a curable silicone composition containing these phosphor particles.
상기 과제를 해결하기 위해, 본 발명에서는,In order to solve the above problem, in the present invention,
피복 KSF 형광체입자로서,As a coated KSF phosphor particle,
상기 피복 KSF 형광체입자는 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자이며, 상기 폴리머가, (메트)아크릴산에스테르 중합체이고, 상기 폴리머의 비율이, 상기 피복 KSF 형광체입자 전체의 0.1~20질량%의 범위인 것을 특징으로 하는 피복 KSF 형광체입자를 제공한다.The covered KSF phosphor particles are KSF phosphor particles having a surface coating by a polymer, the polymer is a (meth)acrylic acid ester polymer, and the proportion of the polymer is in the range of 0.1 to 20% by mass of the total of the covered KSF phosphor particles. Provided are coated KSF phosphor particles, characterized in that:
본 발명의 피복 KSF 형광체입자이면, 고온조건하에 있어서도 KSF 형광체로부터의 산성 물질의 방출이 억제되고, 특히, 이 형광체를 함유하는 경화성 실리콘 조성물의 경화물에 있어서, 실리콘 수지의 분해를 방지할 수 있다.With the coated KSF phosphor particles of the present invention, release of acidic substances from the KSF phosphor is suppressed even under high temperature conditions, and decomposition of the silicone resin can be prevented, especially in the case of a cured product of a curable silicone composition containing this phosphor. .
본 발명의 피복 KSF 형광체입자에서는, 상기 KSF 형광체가, K2SiF6:Mn4+로 표시되는 형광체인 것이 바람직하다.In the coated KSF phosphor particles of the present invention, the KSF phosphor is preferably a phosphor represented by K 2 SiF 6 :Mn 4+ .
이러한 KSF 형광체이면, 보다 높은 발광효율이 얻어진다.With this KSF phosphor, higher luminous efficiency can be obtained.
또한, 본 발명의 피복 KSF 형광체입자에서는, 상기 (메트)아크릴산에스테르 중합체가, 1분자 중에 규소원자에 직접 결합한 수소원자를 적어도 1개 갖는 (메트)아크릴산에스테르를 구성단위에 포함하는 것이 바람직하다.In addition, in the coated KSF phosphor particle of the present invention, the (meth)acrylic acid ester polymer preferably contains as a structural unit a (meth)acrylic acid ester having at least one hydrogen atom directly bonded to a silicon atom in one molecule.
이러한 중합체는, 가스배리어성이 높기 때문에, KSF 형광체입자 표면에 코팅하면, 고온환경하에 있어서, KSF 형광체로부터의 산성 물질의 방출을 억제할 수 있다.Since these polymers have high gas barrier properties, when coated on the surface of KSF phosphor particles, the release of acidic substances from the KSF phosphor can be suppressed in a high temperature environment.
또한 본 발명은, 상기 피복 KSF 형광체입자의 제조방법으로서,Additionally, the present invention provides a method for producing the coated KSF phosphor particles,
(1) (A)(메트)아크릴산에스테르 중합체 및 (B)이 중합체를 용해하는 용제를 포함하는 코팅 조성물을 준비하고, KSF 형광체입자와, 상기 코팅 조성물을 혼합하는 공정, 및(1) preparing a coating composition containing (A) a (meth)acrylic acid ester polymer and (B) a solvent dissolving the polymer, mixing the KSF phosphor particles and the coating composition, and
(2) 상기 용제를 휘발시키는 공정(2) Process of volatilizing the solvent
을 포함하는 것을 특징으로 하는 피복 KSF 형광체입자의 제조방법을 제공한다.It provides a method for producing coated KSF phosphor particles comprising a.
이러한 피복 KSF 형광체입자의 제조방법이면, KSF 형광체입자의 표면을 효율적으로 코팅할 수 있다.With this method for producing covered KSF phosphor particles, the surface of the KSF phosphor particles can be coated efficiently.
이 경우, 상기 KSF 형광체로서, K2SiF6:Mn4+로 표시되는 형광체를 이용하는 것이 바람직하다.In this case, it is preferable to use a phosphor represented by K 2 SiF 6 :Mn 4+ as the KSF phosphor.
이러한 KSF 형광체입자를 이용하면, 보다 발광효율이 높은 피복 KSF 형광체입자를 얻을 수 있다.By using these KSF phosphor particles, coated KSF phosphor particles with higher luminous efficiency can be obtained.
또한, 상기 제조방법에서는, 상기 (메트)아크릴산에스테르 중합체로서, 1분자 중에 규소원자에 직접 결합한 수소원자를 적어도 1개 갖는 (메트)아크릴산에스테르를 구성단위에 포함하는 중합체를 이용하는 것이 바람직하다.In addition, in the above production method, it is preferable to use, as the (meth)acrylic acid ester polymer, a polymer whose structural units include (meth)acrylic acid ester, which has at least one hydrogen atom directly bonded to a silicon atom in one molecule.
이러한 중합체를 이용하면, 고온환경하에 있어서, KSF 형광체로부터의 산성 물질의 방출을 보다 억제할 수 있기 때문에, 안정성이 높은 피복 KSF 형광체입자를 얻을 수 있다.By using such a polymer, the release of acidic substances from the KSF phosphor can be further suppressed in a high-temperature environment, and thus coated KSF phosphor particles with high stability can be obtained.
또한 본 발명은, 상기 피복 KSF 형광체입자를 함유하는 것을 특징으로 하는 경화성 실리콘 조성물을 제공한다.The present invention also provides a curable silicone composition comprising the above-mentioned coated KSF phosphor particles.
본 발명의 경화성 실리콘 조성물은, 그 경화물에 있어서, 고온조건하에서의 KSF 형광체에서 유래하는 산성 물질에 의한 실리콘의 분해를 방지할 수 있기 때문에, 광반도체 소자의 봉지재 용도로 유용하다.The curable silicone composition of the present invention is useful as an encapsulant for optical semiconductor devices because the cured product can prevent decomposition of silicon by acidic substances derived from KSF phosphors under high temperature conditions.
또한 본 발명은, 상기 경화성 실리콘 조성물의 경화물로 광반도체 소자가 봉지된 것을 특징으로 하는 광반도체 장치를 제공한다.Additionally, the present invention provides an optical semiconductor device characterized in that the optical semiconductor element is encapsulated with a cured product of the curable silicone composition.
이러한 광반도체 장치는, 고온환경하에서도 광반도체 소자가 안정적으로 봉지되어 있기 때문에, 신뢰성이 높다.Such optical semiconductor devices are highly reliable because the optical semiconductor elements are stably sealed even in a high temperature environment.
본 발명의 폴리머에 의한 표면코팅을 갖는 KSF 형광체는, 고온조건하에 있어서도 KSF 형광체로부터의 산성 물질의 방출이 억제되고, 이 형광체를 함유하는 경화성 실리콘 조성물의 경화물에 있어서, 실리콘 수지의 분해를 방지할 수 있기 때문에, 광반도체 소자의 봉지재 용도로 유용하다.The KSF phosphor having a surface coating using the polymer of the present invention suppresses the release of acidic substances from the KSF phosphor even under high temperature conditions, and prevents decomposition of the silicone resin in the cured product of the curable silicone composition containing this phosphor. Because it can be used, it is useful as a sealing material for optical semiconductor devices.
상기 서술한 바와 같이, KSF 형광체를 경화성 수지에 분산시킨 봉지재를 고출력의 LED 용도로 사용한 경우, 고온환경하에 있어서 KSF 형광체로부터 산성 물질이 발생하는 문제가 있었다. 이 때문에, 고온환경하에서도 안정된 KSF 형광체의 개발이 요구되고 있었다.As described above, when an encapsulant in which KSF phosphor is dispersed in a curable resin is used for high-output LED purposes, there is a problem in that acidic substances are generated from the KSF phosphor in a high temperature environment. For this reason, there was a demand for the development of a KSF phosphor that was stable even in a high temperature environment.
본 발명자들은, 상기 목적을 달성하기 위해 예의 검토한 결과, 특정 비율의 (메트)아크릴산에스테르 중합체에 의한 표면코팅을 갖는 KSF 형광체이면, 상기 과제를 해결할 수 있는 것을 발견하여, 본 발명을 완성시켰다.As a result of intensive studies to achieve the above object, the present inventors have discovered that the above problem can be solved by using a KSF phosphor having a surface coating of a specific ratio of (meth)acrylic acid ester polymer, and have completed the present invention.
즉, 본 발명은, 피복 KSF 형광체입자로서, 상기 피복 KSF 형광체입자는 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자이며, 상기 폴리머가, (메트)아크릴산에스테르 중합체이고, 상기 폴리머의 비율이, 상기 피복 KSF 형광체입자 전체의 0.1~20질량%의 범위인 것을 특징으로 하는 피복 KSF 형광체입자이다.That is, the present invention is a coated KSF phosphor particle, wherein the coated KSF phosphor particle is a KSF phosphor particle having a surface coating by a polymer, the polymer is a (meth)acrylic acid ester polymer, and the ratio of the polymer is the coating. It is a coated KSF phosphor particle characterized in that it is in the range of 0.1 to 20% by mass of the total KSF phosphor particle.
이하, 본 발명에 대하여 상세히 설명하는데, 본 발명은 이들로 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
[피복 KSF 형광체입자][Coated KSF phosphor particles]
본 발명의 피복 KSF 형광체입자는, 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자로서, 상기 폴리머가, (메트)아크릴산에스테르 중합체인 것을 특징으로 한다.The coated KSF phosphor particles of the present invention are KSF phosphor particles having a surface coating made of a polymer, and the polymer is a (meth)acrylic acid ester polymer.
피복 KSF 형광체입자는, 상기 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자이면 되고, 그 태양은 특별히 한정되지 않는다. 예를 들어, 1개의 KSF 형광체입자가 폴리머에 의해 표면코팅된 것일 수도 있고, 그들의 집합체일 수도 있다. 2개 이상의 KSF 형광체입자가 폴리머에 의해 표면코팅되어 있을 수도 있다. 또한, 폴리머에 의한 표면코팅은 단층일 수도, 2개 이상의 층으로 이루어질 수도 있고, 2층 이상의 표면코팅은, 각 코팅이 동일할 수도 상이할 수도 있다. 2개 이상의 KSF 형광체입자가 폴리머에 의해 표면코팅되어 있는 것으로는, KSF 형광체입자가 응집된 2차 입자가 폴리머에 의해 코팅되어 1개의 입자를 형성하고 있는 것을 들 수 있다.The coated KSF phosphor particles may be KSF phosphor particles having a surface coating using the above-described polymer, and the aspect thereof is not particularly limited. For example, one KSF phosphor particle may be surface-coated with a polymer, or it may be an aggregate thereof. Two or more KSF phosphor particles may be surface coated with a polymer. In addition, the surface coating made of polymer may be a single layer or may consist of two or more layers, and for the surface coating of two or more layers, each coating may be the same or different. Examples of two or more KSF phosphor particles surface-coated with a polymer include secondary particles in which KSF phosphor particles are aggregated and coated with a polymer to form one particle.
이하, 피복 KSF 형광체입자를 구성하는 각 성분에 대하여 설명한다.Hereinafter, each component constituting the coated KSF phosphor particles will be described.
[KSF 형광체][KSF phosphor]
KSF 형광체(망간 부활 규복불화물 형광체)는, K2SiF6결정에 Mn을 첨가한 적색형광체이다.KSF phosphor (manganese-activated silica fluoride phosphor) is a red phosphor obtained by adding Mn to a K 2 SiF 6 crystal.
본 발명에서 호적하게 이용하는 KSF 형광체는, K2SiF6에 4가의 Mn을 발광이온으로서 첨가한 (K2SiF6:Mn4+)로 표시되는 형광체이며, 피크파장 455nm의 광으로 여기한 경우, 600nm 내지 660nm의 발광을 발생시킨다. 이러한 K2SiF6:Mn4+로 표시되는 형광체이면, 보다 높은 발광효율이 얻어진다.The KSF phosphor suitably used in the present invention is a phosphor represented by (K 2 SiF 6 :Mn 4+ ) in which tetravalent Mn is added as a luminescent ion to K 2 SiF 6 , and when excited with light with a peak wavelength of 455 nm, Generates light emission of 600nm to 660nm. If it is a phosphor expressed as K 2 SiF 6 :Mn 4+ , higher luminous efficiency can be obtained.
또한, KSF 형광체의 평균입경은, 10~100μm가 바람직하고, 보다 바람직하게는 20~50μm이다.Additionally, the average particle diameter of the KSF phosphor is preferably 10 to 100 μm, and more preferably 20 to 50 μm.
한편, 본 발명에 있어서의 평균입경은, 레이저회절·산란법에 의해 얻어진 체적 기준의 입도분포에 있어서의 메디안직경(D50)이다.Meanwhile, the average particle diameter in the present invention is the median diameter (D50) in the volume-based particle size distribution obtained by the laser diffraction/scattering method.
KSF 형광체는, 종래 공지의 방법으로 제조한 것일 수 있고, 예를 들어, 불화규소 및 불화망간 등의 금속불화물 원료를 불화수소산에 용해 또는 분산시키고, 가열하여 증발건고시켜서 얻은 것을 이용할 수 있다.The KSF phosphor may be manufactured by a conventionally known method. For example, it may be obtained by dissolving or dispersing metal fluoride raw materials such as silicon fluoride and manganese fluoride in hydrofluoric acid, heating, and evaporating to dryness.
[(A)성분: (메트)아크릴산에스테르 중합체][(A) Ingredient: (meth)acrylic acid ester polymer]
본 발명의 KSF 형광체입자의 표면을 코팅하는 폴리머는, (메트)아크릴산에스테르 중합체(이하, (A)성분)이다.The polymer that coats the surface of the KSF phosphor particles of the present invention is a (meth)acrylic acid ester polymer (hereinafter, component (A)).
본 성분은 가스배리어성이 높기 때문에, KSF 형광체에 코팅하면 고온환경하에 있어서, KSF 형광체로부터의 산성 물질의 방출을 억제한다.Since this component has high gas barrier properties, when coated on KSF phosphor, it suppresses the release of acidic substances from KSF phosphor in a high temperature environment.
본 발명에 있어서, (메트)아크릴산에스테르는, 아크릴산에스테르, 메타크릴산에스테르 또는 그 양방을 나타내고, 아크릴산에스테르로는, 예를 들어, 아크릴산메틸, 아크릴산에틸, 아크릴산n-부틸, 아크릴산이소부틸, 아크릴산이소펜틸, 아크릴산n-헥실, 아크릴산이소옥틸, 아크릴산2-에틸헥실, 아크릴산n-옥틸, 아크릴산이소노닐, 아크릴산n-데실, 아크릴산이소데실 등을 들 수 있다. 메타크릴산에스테르로는, 예를 들어 메타크릴산메틸, 메타크릴산에틸, 메타크릴산n-부틸, 메타크릴산이소부틸, 메타크릴산이소펜틸, 메타크릴산n-헥실, 메타크릴산이소옥틸, 메타크릴산-2-에틸헥실, 메타크릴산n-옥틸, 메타크릴산이소노닐, 메타크릴산n-데실, 메타크릴산이소데실 등을 들 수 있다. 그 중에서도, 알킬기의 탄소원자수가 1~12, 특히 알킬기의 탄소원자수가 1~4인 아크릴산알킬에스테르 및 메타크릴산알킬에스테르가 바람직하다. 이들은, 1종 단독으로도 또는 2종 이상을 조합해서도 사용할 수 있다.In the present invention, (meth)acrylic acid ester represents acrylic acid ester, methacrylic acid ester, or both, and examples of acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid. Isopentyl, n-hexyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, etc. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, and isoxal methacrylate. Til, 2-ethylhexyl methacrylate, n-octyl methacrylate, isononyl methacrylate, n-decyl methacrylate, and isodecyl methacrylate. Among them, alkyl acrylates and alkyl methacrylates in which the alkyl group has 1 to 12 carbon atoms, and especially alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, are preferable. These can be used either individually or in combination of two or more types.
(A)성분은, 1분자 중에 규소원자에 직접 결합한 수소원자(이하, SiH기라고 한다)를 적어도 1개 갖는 (메트)아크릴산에스테르를 구성단위에 포함하는 것이 바람직하다. 이러한 (A)성분은, 1분자 중에 SiH기를 적어도 1개 갖는 (메트)아크릴산에스테르를 단량체성분으로서 포함하는 중합체 또는 공중합체일 수 있다.It is preferable that component (A) contains as a structural unit a (meth)acrylic acid ester having at least one hydrogen atom (hereinafter referred to as SiH group) directly bonded to a silicon atom in one molecule. This component (A) may be a polymer or copolymer containing (meth)acrylic acid ester having at least one SiH group in one molecule as a monomer component.
1분자 중에 SiH기를 적어도 1개 갖는 (메트)아크릴산에스테르로는, 예를 들어, 이하의 식(1)로 표시되는 화합물을 들 수 있다.Examples of (meth)acrylic acid esters having at least one SiH group in one molecule include compounds represented by the following formula (1).
[화학식 1][Formula 1]
(식 중, R은, 수소원자 또는 메틸기이고, R1은, 독립적으로, 탄소원자수 1~10의 1가 탄화수소기이고, R2는, 탄소원자수 1~10의 알킬렌기이고, n은, 0, 1 또는 2이다.)(In the formula, R is a hydrogen atom or a methyl group, R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, and n is 0. , 1 or 2.)
R1은, 구체적으로는 메틸기, 에틸기, 프로필기 등의 탄소원자수 1~10, 바람직하게는 탄소원자수 1~6의 알킬기, 페닐기 등의 탄소원자수 6~10의 아릴기 등이 예시되고, 메틸기, 페닐기가 바람직하다.R 1 is specifically exemplified by an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, such as a phenyl group, etc., a methyl group, A phenyl group is preferred.
R2는, 메틸렌기, 에틸렌기, 프로필렌기, 부틸렌기 등의 탄소원자수 1~10의 알킬렌기가 예시되고, 탄소원자수 1~3의 알킬렌기가 바람직하다.Examples of R 2 include alkylene groups having 1 to 10 carbon atoms, such as methylene group, ethylene group, propylene group, and butylene group, and alkylene groups having 1 to 3 carbon atoms are preferable.
(A)성분 중의 1분자 중에 SiH기를 적어도 1개 갖는 (메트)아크릴산에스테르단위의 함유비율은, 10~100질량%가 바람직하고, 20~50질량%가 보다 바람직하다.(A) The content ratio of the (meth)acrylic acid ester unit having at least one SiH group per molecule in the component is preferably 10 to 100% by mass, and more preferably 20 to 50% by mass.
(A)성분은, 상기 (메트)아크릴산에스테르를 2,2’-아조비스이소부티로니트릴(AIBN) 등의 라디칼 중합개시제를 이용하여 (공)중합함으로써 얻어진다.Component (A) is obtained by (co)polymerizing the above-mentioned (meth)acrylic acid ester using a radical polymerization initiator such as 2,2'-azobisisobutyronitrile (AIBN).
(A)성분의 분자량은, 겔 퍼미에이션 크로마토그래피(GPC)로 측정되는 폴리스티렌 환산의 수평균분자량(Mn)으로, 1,000~1,000,000이 바람직하고, 10,000~100,000이 보다 바람직하다(전개용매: 테트라하이드로푸란).The molecular weight of component (A) is the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC), and is preferably 1,000 to 1,000,000, more preferably 10,000 to 100,000 (developing solvent: tetrahydro Puran).
(A)성분의 폴리머에 의한 KSF 형광체의 코팅량(폴리머의 비율)은, 피복 KSF 형광체입자(표면코팅을 갖는 KSF 형광체입자) 전체에 대하여, 폴리머의 비율이 0.1~20질량%이고, 바람직하게는 1~10질량%, 특히 바람직하게는 1~5질량%이다. 코팅량이 적은 경우는, KSF 형광체로부터 발생하는 산성 물질을 차단하는 능력이 열등하고, 코팅량이 많은 경우는 KSF 형광체끼리가 응집하여, LED의 광학특성에 영향이 발생하는 경우가 있거나, 열에 의해 변색되는 경우가 있다.The coating amount (polymer ratio) of the KSF phosphor by the polymer of component (A) is preferably 0.1 to 20% by mass, based on the total of the covered KSF phosphor particles (KSF phosphor particles with a surface coating). is 1 to 10 mass%, particularly preferably 1 to 5 mass%. If the coating amount is small, the ability to block acidic substances generated from the KSF phosphor is inferior, and if the coating amount is large, the KSF phosphor may aggregate with each other, affecting the optical characteristics of the LED or causing discoloration due to heat. There are cases.
[피복 KSF 형광체입자의 제조방법][Method for producing coated KSF phosphor particles]
본 발명의 폴리머에 의한 표면코팅을 갖는 KSF 형광체의 제조방법은, 특별히 한정되지 않고, 공지 기술을 적당히 채용하면 된다.The method for producing the KSF phosphor having a surface coating using the polymer of the present invention is not particularly limited, and known techniques may be appropriately employed.
본 발명의 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자는, 바람직하게는,KSF phosphor particles having a surface coating using the polymer of the present invention are preferably,
(1) (A)(메트)아크릴산에스테르 중합체 및 (B)이 중합체를 용해하는 용제(이하, (B)성분이라고 한다)를 포함하는 코팅 조성물을 준비하고, KSF 형광체입자와, 상기 코팅 조성물을 혼합하는 공정, 및(1) Prepare a coating composition containing (A) a (meth)acrylic acid ester polymer and (B) a solvent for dissolving this polymer (hereinafter referred to as component (B)), and mix the KSF phosphor particles and the coating composition. mixing process, and
(2) 상기 용제를 휘발시키는 공정(2) Process of volatilizing the solvent
을 포함하는 제조방법에 의해 얻어진다.It is obtained by a manufacturing method comprising:
공정(1) 후에 공정(2)을 행할 수도, 공정(1) 및 공정(2)을 동시에 행할 수도 있고, 나아가, 원하는 코팅량에 따라, 공정(1) 및 공정(2)을 반복하여 행할 수도 있다. (A)성분의 조성을 변경하여 공정(1) 및 공정(2)을 반복하여 행함으로써 상이한 코팅층을 갖는 피복 KSF 형광체입자를 얻을 수도 있다.Process (2) may be performed after process (1), process (1) and process (2) may be performed simultaneously, or further, depending on the desired coating amount, process (1) and process (2) may be repeated. there is. By changing the composition of component (A) and repeating steps (1) and (2), coated KSF phosphor particles with different coating layers can be obtained.
공정(1)에 있어서 (A)성분 및 (B)용제를 포함하는 코팅 조성물을 얻으려면, 공지의 교반, 혼합, 용해장치를 이용하면 된다. KSF 형광체입자와 코팅 조성물을 혼합하는 장치로는, 생산 스케일에 따라 설정하면 되고, 스패출러와 플라스크나 증발접시의 조합, 헨셀믹서, 수퍼믹서 등의 교반혼합기를 들 수 있다. 공정(2)에 있어서 KSF 형광체입자와 코팅 조성물의 혼합물로부터 용제를 휘발시키려면, 공지의 교반건조장치를 이용하면 된다. 교반건조장치가 가열수단이나 감압수단을 구비하고 있으면 용제를 효율 좋게 휘발시킬 수 있다. 공정(1) 및 공정(2)을 동시에 행하는 경우에는, KSF 형광체입자, (A)(메트)아크릴산에스테르 중합체 및 (B)용제를 포함하는 코팅 조성물을 충분히 교반, 혼합, 건조하는 수단을 구비한 장치를 이용하면 된다. 이 경우도 상기 장치는 추가로 가열수단이나 감압수단을 구비하고 있을 수 있다.To obtain a coating composition containing component (A) and solvent (B) in step (1), a known stirring, mixing, and dissolving device may be used. The device for mixing KSF phosphor particles and the coating composition can be set according to the production scale and includes a combination of a spatula and a flask or evaporation dish, and a stirring mixer such as a Henschel mixer or super mixer. In step (2), to volatilize the solvent from the mixture of KSF phosphor particles and the coating composition, a known stirring drying device may be used. If the stirring drying device is equipped with a heating means or a pressure reducing means, the solvent can be volatilized efficiently. When performing steps (1) and (2) simultaneously, a coating composition containing KSF phosphor particles, (A) (meth)acrylic acid ester polymer, and (B) solvent is provided with means for sufficiently stirring, mixing, and drying. You can use the device. In this case as well, the device may additionally be equipped with a heating means or a pressure reducing means.
예를 들어, 소량인 경우는, 용기에 KSF 형광체입자를 넣고, 코팅 조성물을 첨가 후, 스패출러 등을 이용하여 교반하면서 용제를 휘발시키는 방법이 있다. 한편, 다량의 KSF 형광체입자를 폴리머코팅하는 경우는, 이배퍼레이터 등의 탈기장치를 구비한 교반장치를 이용하여 코팅하는 것이 가능하다.For example, in the case of a small amount, there is a method of putting KSF phosphor particles in a container, adding the coating composition, and then volatilizing the solvent while stirring using a spatula or the like. On the other hand, when polymer coating a large amount of KSF phosphor particles, it is possible to coat using a stirring device equipped with a degassing device such as an evaporator.
또한, 폴리머코팅 중에 KSF 형광체입자가 응집된 경우는, 용기로부터 일단 취출하고, 분쇄 후, 건조함으로써 응집이 없는 KSF 형광체입자를 얻는 것이 가능하다.Additionally, when the KSF phosphor particles aggregate during polymer coating, it is possible to obtain KSF phosphor particles without agglomeration by taking them out of the container, pulverizing them, and then drying them.
[코팅 조성물][Coating composition]
본 발명의 피복 KSF 형광체입자의 제조방법에 있어서 이용하는 코팅 조성물은, KSF 형광체입자와, 상기 (A)성분 및 (A)성분을 용해하는 용제((B)성분)를 포함한다. 코팅 조성물은, 필요에 따라 (A), (B)성분 이외의 성분을 포함할 수도 있다.The coating composition used in the method for producing coated KSF phosphor particles of the present invention contains KSF phosphor particles, the component (A), and a solvent (component (B)) that dissolves the component (A). The coating composition may contain components other than components (A) and (B) as needed.
[(B)성분][(B) Ingredient]
(B)성분의 용제로는, (A)성분을 용해하고, 코팅 조성물이 균일한 용액으로서 얻어지는 유기용제이면 한정되는 것은 아니고, 공지의 유기용제를 사용할 수 있다. 예를 들어 자일렌, 톨루엔, 벤젠 등의 방향족 탄화수소계 용제, 헵탄, 헥산 등의 지방족 탄화수소계 용제, 트리클로로에틸렌, 퍼클로로에틸렌, 염화메틸렌 등의 할로겐화 탄화수소계 용제, 아세트산에틸 등의 에스테르계 용제, 메틸이소부틸케톤, 메틸에틸케톤, 시클로헥사논 등의 케톤계 용제, 에탄올, 이소프로판올, 부탄올 등의 알코올계 용제, 리그로인 등의 석유계 용제, 디에틸에테르 등의 에테르계 용제, 고무휘발유, 실리콘계 용제 등을 들 수 있다. 이들 중에서, 방향족 탄화수소계 용제, 에스테르계 용제가 바람직하다. 원하는 증발속도에 따라, 1종 단독으로도 2종 이상을 조합하여 혼합용제로서도 이용할 수 있다.The solvent for component (B) is not limited as long as it is an organic solvent that dissolves component (A) and the coating composition is obtained as a uniform solution, and any known organic solvent can be used. For example, aromatic hydrocarbon solvents such as xylene, toluene, and benzene, aliphatic hydrocarbon solvents such as heptane and hexane, halogenated hydrocarbon solvents such as trichlorethylene, perchlorethylene, and methylene chloride, and ester solvents such as ethyl acetate. , ketone-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone, alcohol-based solvents such as ethanol, isopropanol, and butanol, petroleum-based solvents such as ligroin, ether-based solvents such as diethyl ether, rubber gasoline, and silicone-based solvents. Solvents, etc. can be mentioned. Among these, aromatic hydrocarbon-based solvents and ester-based solvents are preferable. Depending on the desired evaporation rate, one type can be used alone or two or more types can be combined and used as a mixed solvent.
(B)성분의 배합량은, 작업성에 맞추어 어떠한 양이어도 되는데, 바람직하게는 코팅 조성물 전체의 70~99.9질량%, 특히 바람직하게는 80~99.5질량%이다.The compounding amount of component (B) may be any amount depending on workability, but is preferably 70 to 99.9% by mass of the entire coating composition, and particularly preferably 80 to 99.5% by mass.
[기타 성분][Other ingredients]
기타 성분으로는, 산화방지제 등을 들 수 있다.Other ingredients include antioxidants and the like.
[경화성 실리콘 조성물][Curable silicone composition]
본 발명의 경화성 실리콘 조성물은, 경화성 실리콘 수지와 상기 피복 KSF 형광체입자를 함유하는 것이다. 경화성 실리콘 수지는 특별히 한정되지 않는데, 예를 들어 KER-2936-A/B(신에쓰화학공업(주)제) 등의 LED 봉지재용인 것을 들 수 있다.The curable silicone composition of the present invention contains a curable silicone resin and the above-mentioned coated KSF phosphor particles. The curable silicone resin is not particularly limited, and examples thereof include those for LED encapsulation materials such as KER-2936-A/B (manufactured by Shin-Etsu Chemical Co., Ltd.).
본 발명의 경화성 실리콘 조성물은, 그 경화물에 있어서, 고온조건하에서의 KSF 형광체에서 유래하는 산성 물질에 의한 실리콘의 분해를 방지할 수 있기 때문에, 예를 들어 광반도체 소자의 봉지재 용도로 유용하다.The curable silicone composition of the present invention can prevent decomposition of silicon by acidic substances derived from KSF phosphors under high temperature conditions in the cured product, and is therefore useful as a sealant for optical semiconductor devices, for example.
[광반도체 장치][Optical semiconductor device]
본 발명은, 상기 경화성 실리콘 조성물의 경화물로 광반도체 소자가 봉지된 광반도체 장치를 제공한다.The present invention provides an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable silicone composition.
본 발명의 피복 KSF 형광체입자는, 고온조건하에 있어서도 KSF 형광체로부터의 산성 물질의 방출이 억제되고, 이 형광체를 함유하는 경화성 실리콘 조성물의 경화물에 있어서, 실리콘 수지의 분해를 방지할 수 있다. 이 때문에, 상기 경화성 실리콘 조성물의 경화물로 광반도체 소자가 봉지된 광반도체 장치는, 고온환경하에서도 광반도체 소자가 안정적으로 봉지되어 있으므로, 경시 열화되기 어렵고 신뢰성이 높다.The coated KSF phosphor particle of the present invention suppresses the release of acidic substances from the KSF phosphor even under high temperature conditions, and can prevent decomposition of the silicone resin in a cured product of a curable silicone composition containing this phosphor. For this reason, an optical semiconductor device in which an optical semiconductor element is encapsulated with a cured product of the curable silicone composition is unlikely to deteriorate over time and has high reliability because the optical semiconductor element is stably encapsulated even in a high temperature environment.
실시예Example
이하, 실시예를 이용하여 본 발명을 구체적으로 설명하는데, 이들 실시예는 본 발명을 전혀 제한하는 것은 아니다. 한편, 코팅 조성물의 불휘발분은, 조성물을 샬레에 1.5g 계량하고, 105℃ 3시간의 조건으로 가열하기 전후의 질량차로부터 산출하였다. 또한, 분자량(수평균분자량Mn, 중량평균분자량Mw)은 GPC측정(전개용매: 테트라하이드로푸란)에 있어서의 폴리스티렌 환산의 값이다. 평균입경은, 레이저회절·산란법에 의해 얻어진 체적 기준의 입도분포에 있어서의 메디안직경(D50)이다.Hereinafter, the present invention will be described in detail using examples, but these examples do not limit the present invention at all. Meanwhile, the non-volatile content of the coating composition was calculated from the difference in mass before and after weighing 1.5 g of the composition in a petri dish and heating it at 105°C for 3 hours. In addition, the molecular weight (number average molecular weight Mn, weight average molecular weight Mw) is a value converted to polystyrene in GPC measurement (developing solvent: tetrahydrofuran). The average particle diameter is the median diameter (D50) in the volume-based particle size distribution obtained by the laser diffraction/scattering method.
[합성예 1][Synthesis Example 1]
메타크릴산메틸 60질량부, 이소프로필알코올(IPA):아세트산에틸=100:500(질량비)의 혼합용제 600질량부, 및 AIBN 0.5질량부를 80℃에서 3시간 교반하여, 메타크릴산메틸 중합체(Mn: 83,540, Mw: 124,550)를 함유하는 코팅 조성물(불휘발분 8.0질량%)을 얻었다.60 parts by mass of methyl methacrylate, 600 parts by mass of a mixed solvent of isopropyl alcohol (IPA):ethyl acetate = 100:500 (mass ratio), and 0.5 parts by mass of AIBN were stirred at 80°C for 3 hours to form a methyl methacrylate polymer ( A coating composition containing (Mn: 83,540, Mw: 124,550) (non-volatile matter: 8.0% by mass) was obtained.
[합성예 2][Synthesis Example 2]
메타크릴산메틸 43질량부, 하기 식으로 표시되는 SiH함유 메타크릴산에스테르 22질량부, IPA:아세트산에틸=100:500(질량비) 혼합용제 600질량부, 및 AIBN 0.5질량부를 80℃에서 3시간 교반하여, SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체(Mn: 49,240, Mw: 103,130)를 함유하는 코팅 조성물(불휘발분 6.0질량%)을 얻었다.43 parts by mass of methyl methacrylate, 22 parts by mass of SiH-containing methacrylic acid ester expressed by the formula below, 600 parts by mass of mixed solvent of IPA:ethyl acetate = 100:500 (mass ratio), and 0.5 parts by mass of AIBN at 80°C for 3 hours. By stirring, a coating composition (non-volatile matter 6.0% by mass) containing SiH group-containing methacrylic acid ester-methyl methacrylate copolymer (Mn: 49,240, Mw: 103,130) was obtained.
0질량%)를 얻었다.0 mass%) was obtained.
[화학식 2][Formula 2]
[실시예 1][Example 1]
KSF 형광체(K2SiF6:Mn4+, D50: 25μm) 5g을 플라스크에 넣고, 합성예 1에서 얻어진 메타크릴산메틸 중합체를 함유하는 코팅 조성물을 1g 첨가하고, 스패출러를 이용하여 혼합을 행하였다. 용제를 휘발시키면서 5분간 혼합을 계속하여, 폴리머에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. 폴리머코팅을 갖는 KSF 형광체 전체에 대한 메타크릴산메틸 중합체의 코팅량은 1.6질량%였다.5 g of KSF phosphor (K 2 SiF 6 :Mn 4+ , D50: 25 μm) was placed in a flask, 1 g of the coating composition containing the methyl methacrylate polymer obtained in Synthesis Example 1 was added, and mixing was performed using a spatula. did. Mixing was continued for 5 minutes while volatilizing the solvent, and a KSF phosphor with a polymer surface coating was obtained. The coating amount of methyl methacrylate polymer for the entire KSF phosphor with polymer coating was 1.6% by mass.
[실시예 2][Example 2]
KSF 형광체(K2SiF6:Mn4+, D50: 25μm) 5g을 플라스크에 넣고, 합성예 2에서 얻어진 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체를 함유하는 코팅 조성물을 1g 첨가하고, 스패출러를 이용하여 혼합을 행하였다. 용제를 휘발시키면서 5분간 혼합을 계속하여, 폴리머에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. 폴리머코팅을 갖는 KSF 형광체 전체에 대한 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체의 코팅량은 1.2질량%였다.5 g of KSF phosphor (K 2 SiF 6 :Mn 4+ , D50: 25 μm) was placed in a flask, and 1 g of the coating composition containing the SiH group-containing methacrylic acid ester-methyl methacrylate copolymer obtained in Synthesis Example 2 was added. , mixing was performed using a spatula. Mixing was continued for 5 minutes while volatilizing the solvent, and a KSF phosphor with a polymer surface coating was obtained. The coating amount of SiH group-containing methacrylic acid ester-methyl methacrylate copolymer for the entire KSF phosphor with polymer coating was 1.2% by mass.
[실시예 3][Example 3]
실시예 2와 동일한 조작을 반복하여 3회 행해서, 폴리머에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. 폴리머코팅을 갖는 KSF 형광체 전체에 대한 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체의 코팅량은 3.6질량%였다.The same operation as in Example 2 was repeated three times to obtain a KSF phosphor with a polymer surface coating. The coating amount of SiH group-containing methacrylic acid ester-methyl methacrylate copolymer for the entire KSF phosphor with polymer coating was 3.6% by mass.
[비교예 1][Comparative Example 1]
KSF 형광체(K2SiF6:Mn4+, D50: 25μm) 5g을 플라스크에 넣고, 합성예 2에서 얻어진 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체를 함유하는 코팅 조성물을 0.05g 첨가하고, 스패출러를 이용하여 혼합을 행하였다. 용제를 휘발시키면서 5분간 혼합을 계속하여, 폴리머에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. 폴리머코팅을 갖는 KSF 형광체 전체에 대한 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체의 코팅량은 0.06질량%였다.5 g of KSF phosphor (K 2 SiF 6 :Mn 4+ , D50: 25 μm) was placed in a flask, and 0.05 g of the coating composition containing the SiH group-containing methacrylic acid ester-methyl methacrylate copolymer obtained in Synthesis Example 2 was added. And mixing was performed using a spatula. Mixing was continued for 5 minutes while volatilizing the solvent, and a KSF phosphor with a polymer surface coating was obtained. The coating amount of SiH group-containing methacrylic acid ester-methyl methacrylate copolymer for the entire KSF phosphor with polymer coating was 0.06% by mass.
[비교예 2][Comparative Example 2]
KSF 형광체(K2SiF6:Mn4+, D50: 25μm) 5g을 플라스크에 넣고, 합성예 2에서 얻어진 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체를 함유하는 코팅 조성물을 20g 첨가하고, 스패출러를 이용하여 혼합을 행하였다. 용제를 휘발시키면서 30분간 혼합을 계속 후, 샬레 위에 얇게 펴서 25℃에서 12시간 자연건조시켜, 폴리머에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. 폴리머코팅을 갖는 KSF 형광체 전체에 대한 SiH기함유 메타크릴산에스테르-메타크릴산메틸 공중합체의 코팅량은 26질량%였다.5 g of KSF phosphor (K 2 SiF 6 :Mn 4+ , D50: 25 μm) was placed in a flask, and 20 g of the coating composition containing the SiH group-containing methacrylic acid ester-methyl methacrylate copolymer obtained in Synthesis Example 2 was added. , mixing was performed using a spatula. After continuing mixing for 30 minutes while volatilizing the solvent, it was spread thinly on a petri dish and dried naturally at 25°C for 12 hours to obtain a KSF phosphor with a polymer surface coating. The coating amount of SiH group-containing methacrylic acid ester-methyl methacrylate copolymer for the entire KSF phosphor with polymer coating was 26% by mass.
[비교예 3][Comparative Example 3]
KSF 형광체(K2SiF6:Mn4+, D50: 25μm) 5g을 플라스크에 넣고, 메타크릴옥시프로필트리메톡시실란의 1질량% 아세톤 용액을 10g 첨가하고, 스패출러를 이용하여 혼합을 행하였다. 용제를 휘발시키면서 30분간 혼합을 계속 후, 샬레 위에 얇게 펴서 25℃에서 12시간 자연건조시켜, 실란커플링제에 의한 표면코팅을 갖는 KSF 형광체를 얻었다. KSF 형광체 전체에 대한 실란커플링제의 코팅량은 2질량%였다.5 g of KSF phosphor (K 2 SiF 6 :Mn 4+ , D50: 25 μm) was placed in a flask, 10 g of a 1% by mass acetone solution of methacryloxypropyltrimethoxysilane was added, and mixing was performed using a spatula. . After continuing to mix for 30 minutes while volatilizing the solvent, it was spread thinly on a petri dish and dried naturally at 25°C for 12 hours to obtain a KSF phosphor with a surface coating using a silane coupling agent. The coating amount of silane coupling agent for the entire KSF phosphor was 2% by mass.
실시예 1~3 및 비교예 1~3에서 얻어진 폴리머 및 실란커플링제에 의한 표면코팅을 갖는 KSF 형광체, 그리고, 표면코팅을 갖지 않는 KSF 형광체(비교예 4)에 대하여, 이하의 내열시험을 행한 결과를 표 1에 나타낸다.The following heat resistance test was performed on the KSF phosphor having a surface coating using the polymer and silane coupling agent obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and the KSF phosphor without a surface coating (Comparative Example 4). The results are shown in Table 1.
[내열시험][Heat resistance test]
폴리에틸렌제 용기에, LED용 경화성 실리콘 수지(KER-2936-A/B, 신에쓰화학공업(주)제) 2g과, KSF 형광체 0.4g을 넣고, 혼합한 후, 알루미늄샬레에 0.8g을 각각 칭량하여 취하고, 200℃의 환경에 100시간 및 300시간 노출한 후의 외관 및 질량의 변화에 의해 내열성을 평가하였다. 외관에 대해서는 육안으로 색을 관찰하고, 질량변화율은, (소정시간 후의 질량-0시간의 시점에서의 질량)/0시간의 시점에서의 질량×100(%)으로 하여 산출하였다.In a polyethylene container, add 2 g of curable silicone resin for LED (KER-2936-A/B, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.4 g of KSF phosphor, mix, and weigh 0.8 g of each in an aluminum dish. was taken, and heat resistance was evaluated based on changes in appearance and mass after exposure to an environment at 200°C for 100 and 300 hours. Regarding the appearance, the color was observed with the naked eye, and the mass change rate was calculated as (mass after a predetermined time - mass at 0 hours)/mass at 0 hours x 100 (%).
[표 1][Table 1]
표 1에 나타내는 바와 같이, 실시예 1~3에서 얻어진 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자에 관해서는, 200℃, 300시간 후에 있어서도, 외관은 동등하고, 중량변화도 매우 작아 양호한 결과인 것에 반해, 비교예 1과 같은 코팅량이 적은 KSF 형광체입자를 사용한 경우, 비교예 3과 같은 실란커플링제에 의한 표면코팅을 갖는 KSF 형광체를 사용한 경우 및 비교예 4와 같은 표면코팅을 갖지 않는 KSF 형광체를 사용한 경우는, 실리콘 수지의 분해에 의한 질량감소가 매우 컸다. 또한, 비교예 2와 같은 코팅량이 지나치게 많은 KSF 형광체입자를 사용한 경우는, 메타크릴산에스테르 중합체 자체의 변색이 발생하기 때문에, 광반도체 장치의 봉지재에의 적용은 곤란하였다.As shown in Table 1, regarding the KSF phosphor particles having a surface coating using the polymer obtained in Examples 1 to 3, even after 300 hours at 200°C, the appearance was the same and the weight change was very small, showing good results. On the other hand, when KSF phosphor particles with a small coating amount as in Comparative Example 1 were used, when KSF phosphor particles with a surface coating by a silane coupling agent as in Comparative Example 3 were used, and when KSF phosphor without a surface coating as in Comparative Example 4 were used. When used, the mass loss due to decomposition of the silicone resin was very large. In addition, when KSF phosphor particles with an excessively large coating amount as in Comparative Example 2 were used, discoloration of the methacrylic acid ester polymer itself occurred, making application to the encapsulation material of optical semiconductor devices difficult.
한편, 본 발명은, 상기 실시형태로 한정되는 것은 아니다. 상기 실시형태는 예시이며, 본 발명의 특허청구범위에 기재된 기술적 사상과 실질적으로 동일한 구성을 갖고, 동일한 작용 효과를 나타내는 것은, 어떠한 것이어도 본 발명의 기술적 범위에 포함된다.Meanwhile, the present invention is not limited to the above embodiments. The above-mentioned embodiment is an example, and anything that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits the same operation and effect is included in the technical scope of the present invention.
Claims (8)
상기 피복 KSF 형광체입자는 폴리머에 의한 표면코팅을 갖는 KSF 형광체입자이며, 상기 폴리머가, (메트)아크릴산에스테르 중합체이고, 상기 폴리머의 비율이, 상기 피복 KSF 형광체입자 전체의 0.1~20질량%의 범위인 것을 특징으로 하는 피복 KSF 형광체입자.As a coated KSF phosphor particle,
The covered KSF phosphor particles are KSF phosphor particles having a surface coating by a polymer, the polymer is a (meth)acrylic acid ester polymer, and the proportion of the polymer is in the range of 0.1 to 20% by mass of the total of the covered KSF phosphor particles. Coated KSF phosphor particles, characterized in that.
상기 KSF 형광체가, K2SiF6:Mn4+로 표시되는 형광체인 것을 특징으로 하는 피복 KSF 형광체입자.According to paragraph 1,
A covered KSF phosphor particle, characterized in that the KSF phosphor is a phosphor represented by K 2 SiF 6 :Mn 4+ .
상기 (메트)아크릴산에스테르 중합체가, 1분자 중에 규소원자에 직접 결합한 수소원자를 1개 이상 갖는 (메트)아크릴산에스테르를 구성단위에 포함하는 것을 특징으로 하는 피복 KSF 형광체입자.According to claim 1 or 2,
Coated KSF phosphor particles, wherein the (meth)acrylic acid ester polymer contains as a structural unit a (meth)acrylic acid ester having at least one hydrogen atom directly bonded to a silicon atom in one molecule.
(1) (A)(메트)아크릴산에스테르 중합체 및 (B)이 중합체를 용해하는 용제를 포함하는 코팅 조성물을 준비하고, KSF 형광체입자와, 상기 코팅 조성물을 혼합하는 공정, 및
(2) 상기 용제를 휘발시키는 공정
을 포함하는 것을 특징으로 하는 피복 KSF 형광체입자의 제조방법.A method for producing the coated KSF phosphor particles according to claim 1,
(1) preparing a coating composition containing (A) a (meth)acrylic acid ester polymer and (B) a solvent dissolving the polymer, mixing the KSF phosphor particles and the coating composition, and
(2) Process of volatilizing the solvent
A method for producing coated KSF phosphor particles comprising:
상기 KSF 형광체로서, K2SiF6:Mn4+로 표시되는 형광체를 이용하는 것을 특징으로 하는 피복 KSF 형광체입자의 제조방법.According to clause 4,
A method for producing coated KSF phosphor particles, characterized in that a phosphor represented by K 2 SiF 6 :Mn 4+ is used as the KSF phosphor.
상기 (메트)아크릴산에스테르 중합체로서, 1분자 중에 규소원자에 직접 결합한 수소원자를 1개 이상 갖는 (메트)아크릴산에스테르를 구성단위에 포함하는 중합체를 이용하는 것을 특징으로 하는 피복 KSF 형광체입자의 제조방법.According to clause 4 or 5,
A method for producing coated KSF phosphor particles, characterized in that, as the (meth)acrylic acid ester polymer, a polymer containing as a structural unit a (meth)acrylic acid ester having at least one hydrogen atom directly bonded to a silicon atom in one molecule is used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021147013A JP2023039744A (en) | 2021-09-09 | 2021-09-09 | Clad ksf phosphor, manufacturing method of phosphor, curable silicone composition containing phosphor and light semiconductor device |
| JPJP-P-2021-147013 | 2021-09-09 | ||
| PCT/JP2022/030930 WO2023037831A1 (en) | 2021-09-09 | 2022-08-16 | Coated ksf phosphor, method for producing same, curable silicone composition containing same, and opto-semiconductor device |
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| JP (1) | JP2023039744A (en) |
| KR (1) | KR20240055739A (en) |
| CN (1) | CN117858933A (en) |
| TW (1) | TW202328379A (en) |
| WO (1) | WO2023037831A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012224536A (en) | 2011-04-08 | 2012-11-15 | Shin-Etsu Chemical Co Ltd | Method of manufacturing complex fluoride and complex fluoride fluorescent material |
| WO2015093430A1 (en) | 2013-12-17 | 2015-06-25 | 電気化学工業株式会社 | Method for producing fluorescent substance |
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| MY181973A (en) * | 2012-12-28 | 2021-01-15 | Shinetsu Chemical Co | Phosphor surface treatment method |
| KR102337406B1 (en) * | 2014-12-09 | 2021-12-13 | 삼성전자주식회사 | Fluoride phosphor, method of manufacturing the same, light emitting device, display apparatus and illumination apparatus |
| US20170125650A1 (en) * | 2015-11-02 | 2017-05-04 | Nanoco Technologies Ltd. | Display devices comprising green-emitting quantum dots and red KSF phosphor |
| WO2017094832A1 (en) * | 2015-12-04 | 2017-06-08 | 東レ株式会社 | Fluorescent sheet, light-emitting element using same, light source unit, display, and production method for light-emitting element |
| US11008509B2 (en) * | 2016-06-27 | 2021-05-18 | Current Lighting Solutions, Llc | Coated manganese doped phosphors |
| JPWO2020255881A1 (en) * | 2019-06-21 | 2020-12-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012224536A (en) | 2011-04-08 | 2012-11-15 | Shin-Etsu Chemical Co Ltd | Method of manufacturing complex fluoride and complex fluoride fluorescent material |
| WO2015093430A1 (en) | 2013-12-17 | 2015-06-25 | 電気化学工業株式会社 | Method for producing fluorescent substance |
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| JP2023039744A (en) | 2023-03-22 |
| CN117858933A (en) | 2024-04-09 |
| WO2023037831A1 (en) | 2023-03-16 |
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