JP2016194088A - Method for producing coated phosphor - Google Patents
Method for producing coated phosphor Download PDFInfo
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- JP2016194088A JP2016194088A JP2016137348A JP2016137348A JP2016194088A JP 2016194088 A JP2016194088 A JP 2016194088A JP 2016137348 A JP2016137348 A JP 2016137348A JP 2016137348 A JP2016137348 A JP 2016137348A JP 2016194088 A JP2016194088 A JP 2016194088A
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- phosphor
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- oxide powder
- silicon dioxide
- sulfide
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 122
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 61
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 14
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- 239000000203 mixture Substances 0.000 claims abstract description 4
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- 239000002245 particle Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 9
- -1 alkoxysilane Chemical compound 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 47
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 41
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
Description
本発明は、被覆材料によって蛍光体が被覆されている被覆蛍光体の製造方法に関するものである。 The present invention relates to a method for producing a coated phosphor in which a phosphor is coated with a coating material.
従来、硫化物蛍光体は、水などによって加水分解反応が起こり、酸化物や水酸化物に変化してしまい、著しく発光強度、輝度等の特性が落ちることが知られている。 Conventionally, it is known that sulfide phosphors undergo a hydrolysis reaction due to water or the like and change into oxides or hydroxides, and characteristics such as emission intensity and luminance are significantly reduced.
特許文献１及び特許文献２には、ゾルゲル法により、金属アルコキシドを用いて蛍光体表面を二酸化ケイ素で被覆することによって、蛍光体を水と触れさせないようにし、加水分解による蛍光体の劣化を防ぎ、蛍光体の特性（発光強度、輝度等）を維持することが記載されている。 In Patent Document 1 and Patent Document 2, the surface of a phosphor is coated with silicon dioxide using a metal alkoxide by a sol-gel method so that the phosphor does not come into contact with water, and deterioration of the phosphor due to hydrolysis is prevented. And maintaining the characteristics (emission intensity, luminance, etc.) of the phosphor.
しかしながら、特許文献１及び特許文献２に記載の方法により耐湿を行ったとしても、耐湿が不完全であり、高温高湿下においては、硫化物蛍光体が水と反応してしまい、硫化物蛍光体から硫化水素等の硫黄系ガスが放出されてしまう。硫黄系ガスが放出されてしまうと、電子材料系において電極等が腐食され、導電性の悪化等を招いてしまう。 However, even if moisture resistance is performed by the methods described in Patent Document 1 and Patent Document 2, the moisture resistance is incomplete, and under high temperature and high humidity, the sulfide phosphor reacts with water, and the sulfide fluorescence. Sulfur-based gas such as hydrogen sulfide is released from the body. When the sulfur-based gas is released, the electrodes and the like are corroded in the electronic material system, leading to deterioration of conductivity.
本発明は、このような実情に鑑みて提案されたものであり、高温高湿下において硫黄系ガスの放出を抑制することができる被覆蛍光体及び被覆蛍光体の製造方法を提供することを目的とする。 The present invention has been proposed in view of such circumstances, and an object of the present invention is to provide a coated phosphor and a method for producing the coated phosphor that can suppress the release of sulfur-based gas under high temperature and high humidity. And
本発明に係る被覆蛍光体の製造方法は、硫化物蛍光体とアルコキシシランと酸化亜鉛粉末と触媒とを溶媒中で混合して得られた混合液を固相と液相とに分離し、分離した固相を乾燥し、１５０〜２５０℃で焼成処理することにより、酸化亜鉛粉末が含有され上記アルコキシシランから形成される二酸化ケイ素膜によって硫化物蛍光体を被覆させる混合工程を有する。 The method for producing a coated phosphor according to the present invention separates a mixed solution obtained by mixing a sulfide phosphor, an alkoxysilane, a zinc oxide powder, and a catalyst in a solvent into a solid phase and a liquid phase, and separates them. The mixed solid phase is dried and baked at 150 to 250 ° C., whereby a sulfide phosphor is coated with a silicon dioxide film containing zinc oxide powder and formed from the alkoxysilane.
本発明によれば、硫化物蛍光体の加水分解によって硫化物蛍光体から放出される硫黄系ガスが金属酸化物粉末に吸着されるため、高温高湿下において硫黄系ガスの放出を抑制することができる。 According to the present invention, since the sulfur-based gas released from the sulfide phosphor by the hydrolysis of the sulfide phosphor is adsorbed by the metal oxide powder, the release of the sulfur-based gas under high temperature and high humidity is suppressed. Can do.
以下、本発明の実施の形態（以下、「本実施の形態」という。）について、図面を参照しながら下記順序にて詳細に説明する。
１．被覆蛍光体（図１〜図５）
２．被覆蛍光体の製造方法
３．被覆蛍光体の適用例（図６〜図８）
４．実施例（図９、図１０）
Hereinafter, embodiments of the present invention (hereinafter referred to as “present embodiments”) will be described in detail in the following order with reference to the drawings.
1. Coated phosphor (FIGS. 1 to 5)
2. 2. Method for producing coated phosphor Application examples of coated phosphor (FIGS. 6 to 8)
4). Example (FIGS. 9 and 10)
＜１．被覆蛍光体＞
本実施の形態に係る被覆蛍光体１は、例えば図１に示すように、硫化物蛍光体２が、金属酸化物粉末３が含有された二酸化ケイ素膜４によって被覆されている。金属酸化物粉末３が含有された二酸化ケイ素膜４によって硫化物蛍光体２が被覆されていることにより、硫化物蛍光体２の加水分解によって硫化物蛍光体２から放出される硫黄系ガスが、金属酸化物粉末３に吸着される。そのため、例えば高温高湿下において硫化物蛍光体２からの硫黄系ガスの放出を抑制することができる。したがって、例えば、電子材料系において電極等が腐食され、導電性の悪化等を招いてしまうことを防止することができる。なお、被覆蛍光体１は、図１に示すように、単位粒子と考えられるものを一次粒子としたときに、図２に示すように、一次粒子が２以上連結した二次粒子であってもよい。
<1. Coated phosphor>
In the coated phosphor 1 according to the present embodiment, for example, as shown in FIG. 1, a sulfide phosphor 2 is covered with a silicon dioxide film 4 containing a metal oxide powder 3. By covering the sulfide phosphor 2 with the silicon dioxide film 4 containing the metal oxide powder 3, the sulfur-based gas released from the sulfide phosphor 2 by hydrolysis of the sulfide phosphor 2 is Adsorbed on the metal oxide powder 3. Therefore, for example, release of sulfur-based gas from the sulfide phosphor 2 can be suppressed under high temperature and high humidity. Therefore, for example, it is possible to prevent the electrodes and the like from being corroded in the electronic material system, resulting in deterioration of conductivity. As shown in FIG. 1, the coated phosphor 1 may be a secondary particle in which two or more primary particles are connected as shown in FIG. Good.
硫化物蛍光体２としては、特に限定されないが、例えば、ＳｒＧａ２Ｓ４：ＥｕやＣａＳ：Ｅｕが用いられる。硫化物蛍光体２は、例えば、メジアン径（ｄ５０）が、５〜１５μｍ程度のものを用いることができる。 The sulfide phosphor 2 is not particularly limited, for example, SrGa 2 S 4: Eu and CaS: Eu is used. As the sulfide phosphor 2, for example, one having a median diameter (d 50 ) of about 5 to 15 μm can be used.
金属酸化物粉末３としては、硫黄系ガス、例えば、硫化水素を吸着する能力に優れ、硫黄系ガスの抑制効果を奏することができるものが好ましい。このような金属酸化物粉末３としては、例えば、酸化亜鉛粉末や酸化アルミニウム（Ａｌ２Ｏ３）粉末が挙げられ、特に、硫黄系ガスの抑制効果をより効果的に奏することができる観点から、酸化亜鉛粉末を用いることが好ましい。また、金属酸化物粉末３としては、表面処理を施したものを用いてもよい。 The metal oxide powder 3 is preferably one that has an excellent ability to adsorb a sulfur-based gas, for example, hydrogen sulfide, and can exhibit a sulfur-based gas suppressing effect. Examples of such metal oxide powder 3 include zinc oxide powder and aluminum oxide (Al 2 O 3 ) powder, and in particular, from the viewpoint of more effectively exhibiting the sulfur-based gas suppression effect. It is preferable to use zinc oxide powder. Moreover, as the metal oxide powder 3, a surface-treated powder may be used.
金属酸化物粉末３は、粒径が０．２μｍ以下であることが好ましい。金属酸化物粉末３の粒径を０．２μｍ以下とすることにより、硫化物蛍光体２の加水分解によって硫化物蛍光体２から放出される硫黄系ガスを、金属酸化物粉末３が吸着する能力が乏しくならないようにすることができる。これにより、硫化物蛍光体２からの硫黄系ガスの放出を効果的に抑制することができる。 The metal oxide powder 3 preferably has a particle size of 0.2 μm or less. The ability of the metal oxide powder 3 to adsorb the sulfur-based gas released from the sulfide phosphor 2 by hydrolysis of the sulfide phosphor 2 by setting the particle size of the metal oxide powder 3 to 0.2 μm or less. Can be kept from becoming scarce. Thereby, discharge | release of the sulfur type gas from the sulfide fluorescent substance 2 can be suppressed effectively.
金属酸化物粉末３の量は、１００質量部の硫化物蛍光体２に対して、１質量部以上、２０質量部未満とすることが好ましく、５質量部以上、１０質量部以下とすることがより好ましい。１００質量部の硫化物蛍光体２に対して、金属酸化物粉末３の量を１質量部以上とすることにより、金属酸化物粉末３の有効な吸着作用を得ることができる、すなわち、金属酸化物粉末３が硫黄系ガスを吸着する能力が乏しくならないようにすることができる。また、１００質量部の硫化物蛍光体２に対して、金属酸化物粉末３の量を２０質量部未満とすることにより、硫化物蛍光体２の特性、例えばピーク強度や輝度が低下してしまうことを防止することができる。 The amount of the metal oxide powder 3 is preferably 1 part by mass or more and less than 20 parts by mass, preferably 5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the sulfide phosphor 2. More preferred. By setting the amount of the metal oxide powder 3 to 1 part by mass or more with respect to 100 parts by mass of the sulfide phosphor 2, an effective adsorption action of the metal oxide powder 3 can be obtained. It is possible to prevent the product powder 3 from having a poor ability to adsorb sulfur-based gas. Further, when the amount of the metal oxide powder 3 is less than 20 parts by mass with respect to 100 parts by mass of the sulfide phosphor 2, the characteristics of the sulfide phosphor 2, such as peak intensity and luminance, are reduced. This can be prevented.
二酸化ケイ素膜４は、硫化物蛍光体２の表面に形成され、硫化物蛍光体２の表面を被覆する。硫化物蛍光体２を二酸化ケイ素膜４によって被覆させることにより、硫化物蛍光体２が水と触れないようにして、加水分解によって硫化物蛍光体２が劣化してしまうことを防止することができる。これにより、硫化物蛍光体２の特性、例えば、発光強度や輝度が低下してしまうことを防止することができ、硫化物蛍光体２の特性を維持することができる。二酸化ケイ素膜４は、例えば、アルコキシシランの加水分解（ゾルゲル法）によって生成されている。 The silicon dioxide film 4 is formed on the surface of the sulfide phosphor 2 and covers the surface of the sulfide phosphor 2. By covering the sulfide phosphor 2 with the silicon dioxide film 4, it is possible to prevent the sulfide phosphor 2 from deteriorating due to hydrolysis so that the sulfide phosphor 2 does not come into contact with water. . Thereby, it is possible to prevent the characteristics of the sulfide phosphor 2, for example, the emission intensity and luminance from being lowered, and the characteristics of the sulfide phosphor 2 can be maintained. The silicon dioxide film 4 is produced, for example, by hydrolysis (sol-gel method) of alkoxysilane.
二酸化ケイ素膜４の厚さは、二酸化ケイ素膜４によって金属酸化物粉末３が覆われる程度とすることが好ましい。例えば、粒径が０．２μｍ以下の金属酸化物粉末３を用いた場合には、二酸化ケイ素膜４の厚さは、５０〜１５０ｎｍとすることが好ましい。二酸化ケイ素膜４の厚さを５０ｎｍ以上とすることにより、加水分解によって硫化物蛍光体２が劣化してしまうことをより効果的に防止することができる。また、二酸化ケイ素膜４の厚さを１５０ｎｍ以下とすることにより、硫化物蛍光体２の特性、例えばピーク強度や輝度が低下してしまうことを防止することができる。 The thickness of the silicon dioxide film 4 is preferably such that the metal oxide powder 3 is covered with the silicon dioxide film 4. For example, when the metal oxide powder 3 having a particle size of 0.2 μm or less is used, the thickness of the silicon dioxide film 4 is preferably 50 to 150 nm. By setting the thickness of the silicon dioxide film 4 to 50 nm or more, it is possible to more effectively prevent the sulfide phosphor 2 from being deteriorated by hydrolysis. Further, by setting the thickness of the silicon dioxide film 4 to 150 nm or less, it is possible to prevent the characteristics of the sulfide phosphor 2 such as peak intensity and luminance from being lowered.
上述したように、被覆蛍光体１は、金属酸化物粉末３が含有された二酸化ケイ素膜４によって硫化物蛍光体２が被覆されていることにより、硫化物蛍光体２の加水分解によって硫化物蛍光体２から放出される硫黄系ガスが金属酸化物粉末３に吸着される。そのため、例えば高温高湿下において硫化物蛍光体２からの硫黄系ガスの放出を抑制することができる。 As described above, in the coated phosphor 1, the sulfide phosphor 2 is coated with the silicon dioxide film 4 containing the metal oxide powder 3, so that the sulfide phosphor 2 is hydrolyzed by the hydrolysis of the sulfide phosphor 2. The sulfur-based gas released from the body 2 is adsorbed by the metal oxide powder 3. Therefore, for example, release of sulfur-based gas from the sulfide phosphor 2 can be suppressed under high temperature and high humidity.
また、被覆蛍光体１は、金属酸化物粉末３が含有された二酸化ケイ素膜４によって硫化物蛍光体２が被覆されていることにより、硫化物蛍光体２が水と触れないようにして、加水分解によって硫化物蛍光体２が劣化してしまうことを防止することができる。これにより、硫化物蛍光体２の特性が低下してしまうことを防止することができる。 Further, the coated phosphor 1 is coated with the sulfide phosphor 2 by the silicon dioxide film 4 containing the metal oxide powder 3, so that the sulfide phosphor 2 does not come into contact with water so as to be in contact with water. It is possible to prevent the sulfide phosphor 2 from deteriorating due to the decomposition. Thereby, it can prevent that the characteristic of sulfide fluorescent substance 2 falls.
なお、被覆蛍光体１は、図３〜図５に示すように、硫化物蛍光体２が、二層以上の二酸化ケイ素膜４によって被覆されており、少なくともいずれかの二酸化ケイ素膜４中に金属酸化物粉末３が含有されていてもよい。 As shown in FIGS. 3 to 5, in the coated phosphor 1, the sulfide phosphor 2 is covered with two or more layers of silicon dioxide film 4, and at least one of the silicon dioxide films 4 has a metal Oxide powder 3 may be contained.
図３に示すように、被覆蛍光体１は、硫化物蛍光体２上に、二層の二酸化ケイ素膜４、すなわち、金属酸化物粉末３が含有された二酸化ケイ素膜４Ａと、金属酸化物粉末３が含有された二酸化ケイ素膜４Ｂとがこの順番で被覆されていてもよい。また、図４に示すように、被覆蛍光体１は、硫化物蛍光体２上に、金属酸化物粉末３が含有された二酸化ケイ素膜４Ａと、シリカ皮膜、すなわち、金属酸化物粉末３が含有されていない二酸化ケイ素膜４Ｂとがこの順番で被覆されていてもよい。さらに、図５に示すように、被覆蛍光体１は、硫化物蛍光体２上に、金属酸化物粉末３が含有されていない二酸化ケイ素膜４Ａと、金属酸化物粉末３が含有された二酸化ケイ素膜４Ｂとがこの順番で被覆されていてもよい。 As shown in FIG. 3, the coated phosphor 1 includes a two-layered silicon dioxide film 4 on a sulfide phosphor 2, that is, a silicon dioxide film 4 A containing a metal oxide powder 3, and a metal oxide powder. The silicon dioxide film 4B containing 3 may be coated in this order. As shown in FIG. 4, the coated phosphor 1 includes a silicon dioxide film 4 </ b> A containing a metal oxide powder 3 and a silica film, that is, a metal oxide powder 3 on a sulfide phosphor 2. The silicon dioxide film 4B that has not been formed may be coated in this order. Further, as shown in FIG. 5, the coated phosphor 1 includes a silicon dioxide film 4 </ b> A that does not contain the metal oxide powder 3 and a silicon dioxide that contains the metal oxide powder 3 on the sulfide phosphor 2. The film 4B may be coated in this order.
これらの図３〜図５に示す被覆蛍光体１の中では、例えば高温高湿下において硫化物蛍光体２からの硫黄系ガスの放出をより効果的に抑制する観点から、少なくとも二酸化ケイ素膜４Ｂに金属酸化物粉末３が含有されている図３及び図５に示すものが好ましい。すなわち、最表面側の二酸化ケイ素膜４Ｂに金属酸化物粉末３が含有されている被覆蛍光体１が好ましい。 Among these coated phosphors 1 shown in FIGS. 3 to 5, at least the silicon dioxide film 4 </ b> B from the viewpoint of more effectively suppressing the release of sulfur-based gas from the sulfide phosphor 2 under high temperature and high humidity, for example. The metal oxide powder 3 is preferably shown in FIGS. 3 and 5. That is, the coated phosphor 1 in which the metal oxide powder 3 is contained in the outermost silicon dioxide film 4B is preferable.
＜２．被覆蛍光体の製造方法＞
本実施の形態に係る被覆蛍光体の製造方法は、硫化物蛍光体２と、アルコキシシランと、金属酸化物粉末３と、触媒とを溶媒中で混合し、金属酸化物粉末３が含有されアルコキシシランから形成される二酸化ケイ素膜４によって硫化物蛍光体２を被覆させる混合工程を有する。次いで、本実施の形態に係る被覆蛍光体の製造方法は、混合液を固相と液相とに分離する分離工程を有する。
<2. Method for producing coated phosphor>
In the method for producing a coated phosphor according to the present embodiment, a sulfide phosphor 2, an alkoxysilane, a metal oxide powder 3, and a catalyst are mixed in a solvent, and the metal oxide powder 3 is contained in the alkoxy. A mixing step of covering the sulfide phosphor 2 with the silicon dioxide film 4 formed of silane; Next, the method for manufacturing the coated phosphor according to the present embodiment includes a separation step of separating the mixed solution into a solid phase and a liquid phase.
（混合工程）
アルコキシシランは、エトキシド、メトキシド、イソプロポキシド等から選択することができ、例えば、テトラエトキシシランやテトラメトキシシランが挙げられる。また、アルコキシシランは、ポリエチルシリケート等のアルコキシシランオリゴマーや加水分解縮合物であってもよい。さらに、アルコキシシランは、アルキルアルコキシシラン等のように、ゾルゲル反応に寄与しないアルキル基、アミノ基、メルカプト基等を有するシランカップリング剤を用いてもよい。
(Mixing process)
The alkoxysilane can be selected from ethoxide, methoxide, isopropoxide and the like, and examples thereof include tetraethoxysilane and tetramethoxysilane. The alkoxysilane may be an alkoxysilane oligomer such as polyethyl silicate or a hydrolysis condensate. Further, as the alkoxysilane, a silane coupling agent having an alkyl group, an amino group, a mercapto group, or the like that does not contribute to the sol-gel reaction, such as an alkylalkoxysilane, may be used.
溶媒は、特に限定されず、例えば、水、有機溶媒等を用いることができる。有機溶媒としては、アルコール、エーテル、ケトン、多価アルコール類等を用いることができる。アルコールとしては、メタノール、エタノール、プロパノール、ペンタノール等を用いることができる。多価アルコール類としては、エチレングリコール、プロピレングリコール、ジエチレングリコール等を用いることができる。また、溶媒は、二種以上を組み合わせたものを用いてもよい。 A solvent is not specifically limited, For example, water, an organic solvent, etc. can be used. As the organic solvent, alcohol, ether, ketone, polyhydric alcohol and the like can be used. As the alcohol, methanol, ethanol, propanol, pentanol and the like can be used. As polyhydric alcohols, ethylene glycol, propylene glycol, diethylene glycol and the like can be used. Moreover, what combined 2 or more types may be used for a solvent.
触媒は、アルコキシシランの加水分解や重縮合反応を開始させるためのものであり、例えば、酸性触媒や塩基性触媒を用いることができる。酸性触媒しては、塩酸、硫酸、ホウ酸、硝酸、過塩素酸、テトラフルオロホウ酸、ヘキサフルオロ砒素酸、臭化水素酸、酢酸、シュウ酸、メタンスルホン酸等が挙げられる。塩基性触媒としては、水酸化ナトリウムなどのアルカリ金属の水酸化物、アンモニア等が挙げられる。これらの触媒の中では、硫化物蛍光体２の劣化を効果的に防止する観点から、塩基性触媒を用いることが好ましい。なお、触媒としては、これらの酸性触媒や塩基性触媒を二種以上併用してもよい。 The catalyst is for initiating hydrolysis or polycondensation reaction of alkoxysilane. For example, an acidic catalyst or a basic catalyst can be used. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, boric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, acetic acid, oxalic acid, methanesulfonic acid and the like. Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, ammonia and the like. Among these catalysts, it is preferable to use a basic catalyst from the viewpoint of effectively preventing the deterioration of the sulfide phosphor 2. As the catalyst, two or more of these acidic catalysts and basic catalysts may be used in combination.
硫化物蛍光体２と、金属酸化物粉末３との配合量は、１００質量部の硫化物蛍光体２に対して、１質量部以上、２０質量部未満以下の金属酸化物粉末３を配合することが好ましい。上述したように、１００質量部の硫化物蛍光体２に対して、１質量部以上の金属酸化物粉末３を配合することにより、金属酸化物粉末３の有効な吸着作用を得ることができる。また、１００質量部の硫化物蛍光体２に対して、２０質量部未満の金属酸化物粉末３を配合することにより、硫化物蛍光体２の特性、例えばピーク強度や輝度が低下してしまうことを防止することができる。 The compounding amount of the sulfide phosphor 2 and the metal oxide powder 3 is 1 part by mass or more and less than 20 parts by mass or less of the metal oxide powder 3 with respect to 100 parts by mass of the sulfide phosphor 2. It is preferable. As described above, an effective adsorption action of the metal oxide powder 3 can be obtained by blending 1 part by mass or more of the metal oxide powder 3 with respect to 100 parts by mass of the sulfide phosphor 2. In addition, by blending less than 20 parts by mass of the metal oxide powder 3 with respect to 100 parts by mass of the sulfide phosphor 2, the characteristics of the sulfide phosphor 2, such as peak intensity and luminance, are reduced. Can be prevented.
（分離工程）
分離工程では、上述した混合工程において、硫化物蛍光体２とアルコキシシランとを溶媒中で混合させた混合液を固相と液相とに分離することにより、固相である被覆蛍光体を混合液中から得る。
(Separation process)
In the separation step, in the mixing step described above, the mixed phosphor in which the sulfide phosphor 2 and the alkoxysilane are mixed in a solvent is separated into a solid phase and a liquid phase, thereby mixing the coated phosphor as a solid phase. Obtain from liquid.
例えば、分離工程においては、吸引濾過器を用いて、混合液を固相と液相とに分離し、分離した固相を乾燥し、乾燥して得られた試料を解砕し、焼成処理を行う。これにより、金属酸化物粉末３が含有された二酸化ケイ素膜４によって硫化物蛍光体２が被覆された被覆蛍光体１を得ることができる。 For example, in the separation step, a mixed solution is separated into a solid phase and a liquid phase using a suction filter, the separated solid phase is dried, a sample obtained by drying is crushed, and subjected to a firing treatment. Do. Thereby, the coated phosphor 1 in which the sulfide phosphor 2 is coated with the silicon dioxide film 4 containing the metal oxide powder 3 can be obtained.
分離した固相を乾燥させる温度は、使用する溶媒に応じて変更することが可能であるが、８０〜１１０℃とすることが好ましい。また、分離した固相を乾燥させる時間は、２時間以上とすることが好ましい。 Although the temperature which dries the isolate | separated solid phase can be changed according to the solvent to be used, it is preferable to set it as 80-110 degreeC. The time for drying the separated solid phase is preferably 2 hours or longer.
試料を焼成する温度は、１５０〜２５０℃とすることが好ましい。また、粉砕した試料を焼成する時間は、８時間以上とすることが好ましい。 The temperature for firing the sample is preferably 150 to 250 ° C. The time for firing the crushed sample is preferably 8 hours or longer.
なお、上述した説明では、被覆蛍光体１を製造する際に、硫化物蛍光体２に対する二酸化ケイ素膜４の被覆処理を１回だけ行う方法、すなわち、硫化物蛍光体２に二酸化ケイ素膜４を一層だけ被覆させる方法について説明したが、この例に限定されるものではない。例えば、二酸化ケイ素膜４の被覆処理を繰り返し行って、硫化物蛍光体２に二層以上の二酸化ケイ素膜４を被覆させるようにしてもよい。本実施の形態に係る被覆蛍光体の製造方法では、硫化物蛍光体２に多層の二酸化ケイ素膜４を被覆させると、硫化物蛍光体２のピーク強度が低下してしまうため、被覆処理の回数を２〜３回とすることが好ましい。 In the above description, when the coated phosphor 1 is manufactured, the method of coating the sulfide phosphor 2 with the silicon dioxide film 4 only once, that is, the silicon dioxide film 4 is applied to the sulfide phosphor 2. Although the method of coating only one layer has been described, it is not limited to this example. For example, the coating process of the silicon dioxide film 4 may be repeatedly performed so that the sulfide phosphor 2 is coated with two or more layers of the silicon dioxide film 4. In the method for manufacturing a coated phosphor according to the present embodiment, when the sulfide phosphor 2 is coated with the multilayer silicon dioxide film 4, the peak intensity of the sulfide phosphor 2 is reduced. Is preferably 2 to 3 times.
＜３．被覆蛍光体の適用例＞
上述した被覆蛍光体の製造方法で得られる被覆蛍光体１は、例えば、白色光源や照明装置に適用することができる。
<3. Application example of coated phosphor>
The coated phosphor 1 obtained by the above-described coated phosphor manufacturing method can be applied to, for example, a white light source or a lighting device.
＜３−１．白色光源＞
まず、本実施の形態に係る白色光源を、図６に示す断面図を用いて説明する。図６に示すように、白色光源１０は、素子基板１１上に形成されたパッド部１２上に青色発光素子１３を有している。素子基板１１には、青色発光素子１３を駆動するための電力を供給する電極１４、１５が絶縁性を保って形成され、それぞれの電極１４、１５は、例えばリード線１６、１７によって青色発光素子１３に接続されている。
<3-1. White light source>
First, the white light source according to the present embodiment will be described with reference to the cross-sectional view shown in FIG. As shown in FIG. 6, the white light source 10 has a blue light emitting element 13 on a pad portion 12 formed on an element substrate 11. Electrodes 14 and 15 for supplying electric power for driving the blue light emitting element 13 are formed on the element substrate 11 while maintaining insulation, and the respective electrodes 14 and 15 are formed by, for example, lead wires 16 and 17 with the blue light emitting element. 13 is connected.
また、青色発光素子１３の周囲には、例えば樹脂層１８が設けられ、その樹脂層１８には、青色発光素子１３上を開口する開口部１９が形成されている。この開口部１９には、青色発光素子１３の発光方向に開口面積が広くなる傾斜面に形成され、その傾斜面には反射膜２０が形成されている。すなわち、すり鉢状の開口部１９を有する樹脂層１８において、開口部１９の反射膜２０で覆われ、開口部１９の底面に青色発光素子１３が配置された状態となっている。そして、開口部１９内に、赤色蛍光体と緑色蛍光体とを透明樹脂に混線した混練物２１が、青色発光素子１３を覆う状態で埋め込まれて白色光源１０が構成されている。 Further, for example, a resin layer 18 is provided around the blue light emitting element 13, and an opening 19 that opens on the blue light emitting element 13 is formed in the resin layer 18. The opening 19 is formed on an inclined surface whose opening area is widened in the light emitting direction of the blue light emitting element 13, and a reflective film 20 is formed on the inclined surface. That is, the resin layer 18 having the mortar-shaped opening 19 is covered with the reflective film 20 of the opening 19, and the blue light emitting element 13 is disposed on the bottom surface of the opening 19. And the kneaded material 21 which mixed the red fluorescent substance and the green fluorescent substance in the transparent resin in the opening part 19 is embedded in the state which covers the blue light emitting element 13, and the white light source 10 is comprised.
緑色蛍光体としては、上述した被覆蛍光体１が用いられる。この緑色蛍光体は、緑色波長帯でピーク発光波長が得られ、発光強度が強く、輝度が高い。そのため、青色発光素子の青色光、赤色蛍光体による赤色光、および緑色蛍光体による緑色光からなる光の３原色による色域が広い明るい白色光を得ることができる。 As the green phosphor, the above-described coated phosphor 1 is used. This green phosphor has a peak emission wavelength in the green wavelength band, a high emission intensity, and a high luminance. Therefore, it is possible to obtain bright white light having a wide color gamut by the three primary colors of blue light of the blue light emitting element, red light by the red phosphor, and green light by the green phosphor.
＜３−２．照明装置＞
次に、本実施の形態に係る照明装置を、図７を用いて説明する。図７に示すように、照明装置２２は、照明基板２３上に図６を用いて説明した白色光源１０が複数配置されている。その配置例は、例えば、図７（Ａ）に示すように、正方格子配列としてもよく、または図７（Ｂ）に示すように、１行おきに例えば１／２ピッチずつずらした配列としてもよい。また、ずらすピッチは、１／２に限らず、１／３ピッチ、１／４ピッチであってもよい。さらには、１行ごとに、もしくは複数行（例えば２行）ごとにずらしてもよい。
<3-2. Lighting device>
Next, the lighting device according to this embodiment will be described with reference to FIG. As shown in FIG. 7, in the illumination device 22, a plurality of the white light sources 10 described with reference to FIG. 6 are arranged on the illumination substrate 23. The arrangement example may be, for example, a square lattice arrangement as shown in FIG. 7 (A), or an arrangement shifted every other row, for example, by 1/2 pitch as shown in FIG. 7 (B). Good. Further, the shifting pitch is not limited to 1/2, and may be 1/3 pitch or 1/4 pitch. Furthermore, you may shift every 1 line or every several lines (for example, 2 lines).
また、図示はしていないが、１列おきに例えば１／２ピッチずつずらした配列としてもよい。ずらすピッチは、１／２に限らず、１／３ピッチ、１／４ピッチであってもよい。さらに、１行ごとに、もしくは複数行（例えば２行）ごとにずらしてもよい。すなわち、白色光源１０のずらし方は、限定されるものではない。 Further, although not shown in the figure, the arrangement may be shifted every other column, for example, by 1/2 pitch. The shifting pitch is not limited to 1/2, and may be 1/3 pitch or 1/4 pitch. Further, it may be shifted every line or every plural lines (for example, 2 lines). That is, how to shift the white light source 10 is not limited.
白色光源１０は、図６を参照して説明したものと同様な構成を有するものである。すなわち、白色光源１０は、青色発光素子１３上に、赤色蛍光体と緑色蛍光体を透明樹脂に混練した混練物２１を有するものである。緑色蛍光体には、上述した緑色蛍光体が用いられる。 The white light source 10 has the same configuration as that described with reference to FIG. That is, the white light source 10 has a kneaded material 21 in which a red phosphor and a green phosphor are kneaded with a transparent resin on the blue light emitting element 13. The green phosphor described above is used as the green phosphor.
また、照明装置２２は、点発光とほぼ同等の白色光源１０が照明基板２３上に、縦横に複数配置されていることから、面発光と同等になるので、例えば液晶表示装置のバックライトとして用いることができる。また、照明装置２２は、通常の照明装置、撮影用の照明装置、工事現場用の照明装置等、種々の用途の照明装置に用いることができる。 The illumination device 22 is equivalent to surface light emission because a plurality of white light sources 10 substantially equivalent to point light emission are arranged vertically and horizontally on the illumination substrate 23, so that it is used as, for example, a backlight of a liquid crystal display device. be able to. Moreover, the illuminating device 22 can be used for various illuminating devices such as a normal illuminating device, a photographing illuminating device, and a construction site illuminating device.
照明装置２２は、白色光源１０を用いているため、色域が広い明るい、白色光を得ることができる。例えば、液晶表示装置のバックライトに用いた場合に、表示画面において輝度の高い純白色を得ることができ、表示画面の品質の向上を図ることができる。 Since the illumination device 22 uses the white light source 10, it can obtain bright white light with a wide color gamut. For example, when used for a backlight of a liquid crystal display device, pure white with high luminance can be obtained on the display screen, and the quality of the display screen can be improved.
また、本実施の形態に係る被覆蛍光体１は、例えば、照明装置における蛍光体シートに適用することができる。例えば図８に示すように、照明装置２４は、青色発光素子が凸型の表面形状の透明樹脂で包含された発光構造体２５と、発光構造体２５が二次元配置された基板２６と、青色発光素子の青色光を拡散する拡散板２７と、基板２６と離間して配置され、青色発光素子の青色光から白色光を得る粉末状の蛍光体を含有する蛍光体シート２８と、光学フィルム２９とを備える。 The coated phosphor 1 according to the present embodiment can be applied to a phosphor sheet in a lighting device, for example. For example, as shown in FIG. 8, the lighting device 24 includes a light emitting structure 25 in which a blue light emitting element is covered with a convex surface-shaped transparent resin, a substrate 26 on which the light emitting structure 25 is two-dimensionally arranged, A diffusing plate 27 that diffuses blue light of the light emitting element, a phosphor sheet 28 that is disposed apart from the substrate 26 and contains powdered phosphor that obtains white light from the blue light of the blue light emitting element, and an optical film 29 With.
基板２６と蛍光体シート２８とは、約１０〜５０ｍｍ程度離間して配置され、照明装置２４は、いわゆるリモート蛍光体構造を構成する。基板２６と蛍光体シート２８との間隙は、複数の支持柱や反射板によって保持され、基板２６と蛍光体シート２８とがなす空間を支持柱や反射板が四方で囲むように設けられている。 The board | substrate 26 and the fluorescent substance sheet 28 are spaced apart and about 10-50 mm, and the illuminating device 24 comprises what is called a remote fluorescent substance structure. The gap between the substrate 26 and the phosphor sheet 28 is held by a plurality of support pillars and reflectors, and is provided so that the support pillars and reflectors surround the space formed by the substrate 26 and the phosphor sheet 28 in all directions. .
発光構造体２５は、青色発光素子として例えばＩｎＧａＮ系の青色ＬＥＤ（Light Emitting Diode）チップを有する、いわゆるＬＥＤパッケージを構成する。 The light emitting structure 25 constitutes a so-called LED package having, for example, an InGaN blue LED (Light Emitting Diode) chip as a blue light emitting element.
基板２６は、フェノール、エポキシ、ポリイミド、ポリエステル、ビスマレイミドトリアジン、アリル化ポリフェニレンオキサイドなどの樹脂を利用したガラス布基材から構成される。基板２６上には、所定ピッチで等間隔に発光構造体２５が、蛍光体シート２８の全面に対応して二次元に配置される。また、必要に応じて、基板２６上の発光構造体２５の搭載面に反射処理を施してもよい。 The board | substrate 26 is comprised from the glass cloth base material using resin, such as a phenol, an epoxy, a polyimide, polyester, bismaleimide triazine, and allylated polyphenylene oxide. On the substrate 26, the light emitting structures 25 are two-dimensionally arranged corresponding to the entire surface of the phosphor sheet 28 at equal intervals with a predetermined pitch. Moreover, you may perform a reflection process to the mounting surface of the light emission structure 25 on the board | substrate 26 as needed.
拡散板２７は、発光構造体２５からの放射光を光源の形状が見えなくなる程度に広範囲に拡散するものである。拡散板２７としては、全光線透過率が２０％以上８０％以下のものが用いられる。 The diffusion plate 27 diffuses the radiated light from the light emitting structure 25 over a wide range to such an extent that the shape of the light source becomes invisible. As the diffusing plate 27, one having a total light transmittance of 20% or more and 80% or less is used.
蛍光体シート２８は、青色発光素子の青色光から白色光を得る粉末状の蛍光体を含有する。蛍光体の粉末は、平均粒径が数μｍ〜数十μｍのものを用いる。これにより蛍光体シート２８の光散乱効果を向上させることができる。 The phosphor sheet 28 contains a powdered phosphor that obtains white light from the blue light of the blue light emitting element. The phosphor powder having an average particle size of several μm to several tens of μm is used. Thereby, the light scattering effect of the phosphor sheet 28 can be improved.
光学フィルム２９は、例えば液晶表示装置の視認性を向上させるための反射型偏光フィルム、レンズフィルム、拡散フィルムなどで構成される。ここで、レンズフィルムは、一方の面に微小なレンズが配列形成された光学フィルムであり、拡散光の正面方向の指向性を高めて輝度を高めるためのものである。 The optical film 29 is composed of, for example, a reflective polarizing film, a lens film, a diffusion film, etc. for improving the visibility of the liquid crystal display device. Here, the lens film is an optical film in which minute lenses are arrayed on one surface, and is for increasing the directivity of diffused light in the front direction and increasing the luminance.
以上説明したように、被覆蛍光体１を白色光源１０、照明装置２２及び照明装置２４に適用することにより、例えば高温高湿下において硫化物蛍光体２からの硫黄系ガスの放出を抑制することができる。これにより、白色光源１０、照明装置２２及び照明装置２４において電極等が腐食され、導電性の悪化等を招いてしまうことを防止することができる。 As described above, by applying the coated phosphor 1 to the white light source 10, the illuminating device 22, and the illuminating device 24, for example, the release of sulfur-based gas from the sulfide phosphor 2 under high temperature and high humidity is suppressed. Can do. Thereby, it can prevent that an electrode etc. are corroded in the white light source 10, the illuminating device 22, and the illuminating device 24, and the deterioration of electroconductivity etc. is caused.
以下、本発明の実施例について説明する。本実施例では、実施例１〜実施例９、比較例１、比較例２において得られた未被覆蛍光体又は被覆蛍光体について、発光特性評価、高温高湿環境試験及び銀片腐食試験を行った。なお、本発明は、これらの実施例に限定されるものではない。 Examples of the present invention will be described below. In this example, the uncoated phosphor or the coated phosphor obtained in Examples 1 to 9, Comparative Example 1 and Comparative Example 2 were subjected to luminescent property evaluation, high temperature and high humidity environment test, and silver piece corrosion test. It was. The present invention is not limited to these examples.
（実施例１）
樹脂容器（ＰＥ）に、第一配合物（硫化物蛍光体（ＳｒＧａ２Ｓ４：Ｅｕ）１０ｇ、エタノール８０ｇ、純水５ｇ、２８％のアンモニア水６ｇ）と、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）０．１ｇ（硫化物蛍光体１００質量部に対して１質量部）を投入し、マグネチックスターラーを投入し、４０℃の恒温槽にて１０分間攪拌後、第二配合物（テトラエトキシシラン５ｇ、エタノール３５ｇ）を投入した。第二配合物の投入が完了した時点を０分として３時間攪拌を行った。攪拌終了後、真空ポンプを用いて吸引濾過を行い、回収したサンプルをビーカーに移し、水やエタノールで洗浄後、再度濾過を行い、サンプルを回収した。回収したサンプルを８５℃で２時間乾燥し、２００℃で８時間焼成を行い、被覆蛍光体を得た。
Example 1
In a resin container (PE), a first compound (sulfide phosphor (SrGa 2 S 4 : Eu) 10 g, ethanol 80 g, pure water 5 g, 28% ammonia water 6 g) and a particle size of 0.1-0. 0.1 g of 2 μm zinc oxide powder (K-FRESH MZO, manufactured by Teika) (1 part by mass with respect to 100 parts by mass of the sulfide phosphor) is introduced, a magnetic stirrer is introduced, and a 40 ° C. constant temperature bath After stirring for 10 minutes, the second compound (5 g of tetraethoxysilane, 35 g of ethanol) was added. Stirring was carried out for 3 hours with the time when the addition of the second formulation was completed as 0 minutes. After the stirring, suction filtration was performed using a vacuum pump, and the collected sample was transferred to a beaker, washed with water or ethanol, and then filtered again to collect the sample. The collected sample was dried at 85 ° C. for 2 hours and baked at 200 ° C. for 8 hours to obtain a coated phosphor.
（実施例２）
実施例２では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を０．５ｇ（硫化物蛍光体１００質量部に対して５質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Example 2)
In Example 2, 0.5 g (5 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. Except for the above, a coated phosphor was obtained in the same manner as in Example 1.
（実施例３）
実施例３では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を１．０ｇ（硫化物蛍光体１００質量部に対して１０質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
Example 3
In Example 3, 1.0 g (10 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. Except for the above, a coated phosphor was obtained in the same manner as in Example 1.
（実施例４）
実施例４では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を２．０ｇ（硫化物蛍光体１００質量部に対して２０質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
Example 4
In Example 4, 2.0 g (20 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. Except for the above, a coated phosphor was obtained in the same manner as in Example 1.
（実施例５）
実施例５では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を５．０ｇ（硫化物蛍光体１００質量部に対して５０質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Example 5)
In Example 5, 5.0 g (50 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. Except for the above, a coated phosphor was obtained in the same manner as in Example 1.
（実施例６）
実施例６では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を１０．０ｇ（硫化物蛍光体１００質量部に対して１００質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Example 6)
In Example 6, 10.0 g (100 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. Except for the above, a coated phosphor was obtained in the same manner as in Example 1.
（実施例７）
実施例７では、粒径が０．６〜０．８μｍの酸化亜鉛粉末（堺化学製）を０．５ｇ（硫化物蛍光体１００質量部に対して５質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Example 7)
Example 7 was carried out except that 0.5 g (5 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (manufactured by Sakai Chemical) having a particle size of 0.6 to 0.8 μm was used. A coated phosphor was obtained in the same manner as in Example 1.
（実施例８）
実施例８では、粒径が０．０２〜０．０３μｍの酸化亜鉛粉末（ＦＩＮＥＸ、堺化学製）を０．５ｇ（硫化物蛍光体１００質量部に対して５質量部）用いたこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Example 8)
In Example 8, except that 0.5 g of zinc oxide powder (FINEX, manufactured by Sakai Chemical) having a particle size of 0.02 to 0.03 μm was used (5 parts by mass with respect to 100 parts by mass of the sulfide phosphor). In the same manner as in Example 1, a coated phosphor was obtained.
（実施例９）
実施例９では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を合計１．０ｇ（硫化物蛍光体１００質量部に対して合計１０質量部）用いたこと、２回被覆処理を行ったこと以外は、実施例１と同様にして被覆蛍光体を得た。実施例９で得られた被覆蛍光体１は、図３に示すように、硫化物蛍光体上に、二層の二酸化ケイ素膜、すなわち、酸化亜鉛粉末が含有された二酸化ケイ素膜と、酸化亜鉛粉末が含有された二酸化ケイ素膜とがこの順番で被覆されている。
Example 9
In Example 9, for a total of 1.0 g of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm (a total of 10 parts by mass with respect to 100 parts by mass of the sulfide phosphor) The coated phosphor was obtained in the same manner as in Example 1 except that the coating treatment was performed twice. As shown in FIG. 3, the coated phosphor 1 obtained in Example 9 includes a two-layered silicon dioxide film, that is, a silicon dioxide film containing zinc oxide powder on a sulfide phosphor, and zinc oxide. The silicon dioxide film containing the powder is coated in this order.
（実施例１０）
実施例１０では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を０．５ｇ（硫化物蛍光体１００質量部に対して５質量部）用いたこと、２回被覆処理を行ったこと以外は、実施例１と同様にして被覆蛍光体を得た。実施例１０で得られた被覆蛍光体１は、図４に示すように、硫化物蛍光体上に、二層の二酸化ケイ素膜、すなわち、酸化亜鉛粉末が含有された二酸化ケイ素膜と、酸化亜鉛粉末が含有されていない二酸化ケイ素膜とがこの順番で被覆されている。
(Example 10)
In Example 10, 0.5 g (5 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. A coated phosphor was obtained in the same manner as in Example 1 except that the coating treatment was performed twice. As shown in FIG. 4, the coated phosphor 1 obtained in Example 10 includes a two-layered silicon dioxide film, that is, a silicon dioxide film containing zinc oxide powder on a sulfide phosphor, and zinc oxide. A silicon dioxide film containing no powder is coated in this order.
（実施例１１）
実施例１１では、粒径が０．１〜０．２μｍの酸化亜鉛粉末（Ｋ−ＦＲＥＳＨ ＭＺＯ、テイカ製）を０．５ｇ（硫化物蛍光体１００質量部に対して５質量部）用いたこと、２回被覆処理を行ったこと以外は、実施例１と同様にして被覆蛍光体を得た。実施例１１で得られた被覆蛍光体１は、図５に示すように、硫化物蛍光体上に、二層の二酸化ケイ素膜、すなわち、酸化亜鉛粉末が含有されていない二酸化ケイ素膜と、酸化亜鉛粉末が含有された二酸化ケイ素膜とがこの順番で被覆されている。
(Example 11)
In Example 11, 0.5 g (5 parts by mass with respect to 100 parts by mass of the sulfide phosphor) of zinc oxide powder (K-FRESH MZO, manufactured by Teika) having a particle size of 0.1 to 0.2 μm was used. A coated phosphor was obtained in the same manner as in Example 1 except that the coating treatment was performed twice. As shown in FIG. 5, the coated phosphor 1 obtained in Example 11 includes a two-layered silicon dioxide film on the sulfide phosphor, that is, a silicon dioxide film not containing zinc oxide powder, and an oxidized material. The silicon dioxide film containing the zinc powder is coated in this order.
（比較例１）
比較例１では、被覆処理を施していない蛍光体（未被覆蛍光体）（ＳｒＧａ２Ｓ４：Ｅｕ）１０ｇをそのまま用いた。
(Comparative Example 1)
In Comparative Example 1, 10 g of a phosphor not subjected to coating treatment (uncoated phosphor) (SrGa 2 S 4 : Eu) was used as it was.
（比較例２）
比較例２では、酸化亜鉛粉末を用いなかったこと以外は、実施例１と同様にして被覆蛍光体を得た。
(Comparative Example 2)
In Comparative Example 2, a coated phosphor was obtained in the same manner as in Example 1 except that no zinc oxide powder was used.
実施例１〜実施例１１及び比較例１、比較例２についてまとめたものを表１に示す。表１において、被覆処理の欄の丸数字（１、２）は、それぞれ１回目の被覆処理又は２回目の被覆処理のことを示す。また、表１において、「ＺｎＯ混合」とは、酸化亜鉛粉末が含有された二酸化ケイ素膜であり、「シリカ」とは、酸化亜鉛粉末が含有されていない二酸化ケイ素膜である。 Table 1 shows a summary of Examples 1 to 11 and Comparative Examples 1 and 2. In Table 1, the circled numbers (1, 2) in the column of the coating process indicate the first coating process or the second coating process, respectively. In Table 1, “ZnO mixture” is a silicon dioxide film containing zinc oxide powder, and “silica” is a silicon dioxide film containing no zinc oxide powder.
＜発光特性評価＞
ＦＰ６５００（日本分光（株）製）を用いて、実施例１〜実施例１１及び比較例１、比較例２で得られた未被覆蛍光体又は被覆蛍光体の発光特性を評価した。発光特性評価の結果を表１に示す。発光特性としては、輝度、ピーク波長、ピーク強度、試料吸収率、内部量子効率及び外部量子効率を評価した。ピーク強度は、未被覆蛍光体（比較例１）のピーク強度を１としたときの各被覆蛍光体のピーク強度を表す。試料吸収率は、励起光の試料による減少分の入射光の比である。また、内部量子効率は、試料から放出される蛍光の光子数から、試料に吸収される励起光の光子数を割った値である。外部量子効率は、試料吸収率に内部量子効率を乗じた値（（試料吸収率）×（内部量子効率））である。
<Emission characteristic evaluation>
Using FP6500 (manufactured by JASCO Corporation), the emission characteristics of the uncoated phosphor or the coated phosphor obtained in Examples 1 to 11 and Comparative Examples 1 and 2 were evaluated. Table 1 shows the results of the evaluation of the light emission characteristics. As the light emission characteristics, luminance, peak wavelength, peak intensity, sample absorption rate, internal quantum efficiency, and external quantum efficiency were evaluated. The peak intensity represents the peak intensity of each coated phosphor when the peak intensity of the uncoated phosphor (Comparative Example 1) is 1. The sample absorption rate is a ratio of incident light that is reduced by the sample of excitation light. The internal quantum efficiency is a value obtained by dividing the number of photons of excitation light absorbed by the sample from the number of photons of fluorescence emitted from the sample. The external quantum efficiency is a value obtained by multiplying the sample absorption rate by the internal quantum efficiency ((sample absorption rate) × (internal quantum efficiency)).
実施例２、実施例３、実施例１１で得られた被覆蛍光体は、発光特性に関して、未被覆蛍光体（比較例１）と同等であることが分かった。 The coated phosphors obtained in Example 2, Example 3, and Example 11 were found to be equivalent to the uncoated phosphor (Comparative Example 1) in terms of light emission characteristics.
また、実施例１、実施例７、実施例８、実施例１０で得られた被覆蛍光体は、発光特性に関して、未被覆蛍光体（比較例１）よりも良好であることが分かった。これは、二酸化ケイ素膜によるレンズ効果により、被覆蛍光体の外部から内部に光が入射しやすくなり、また、被覆蛍光体の内部から外部に光が出射しやすくなったためと考えられる。 It was also found that the coated phosphors obtained in Example 1, Example 7, Example 8, and Example 10 were better than the uncoated phosphor (Comparative Example 1) in terms of light emission characteristics. This is presumably because light is easily incident from the outside to the inside of the coated phosphor due to the lens effect of the silicon dioxide film, and light is easily emitted from the inside to the outside of the coated phosphor.
さらに、実施例９で得られた被覆蛍光体、すなわち硫化物蛍光体１００質量部に対して５質量部の酸化亜鉛を用いて被覆処理を２回（合計１０質量部）行った被覆蛍光体は、発光特性に関して、１０質量部の酸化亜鉛を用いて被覆処理を１回行った被覆蛍光体（実施例３）と同等以上であることが分かった。 Furthermore, the coated phosphor obtained in Example 9, that is, the coated phosphor that was coated twice (total 10 parts by mass) with 5 parts by mass of zinc oxide with respect to 100 parts by mass of the sulfide phosphor. The emission characteristics were found to be equivalent to or better than the coated phosphor (Example 3) that was coated once with 10 parts by mass of zinc oxide.
一方、酸化亜鉛の配合量が２０質量部以上である実施例４〜実施例６で得られた被覆蛍光体は、発光特性に関して、未被覆の蛍光体（比較例１）よりも低下してしまうことが分かった。 On the other hand, the coated phosphors obtained in Examples 4 to 6 in which the blending amount of zinc oxide is 20 parts by mass or more are lower than the uncoated phosphor (Comparative Example 1) with respect to the emission characteristics. I understood that.
＜高温高湿環境試験＞
高温高湿環境変化試験では、実施例１〜実施例９、比較例１、比較例２で得られた評価サンプルについて、６０℃、９０％ＲＨの高温高湿試験により、初期発光強度等から試験終了後５００時間後までの変化を確認した。発光強度測定には、分光光度計ＦＰ−６５００（日本分光（株）製）を用いた。高温高湿環境変化試験の結果を表２及び図９に示す。
<High temperature and high humidity environment test>
In the high-temperature and high-humidity environmental change test, the evaluation samples obtained in Examples 1 to 9, Comparative Example 1 and Comparative Example 2 were tested from the initial light emission intensity and the like by the high-temperature and high-humidity test of 60 ° C. and 90% RH The change until 500 hours after completion was confirmed. A spectrophotometer FP-6500 (manufactured by JASCO Corporation) was used for measuring the emission intensity. The results of the high temperature and high humidity environment change test are shown in Table 2 and FIG.
未被覆蛍光体（比較例１）は、６０℃、９０％ＲＨの高温高湿試験の５００時間後において発光強度が半減してしまうことが分かった。一方、二酸化ケイ素膜によって被覆された被覆蛍光体（比較例２）は、発光強度を略１００％維持することができることが分かった。 It was found that the emission intensity of the uncoated phosphor (Comparative Example 1) was halved after 500 hours of the high temperature and high humidity test at 60 ° C. and 90% RH. On the other hand, it was found that the coated phosphor coated with the silicon dioxide film (Comparative Example 2) can maintain the light emission intensity of approximately 100%.
酸化亜鉛粉末が含有された二酸化ケイ素膜によって被覆された被覆蛍光体（実施例１〜実施例９）は、発光強度維持率を略１００％に維持することができ、また、比較例２で得られた被覆蛍光体よりも発光強度維持率が良好となるものがあることが分かった。これらの結果から、酸化亜鉛は、高温高湿環境下における発光強度維持率に関して、二酸化ケイ素膜に悪影響を及ぼさないことが分かった。 The coated phosphors (Examples 1 to 9) coated with the silicon dioxide film containing the zinc oxide powder can maintain the emission intensity maintenance rate at about 100%, and are obtained in Comparative Example 2. It was found that there are some which have a better emission intensity maintenance rate than the coated phosphors obtained. From these results, it was found that zinc oxide does not adversely affect the silicon dioxide film with respect to the emission intensity maintenance rate in a high temperature and high humidity environment.
＜銀片腐食試験＞
硫化水素ガスの放出の指標として銀片試験を行った。直径１５ｍｍ、厚さ２ｍｍの銀片（ＪＩＳ Ｈ ２１４１ 「銀地金」に規定されている銀地金（純度９９．９５％以上））を金属研磨剤（ピカール、日本磨料工業社製）で研磨し、アセトン中で超音波洗浄した。図１０に示すように、超音波洗浄後の銀片３０を密閉ビン３１（１００ｍｌのガラス製秤量ビン）の蓋３２の裏３２Ａに両面テープで張り付けた。湿度１００％ＲＨとするために、ガラスセル３３に水を加え、密閉ビン３１に入れた。また、密閉ビン３１内部の低面上に、実施例１〜実施例１１及び比較例１、比較例２で得られた被覆蛍光体（未被覆蛍光体）３４を置いた。密閉ビン３１の蓋３２を閉め、パラフィルム、ポリイミドテープで止め、８５℃で６時間オーブンに入れた。
<Silver piece corrosion test>
A silver piece test was conducted as an index of hydrogen sulfide gas release. Polishing a piece of silver with a diameter of 15 mm and a thickness of 2 mm (silver bullion (purity 99.95% or more) specified in JIS H 2141 “silver bullion”) with a metal abrasive (Pical, manufactured by Nippon Abrasives Co., Ltd.) And ultrasonically cleaned in acetone. As shown in FIG. 10, the silver piece 30 after ultrasonic cleaning was stuck to the back 32A of the lid 32 of the sealed bottle 31 (100 ml glass weighing bottle) with double-sided tape. In order to obtain a humidity of 100% RH, water was added to the glass cell 33 and placed in the sealed bottle 31. In addition, the coated phosphors (uncoated phosphors) 34 obtained in Examples 1 to 11 and Comparative Examples 1 and 2 were placed on the lower surface inside the sealed bottle 31. The lid 32 of the airtight bottle 31 was closed, stopped with parafilm and polyimide tape, and placed in an oven at 85 ° C. for 6 hours.
銀片試験の評価は、ＦＰ６５００にて３８０〜７８０ｎｍの波長での反射率を測定して平均化することで求めた平均反射率を評価した。平均反射率の結果を表３に示す。 Evaluation of the silver piece test evaluated the average reflectance calculated | required by measuring and averaging the reflectance in the wavelength of 380-780 nm in FP6500. The results of average reflectance are shown in Table 3.
比較例１で得られた未被覆蛍光体を用いたときと、比較例２で得られた被覆蛍光体を用いたときを比較すると、比較例２で得られた被覆蛍光体を用いたときは、硫化物蛍光体が二酸化ケイ素膜で被覆されているため、銀の腐食が若干改善されていることが分かった。 When the uncoated phosphor obtained in Comparative Example 1 is used and the coated phosphor obtained in Comparative Example 2 is used, the coated phosphor obtained in Comparative Example 2 is used. It was found that the corrosion of silver was slightly improved because the sulfide phosphor was coated with a silicon dioxide film.
酸化亜鉛が含有された二酸化ケイ素膜によって被覆した実施例１〜実施例１１で得られた被覆蛍光体では、比較例１で得られた未被覆蛍光体と比較して、約２倍以上の平均反射率が得られ、腐食をより抑えることができることが分かった。これは、被覆蛍光体中の硫化物蛍光体の加水分解によって硫化物蛍光体から放出される硫黄系ガスが酸化亜鉛粉末に吸着され、硫黄系ガスの放出を抑制することができたためと考えられる。 In the coated phosphors obtained in Examples 1 to 11 coated with the silicon dioxide film containing zinc oxide, the average of about twice or more compared with the uncoated phosphor obtained in Comparative Example 1 It was found that reflectance was obtained and corrosion could be further suppressed. This is thought to be because the sulfur-based gas released from the sulfide phosphor by the hydrolysis of the sulfide phosphor in the coated phosphor was adsorbed by the zinc oxide powder and the release of the sulfur-based gas could be suppressed. .
実施例７で得られた被覆蛍光体は、平均反射率の結果に関して、比較例２で得られた被覆蛍光体と同等の結果であるが、目視による外観評価については、比較例２で得られた被覆蛍光体よりも良好であった。 The coated phosphor obtained in Example 7 is the same result as the coated phosphor obtained in Comparative Example 2 with respect to the result of the average reflectance, but the visual appearance evaluation is obtained in Comparative Example 2. Better than the coated phosphor.
粒径の小さい酸化亜鉛（０．０２〜０．０３μｍ）を用いた実施例８で得られた被覆蛍光体は、粒径が０．１〜０．２μｍの酸化亜鉛を用いた実施例１〜実施例６で得られた被覆蛍光体と同等の平均反射率が得られることが分かった。 The coated phosphor obtained in Example 8 using zinc oxide having a small particle size (0.02 to 0.03 μm) was used in Examples 1 to 1 using zinc oxide having a particle size of 0.1 to 0.2 μm. It was found that an average reflectance equivalent to that of the coated phosphor obtained in Example 6 was obtained.
硫化物蛍光体１００質量部に対して５質量部の酸化亜鉛を用いて被覆処理を２回行った被覆蛍光体（実施例９）は、発光特性に関して、１０質量部の酸化亜鉛を用いて被覆処理を１回行った被覆蛍光体（実施例３）よりも、平均反射率が向上することが分かった。 The coated phosphor (Example 9), which was coated twice using 5 parts by mass of zinc oxide with respect to 100 parts by mass of the sulfide phosphor, was coated with 10 parts by mass of zinc oxide in terms of emission characteristics. It was found that the average reflectance was improved as compared with the coated phosphor (Example 3) that was processed once.
同じ量の酸化亜鉛粉末（硫化物蛍光体１００質量部に対して５質量部）を用いた実施例２、実施例１０、実施例１１で得られた被覆蛍光体の中では、実施例２で得られた被覆蛍光体と実施例１０で得られた被覆蛍光体の平均反射率を比較すると、同じであることが分かった。また、実施例２で得られた被覆蛍光体と、実施例１１で得られた被覆蛍光体の平均反射率を比較すると、実施例１１で得られた被覆蛍光体の方が結果が良好であることが分かった。これらの結果から、実施例２、実施例１０、実施例１１で得られた被覆蛍光体の中では、実施例１１で得られた被覆蛍光体は、最も高い平均反射率が得られ、腐食をより抑えることができることが分かった。これは、被覆蛍光体において、硫化物蛍光体が、二層以上の二酸化ケイ素膜によって被覆されており、最表面側の二酸化ケイ素膜中に金属酸化物粉末である酸化亜鉛粉末が含有されているためと考えられる。 Among the coated phosphors obtained in Example 2, Example 10 and Example 11 using the same amount of zinc oxide powder (5 parts by mass with respect to 100 parts by mass of sulfide phosphor), Example 2 When the average reflectances of the obtained coated phosphor and the coated phosphor obtained in Example 10 were compared, it was found to be the same. Moreover, when the average reflectance of the coated phosphor obtained in Example 2 and the coated phosphor obtained in Example 11 is compared, the coated phosphor obtained in Example 11 has better results. I understood that. From these results, among the coated phosphors obtained in Example 2, Example 10, and Example 11, the coated phosphor obtained in Example 11 has the highest average reflectivity, and exhibits corrosion. It turned out that it can suppress more. This is because in the coated phosphor, the sulfide phosphor is coated with two or more layers of silicon dioxide film, and the zinc oxide powder, which is a metal oxide powder, is contained in the outermost silicon dioxide film. This is probably because of this.
１ 被覆蛍光体、２ 硫化物蛍光体、３ 金属酸化物粉末、４ 二酸化ケイ素膜、１０ 白色光源、１１ 素子基板、１２ パッド部、１３ 青色発光素子、１４ 電極、１５ 電極、１６ リード線、１７ リード線、１８ 樹脂層、１９ 開口部、２０ 反射膜、２１ 混練物、２２ 照明装置、２３ 照明基板、２４ 照明装置、２５ 発光構造体、２６ 基板、２７ 拡散板、２８ 蛍光体シート、２９ 光学フィルム、３０ 銀片、３１ 密閉ビン、３２ 蓋、３３ ガラスセル、３４ 被覆蛍光体 DESCRIPTION OF SYMBOLS 1 Coated fluorescent substance, 2 Sulfide fluorescent substance, 3 Metal oxide powder, 4 Silicon dioxide film, 10 White light source, 11 Element substrate, 12 Pad part, 13 Blue light emitting element, 14 Electrode, 15 Electrode, 16 Lead wire, 17 Lead wire, 18 resin layer, 19 opening, 20 reflective film, 21 kneaded product, 22 illumination device, 23 illumination substrate, 24 illumination device, 25 light emitting structure, 26 substrate, 27 diffuser plate, 28 phosphor sheet, 29 optical Film, 30 silver pieces, 31 sealed bottle, 32 lid, 33 glass cell, 34 coated phosphor
Claims (6)
上記二酸化ケイ素膜の厚みが５０〜１５０ｎｍである請求項２記載の被覆蛍光体の製造方法。 The zinc oxide powder has a particle size of 0.2 μm or less,
The method for producing a coated phosphor according to claim 2, wherein the silicon dioxide film has a thickness of 50 to 150 nm.
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| JPH02308892A (en) * | 1989-05-23 | 1990-12-21 | Toshiba Corp | Fluorescent material and its treatment |
| JP2000505041A (en) * | 1996-10-31 | 2000-04-25 | ロディア シミ | Compounds based on alkaline earth metals, sulfur and aluminum, gallium or indium, their preparation and their use as luminophores |
| JP2009526089A (en) * | 2005-12-01 | 2009-07-16 | サーノフ コーポレーション | Moisture protection phosphor and LED lighting device |
| WO2012077656A1 (en) * | 2010-12-09 | 2012-06-14 | 三井金属鉱業株式会社 | Sulfur-containing phosphor coated with zno compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02308892A (en) * | 1989-05-23 | 1990-12-21 | Toshiba Corp | Fluorescent material and its treatment |
| JP2000505041A (en) * | 1996-10-31 | 2000-04-25 | ロディア シミ | Compounds based on alkaline earth metals, sulfur and aluminum, gallium or indium, their preparation and their use as luminophores |
| JP2009526089A (en) * | 2005-12-01 | 2009-07-16 | サーノフ コーポレーション | Moisture protection phosphor and LED lighting device |
| WO2012077656A1 (en) * | 2010-12-09 | 2012-06-14 | 三井金属鉱業株式会社 | Sulfur-containing phosphor coated with zno compound |
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