WO2013118331A1 - Fluorophore and light emitting device - Google Patents

Fluorophore and light emitting device Download PDF

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Publication number
WO2013118331A1
WO2013118331A1 PCT/JP2012/070393 JP2012070393W WO2013118331A1 WO 2013118331 A1 WO2013118331 A1 WO 2013118331A1 JP 2012070393 W JP2012070393 W JP 2012070393W WO 2013118331 A1 WO2013118331 A1 WO 2013118331A1
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phosphor
light emitting
mass
nitride
oxynitride
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PCT/JP2012/070393
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French (fr)
Japanese (ja)
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慶太 小林
史博 中原
市川　恒希
水谷　晋
康人 伏井
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電気化学工業株式会社
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • 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

Definitions

  • the present invention relates to a phosphor used in an LED (Light Emitting Diode) and a light emitting device using the LED.
  • LED Light Emitting Diode
  • a phosphor used in a white light emitting device there is a combination of ⁇ -type sialon and a red light emitting phosphor (see Patent Document 1), and a phosphor in which a red light emitting phosphor having a specific color coordinate and a green light emitting phosphor are combined. Yes (see Patent Document 2).
  • An object of the present invention is to provide a phosphor having both high luminance and high reliability by adding an oxynitride phosphor to a specific nitride phosphor, and further using this phosphor. It is to provide a white light emitting device.
  • the present invention includes an oxynitride phosphor (A) having a peak wavelength of 540 nm to 545 nm, a fluorescence intensity of 260% to 280%, and a nitride phosphor (B) having a peak wavelength of 615 nm to 625 nm, and an acid. It is a phosphor in which the blending ratio of the nitride phosphor (A) is 74 mass% or more and 89 mass% or less, and the blending ratio of the nitride phosphor (B) is 11 mass% or more and 19 mass% or less.
  • the respective relationships are a + b ⁇ 88% by mass and 4.0 ⁇ a / b ⁇ 8. 0 is preferred.
  • the oxynitride phosphor (A) is preferably ⁇ -type sialon, and the nitride phosphor (B) is preferably SCASN.
  • the invention from another aspect of the present application is a light emitting device including the above-described phosphor and an LED having the phosphor mounted on a light emitting surface.
  • a phosphor having high brightness, high temperature characteristics and long-term reliability, and a white light emitting device using the phosphor can be provided.
  • the present invention is a phosphor having an oxynitride phosphor (A) having a peak wavelength of 540 nm to 545 nm and a fluorescence intensity of 260% to 280% and a nitride phosphor (B) having a peak wavelength of 615 nm to 625 nm. .
  • the blending ratio of the oxynitride phosphor (A) is 74% by mass or more and 89% by mass or less, and the blending ratio of the nitride phosphor (B) is 11% by mass or more and 19% by mass or less. If the blending ratio of the oxynitride phosphor (A) is too small, the luminance tends to be low, and if it is too large, it tends to be difficult to obtain high color rendering properties.
  • nitride phosphor (B ) Is too low, high color rendering is not exhibited, and when it is severe, white light itself tends to be lost, and when it is too high, luminance tends to decrease and white light tends not to be obtained.
  • the fluorescence intensity of the phosphor is expressed as a relative value in% with the peak height of the standard sample (YAG, specifically, P46Y3 manufactured by Mitsubishi Chemical Corporation) as 100%.
  • the fluorescence intensity measuring instrument is an F-7000 spectrophotometer manufactured by Hitachi High-Tech Co., Ltd.
  • the measuring method is as follows. ⁇ Measurement method> 1) Sample set: A quartz cell was filled with a measurement sample and a standard sample, and each sample was alternately set on a measuring machine and measured. The filling was performed up to about 3/4 of the cell height so that the relative filling density was about 35%. 2) Measurement: Excited with 455 nm light, the height of the maximum peak from 500 nm to 700 nm was read. The measurement was performed 5 times, and the average value of the remaining three points was obtained except for the maximum value and the minimum value.
  • the oxynitride phosphor (A) in the present invention is a green light emitting oxynitride phosphor having a peak wavelength of 540 nm to 545 nm and a fluorescence intensity of 260% to 280%. Specifically, there is ⁇ -type sialon, and more specifically, there is Aron Bright (registered trademark) of Denki Kagaku Kogyo Co., Ltd.
  • the nitride phosphor (B) in the present invention is a nitride phosphor having a peak wavelength of 615 nm or more and 625 nm or less. Specifically, it is a red phosphor abbreviated as SCASN and called Escazun, and more specifically, there is Mitsubishi Chemical Corporation BR-102D (peak wavelength 620 nm).
  • the nitride phosphor (B) includes an Intematix R6436 (peak wavelength: 630 nm), R6535 (peak wavelength: 640 nm), and Mitsubishi for adjusting the peak wavelength within a range not exceeding the addition amount of the nitride phosphor (B). Chemicals such as BR-102C, BR-102F (peak wavelength 630 nm), BR-101A (peak wavelength 650 nm), etc. may be mixed.
  • the amount of oxynitride phosphor (A) and nitride phosphor (B) should be large, and when the respective blending ratios are a and b, Is preferably 88% by mass ⁇ a + b.
  • the nitride phosphor (B) has lower visibility than the oxynitride phosphor (A) and is inferior in brightness, so its blending ratio is preferably low. However, if it is too low, the color rendering property is also lowered. However, since the LED does not show white light in a severe case, the range of 4.0 ⁇ a / b ⁇ 8.0 is preferable.
  • the mixing means of the oxynitride phosphor (A) and the nitride phosphor (B), and other phosphors can be appropriately selected as long as it can be uniformly mixed or mixed to a desired mixing degree.
  • this mixing means it is premised that impurities are not mixed and the shape and particle size of the phosphor are not clearly changed.
  • the invention from another viewpoint of the present application is a light emitting device having a mixed phosphor and an LED having the phosphor mounted on a light emitting surface as described above.
  • the phosphor when mounted on the light emitting surface of the LED is sealed by a sealing member.
  • the sealing member includes a resin and glass, and the resin includes a silicone resin.
  • the LED it is preferable to appropriately select a red light emitting LED, a blue light emitting LED, or an LED emitting another color in accordance with the color finally emitted.
  • the LED is formed of a gallium nitride semiconductor.
  • the peak wavelength is preferably from 440 nm to 460 nm, and more preferably from 445 nm to 455 nm.
  • the LED light emitting part preferably has a size of 0.5 mm square or more.
  • the size of the LED chip can be appropriately selected as long as it has the area of the light emitting portion, and is preferably 1.0 mm ⁇ 0.5 mm, more preferably 1.2 mm ⁇ 0.6 mm.
  • the phosphors shown in Table 1 are the oxynitride phosphors (A) and nitride phosphors (B) used in Examples and Comparative Examples.
  • the oxynitride phosphors (A) in Table 1 only P1 is a phosphor having a peak wavelength of 540 to 545 nm and a fluorescence intensity of 260 to 280% within the range of claim 1.
  • the nitride phosphors (B) in Table 1 only P6 is a phosphor having a peak wavelength of 615 nm or more and 625 nm or less within the range of claim 1.
  • the phosphor of Example 1 is 74% by mass of the phosphor of P1 in Table 1 as the oxynitride phosphor (A), and 13% by mass of the phosphor of P6 in Table 1 as the nitride phosphor (B). In addition, 13 mass% of the phosphor of P4 in Table 1 which is a comparative example of the oxynitride phosphor (A) is blended as the other phosphor. The values of P1 to P8 in the phosphor structure in Table 2 are mass%.
  • the phosphor was mounted on the LED by placing the LED on the bottom of the concave package body, wire bonding the electrode on the substrate, and then injecting the mixed phosphor from the microsyringe. After mounting the phosphor, it was cured at 120 ° C., and then post-cured at 110 ° C. for 10 hours and sealed.
  • the LED used had an emission peak wavelength of 448 nm and a chip size of 1.0 mm ⁇ 0.5 mm.
  • the evaluation shown in Table 2 will be described. As an initial evaluation in Table 2, the evaluation of color rendering was adopted. For the evaluation of color rendering, a color reproduction range was adopted, and the area was expressed as an area (%) of the NTSC standard ratio in color coordinates. The larger the number, the higher the color rendering.
  • the pass condition for evaluation is 72% or more, which is a condition adopted for general LED-TV.
  • the luminance in Table 2 was evaluated by the luminous flux (lm) at 25 ° C. The measured value after applying a current of 60 mA for 10 minutes was taken. The pass condition of evaluation is 26.4 lm or more. Since this value varies depending on the measuring machine and conditions, it is a value set as (lower limit value of the example) ⁇ 90% for relative comparison with the example.
  • the high temperature characteristics shown in Table 2 were evaluated based on attenuation with respect to 25 ° C. light flux. It is a value when the light flux at 50 ° C., 100 ° C., and 150 ° C. is measured and 25 ° C. is taken as 100%.
  • the pass conditions for evaluation are 97% or more at 50 ° C, 95% or more at 100 ° C, and 90% or more at 150 ° C. This value is not a standard value common to the world, but is currently considered as a guideline for highly reliable light-emitting elements.
  • the long-term reliability shown in Table 2 is that the light flux is measured at 85 ° C. and 85% RH for 500 hours (HRS) and 2,000 hours, and then taken out and dried at room temperature. This is the attenuation value of the luminous flux.
  • the pass conditions for the evaluation are 96% or more at 500 hrs and 93% or more at 2,000 hrs. This is a value that cannot be achieved without a highly reliable phosphor.
  • the examples of the present invention show relatively good color reproducibility and luminous flux values, and the luminous flux attenuation is relatively small when stored for a long time under high temperature or high temperature and high humidity.
  • Comparative Examples 1, 2, 3, 4, 5, and 8 have small light flux values, and Comparative Examples 1, 3, 4, 7, 8, and 9 have poor color reproducibility.
  • Comparative Examples 1, 2, 3, 4, and 6 in which silicate phosphors outside the scope of the present invention are used for the oxynitride phosphor (A), the high temperature characteristics and long-term reliability are inferior and the reliability is low.
  • the LED package cannot be expected to be applied to products such as televisions and monitors.
  • the phosphor of the present invention is used for a white light emitting device.
  • the white light emitting device of the present invention is used for a backlight of a liquid crystal panel, an illumination device, a signal device, and an image display device.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Led Device Packages (AREA)
  • Luminescent Compositions (AREA)

Abstract

This fluorophore comprises an oxynitride fluorophore (A) having a peak wavelength of 540 nm to 545 nm inclusive and a fluorescence intensity of 260% to 280% inclusive, and a nitride fluorophore (B) having a peak wavelength of 615 nm to 625 nm inclusive, wherein the mixing proportion of the oxynitride fluorophore (A) is from 74 mass% to 89 mass% inclusive, and the mixing proportion of the nitride fluorophore (B) is from 11 mass% to 19 mass% inclusive.

Description

蛍光体及び発光装置Phosphor and light emitting device
　本発明は、ＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）に用いられる蛍光体及びＬＥＤを用いた発光装置に関する。 The present invention relates to a phosphor used in an LED (Light Emitting Diode) and a light emitting device using the LED.
　白色発光装置に用いられる蛍光体として、β型サイアロンと赤色発光蛍光体の組み合わせがあり（特許文献１参照）、特定の色座標を有する赤色発光蛍光体と緑色発光蛍光体を組み合わせた蛍光体がある（特許文献２参照）。 As a phosphor used in a white light emitting device, there is a combination of β-type sialon and a red light emitting phosphor (see Patent Document 1), and a phosphor in which a red light emitting phosphor having a specific color coordinate and a green light emitting phosphor are combined. Yes (see Patent Document 2).
特開２００７－１８０４８３号公報Japanese Patent Laid-Open No. 2007-180483 特開２００８－１６６８２５号公報JP 2008-166825 A
　本発明の目的は、従来からある特定の窒化物蛍光体に酸窒化物蛍光体を加えて高輝度と高信頼性を両立させた蛍光体を提供することにあり、さらに、この蛍光体を用いた白色発光装置を提供することにある。 An object of the present invention is to provide a phosphor having both high luminance and high reliability by adding an oxynitride phosphor to a specific nitride phosphor, and further using this phosphor. It is to provide a white light emitting device.
　本発明は、ピーク波長５４０ｎｍ以上５４５ｎｍ以下、蛍光強度２６０％以上２８０％以下の酸窒化物蛍光体（Ａ）と、ピーク波長６１５ｎｍ以上６２５ｎｍ以下の窒化物蛍光体（Ｂ）とを有し、酸窒化物蛍光体（Ａ）の配合割合が７４質量％以上８９質量％以下であり、窒化物蛍光体（Ｂ）の配合割合が１１質量％以上１９質量％以下である蛍光体である。 The present invention includes an oxynitride phosphor (A) having a peak wavelength of 540 nm to 545 nm, a fluorescence intensity of 260% to 280%, and a nitride phosphor (B) having a peak wavelength of 615 nm to 625 nm, and an acid. It is a phosphor in which the blending ratio of the nitride phosphor (A) is 74 mass% or more and 89 mass% or less, and the blending ratio of the nitride phosphor (B) is 11 mass% or more and 19 mass% or less.
　酸窒化物蛍光体（Ａ）及び窒化物蛍光体（Ｂ）の配合比をａ及びｂとしたときに、それぞれの関係は、ａ＋ｂ≧８８質量％、且つ４．０≦ａ／ｂ≦８．０であることが好ましい。 When the blending ratio of the oxynitride phosphor (A) and the nitride phosphor (B) is a and b, the respective relationships are a + b ≧ 88% by mass and 4.0 ≦ a / b ≦ 8. 0 is preferred.
　酸窒化物蛍光体（Ａ）がβ型サイアロン、窒化物蛍光体（Ｂ）がＳＣＡＳＮであるのが好ましい。 The oxynitride phosphor (A) is preferably β-type sialon, and the nitride phosphor (B) is preferably SCASN.
　本願の他の観点からの発明は、前述の蛍光体と、当該蛍光体を発光面に搭載したＬＥＤとを有する発光装置である。 The invention from another aspect of the present application is a light emitting device including the above-described phosphor and an LED having the phosphor mounted on a light emitting surface.
　本発明によれば、高輝度で高温特性と長期信頼性を有する蛍光体及びこの蛍光体を用いた白色発光装置を提供することができる。 According to the present invention, a phosphor having high brightness, high temperature characteristics and long-term reliability, and a white light emitting device using the phosphor can be provided.
　本発明は、ピーク波長５４０ｎｍ以上５４５ｎｍ以下、蛍光強度２６０％以上２８０％以下の酸窒化物蛍光体（Ａ）と、ピーク波長６１５ｎｍ以上６２５ｎｍ以下の窒化物蛍光体（Ｂ）を有する蛍光体である。 The present invention is a phosphor having an oxynitride phosphor (A) having a peak wavelength of 540 nm to 545 nm and a fluorescence intensity of 260% to 280% and a nitride phosphor (B) having a peak wavelength of 615 nm to 625 nm. .
　この２種の蛍光体を混在させることにより、高輝度で高温特性と長期信頼性を有する蛍光体を得ることができた。 By mixing these two kinds of phosphors, a phosphor having high brightness, high temperature characteristics and long-term reliability could be obtained.
　酸窒化物蛍光体（Ａ）の配合割合は７４質量％以上８９質量％以下であり、窒化物蛍光体（Ｂ）の配合割合は１１質量％以上１９質量％以下である。酸窒化物蛍光体（Ａ）の配合割合は、あまりに少ないと輝度が低くなる傾向にあり、あまりに多いと高い演色性を得難くなる傾向にあるため、かかる範囲が好ましく、窒化物蛍光体（Ｂ）の配合割合も、あまりに少ないと高い演色性を示さず、甚だしい場合には白色光そのものが得られなくなる傾向にあり、あまりに多いと輝度が低下し、更には白色光が得られなくなる傾向にある。 The blending ratio of the oxynitride phosphor (A) is 74% by mass or more and 89% by mass or less, and the blending ratio of the nitride phosphor (B) is 11% by mass or more and 19% by mass or less. If the blending ratio of the oxynitride phosphor (A) is too small, the luminance tends to be low, and if it is too large, it tends to be difficult to obtain high color rendering properties. Therefore, such a range is preferable, and the nitride phosphor (B ) Is too low, high color rendering is not exhibited, and when it is severe, white light itself tends to be lost, and when it is too high, luminance tends to decrease and white light tends not to be obtained. .
　蛍光体の蛍光強度は、標準試料（ＹＡＧ、具体的には三菱化学株式会社製Ｐ４６Ｙ３）のピーク高さを１００％とした相対値を％表示したものである。蛍光強度の測定機は、株式会社日立ハイテック製Ｆ－７０００形分光光度計を用い、測定方法は、次のものである。
＜測定法＞
　１）試料セット：石英製セルに測定試料及び標準試料をそれぞれ充填し、測定機に交互にセットして測定した。充填は、相対充填密度３５％程度になるようにしてセル高さの３／４程度まで充填した。
　２）測定：４５５ｎｍの光で励起し、５００ｎｍから７００ｎｍの最大ピークの高さを読み取った。測定を５回行ない、最大値、最小値を除いて残りの３点の平均値とした。 The fluorescence intensity of the phosphor is expressed as a relative value in% with the peak height of the standard sample (YAG, specifically, P46Y3 manufactured by Mitsubishi Chemical Corporation) as 100%. The fluorescence intensity measuring instrument is an F-7000 spectrophotometer manufactured by Hitachi High-Tech Co., Ltd. The measuring method is as follows.
<Measurement method>
1) Sample set: A quartz cell was filled with a measurement sample and a standard sample, and each sample was alternately set on a measuring machine and measured. The filling was performed up to about 3/4 of the cell height so that the relative filling density was about 35%.
2) Measurement: Excited with 455 nm light, the height of the maximum peak from 500 nm to 700 nm was read. The measurement was performed 5 times, and the average value of the remaining three points was obtained except for the maximum value and the minimum value.
　本発明における酸窒化物蛍光体（Ａ）は、ピーク波長５４０ｎｍ以上５４５ｎｍ以下、蛍光強度２６０％以上２８０％以下の緑色発光酸窒化物蛍光体である。具体的には、β型サイアロンがあり、より具体的には、電気化学工業株式会社アロンブライト（登録商標）がある。 The oxynitride phosphor (A) in the present invention is a green light emitting oxynitride phosphor having a peak wavelength of 540 nm to 545 nm and a fluorescence intensity of 260% to 280%. Specifically, there is β-type sialon, and more specifically, there is Aron Bright (registered trademark) of Denki Kagaku Kogyo Co., Ltd.
　本発明における窒化物蛍光体（Ｂ）は、ピーク波長６１５ｎｍ以上６２５ｎｍ以下の窒化物蛍光体である。具体的には、ＳＣＡＳＮと略されてエスカズンとよばれる赤色蛍光体であり、より具体的には、三菱化学株式会社ＢＲ－１０２Ｄ（ピーク波長６２０ｎｍ）がある。この窒化物蛍光体（Ｂ）には、窒化物蛍光体（Ｂ）の添加量を超えない範囲で、ピーク波長の調整用としてＩｎｔｅｍａｔｉｘ社Ｒ６４３６（ピーク波長６３０ｎｍ）やＲ６５３５（ピーク波長６４０ｎｍ）、三菱化学株式会社のＢＲ－１０２Ｃ、ＢＲ－１０２Ｆ（ピーク波長６３０ｎｍ）又はＢＲ－１０１Ａ（ピーク波長６５０ｎｍ）等を混在させても良い。 The nitride phosphor (B) in the present invention is a nitride phosphor having a peak wavelength of 615 nm or more and 625 nm or less. Specifically, it is a red phosphor abbreviated as SCASN and called Escazun, and more specifically, there is Mitsubishi Chemical Corporation BR-102D (peak wavelength 620 nm). The nitride phosphor (B) includes an Intematix R6436 (peak wavelength: 630 nm), R6535 (peak wavelength: 640 nm), and Mitsubishi for adjusting the peak wavelength within a range not exceeding the addition amount of the nitride phosphor (B). Chemicals such as BR-102C, BR-102F (peak wavelength 630 nm), BR-101A (peak wavelength 650 nm), etc. may be mixed.
　高輝度かつ高信頼性を維持するために、酸窒化物蛍光体（Ａ）及び窒化物蛍光体（Ｂ）の配合量は多い方がよく、それぞれの配合割合をａ、ｂとしたとき、それぞれの関係は８８質量％≦ａ＋ｂであることが好ましい。 In order to maintain high luminance and high reliability, the amount of oxynitride phosphor (A) and nitride phosphor (B) should be large, and when the respective blending ratios are a and b, Is preferably 88% by mass ≦ a + b.
　窒化物蛍光体（Ｂ）は酸窒化物蛍光体（Ａ）に比べて視感度が低く、明るさに劣るため、その配合比は、低い方が好ましいが、あまりに低いと演色性までもが低下し、甚だしい場合にはＬＥＤが白色光を示さなくなるため、４．０≦ａ／ｂ≦８．０の範囲が好ましい。 The nitride phosphor (B) has lower visibility than the oxynitride phosphor (A) and is inferior in brightness, so its blending ratio is preferably low. However, if it is too low, the color rendering property is also lowered. However, since the LED does not show white light in a severe case, the range of 4.0 ≦ a / b ≦ 8.0 is preferable.
　酸窒化物蛍光体（Ａ）と窒化物蛍光体（Ｂ）、更には他の蛍光体との混合手段は、均一に混合又は希望する混合度合いに混合できれば、適宜選択できるものである。この混合手段にあっては、不純物が混入したり、蛍光体の形状や粒度が明らかに変わったりしないことが前提である。 The mixing means of the oxynitride phosphor (A) and the nitride phosphor (B), and other phosphors can be appropriately selected as long as it can be uniformly mixed or mixed to a desired mixing degree. In this mixing means, it is premised that impurities are not mixed and the shape and particle size of the phosphor are not clearly changed.
　本願の他の観点からの発明は、上述のように、混合した蛍光体と、当該蛍光体を発光面に搭載したＬＥＤとを有する発光装置である。ＬＥＤの発光面に搭載される際の蛍光体は、封止部材によって封止されたものである。封止部材としては、樹脂とガラスがあり、樹脂としてはシリコーン樹脂がある。ＬＥＤとしては、最終的に発光される色に合わせて赤色発光ＬＥＤ、青色発光ＬＥＤ、他の色を発光するＬＥＤを適宜選択することが好ましく、青色発光ＬＥＤの場合、窒化ガリウム系半導体で形成され、ピーク波長は４４０ｎｍ以上４６０ｎｍ以下にあるものが好ましく、さらに好ましくは、ピーク波長は、４４５ｎｍ以上４５５ｎｍ以下である。ＬＥＤの発光部の大きさは０．５ｍｍ角以上のものが好ましい。ＬＥＤチップの大きさは、かかる発光部の面積を有するものであれば適宜選択でき、好ましくは、１．０ｍｍ×０．５ｍｍ、更に好ましくは１．２ｍｍ×０．６ｍｍである。 The invention from another viewpoint of the present application is a light emitting device having a mixed phosphor and an LED having the phosphor mounted on a light emitting surface as described above. The phosphor when mounted on the light emitting surface of the LED is sealed by a sealing member. The sealing member includes a resin and glass, and the resin includes a silicone resin. As the LED, it is preferable to appropriately select a red light emitting LED, a blue light emitting LED, or an LED emitting another color in accordance with the color finally emitted. In the case of a blue light emitting LED, the LED is formed of a gallium nitride semiconductor. The peak wavelength is preferably from 440 nm to 460 nm, and more preferably from 445 nm to 455 nm. The LED light emitting part preferably has a size of 0.5 mm square or more. The size of the LED chip can be appropriately selected as long as it has the area of the light emitting portion, and is preferably 1.0 mm × 0.5 mm, more preferably 1.2 mm × 0.6 mm.
　本発明に係る実施例を、表及び比較例を用いて詳細に説明する。 Examples according to the present invention will be described in detail using tables and comparative examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示した蛍光体は、実施例及び比較例で用いた酸窒化物蛍光体（Ａ）及び窒化物蛍光体（Ｂ）である。表１の酸窒化物蛍光体（Ａ）のうち、Ｐ１だけが請求項１記載の範囲内の５４０ｎｍ以上５４５ｎｍ以下のピーク波長、２６０％以上２８０％以下の蛍光強度を有する蛍光体である。表１の窒化物蛍光体（Ｂ）のうち、Ｐ６のみが請求項１記載の範囲内の６１５ｎｍ以上６２５ｎｍ以下のピーク波長を有する蛍光体である。 The phosphors shown in Table 1 are the oxynitride phosphors (A) and nitride phosphors (B) used in Examples and Comparative Examples. Of the oxynitride phosphors (A) in Table 1, only P1 is a phosphor having a peak wavelength of 540 to 545 nm and a fluorescence intensity of 260 to 280% within the range of claim 1. Of the nitride phosphors (B) in Table 1, only P6 is a phosphor having a peak wavelength of 615 nm or more and 625 nm or less within the range of claim 1.
　これら蛍光体を表２の割合で混合して、実施例、比較例に係る蛍光体を得た。 These phosphors were mixed at a ratio shown in Table 2 to obtain phosphors according to Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１の蛍光体は、酸窒化物蛍光体（Ａ）としての表１のＰ１の蛍光体を７４質量％、窒化物蛍光体（Ｂ）としての表１のＰ６の蛍光体を１３質量％及びそれ以外の蛍光体として酸窒化物蛍光体（Ａ）の比較例である表１のＰ４の蛍光体を１３質量％配合したものである。表２での蛍光体の構成におけるＰ１乃至Ｐ８の値は質量％である。蛍光体同士の混合にあっては、合計２．５ｇを計量してビニール袋内で混合した上、シリコーン樹脂（東レダウコーニング株式会社ＯＥ６６５６）４７．５ｇと一緒に自転公転式の混合機（株式会社シンキー製「あわとり練太郎」ＡＲＥ－３１０（登録商標））で混合した。表２のａ＋ｂ及びａ／ｂは、酸窒化物蛍光体（Ａ）の実施例であるＰ１の配合割合をａ、窒化物蛍光体（Ｂ）の実施例であるＰ６の配合割合をｂとしたときの値である。但し、窒化物蛍光体（Ｂ）のＰ７及びＰ８は、Ｐ６の配合量を超えた場合（比較例５と比較例９）、権利範囲外となるので、ｂの値の対象となっていない。 The phosphor of Example 1 is 74% by mass of the phosphor of P1 in Table 1 as the oxynitride phosphor (A), and 13% by mass of the phosphor of P6 in Table 1 as the nitride phosphor (B). In addition, 13 mass% of the phosphor of P4 in Table 1 which is a comparative example of the oxynitride phosphor (A) is blended as the other phosphor. The values of P1 to P8 in the phosphor structure in Table 2 are mass%. When mixing phosphors, a total of 2.5 g was weighed and mixed in a plastic bag, and a rotating and rotating mixer (stock) It was mixed with “Shintaro Awatori” (ARE-310 (registered trademark)) manufactured by Shinky. In a + b and a / b in Table 2, the mixing ratio of P1 which is an example of the oxynitride phosphor (A) is a, and the mixing ratio of P6 which is an example of the nitride phosphor (B) is b. Is the time value. However, when P7 and P8 of the nitride phosphor (B) exceed the blending amount of P6 (Comparative Example 5 and Comparative Example 9), they are outside the scope of the right and are not subject to the value of b.
　ＬＥＤへの蛍光体の搭載は、凹型のパッケージ本体の底部にＬＥＤを置いて、基板上の電極とワイヤボンディングした後、混合した蛍光体をマイクロシリンジから注入して行なった。蛍光体の搭載後、１２０℃で硬化させた後、１１０℃×１０時間のポストキュアを施して封止した。ＬＥＤは、発光ピーク波長４４８ｎｍで、チップ１．０ｍｍ×０．５ｍｍの大きさのものを用いた。 The phosphor was mounted on the LED by placing the LED on the bottom of the concave package body, wire bonding the electrode on the substrate, and then injecting the mixed phosphor from the microsyringe. After mounting the phosphor, it was cured at 120 ° C., and then post-cured at 110 ° C. for 10 hours and sealed. The LED used had an emission peak wavelength of 448 nm and a chip size of 1.0 mm × 0.5 mm.
　表２で示した評価について説明する。
　表２の初期評価として、演色性の評価を採用した。演色性の評価には色再現範囲を採用し、色座標におけるＮＴＳＣ規格比の面積（％）で表した。数字が大きいほど演色性が高い。評価の合格条件は７２％以上であり、これは一般的なＬＥＤ－ＴＶ向けに採用されている条件である。 The evaluation shown in Table 2 will be described.
As an initial evaluation in Table 2, the evaluation of color rendering was adopted. For the evaluation of color rendering, a color reproduction range was adopted, and the area was expressed as an area (%) of the NTSC standard ratio in color coordinates. The larger the number, the higher the color rendering. The pass condition for evaluation is 72% or more, which is a condition adopted for general LED-TV.
　表２の輝度は２５℃での光束（ｌｍ）で評価した。電流６０ｍＡを１０分間印加した後の測定値を取った。評価の合格条件は、２６．４ｌｍ以上である。この値は測定機や条件によって変わるため、実施例との相対的な比較するために、（実施例の下限値）×９０％として設定した値である。 The luminance in Table 2 was evaluated by the luminous flux (lm) at 25 ° C. The measured value after applying a current of 60 mA for 10 minutes was taken. The pass condition of evaluation is 26.4 lm or more. Since this value varies depending on the measuring machine and conditions, it is a value set as (lower limit value of the example) × 90% for relative comparison with the example.
　表２の高温特性は、２５℃の光束に対する減衰性で評価した。５０℃、１００℃、１５０℃での光束を測定して、２５℃を１００％とした時の値である。評価の合格条件は、５０℃で９７％以上、１００℃で９５％以上、１５０℃で９０％以上である。この値は、世界共通の規格値ではないが、現状、高信頼性の発光素子の目安と考えられている。 The high temperature characteristics shown in Table 2 were evaluated based on attenuation with respect to 25 ° C. light flux. It is a value when the light flux at 50 ° C., 100 ° C., and 150 ° C. is measured and 25 ° C. is taken as 100%. The pass conditions for evaluation are 97% or more at 50 ° C, 95% or more at 100 ° C, and 90% or more at 150 ° C. This value is not a standard value common to the world, but is currently considered as a guideline for highly reliable light-emitting elements.
　表２の長期信頼性は、８５℃、８５％ＲＨにおいて、それぞれ５００時間（ＨＲＳ）及び２，０００時間放置した後、取り出して室温で乾燥した際の光束を測定し、初期値を１００％としたときの光束の減衰値である。
　評価の合格条件は、５００ｈｒｓで９６％以上、２，０００ｈｒｓで９３％以上である。これは高信頼性の蛍光体でなくては達成できない値である。 The long-term reliability shown in Table 2 is that the light flux is measured at 85 ° C. and 85% RH for 500 hours (HRS) and 2,000 hours, and then taken out and dried at room temperature. This is the attenuation value of the luminous flux.
The pass conditions for the evaluation are 96% or more at 500 hrs and 93% or more at 2,000 hrs. This is a value that cannot be achieved without a highly reliable phosphor.
　表２に示すように、本発明の実施例は、比較的良好な色再現性、光束値を示し、且つ高温や高温高湿下で長期保存した際の光束の減衰も比較的小さい。
　比較例１、２、３、４、５、８は、光束値が小さく、比較例１、３、４、７、８、９では色再現性に劣る。また、酸窒化物蛍光体（Ａ）に本発明の範囲外のシリケート系蛍光体を用いた比較例１、２、３、４、６では、高温特性、長期信頼性に劣り、信頼性の低いＬＥＤパッケージとなって、テレビやモニターなどの製品に適用することは到底望めない。 As shown in Table 2, the examples of the present invention show relatively good color reproducibility and luminous flux values, and the luminous flux attenuation is relatively small when stored for a long time under high temperature or high temperature and high humidity.
Comparative Examples 1, 2, 3, 4, 5, and 8 have small light flux values, and Comparative Examples 1, 3, 4, 7, 8, and 9 have poor color reproducibility. In Comparative Examples 1, 2, 3, 4, and 6 in which silicate phosphors outside the scope of the present invention are used for the oxynitride phosphor (A), the high temperature characteristics and long-term reliability are inferior and the reliability is low. The LED package cannot be expected to be applied to products such as televisions and monitors.
　本発明の蛍光体は、白色発光装置に用いられる。本発明の白色発光装置としては、液晶パネルのバックライト、照明装置、信号装置、画像表示装置に用いられる。 The phosphor of the present invention is used for a white light emitting device. The white light emitting device of the present invention is used for a backlight of a liquid crystal panel, an illumination device, a signal device, and an image display device.

Claims (4)

  1. 　ピーク波長５４０ｎｍ以上５４５ｎｍ以下、蛍光強度２６０％以上２８０％以下の酸窒化物蛍光体（Ａ）と、ピーク波長６１５ｎｍ以上６２５ｎｍ以下の窒化物蛍光体（Ｂ）を有し、酸窒化物蛍光体（Ａ）の配合割合が７４質量％以上８９質量％以下であり、窒化物蛍光体（Ｂ）の配合割合が１１質量％以上１９質量％以下である蛍光体。 An oxynitride phosphor (A) having a peak wavelength of 540 nm to 545 nm and a fluorescence intensity of 260% to 280% and a nitride phosphor (B) having a peak wavelength of 615 nm to 625 nm, A phosphor in which the blending ratio of A) is 74 mass% or more and 89 mass% or less, and the blending ratio of the nitride phosphor (B) is 11 mass% or more and 19 mass% or less.
  2. 　請求項１記載酸窒化物蛍光体（Ａ）及び窒化物蛍光体（Ｂ）の配合割合をａ及びｂとしたときに、ａ＋ｂ≧８８質量％、且つ４．０≦ａ／ｂ≦８．０の関係を有する蛍光体。 When the mixing ratio of the oxynitride phosphor (A) and the nitride phosphor (B) according to claim 1 is a and b, a + b ≧ 88 mass% and 4.0 ≦ a / b ≦ 8.0 A phosphor having the following relationship.
  3. 　酸窒化物蛍光体（Ａ）がβ型サイアロン、窒化物蛍光体（Ｂ）がＳＣＡＳＮである請求項１乃至２のいずれか一項に記載の蛍光体。 The phosphor according to claim 1, wherein the oxynitride phosphor (A) is β-type sialon and the nitride phosphor (B) is SCASN.
  4. 　請求項１乃至３のいずれか一項に記載の蛍光体と、当該蛍光体を発光面に搭載したＬＥＤとを有する発光装置。 A light emitting device comprising: the phosphor according to any one of claims 1 to 3; and an LED having the phosphor mounted on a light emitting surface.
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