JP2017016800A - Rare earth-free white lighting device - Google Patents
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- 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
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- 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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Abstract
Description
本発明は希土類を含まない蛍光体で発光層が形成された白色照明装置に関するものである。 The present invention relates to a white lighting device in which a light emitting layer is formed of a phosphor containing no rare earth.
近年、白色照明装置は白色ＬＥＤに代表されるように携帯電話や様々な表示装置に用いられると同時に省エネルギーなどの観点から蛍光灯の代わりの室内照明装置としても注目されている。白色ＬＥＤは近紫外や青色ＬＥＤを励起光源とし、種々の波長に発光強度を持つ蛍光体を組み合わせて白色光を生み出している。具体的には青色ＬＥＤを励起光に黄色や、緑色、赤色蛍光体を発光させて白色光を得るというものである。（特許文献１） In recent years, white illuminating devices are used in mobile phones and various display devices, as represented by white LEDs, and at the same time, are attracting attention as indoor lighting devices instead of fluorescent lamps from the viewpoint of energy saving. White LEDs use near-ultraviolet or blue LEDs as excitation light sources, and produce white light by combining phosphors having emission intensities at various wavelengths. Specifically, a blue LED emits yellow, green, and red phosphors as excitation light to obtain white light. (Patent Document 1)
しかしながら、複数の蛍光体を組み合わせて得る白色ＬＥＤの白色光には色抜けや特定波長のみに強い発光を示すなどの問題点もあり、室内照明として使用するには演色性を向上させるための努力が必要となる。そのため、照明用白色ＬＥＤに用いる蛍光体は発光波長が幅広い波長に広がり、特定波長に急峻な発光ピークがなく、さらには出来うる限り少ない蛍光体の組み合わせで白色蛍光を示すことが最も望ましい。本発明者等は、鋭意検討した結果、バナジウム酸化物ＡＶＯ3（ＡはＫ、Ｒｂ、Ｃｓからなる群より選ばれる１種以上であって、Ｌｉ、Ｎａ、ＮＨ4からなる群より選ばれる１種以上を含んでいてもよい）が、単一物質でブロードな発光スペクトルを示し、紫外・近紫外光励起により蛍光スペクトルが５００〜５４０ｎｍ付近に極大を持ち４００〜８００ｎｍの範囲にブロードに広がる白色蛍光を発する蛍光体であり、特にＣｓＶＯ3において励起波長３４５ｎｍにおいて内部量子効率８７％を達成する極めて良い蛍光体であることを知見した（非特許文献１）。この蛍光体から発せられる蛍光スペクトルは、現在民生で使われている照明器具、通常の蛍光灯のスペクトルに近い発光スペクトルであることから、白色ＬＥＤ用の蛍光体としても期待される。単独での発光色はＣＩＥ色度座標上で（０.３１、０.４２）付近であるため、一般照明として利用するためには、色度座標上の青色、紫、赤色光のうち少なくとも一つの発光色を持つ蛍光体と組み合わすことで純度の良い白色光が得られる。例えば赤色光を発する蛍光体はＥｕ3+やＰｒ3+を含む蛍光体が好適であり、現在多くの照明装置に用いられている。しかしながら、近年、照明装置のみならず磁石や光学ガラスなど多くの材料に用いられる希土類イオンの原料調達が不安定になる場合の問題が指摘され、希土類フリー材料の開発が求められている。ＡＶＯ3は希土類イオンを含まずに強い発光を示すため、希土類フリー白色照明装置に好適と期待される。 However, the white LED white light obtained by combining a plurality of phosphors has problems such as color loss and strong light emission only at a specific wavelength, and efforts to improve color rendering properties when used as indoor lighting. Is required. For this reason, it is most desirable that the phosphor used in the white LED for illumination has a wide emission wavelength, does not have a sharp emission peak at a specific wavelength, and further exhibits white fluorescence with as few phosphor combinations as possible. As a result of intensive studies, the present inventors have found that vanadium oxide AVO 3 (A is one or more selected from the group consisting of K, Rb, Cs, and 1 selected from the group consisting of Li, Na, NH 4. It may contain more than one species) but exhibits a broad emission spectrum with a single substance, and the fluorescence spectrum has a maximum in the vicinity of 500 to 540 nm and broadly spreads in the range of 400 to 800 nm by excitation with ultraviolet and near ultraviolet light. It was found that the phosphor is a very good phosphor that achieves an internal quantum efficiency of 87% at an excitation wavelength of 345 nm, particularly in CsVO 3 (Non-patent Document 1). Since the fluorescence spectrum emitted from this phosphor is an emission spectrum close to that of lighting fixtures currently used in consumer and ordinary fluorescent lamps, it is also expected as a phosphor for white LEDs. Since the single emission color is in the vicinity of (0.31, 0.42) on the CIE chromaticity coordinates, at least one of blue, purple, and red light on the chromaticity coordinates is required for use as general illumination. By combining with a phosphor having two emission colors, white light with high purity can be obtained. For example, a phosphor that emits red light is preferably a phosphor containing Eu 3+ or Pr 3+ , and is currently used in many lighting devices. However, in recent years, problems have been pointed out when the raw material procurement of rare earth ions used in many materials such as magnets and optical glass as well as lighting devices becomes unstable, and the development of rare earth-free materials has been demanded. Since AVO 3 does not contain rare earth ions and exhibits strong light emission, it is expected to be suitable for a rare earth-free white illumination device.
本発明者は、前述のような従来技術を背景とし、希土類を含まないＡＶＯ3蛍光体を用いた白色照明装置に着目した試験・研究を進める過程で、ＡＶＯ3の単独での発光色は若干比較的大きな緑色成分を含み一般照明用途には発光色調整が望ましいとの知見を得て、複数の蛍光体と混合して発光色を調整することを検討したが、付加する蛍光体の吸収スペクトルが可視光領域にも存在する場合、ＡＶＯ3から発せられるブロードな白色光のスペクトル形状が損なわれるとの問題点が存在することを認識した。特に、ＡＶＯ3と組み合わせて白色光を調整する場合、赤色発光を示すＭｎ2+やＭｎ4+が好適であるとの知見が得られたが、それらの蛍光体は共に可視光に吸収を持つため、ＡＶＯ3が発する蛍光の吸収を回避することが必要であるとの問題点も同時に認識した。 With the background of the above-described conventional technology, the present inventor has made a slight emission color of AVO 3 alone in the course of conducting tests and research focusing on a white illumination device using an AVO 3 phosphor that does not contain a rare earth. Obtaining the knowledge that the emission color adjustment is desirable for general lighting applications that contain a relatively large green component, we studied the adjustment of the emission color by mixing with multiple phosphors, but the absorption spectrum of the added phosphors It has been recognized that there is a problem that the spectral shape of the broad white light emitted from AVO 3 is impaired when is also present in the visible light region. In particular, when adjusting white light in combination with AVO 3 , it was found that Mn 2+ and Mn 4+ showing red light emission are suitable, but both of these phosphors absorb visible light. Therefore, the problem that it is necessary to avoid absorption of fluorescence emitted by AVO 3 was also recognized at the same time.
本発明は、前述のような試験・研究過程で認識された問題点を解決し、８０以上の平均演色評価数Ｒａとなる白色光を発することが可能な希土類イオンを含まない白色照明装置を提供することを課題とする。 The present invention provides a white illumination device that does not contain rare earth ions and that can solve the problems recognized in the test and research processes as described above and can emit white light having an average color rendering index Ra of 80 or more. The task is to do.
本発明者は、前述のような試験・研究の過程で、次の（ａ）〜（ｄ）のような知見を得た。
（ａ）ＡＶＯ3と組み合わせて白色光を調整する場合、赤色発光を示すＭｎ2+やＭｎ4+の両方又はどちらか一方を発光中心とする蛍光体が好適である。
（ｂ）Ｍｎイオンの赤色発光部をＡＶＯ3の広帯域発光部と紫外・近紫外励起光部の間に挿入する配置とすることにより、上述のような白色光スペクトル形状が損なわれるという問題点が解決できる。
（ｃ）ＡＶＯ3蛍光体としてＡdＶＯ3（ＡはＣｓを必ず含有するアルカリ金属で、Ｌｉ、Ｎａ、Ｋ、Ｒｂを含んでいても良い、ｄ＝０.９９〜１.０４）が好適である。
（ｄ）前記配置は、各蛍光体を含有させた透明樹脂を相互に積層させることによっても実現できる。
The inventor has obtained the following findings (a) to (d) in the course of the test and research as described above.
(A) When white light is adjusted in combination with AVO 3 , a phosphor having an emission center in both or one of Mn 2+ and Mn 4+ showing red emission is suitable.
(B) By arranging the red light emitting part of Mn ions to be inserted between the broadband light emitting part of AVO 3 and the ultraviolet / near ultraviolet excitation light part, there is a problem that the white light spectrum shape as described above is impaired. Solvable.
(C) As AVO 3 phosphor, A d VO 3 (A is an alkali metal that necessarily contains Cs and may contain Li, Na, K, and Rb, d = 0.99 to 1.04) is preferable. It is.
(D) The above arrangement can also be realized by laminating transparent resins containing each phosphor.
本発明は、上記のような知見に基づくものであり、この出願によれば、以下の発明が提供される。
＜１＞２５０ｎｍ以上４１０ｎｍ以下の光を発する発光部と、Ｍｎ4+とＭｎ2+の両方若しくはどちらか一方を発光中心とするＭｎ系蛍光体又は該蛍光体を含有する透明樹脂と、ＡdＶＯ3（ＡはＣｓを必ず含有するアルカリ金属で、Ｌｉ、Ｎａ、Ｋ、Ｒｂを含んでいても良い、ｄ＝０.９９〜１.０４）蛍光体又は該蛍光体を含有する透明樹脂とがこの順序で配置され、前記発光部を発光させることによって前記蛍光体が励起されて発光し８０以上の平均演色評価数Ｒａとなる白色光を発することを特徴とする白色照明装置。
＜２＞前記Ｍｎ系蛍光体を含有する透明樹脂と、前記ＡdＶＯ3蛍光体を含有する透明樹脂とは、前記順序で積層されていることを特徴とする＜１＞に記載の白色照明装置。
The present invention is based on the above knowledge, and according to this application, the following invention is provided.
A light emitting unit for emitting light below <1> 250 nm or more 410 nm, and a transparent resin containing a Mn-based phosphor or fluorescent body and both or either the light emission center of the Mn 4+ and Mn 2+, A d VO 3 (A is an alkali metal that necessarily contains Cs and may contain Li, Na, K, and Rb, d = 0.99 to 1.04) a phosphor or a transparent resin containing the phosphor; Are arranged in this order, and the phosphor is excited to emit light by emitting light from the light emitting portion, and emits white light having an average color rendering index Ra of 80 or more.
<2> The white illumination according to <1>, wherein the transparent resin containing the Mn-based phosphor and the transparent resin containing the A d VO 3 phosphor are laminated in the above order. apparatus.
本発明の白色照明装置は、原料調達に懸念がある希土類を含む蛍光体を用いることなく、８０以上の平均演色評価指数Ｒａとなる白色光を発することが可能である。 The white lighting device of the present invention can emit white light having an average color rendering index Ra of 80 or more without using a phosphor containing a rare earth that has a concern for raw material procurement.
本発明において用いるＡdＶＯ3（ｄ＝０.９９〜１.０４）で示されるバナジウム酸化物蛍光粉体は、白色ＬＥＤの励起光源である紫外・近紫外ＬＥＤによって励起出来る２５０〜４１０ｎｍの範囲に強い励起スペクトルを持つため、蛍光ランプで発生する紫外線や紫外・近紫外ＬＥＤ、あるいは紫外・近紫外光を発するＥＬ面発光装置などが励起光源として利用可能である。この励起光によって発せられる蛍光スペクトルは３９０〜８００ｎｍに広がり、緑色成分の比較的強い白色光を発する。ここに長波長側、主として赤色領域に強い発光を持つ蛍光体との組み合わせによって純白色に近づいた発光色を得ることができる。Ｍｎ4+とＭｎ2+の両方あるいはどちらか一方の赤色蛍光を用いれば色度調整可能な希土類イオンフリー白色ＬＥＤとして機能するが、ＡdＶＯ3の蛍光を吸収しない構成で発光装置を作製しなければならない。すなわち、装置底部に２５０ｎｍ以上４１０ｎｍ以下の光を発する発光部、例えば３６５ｎｍ以上４０５ｎｍ以下の光を発する近紫外ＬＥＤを配し、その上部にＭｎ4+とＭｎ2+の両方あるいはどちらか一方を発光中心とする蛍光体あるいは該蛍光体を含有する透明樹脂を配し、さらにその上部に主としてＡにＣｓを含むＡdＶＯ3蛍光体あるいは該蛍光体を含有する透明樹脂を積層させることによって、底部発光装置を発光させることで上部に配した蛍光体層が励起されて発光し８０以上の平均演色評価数Ｒａとなる白色光を発することを特徴とする希土類フリー白色照明装置が作製できる。蛍光体含有樹脂厚等を調整することによって、該励起光源によって励起された蛍光によって形成される光が９０以上の平均演色評価数Ｒａを持ち、全ての演色評価数（Ｒ１〜Ｒ８）と特殊演色評価数（Ｒ９〜Ｒ１５）が８０以上の演色性を持つ、極めて良い白色光を得ることも可能である。これらの構成においては水銀や鉛などを含まないため、環境・人体への悪影響も少ない。したがって、本発明の白色照明装置は、白色ＬＥＤ等としてきわめて有用なものであり、日常灯等の照明器具や各種表示機器に用いられるバックライト等の表示器具等として利用することができる。 The vanadium oxide fluorescent powder represented by A d VO 3 (d = 0.99 to 1.04) used in the present invention is in a range of 250 to 410 nm that can be excited by an ultraviolet / near ultraviolet LED that is an excitation light source of a white LED. Therefore, it is possible to use, as an excitation light source, an ultraviolet ray generated by a fluorescent lamp, an ultraviolet / near ultraviolet LED, or an EL surface emitting device that emits ultraviolet / near ultraviolet light. The fluorescence spectrum emitted by this excitation light spreads to 390 to 800 nm and emits a relatively strong white light with a green component. Here, a light emission color close to pure white can be obtained by combining with a phosphor having a strong light emission on the long wavelength side, mainly in the red region. The use of one of the red fluorescence both or either Mn 4+ and Mn 2+ functions as adjustable chromaticity rare earth ion-free white LED, but to produce a light-emitting device in a configuration that does not absorb the fluorescence of A d VO 3 There must be. That is, a light emitting part that emits light of 250 nm to 410 nm, for example, a near-ultraviolet LED that emits light of 365 nm to 405 nm, is arranged at the bottom of the device, and emits Mn 4+ and / or Mn 2+ on the upper part. disposing a transparent resin containing a phosphor or fluorescent body having a center, by further mainly laminating a transparent resin containing a d VO 3 phosphor or fluorescent body containing Cs in a on the top, bottom By emitting light from the light emitting device, a rare earth-free white illumination device characterized in that the phosphor layer disposed above is excited to emit light and emit white light having an average color rendering index Ra of 80 or more can be produced. By adjusting the thickness of the phosphor-containing resin, the light formed by the fluorescence excited by the excitation light source has an average color rendering index Ra of 90 or more, and all the color rendering indices (R1 to R8) and special color rendering It is also possible to obtain very good white light having a color rendering property of an evaluation number (R9 to R15) of 80 or more. Since these components do not contain mercury or lead, there are few adverse effects on the environment and human body. Therefore, the white lighting device of the present invention is extremely useful as a white LED or the like, and can be used as a lighting device such as a daily light or a display device such as a backlight used in various display devices.
本発明で用いるバナジウム酸化物蛍光粉体は、上記組成式に含まれる元素のみから構成することが望ましいが、内部量子効率を大幅に低下しない範囲（例えば５.０原子％以内、好ましくは１.０原子％以内、より好ましくは０.１原子％以内の範囲）で他の元素（例えば、Ｇｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、ＮＨ4等）を含有することも許容される。Ｍｎ4+とＭｎ2+の両方あるいはどちらか一方を発光中心とする蛍光体としてＭｇ2ＴｉＯ4：Ｍｎ4+やＫ2ＳｉＦ6：Ｍｎ4+などが利用可能である。 The vanadium oxide fluorescent powder used in the present invention is preferably composed only of elements contained in the above composition formula, but the range in which the internal quantum efficiency is not significantly reduced (for example, within 5.0 atomic%, preferably 1. It is allowed to contain other elements (eg, Ge, Mg, Ca, Sr, Ba, Zn, NH 4, etc.) within 0 atomic%, more preferably within 0.1 atomic%. Mg 2 TiO 4 : Mn 4+ , K 2 SiF 6 : Mn 4+, etc. can be used as a phosphor having an emission center of either or both of Mn 4+ and Mn 2+ .
本発明で用いるＡdＶＯ3蛍光体及びＭｎ系蛍光体についての上述のような配置は、それぞれ適宜の透明の支持体（例えば、透明板、透明容器、透明中空体等）により支持乃至保持することにより行っても良いが、好適には、それぞれ透明の樹脂中に含有させ、それらの樹脂を積層させることにより行うことができる。透明の樹脂としては、限定するものではないが、シリコーン樹脂、ポリカーボネート樹脂、スチレン系樹脂、ポリメチルメタクリレート等のアクリル樹脂、ＰＥＴ等のポリエステル樹脂、エポキシ樹脂、アクリロニトリル樹脂等が挙げられる。 Arrangement as described above for A d VO 3 phosphor and Mn phosphor used in the present invention, the support of each of the appropriate transparent (e.g., transparent plate, a transparent container, transparent hollow body, etc.) is supported to hold the However, it can be preferably carried out by laminating these resins in transparent resins. Examples of the transparent resin include, but are not limited to, silicone resins, polycarbonate resins, styrene resins, acrylic resins such as polymethyl methacrylate, polyester resins such as PET, epoxy resins, and acrylonitrile resins.
以下、実施例により本発明を更に詳細に説明するが、本発明は、この実施例に限定されず、本発明の要旨を逸脱しない範囲で適宜材料変更や設定調整等が可能である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this Example, A material change, a setting adjustment, etc. are possible suitably in the range which does not deviate from the summary of this invention.
実施例１
固相法を用いてＣｓＶＯ3の合成を行った。Ｃｓ、Ｖに対して各々Ｃｓ2ＣＯ3、Ｖ2Ｏ5を出発材料とし、Ｃｓ／Ｖ＝１.０５の組成比となるよう秤量して、全量に対し１５ｗｔ％の水を加えて混合した後、室温（２０℃）にて１時間放置後、６０℃で２時間乾燥させ、３５０℃で１２時間仮焼を行った。室温へ取り出したのち、再び１５ｗｔ％の水を加えて混合し、再び３５０℃で１２時間仮焼した。その後、４５０℃まで昇温し１２時間焼成して反応を進行させ、得られた粉体はＣｓＶＯ3と同定された。次にＭｎ4+を含み赤色発光する蛍光体Ｍｇ2ＴｉＯ4：Ｍｎ4+をシリコーン樹脂と混練し３８５ｎｍの近紫外ＬＥＤ上に固定化した後、ＣｓＶＯ3蛍光粉体をシリコーン樹脂と混練し、その上部にさらに固定化することによって希土類フリー白色ＬＥＤを作製した。作製した白色ＬＥＤはＣＩＥ色度座標上で（０.３３、０.３８）で表現される白色光を示し色温度は５５９６Ｋ、Ｒａは９１.１であった。
Example 1
CsVO 3 was synthesized using a solid phase method. Cs 2 CO 3 and V 2 O 5 were used as starting materials for Cs and V, respectively, and weighed so that the composition ratio was Cs / V = 1.05, and 15 wt% water was added to the total amount and mixed. Then, after leaving at room temperature (20 degreeC) for 1 hour, it dried at 60 degreeC for 2 hours, and calcined at 350 degreeC for 12 hours. After taking out to room temperature, 15 wt% water was added and mixed again, and it was calcined again at 350 ° C. for 12 hours. Thereafter, the temperature was raised to 450 ° C. and the reaction was allowed to proceed by baking for 12 hours. The resulting powder was identified as CsVO 3 . Next, the phosphor Mg 2 TiO 4 : Mn 4+ containing Mn 4+ and emitting red light is kneaded with a silicone resin and fixed on a 385 nm near-ultraviolet LED, and then the CsVO 3 fluorescent powder is kneaded with the silicone resin. A rare earth-free white LED was produced by further fixing on the upper part. The produced white LED showed white light expressed by (0.33, 0.38) on the CIE chromaticity coordinates, the color temperature was 5596K, and Ra was 91.1.
比較例１
実施例１に示した手法で作製したＣｓＶＯ3蛍光粉体をシリコーン樹脂と混練し３８５ｎｍの近紫外ＬＥＤ上に固定化することによって希土類フリー白色ＬＥＤを作製した。ＣｓＶＯ3蛍光粉体のみで作製した白色ＬＥＤはＣＩＥ色度座標上で（０.３２、０.４２）で表現される擬白色光を示し色温度は６０２８Ｋ、Ｒａは７０.４であった。
Comparative Example 1
A rare earth-free white LED was produced by kneading the CsVO 3 fluorescent powder produced by the method shown in Example 1 with a silicone resin and immobilizing it on a 385 nm near-ultraviolet LED. The white LED produced only with the CsVO 3 fluorescent powder showed pseudo white light expressed by (0.32, 0.42) on the CIE chromaticity coordinates, the color temperature was 6028K, and the Ra was 70.4.
比較例２
実施例１に示した手法で作製したＣｓＶＯ3蛍光粉体とＭｎ4+を含み赤色発光する蛍光体の両方とシリコーン樹脂とを混練し３８５ｎｍの近紫外ＬＥＤ上に固定化することによって希土類フリー白色ＬＥＤを作製したが、作製した白色ＬＥＤはＣＩＥ色度座標上で（０.３７、０.４５）で表現される黄色発光を示し色温度は４６９５Ｋ、Ｒａは７３.４に留まった。
Comparative Example 2
Rare earth-free white by mixing both CsVO 3 fluorescent powder prepared by the method shown in Example 1, phosphor containing Mn 4+ and emitting red light and silicone resin, and immobilizing on a near-ultraviolet LED of 385 nm. Although the LED was manufactured, the manufactured white LED showed yellow light emission represented by (0.37, 0.45) on the CIE chromaticity coordinates, and the color temperature remained at 4695 K and Ra remained at 73.4.
比較例３
実施例１に示した手法で作製したＣｓＶＯ3蛍光粉体をシリコーン樹脂と混練し３８５ｎｍの近紫外ＬＥＤ上に固定化した後、Ｍｎ4+を含み赤色発光する蛍光体Ｍｇ2ＴｉＯ4：Ｍｎ4+をシリコーン樹脂と混練し、その上部にさらに固定化することによって希土類フリー白色ＬＥＤを作製したが、作製した白色ＬＥＤはＣＩＥ色度座標上で（０.４０、０.４７）で表現される黄色発光を示し色温度は４１７２Ｋ、Ｒａは６９.６に留まった。
Comparative Example 3
A CsVO 3 fluorescent powder produced by the method shown in Example 1 is kneaded with a silicone resin and fixed on a near-ultraviolet LED of 385 nm, and then a phosphor Mg 2 TiO 4 : Mn 4 containing Mn 4+ and emitting red light. A rare earth-free white LED was produced by kneading + with a silicone resin and further fixing it on the upper part. The produced white LED is expressed by (0.40, 0.47) on the CIE chromaticity coordinates. Yellow light was emitted, the color temperature was 4172K, and Ra remained at 69.6.
本発明の白色照明装置は希土類フリー白色照明としてきわめて有用なものであり、資源量の減少等の理由により希土類イオン原料の調達に難が出た際に現在利用されている照明装置の代替装置として利用可能である。 The white lighting device of the present invention is extremely useful as a rare earth-free white lighting, and is an alternative to the lighting device currently used when the procurement of rare earth ion raw materials is difficult due to a decrease in the amount of resources. Is available.
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