JPH07179852A - Stimulable phosphor and fluorescent lamp - Google Patents
Stimulable phosphor and fluorescent lampInfo
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- JPH07179852A JPH07179852A JP32487793A JP32487793A JPH07179852A JP H07179852 A JPH07179852 A JP H07179852A JP 32487793 A JP32487793 A JP 32487793A JP 32487793 A JP32487793 A JP 32487793A JP H07179852 A JPH07179852 A JP H07179852A
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- phosphor
- emission
- fluorescent lamp
- color rendering
- light emitting
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はＥｕを付活した赤色ない
し深赤色発光の蛍光体およびこれを用いた蛍光ランプお
よびこの蛍光体の製造方法に係り、さらに詳しくは、発
光効率が高く、かつ高演色性を呈する３波長域発光型の
蛍光ランプ用に適する赤色ないし深赤色に発光する蛍光
体およびこの蛍光体を用いた蛍光ランプに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor emitting red or deep red light activated by Eu, a fluorescent lamp using the same, and a method for manufacturing the phosphor, more specifically, high luminous efficiency and The present invention relates to a phosphor that emits red or deep red light suitable for a three-wavelength band emission type fluorescent lamp that exhibits high color rendering properties, and a fluorescent lamp that uses this phosphor.
【０００２】[0002]
【従来の技術】周知のように、近年一般照明用蛍光ラン
プとしては、いわゆる３波長域発光型の蛍光ランプが主
流になっている。そして、この種の３波長域発光型蛍光
ランプでは、比較的狭帯域の発光スペクトル分布を有す
る青色発光，緑色発光および赤色発光の３種の混合蛍光
体で、所要の蛍光膜（蛍光体層）を形成した構成を採っ
ている。最近では、さらに演色性を向上させるために青
緑色発光および深赤色発光の蛍光体を混合したタイプの
３波長域発光型蛍光ランプも出現している。2. Description of the Related Art As is well known, in recent years, so-called three-wavelength band emission type fluorescent lamps have become mainstream as fluorescent lamps for general illumination. Then, in this type of three-wavelength band emission type fluorescent lamp, a required fluorescent film (phosphor layer) is formed of three types of mixed phosphors of blue light emission, green light emission and red light emission having a relatively narrow band emission spectrum distribution. Is adopted. Recently, a three-wavelength band emission type fluorescent lamp in which blue-green light emitting phosphors and deep red light emitting phosphors are mixed in order to further improve color rendering properties has appeared.
【０００３】３波長域発光型蛍光ランプ用の赤色発光蛍
光体としては、Ｅｕ付活酸化イットリウム蛍光体（Ｙ，
Ｅｕ）2 Ｏ3 が、また、深赤色発光蛍光体としては、マ
ンガン付活ゲルマン酸塩蛍光体3.5 ＭｇＯ・0.5 ＭｇＦ
2 ・ＧｅＯ2 ：Ｍｎが一般に用いられる。As a red light emitting phosphor for a three-wavelength emission type fluorescent lamp, Eu activated yttrium oxide phosphor (Y,
Eu) 2 O 3 is a manganese-activated germanate phosphor 3.5 MgO · 0.5 MgF as a deep red light-emitting phosphor.
2 · GeO 2 : Mn is generally used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記構
成の３波長域発光型蛍光ランプにおいては、赤色成分の
特殊演色評価数Ｒ９が20〜40であり、平均演色評価数Ｒ
ａおよび他の特殊演色評価数に比較して非常に低いこと
が指摘されている。この原因は、赤色発光蛍光体である
（Ｙ，Ｅｕ）2 Ｏ3 の発光ピーク波長が611nm であり、
深赤色発光蛍光体である3.5 ＭｇＯ・0.5 ＭｇＦ2 ・Ｇ
ｅＯ2 ：Ｍｎの発光ピーク波長が658nm であるためであ
る。シミュレーションでは、Ｒ９の向上に最も有効な発
光は620 〜630nm であることが知られている。この波長
域に発光ピークを有する蛍光体としては、Ｅｕ付活酸化
ガドリニウム蛍光体（Ｇｄ，Ｅｕ）2 Ｏ3 が公知であ
る。この蛍光体は、焼成温度により２種の結晶構造をと
り、1250℃以下では立方晶系となり、1250℃以上では単
斜晶系となる。蛍光体の結晶構造が立方晶系の場合、発
光ピークは611nm であるが、単斜晶系の場合には、発光
ピークは623nm となる。従い、結晶構造が単斜晶系の場
合、Ｒ９の向上に有効な発光スペクトル分布となる。し
かし、この場合の発光効率は（Ｙ，Ｅｕ）2 Ｏ3 の20％
程度であり低い。However, in the three-wavelength band emission type fluorescent lamp having the above structure, the special color rendering index R9 of the red component is 20 to 40, and the average color rendering index R
It is pointed out that it is very low compared to a and other special color rendering indices. This is because the emission peak wavelength of the red-emitting phosphor (Y, Eu) 2 O 3 is 611 nm,
Deep red light emitting phosphor 3.5 MgO · 0.5 MgF 2 · G
This is because the emission peak wavelength of eO 2 : Mn is 658 nm. Simulations show that the most effective emission for improving R9 is 620-630 nm. Eu-activated gadolinium oxide phosphor (Gd, Eu) 2 O 3 is known as a phosphor having an emission peak in this wavelength range. This phosphor has two types of crystal structures depending on the firing temperature, and becomes a cubic system at 1250 ° C or lower and a monoclinic system at 1250 ° C or higher. When the crystal structure of the phosphor is cubic, the emission peak is 611 nm, whereas when it is monoclinic, the emission peak is 623 nm. Therefore, when the crystal structure is a monoclinic system, the emission spectrum distribution is effective for improving R9. However, the luminous efficiency in this case is 20% of that of (Y, Eu) 2 O 3 .
The degree is low.
【０００５】上記説明したごとく、従来の３波長域発光
型蛍光ランプは、赤色成分の特殊演色評価数Ｒ９が低い
という問題がある。また、Ｒ９の向上に好適な発光スペ
クトル分布を有するＥｕ付活酸化ガドリニウム蛍光体は
発光効率が低く、この蛍光体を３波長域発光型蛍光ラン
プに用いた場合、明るさが大幅に低下し、商品価値が下
がるという問題がある。As described above, the conventional three-wavelength band emission type fluorescent lamp has a problem that the special color rendering index R9 of the red component is low. Further, the Eu-activated gadolinium oxide phosphor having an emission spectrum distribution suitable for improving R9 has low emission efficiency, and when this phosphor is used in a three-wavelength emission type fluorescent lamp, the brightness is significantly lowered, There is a problem that the product value will decrease.
【０００６】この課題解決のため、本発明者らがＥｕ付
活酸化ガドリニウム蛍光体について究明した結果、この
蛍光体にＹあるいはＬａを含有させることにより、Ｒ９
向上に有効な発光スペクトル分布を有し、しかも大幅に
発光効率を向上できることを見出した。To solve this problem, the inventors of the present invention have investigated an Eu-activated gadolinium oxide phosphor, and as a result, by incorporating Y or La into this phosphor, R9
It has been found that it has an emission spectrum distribution effective for improvement and can significantly improve the emission efficiency.
【０００７】本発明は上記事情に対処してなされたもの
で、高い発光効率および高演色性を呈する３波長域発光
型の蛍光ランプに適する赤色ないし深赤色に発光する蛍
光体およびこの蛍光体を用いた３波長域発光型蛍光ラン
プの提供を目的とする。The present invention has been made in view of the above circumstances, and provides a red- or deep-red fluorescent material suitable for a three-wavelength band fluorescent lamp having high luminous efficiency and high color rendering property, and the fluorescent material. It is intended to provide a three-wavelength band emission type fluorescent lamp used.
【０００８】[0008]
【課題を解決するための手段】本発明に係る蛍光体は、
一般式（Ｇｄ1-X-Y ＭX ＥｕY ）2 Ｏ3 （ただし、Ｍは
ＹまたはＬａの中から選ばれる少なくとも１種の元素、
X およびY は0.001 ≦X≦0.5 ，0.005 ≦ Y≦0.2 を満
足する数）で表される蛍光体であって、結晶構造が本質
的に単斜晶系であり、254nm の水銀輝線で励起したとき
の発光スペクトル分布が強度比で最も高い第１のピーク
が615nm から630nm の間にある形状を有することを特徴
とし、また、本発明に係る蛍光ランプは、前記本発明に
係る蛍光体を赤色ないし深赤色発光の蛍光体成分として
含有する混合蛍光体で発光層を形成したことを特徴とす
る。The phosphor according to the present invention comprises:
General formula (Gd 1-XY M X Eu Y ) 2 O 3 (wherein M is at least one element selected from Y or La,
X and Y are phosphors represented by 0.001 ≤ X ≤ 0.5 and 0.005 ≤ Y ≤ 0.2), the crystal structure is essentially monoclinic, and excited by the 254 nm mercury emission line. In the fluorescent lamp according to the present invention, the first peak of the emission spectrum distribution has a highest intensity ratio between 615 nm and 630 nm. To the deep red light emitting phosphor component as a phosphor mixture, the light emitting layer is formed.
【０００９】[0009]
【作用】本発明に係る赤色ないし深赤色発光するＥｕ付
活酸化ガドリニウム蛍光体は、安定的に高い発光効率を
有し、かつ高演色性を発揮するのに最適な発光スペクト
ル分布を有する。また、蛍光ランプの発光層とした場合
もすぐれた発光効率および高演色性を呈し、特に赤色成
分の特殊演色評価数Ｒ９に対し大幅に改善効果を発揮す
る光源として機能する。The Eu-activated gadolinium oxide phosphor which emits red or deep red light according to the present invention has a stable high emission efficiency and an optimum emission spectrum distribution for exhibiting a high color rendering property. Further, when it is used as a light emitting layer of a fluorescent lamp, it exhibits excellent light emitting efficiency and high color rendering properties, and particularly functions as a light source exhibiting a significant improvement effect on the special color rendering index R9 of the red component.
【００１０】すなわち本発明に係るＥｕ付活酸化ガドリ
ニウム蛍光体は、従来のＥｕ付活酸化ガドリニウム蛍光
体の製造（合成）過程で、ＹあるいはＬａの酸化物，炭
酸塩等を焼成して容易に酸化物を形成し得る化合物を作
用させることにより合成し得る。この本発明によるＥｕ
付活酸化ガドリニウム蛍光体においては、異種元素とし
て含有させた金属元素の含有組成比が重要な因子を成し
ており、前記一般式中で、ＹまたはＬａの中から選ばれ
る少なくとも１種の元素の含有組成比を表すｘの値が0.
001 未満では発光効率が不充分で、従来のＥｕ付活酸化
ガドリニウム蛍光体の発光効率とあまり差がない。逆
に、0.5 より大きいと蛍光ランプ中で用いた時に早期黒
化が発生し、蛍光ランプの商品価値がなくなってしま
う。したがって、好適な組成範囲は、0.001 以上0.5 以
下である。この中でも0.01以上0.2 以下の場合、特に好
適である。That is, the Eu-activated gadolinium oxide phosphor according to the present invention can be easily prepared by firing Y or La oxides, carbonates, etc. in the process of manufacturing (synthesizing) a conventional Eu-activated gadolinium oxide phosphor. It can be synthesized by reacting a compound capable of forming an oxide. Eu according to the present invention
In the activated gadolinium oxide phosphor, the content composition ratio of the metal elements contained as different elements is an important factor, and in the general formula, at least one element selected from Y and La is selected. The value of x, which represents the composition ratio of, is 0.
If it is less than 001, the luminous efficiency is insufficient and there is not much difference from the luminous efficiency of the conventional Eu-activated gadolinium oxide phosphor. On the other hand, if it exceeds 0.5, blackening occurs early when used in a fluorescent lamp, and the commercial value of the fluorescent lamp is lost. Therefore, the preferable composition range is 0.001 or more and 0.5 or less. Among them, the case of 0.01 or more and 0.2 or less is particularly preferable.
【００１１】また、付活剤であるＥｕの組成も蛍光体の
発光効率に大きく寄与しており、前記一般式中のｙが0.
005 未満では充分な効率が得られず、0.2 を越えると濃
度消光により効率が下がってしまう。したがって、好適
な組成範囲は、0.005 以上0.1 以下である。The composition of Eu as the activator also greatly contributes to the luminous efficiency of the phosphor, and y in the above general formula is 0.
When it is less than 005, sufficient efficiency cannot be obtained, and when it exceeds 0.2, the efficiency is lowered due to concentration quenching. Therefore, the preferable composition range is 0.005 or more and 0.1 or less.
【００１２】さらに、上記本発明に係るＥｕ付活酸化ガ
ドリニウム蛍光体は、結晶構造が立方晶系をとりやすい
ので、製造方法も重要な因子を成している。特に、蛍光
体合成時の焼成温度がポイントで、1250℃以下では結晶
構造はすべて立方晶系となり、1250℃から1300℃では立
方晶系と単斜晶系が共存する。1300℃以上の焼成で本質
的に単斜晶系となる。結晶構造が立方晶系であるとき
は、発光ピーク波長が611nm であり、特殊演色評価数Ｒ
９の向上には全く寄与しない。したがって、1300℃以上
の焼成工程が必要である。Further, since the Eu-activated gadolinium oxide phosphor according to the present invention tends to have a cubic crystal structure, the manufacturing method is also an important factor. In particular, the firing temperature at the time of synthesizing the phosphor is a point, and at 1250 ° C. or less, the crystal structure is all cubic, and at 1250 ° C. to 1300 ° C., cubic and monoclinic coexist. It becomes essentially monoclinic when fired at 1300 ° C or higher. When the crystal structure is cubic, the emission peak wavelength is 611 nm and the special color rendering index R
It does not contribute to the improvement of 9. Therefore, a firing process at 1300 ° C or higher is necessary.
【００１３】[0013]
【実施例】以下、本発明の実施例を説明する。 （実施例−１）本実施例蛍光体の原料として、Ｇｄ2 Ｏ
3 351.6 ｇ，Ｙ2 Ｏ3 2.3 ｇ，Ｅｕ2Ｏ3 7.0 ｇを秤量
し、硝酸に全量溶解する。純水を加えて希釈し、この溶
液にシュウ酸を加えて攪拌すると直ちに沈殿が生成す
る。沈殿が生成しなくなるまでシュウ酸を加えていく。
この沈殿物を集めてアルミナるつぼに入れて、大気中80
0℃で焼成する。この焼成品を粉砕，篩別した後、さら
に大気中1400℃で焼成する。粉砕後、純水でよく洗浄
し、乾燥，篩別すると本実施例の蛍光体が得られる。こ
の蛍光体を分析した結果、次式（Ａ）に示す組成を成し
ていた。EXAMPLES Examples of the present invention will be described below. As a raw material (Example -1) In this example a phosphor, Gd 2 O
3 351.6 g, Y 2 O 3 2.3 g, and Eu 2 O 3 7.0 g are weighed and completely dissolved in nitric acid. Pure water is added to dilute the solution, and oxalic acid is added to this solution and stirred to form a precipitate immediately. Oxalic acid is added until no precipitate forms.
Collect this precipitate and put it in an alumina crucible.
Bake at 0 ° C. After crushing and sieving this baked product, it is further baked at 1400 ° C in the atmosphere. After crushing, washing well with pure water, drying and sieving, the phosphor of this example is obtained. As a result of analyzing this phosphor, the composition shown in the following formula (A) was obtained.
【００１４】 （Ｇｄ0.97Ｙ0.01Ｅｕ0.02）2 Ｏ3 …（Ａ） 比較のため、蛍光体の原料として、Ｇｄ2 Ｏ3 355.3 ｇ
とＥｕ2 Ｏ3 7.0 ｇを秤量し、上記と同様の方法で従来
の蛍光体を調整した。この蛍光体を分析した結果、次式
（Ｂ）に示す組成を成していた。 （Ｇｄ0.98Ｅｕ0.02）2 Ｏ3 …（Ｂ） この従来の蛍光体の254nm 水銀輝線励起による発光輝度
を100 ％とすると、本実施例の蛍光体の発光輝度は 210
％に達した。(Gd 0.97 Y 0.01 Eu 0.02 ) 2 O 3 (A) For comparison, as a raw material of the phosphor, Gd 2 O 3 355.3 g
And 7.0 g of Eu 2 O 3 were weighed, and a conventional phosphor was prepared in the same manner as above. As a result of analyzing this phosphor, the composition shown in the following formula (B) was formed. (Gd 0.98 Eu 0.02 ) 2 O 3 (B) If the emission luminance of this conventional phosphor excited by the 254 nm mercury emission line is 100%, the emission luminance of the phosphor of this embodiment is 210
% Has been reached.
【００１５】次に、本実施例の蛍光体の254nm 水銀輝線
励起による発光スペクトル分布を図１に示す。発光強度
の最も高い第１ピークは623nm であり、次に高い第２ピ
ークは616nm であった。Ｙ元素の含有効果による発光ス
ペクトル分布の変化は特に見られず、特殊演色評価数Ｒ
９の向上に好適である。Next, FIG. 1 shows the emission spectrum distribution of the phosphor of this example excited by the 254 nm mercury emission line. The first peak with the highest emission intensity was 623 nm, and the second peak with the next highest was 616 nm. No particular change in the emission spectrum distribution due to the effect of containing the Y element was observed, and the special color rendering index R
9 is suitable for improvement.
【００１６】また、本実施例の蛍光体のＸ線回折を測定
した。結果を図２に示す。図２（１）が本実施例の蛍光
体のＸ線回折の結果で、結晶構造は典型的な単斜晶系で
あることがわかる。The X-ray diffraction of the phosphor of this example was also measured. The results are shown in Figure 2. FIG. 2A shows the result of X-ray diffraction of the phosphor of this example, which shows that the crystal structure is a typical monoclinic system.
【００１７】比較のために、（Ａ）の合成過程において
大気中1400℃焼成の代わりに大気中1200℃焼成して、上
記と同様に処理して調整した蛍光体のＸ線回折の結果を
図２（２）に示す。この蛍光体の結晶構造は立方晶系で
ある。しかも、発光スペクトル分布は、本実施例の蛍光
体と異なり、発光強度の最も高い第１ピークは611nmで
ある。For comparison, in the synthesis process of (A), instead of baking at 1400 ° C. in air, baking at 1200 ° C. in air and treating the same as above, the result of X-ray diffraction of the prepared phosphor is shown. 2 (2). The crystal structure of this phosphor is cubic. Moreover, the emission spectrum distribution is different from that of the phosphor of this example, and the first peak with the highest emission intensity is 611 nm.
【００１８】（実施例−２）本実施例蛍光体の原料とし
て、Ｇｄ2 Ｏ3 253.8 ｇ，Ｙ2 Ｏ3 45.2ｇ，Ｅｕ2Ｏ3 3
5.2ｇを秤量し、硝酸に全量溶解する。純水を加えて希
釈し、この溶液にシュウ酸を加えると直ちに沈殿が生成
する。沈殿が生成しなくなるまでシュウ酸を加えてい
く。この沈殿物を集めてアルミナるつぼに入れて、大気
中700 ℃で焼成する。この焼成品を粉砕，篩別した後、
さらに大気中1500℃で焼成する。粉砕後、純水でよく洗
浄し、乾燥，篩別すると本実施例の蛍光体が得られる。
この蛍光体を分析した結果、次式（Ｃ）に示す組成を成
していた。[0018] as a starting material (Example - 2) This example phosphor, Gd 2 O 3 253.8 g, Y 2 O 3 45.2g, Eu 2 O 3 3
Weigh 5.2 g and dissolve the whole amount in nitric acid. When pure water is added to dilute the solution and oxalic acid is added to this solution, a precipitate is immediately formed. Oxalic acid is added until no precipitate forms. The precipitate is collected, placed in an alumina crucible, and fired at 700 ° C in the atmosphere. After crushing and sieving this baked product,
Further, it is fired at 1500 ° C in the atmosphere. After crushing, washing well with pure water, drying and sieving, the phosphor of this example is obtained.
As a result of analyzing this phosphor, the composition shown in the following formula (C) was obtained.
【００１９】 （Ｇｄ0.70Ｙ0.20Ｅｕ0.10）2 Ｏ3 …（Ｃ） 比較のため、蛍光体の原料として、Ｇｄ2 Ｏ3 326.3 ｇ
とＥｕ2 Ｏ3 35.2 ｇを秤量し、上記と同様の方法で従
来の蛍光体を調整した。この蛍光体を分析した結果、次
式（Ｄ）に示す組成を成していた。(Gd 0.70 Y 0.20 Eu 0.10 ) 2 O 3 (C) For comparison, as a raw material for the phosphor, Gd 2 O 3 326.3 g
And Eu 2 O 3 35.2 g were weighed, and a conventional phosphor was prepared in the same manner as above. As a result of analyzing this phosphor, the composition shown in the following formula (D) was obtained.
【００２０】（Ｇｄ0.90Ｅｕ0.10）2 Ｏ3 …（Ｄ） この従来の蛍光体の254nm 水銀輝線励起による発光輝度
を100 ％とすると、本実施例の蛍光体の発光輝度は220
％に達した。(Gd 0.90 Eu 0.10 ) 2 O 3 (D) Assuming that the emission luminance of this conventional phosphor excited by the 254 nm mercury emission line is 100%, the emission luminance of the phosphor of this embodiment is 220.
% Has been reached.
【００２１】本実施例の蛍光体の254nm 水銀輝線励起に
よる発光スペクトル分布は実施例−１と同様で、発光強
度の最も高い第１ピークは623nm であり、特殊演色評価
数Ｒ９の向上に好適である。The emission spectrum distribution of the phosphor of this example excited by the 254 nm mercury emission line was the same as that of Example-1, and the first peak with the highest emission intensity was 623 nm, which is suitable for improving the special color rendering index R9. is there.
【００２２】また、本実施例の蛍光体のＸ線回折を測定
したところ、実施例−１と同様に、結晶構造は単斜晶系
であった。 （実施例−３）本実施例蛍光体の原料として、Ｇｄ2 Ｏ
3 308.1 ｇ，Ｌａ2 Ｏ3 32.6ｇ，Ｅｕ2 Ｏ3 17.6ｇを秤
量し、硝酸に全量溶解する。純水を加えて希釈し、この
溶液にシュウ酸ジメチルを加えると直ちに沈殿が生成す
る。沈殿が生成しなくなるまでシュウ酸ジメチルを加え
ていく。この沈殿物を集めてアルミナるつぼに入れて、
大気中900 ℃で焼成する。この焼成品を粉砕，篩別した
後、さらに大気中1300℃で焼成する。粉砕後、純水でよ
く洗浄し、乾燥，篩別すると本実施例の蛍光体が得られ
る。この蛍光体を分析した結果、次式（Ｅ）に示す組成
を成していた。When X-ray diffraction of the phosphor of this example was measured, the crystal structure was a monoclinic system as in Example-1. As a raw material (Example -3) In this example a phosphor, Gd 2 O
3 Weigh out 308.1 g, La 2 O 3 32.6 g, and Eu 2 O 3 17.6 g, and dissolve all in nitric acid. Pure water is added to dilute the solution, and dimethyl oxalate is added to this solution to form a precipitate immediately. Add dimethyl oxalate until no more precipitate is formed. Collect this precipitate and put it in an alumina crucible,
Bake at 900 ℃ in air. After this fired product is crushed and sieved, it is further fired at 1300 ° C in the atmosphere. After crushing, washing well with pure water, drying and sieving, the phosphor of this example is obtained. As a result of analyzing this phosphor, the phosphor had a composition represented by the following formula (E).
【００２３】 （Ｇｄ0.85Ｌａ0.10Ｅｕ0.05）2 Ｏ3 …（Ｅ） 比較のため、蛍光体の原料として、Ｇｄ2 Ｏ3 344.4 ｇ
とＥｕ2 Ｏ3 17.6ｇを秤量し、上記と同様の方法で従来
の蛍光体を調整した。この蛍光体を分析した結果、次式
（Ｆ）に示す組成を成していた。[0023] (Gd 0.85 La 0. 10Eu 0.05) 2 O 3 ... (E) For comparison, as a raw material of the phosphor, Gd 2 O 3 344.4 g
And 17.6 g of Eu 2 O 3 were weighed, and a conventional phosphor was prepared in the same manner as above. As a result of analyzing this phosphor, the composition shown in the following formula (F) was formed.
【００２４】（Ｇｄ0.95Ｅｕ0.05）2 Ｏ3 …（Ｆ） この従来の蛍光体の254nm 水銀輝線励起による発光輝度
を100 ％とすると、本実施例の蛍光体の発光輝度は200
％に達した。(Gd 0.95 Eu 0.05 ) 2 O 3 (F) If the emission brightness of this conventional phosphor excited by the 254 nm mercury emission line is 100%, the emission brightness of the phosphor of this embodiment is 200.
% Has been reached.
【００２５】本実施例の蛍光体の254nm 水銀輝線励起に
よる発光スペクトル分布は実施例−１と同様で、発光強
度の最も高い第１ピークは623nm であり、特殊演色評価
数Ｒ９の向上に好適である。The emission spectrum distribution of the phosphor of this example excited by the 254 nm mercury emission line was the same as that of Example-1, and the first peak with the highest emission intensity was 623 nm, which is suitable for improving the special color rendering index R9. is there.
【００２６】また、本実施例の蛍光体のＸ線回折を測定
したところ、実施例−１と同様に、結晶構造は単斜晶系
であった。 （実施例−４）青色発光蛍光体として（Ｓｒ，Ｃａ，Ｂ
ａ，Ｅｕ）10（ＰＯ4 ）6 Ｃｌ2 、緑色発光蛍光体とし
て（Ｌａ，Ｃｅ，Ｔｂ）ＰＯ４、赤色発光蛍光体として
（Ｙ，Ｅｕ）2 Ｏ3 を用い、深赤色発光蛍光体として本
実施例によるＥｕ付活酸化ガドリニウム蛍光体（実施例
−１）を混合比率が全体の５％になるように混合して、
３波長域発光型蛍光ランプ（直管型20Ｗ蛍光ランプＦＬ
20ＳＳ）を通常の方法により相関色温度5000Ｋになるよ
うに作製した。比較のため、従来の深赤色発光のＥｕ付
活酸化ガドリニウム蛍光体を用いた蛍光ランプも作製し
た。その結果、特殊演色評価数Ｒ９の値は、本実施例に
よる蛍光ランプが50、従来の深赤色発光蛍光体を用いた
蛍光ランプが35であった。また、初期全光束は、従来の
深赤色発光蛍光体を用いた蛍光ランプを100 とすると、
本実施例による蛍光ランプが120 であった。したがっ
て、本実施例の３波長域発光型蛍光ランプは、初期全光
束が20％向上し、さらに特殊演色評価数Ｒ９が15ポイン
ト向上した。When the X-ray diffraction of the phosphor of this example was measured, the crystal structure was a monoclinic system as in Example-1. (Example-4) As a blue light emitting phosphor (Sr, Ca, B
a, Eu) 10 (PO 4 ) 6 Cl 2 , green emission phosphor (La, Ce, Tb) PO 4, red emission phosphor (Y, Eu) 2 O 3 and deep red emission phosphor The Eu-activated gadolinium oxide phosphor according to the example (Example-1) was mixed at a mixing ratio of 5%, and
3-wavelength emission type fluorescent lamp (straight tube type 20W fluorescent lamp FL
20SS) was prepared by a conventional method so that the correlated color temperature was 5000K. For comparison, a fluorescent lamp using a conventional deep red light emitting Eu-activated gadolinium oxide phosphor was also manufactured. As a result, the value of the special color rendering index R9 was 50 for the fluorescent lamp according to this example and 35 for the conventional fluorescent lamp using the deep red light emitting phosphor. In addition, the initial total luminous flux is 100 when the fluorescent lamp using the conventional deep red light emitting phosphor is
The number of fluorescent lamps according to this example was 120. Therefore, in the three-wavelength emission type fluorescent lamp of this example, the initial total luminous flux was improved by 20%, and the special color rendering index R9 was improved by 15 points.
【００２７】（実施例−５）青色発光蛍光体として３
（Ｂａ，Ｍｇ，Ｅｕ，Ｍｎ）Ｏ・８Ａｌ2 Ｏ3 、緑色発
光蛍光体として（Ｌａ，Ｃｅ，Ｔｂ）ＰＯ4 、赤色発光
蛍光体として（Ｙ，Ｅｕ）2 Ｏ3 を用い、深赤色発光蛍
光体として本実施例によるＥｕ付活酸化ガドリニウム蛍
光体（実施例−２）を混合比率が全体の10％になるよう
に混合して、３波長域発光型蛍光ランプ（環管型30Ｗ蛍
光ランプＦＣＬ30）を通常の方法により相関色温度6500
Ｋになるように作製した。比較のため、従来の深赤色発
光のＥｕ付活酸化ガドリニウム蛍光体を用いた蛍光ラン
プも作製した。その結果、特殊演色評価数Ｒ９の値は、
本実施例による蛍光ランプが60、従来の深赤色発光蛍光
体を用いた蛍光ランプが40であった。また、初期全光束
は、従来の深赤色発光蛍光体を用いた蛍光ランプを100
とすると、本実施例による蛍光ランプが130 であった。
したがって、本実施例の３波長域発光型蛍光ランプは、
初期全光束が30％向上し、さらに特殊演色評価数Ｒ９が
25ポイント向上した。(Example-5) 3 as blue light emitting phosphor
(Ba, Mg, Eu, Mn) O.8Al 2 O 3 , green emission phosphor (La, Ce, Tb) PO 4 and red emission phosphor (Y, Eu) 2 O 3 are used, and deep red emission is performed. As the phosphor, the Eu-activated gadolinium oxide phosphor according to the present embodiment (Example-2) was mixed so that the mixing ratio was 10% of the whole, and the three-wavelength band emission type fluorescent lamp (ring tube type 30 W fluorescent lamp) was mixed. FCL30) with a conventional method and a correlated color temperature of 6500
It was manufactured so as to be K. For comparison, a fluorescent lamp using a conventional deep red light emitting Eu-activated gadolinium oxide phosphor was also manufactured. As a result, the value of the special color rendering index R9 is
The number of fluorescent lamps according to this example was 60, and the number of conventional fluorescent lamps using deep red light emitting phosphor was 40. In addition, the initial total luminous flux is 100 for a fluorescent lamp using a conventional deep red light-emitting phosphor.
Then, the number of fluorescent lamps according to this example was 130.
Therefore, the three-wavelength emission type fluorescent lamp of this embodiment is
The initial total luminous flux is improved by 30%, and the special color rendering index R9
Improved by 25 points.
【００２８】（実施例−６〜10）実施例−１と同様の方
法にて調整した本実施例の蛍光体の254nm 水銀輝線励起
による発光輝度および実施例−４と同様の方法にて作製
した本実施例の蛍光ランプの特殊演色評価数Ｒ９の測定
値を表１に示す。なお、比較のため調整した従来のＥｕ
付活酸化ガドリニウム蛍光体の発光輝度を100 とする。(Examples 6 to 10) Luminous intensity of the phosphor of this example adjusted by the same method as in Example 1 and excited by 254 nm mercury emission line, and the same method as in Example 4 were used. Table 1 shows the measured values of the special color rendering index R9 of the fluorescent lamp of this example. The conventional Eu adjusted for comparison
The emission brightness of the activated gadolinium oxide phosphor is set to 100.
【００２９】[0029]
【表１】 なお、上記実施例１〜３に示した蛍光体は特に好適する
Ｍ物質としてＹまたはＬａ量の代表例であるか、Ｙおよ
びＬａを適量混合した蛍光体であってもよい。[Table 1] The phosphors shown in Examples 1 to 3 are typical examples of Y or La as a particularly suitable M substance, or may be phosphors in which Y and La are mixed in appropriate amounts.
【００３０】[0030]
【発明の効果】以上詳述したように、本発明に係る赤色
ないし深赤色発光するＥｕ付活酸化ガドリニウム蛍光体
は、安定的に高い発光効率を有し、かつ高演色性を発揮
するのに最適な発光スペクトル分布を有する。また、蛍
光ランプの発光層とした場合もすぐれた発光効率および
高演色性を呈し、特に赤色成分の特殊演色評価数Ｒ９に
対し大幅に改善効果を発揮する光源として機能する。As described above in detail, the Eu-activated gadolinium oxide phosphor emitting red or deep red light according to the present invention has stable high emission efficiency and high color rendering. It has an optimum emission spectrum distribution. Further, when it is used as a light emitting layer of a fluorescent lamp, it exhibits excellent light emitting efficiency and high color rendering properties, and particularly functions as a light source exhibiting a significant improvement effect on the special color rendering index R9 of the red component.
【図１】本発明のＥｕ付活酸化ガドリニウム蛍光体の25
4nm 水銀輝線励起による発光スペクトル分布を示す図で
ある。FIG. 1 shows 25 Eu-activated gadolinium oxide phosphor of the present invention.
It is a figure which shows the light emission spectrum distribution by 4 nm mercury emission line excitation.
【図２】Ｘ線回折の結果を示す図であり、(1) は本発明
の一実施例のＥｕ付活酸化ガドリニウム蛍光体の例、
(2) は比較のため大気中1200℃で焼成し調整したＥｕ付
活酸化ガドリウム蛍光体の例である。FIG. 2 is a diagram showing a result of X-ray diffraction, where (1) is an example of an Eu-activated gadolinium oxide phosphor according to an embodiment of the present invention,
For comparison, (2) is an example of an Eu-activated gadolinium oxide phosphor prepared by firing at 1200 ° C. in the atmosphere.
Claims (2)
（ただし、ＭはＹまたはＬａの中から選ばれる少なくと
も１種の元素、X およびY は0.001 ≦X ≦0.5，0.005
≦ Y≦0.2 を満足する数）で表される蛍光体であって、
結晶構造が本質的に単斜晶系であり、254nm の水銀輝線
で励起したときの発光スペクトル分布が強度比で最も高
い第１のピークが615nm から630nm の間にある形状を有
することを特徴とする赤色ないし深赤色発光の蛍光体。1. A general formula (Gd 1-XY M X Eu Y ) 2 O 3
(However, M is at least one element selected from Y or La, X and Y are 0.001 ≤ X ≤ 0.5, 0.005
A number satisfying ≦ Y ≦ 0.2),
The crystal structure is essentially monoclinic, and the emission spectrum distribution when excited by the 254 nm mercury emission line has a shape in which the first peak with the highest intensity ratio is between 615 nm and 630 nm. A red to deep red light emitting phosphor.
た蛍光ランプにおいて、前記蛍光体層が請求項１記載の
蛍光体を赤色ないし深赤色発光成分として含有すること
を特徴とする蛍光ランプ。2. A fluorescent lamp having a phosphor layer mounted on the inner wall surface of a glass tube, wherein the phosphor layer contains the phosphor according to claim 1 as a red to deep red light emitting component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32487793A JP3360901B2 (en) | 1993-12-22 | 1993-12-22 | Phosphors and fluorescent lamps |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32487793A JP3360901B2 (en) | 1993-12-22 | 1993-12-22 | Phosphors and fluorescent lamps |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07179852A true JPH07179852A (en) | 1995-07-18 |
| JP3360901B2 JP3360901B2 (en) | 2003-01-07 |
Family
ID=18170636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32487793A Expired - Fee Related JP3360901B2 (en) | 1993-12-22 | 1993-12-22 | Phosphors and fluorescent lamps |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3360901B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008138076A (en) * | 2006-12-01 | 2008-06-19 | Matsushita Electric Ind Co Ltd | Phosphor material mixture, and light-emitting device and plasma-displaying panel using the same |
| WO2012022019A1 (en) * | 2010-08-16 | 2012-02-23 | 海洋王照明科技股份有限公司 | Color-adjustable luminescent powder and preparation method thereof |
-
1993
- 1993-12-22 JP JP32487793A patent/JP3360901B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008138076A (en) * | 2006-12-01 | 2008-06-19 | Matsushita Electric Ind Co Ltd | Phosphor material mixture, and light-emitting device and plasma-displaying panel using the same |
| WO2012022019A1 (en) * | 2010-08-16 | 2012-02-23 | 海洋王照明科技股份有限公司 | Color-adjustable luminescent powder and preparation method thereof |
| CN102933689A (en) * | 2010-08-16 | 2013-02-13 | 海洋王照明科技股份有限公司 | Color-adjustable luminescent powder and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP3360901B2 (en) | 2003-01-07 |
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