JPS6247228B2 - - Google Patents
Info
- Publication number
- JPS6247228B2 JPS6247228B2 JP55011409A JP1140980A JPS6247228B2 JP S6247228 B2 JPS6247228 B2 JP S6247228B2 JP 55011409 A JP55011409 A JP 55011409A JP 1140980 A JP1140980 A JP 1140980A JP S6247228 B2 JPS6247228 B2 JP S6247228B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- calcium halophosphate
- aluminum
- luminous efficiency
- fluorescent lamp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Luminescent Compositions (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Description
【発明の詳細な説明】
本発明はハロりん酸カルシウムけい光体の改良
に関する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to improvements in calcium halophosphate phosphors.
一般にハロりん酸カルシウムけい光体は紫外線
によつて励起され、可視光を発光し巾広い発光ス
ペクトルを持つていることから、一般照明用けい
光ランプに使用されていることは良く知られてい
る。 It is well known that calcium halophosphate phosphors are generally used in fluorescent lamps for general lighting because they are excited by ultraviolet light and emit visible light with a wide emission spectrum. .
さらに、このけい光体は発光色を温白色から青
白色まで任意に変化させることができる、発光効
率が高く廉価である等の優れた特長を持つている
ため、けい光ランプ用けい光体として賞用されて
いる。 Furthermore, this phosphor has excellent features such as being able to change the emitted light color arbitrarily from warm white to bluish-white, and being highly efficient and inexpensive, so it can be used as a phosphor for fluorescent lamps. It is used for awards.
現在のところ、一般照明用けい光体として、ハ
ロりん酸カルシウムけい光体に優るけい光体は存
在しないばかりでなく、このけい光体に置き変り
得る新規けい光体の発明はきわめて困難であると
いわれている。 At present, not only is there no phosphor superior to calcium halophosphate phosphor as a phosphor for general lighting, but it is extremely difficult to invent a new phosphor that can replace this phosphor. It is said that.
従つて、ハロりん酸カルシウムけい光体に関す
る研究は多く、現在まで数多くの改良がおこなわ
れ特性が著しく改善されてきておりすでに特性が
安定しているハロりん酸カルシウムけい光体に飛
躍的な改良を加えることは、非常に困難といわれ
明るさ１パーセントの改良といえども重要な意味
を持つている。 Therefore, there has been a lot of research on calcium halophosphate phosphors, and many improvements have been made to date, resulting in significant improvements in properties.This is a dramatic improvement to calcium halophosphate phosphors, which already have stable properties. It is said to be extremely difficult to add brightness, and even a 1% improvement in brightness has an important meaning.
ところで、ハロりん酸カルシウムけい光体はア
パタイト構造Mx（PO4）6Xy，ｘ≦10，ｙ≦２を
有し、一般式3Ca3（PO4）2・Ca（Ｘ）２：Sb，
Mn（Ｘ＝Ｆ，Clのうち少なくとも一種を表す。）
で表わされ、カルシウム元素の一部は亜鉛
（Zn）、バリウム（Ba）、ストロンチウム（Sr）、
セシウム（Cs）、カドミウム（Cd）等で置換され
ることも公知である。実用的効率を持つ組成は上
記組成よりも幾分金属が不足しており9.5≦ｘ≦
10となつている。 By the way, the calcium halophosphate phosphor has an apatite structure Mx( PO4 ) 6Xy , x≦10, y≦2, and has the general formula 3Ca3 ( PO4 ) 2・Ca(X) 2 :Sb,
Mn (X=F, represents at least one type of Cl.)
Some of the calcium elements are zinc (Zn), barium (Ba), strontium (Sr),
Substitution with cesium (Cs), cadmium (Cd), etc. is also known. The composition with practical efficiency is somewhat deficient in metals than the above composition, and 9.5≦x≦
It's 10.
本発明者等はハロりん酸カルシウムけい光体の
初期発光効率と働程特性を改善する目的で研究を
重ねた結果、ハロりん酸カルシウムけい光体母体
に２〜30ppmのアルミニウム（Al）を含有させ
ることによつて初期発光効率と働程特性が向上す
ることを発見した。 As a result of repeated research aimed at improving the initial luminous efficiency and working characteristics of calcium halophosphate phosphors, the present inventors found that 2 to 30 ppm of aluminum (Al) was added to the matrix of calcium halophosphate phosphors. We have discovered that the initial luminous efficiency and working characteristics can be improved by
なお、働程特性とは初期発光効率の維持率を示
す。 Note that the working characteristic indicates the maintenance rate of initial luminous efficiency.
本発明は初期発光効率と働程特性を改良したハ
ロりん酸カルシウムけい光体を提供するもので、
けい光体の母体にアルミニウムを含有し、このア
ルミニウムの含有重量がけい光体母体重量に対し
て２〜30ppmであることを特徴とする。 The present invention provides a calcium halophosphate phosphor with improved initial luminous efficiency and working characteristics.
It is characterized in that the matrix of the phosphor contains aluminum, and the aluminum content is 2 to 30 ppm based on the weight of the phosphor matrix.
このようなハロりん酸カルシウムけい光体は初
期発光効率が0.5〜２パーセント向上、働程特性
は１〜２パーセントの向上が得られる利点を有す
るもので有り、アルミニウム含有量が2ppm未満
では本発明の効果はなくなり、30ppmを越える
と、本発明の効果がなくなるばかりか、逆に低下
をきたす。 Such a calcium halophosphate phosphor has the advantage of improving initial luminous efficiency by 0.5 to 2 percent and improving working characteristics by 1 to 2 percent, and when the aluminum content is less than 2 ppm, the present invention If the amount exceeds 30 ppm, the effect of the present invention not only disappears but also decreases.
次に本発明けい光体を使用して既知通常のけい
光ランプ製造方法により40ワツト白色ノイズレス
けい光ランプを製作すると同時に、アルミニウム
を含有していないけい光体について、前記と同様
にして比較用けい光ランプを製作して比較した結
果、初期発光効率は0.5〜２パーセント向上、
3000時間点灯後の働程特性は１〜２パーセント向
上の効果を得ることを確認した。 Next, a 40 watt white noiseless fluorescent lamp was manufactured using the phosphor of the present invention by a conventional known fluorescent lamp manufacturing method, and at the same time, a phosphor containing no aluminum was manufactured for comparison in the same manner as above. As a result of manufacturing and comparing fluorescent lamps, the initial luminous efficiency was improved by 0.5 to 2%.
It was confirmed that the working characteristics after 3000 hours of lighting were improved by 1 to 2%.
以下、実施例にもとずいて本発明を詳細に説明
する。 Hereinafter, the present invention will be explained in detail based on Examples.
実施例 １
CaHPO4107.0ｇ，CaCO333.4ｇ，CaF28.8ｇ，
NH4Cl1.5ｇ，Sb2O31.7ｇ，MnCO31.4ｇ，
Al2O30.004ｇをそれぞれ秤量して、ボールミルに
て十分に混合する。この混合物をふた付き石英る
つぼに投入してN2雰囲気中で1200℃の温度で1.5
時間焼成する。次にこの焼成物を乳鉢にて粗粉砕
後、100メツシユのふるいを通過させ、さらにボ
ールミルにて粉砕して、通気法での平均粒度が６
ミクロンになるまで粉砕する。Example 1 CaHPO 4 107.0g, CaCO 3 33.4g, CaF 2 8.8g,
NH 4 Cl 1.5 g, Sb 2 O 3 1.7 g, MnCO 3 1.4 g,
Weigh out 0.004 g of Al 2 O 3 and mix thoroughly using a ball mill. This mixture was put into a quartz crucible with a lid and heated to 1.5 at a temperature of 1200 °C in an N2 atmosphere.
Bake for an hour. Next, this fired product was coarsely ground in a mortar, passed through a 100-mesh sieve, and further ground in a ball mill to achieve an average particle size of 6.
Grind to micron size.
このようにして得られたハロりん酸カルシウム
けい光体中のアルミニウムの定量分析を行なつた
結果、アルミニウムの含有重量はけい光体母体重
量に対して16ppmであることを確認した。 As a result of quantitative analysis of aluminum in the calcium halophosphate phosphor thus obtained, it was confirmed that the weight of aluminum was 16 ppm based on the weight of the phosphor matrix.
さらに、本実施例によつて得られたハロりん酸
カルシウムけい光体を既知通常のけい光ランプ製
造方法により40ワツト白色ノイズレスけい光ラン
プを製作した。一方、アルミニウムを含有しない
ハロりん酸カルシウムけい光体を前記と同様にし
て製作した比較用けい光ランプと比較した結果、
本実施例のハロりん酸カルシウムけい光体を用い
たけい光ランプはアルミニウムを含有していない
ハロりん酸カルシウムけい光体を用いた比較用け
い光ランプに比較して、初期発光効率は２パーセ
ント向上、3000時間点灯後の働程特性も２パーセ
ント毎向上した。 Further, a 40 watt white noiseless fluorescent lamp was fabricated using the calcium halophosphate phosphor obtained in this example by a known conventional fluorescent lamp manufacturing method. On the other hand, as a result of comparison with a comparative fluorescent lamp made in the same manner as above using a calcium halophosphate phosphor that does not contain aluminum,
The fluorescent lamp using the calcium halophosphate phosphor of this example has an initial luminous efficiency of 2% compared to a comparative fluorescent lamp using a calcium halophosphate phosphor that does not contain aluminum. The working characteristics after 3000 hours of lighting also improved by 2%.
実施例 ２
前記、実施例と同様にCaHPO4107.0ｇ、
CaCO333.4ｇ、CaF28.8ｇ、NH4Cl1.5ｇ、
Sb2O31.7ｇとAl2O30.002ｇをそれぞれ秤量してボ
ールミルにて十分混合する。この混合物をふた付
き石英ルツボに投入してN2雰囲気中で1200℃の
温度で1.5時間焼成する。次にこの焼成物を乳鉢
にて粗粉砕後100メツシユのふるいを通過させ、
さらにボールミルにて粉砕して通気法での平均粒
度が６ミクロンになるまで粉砕する。Example 2 107.0 g of CaHPO 4 as in the example above,
CaCO 3 33.4g, CaF 2 8.8g, NH 4 Cl 1.5g,
1.7 g of Sb 2 O 3 and 0.002 g of Al 2 O 3 were each weighed and thoroughly mixed in a ball mill. This mixture is placed in a quartz crucible with a lid and fired at a temperature of 1200° C. for 1.5 hours in an N 2 atmosphere. Next, this fired product was coarsely ground in a mortar and passed through a 100 mesh sieve.
The mixture is further pulverized in a ball mill until the average particle size is 6 microns by aeration method.
このようにして得られたハロりん酸カルシウム
けい光体中のアルミニウムの定量分析を行なつた
結果、アルミニウムの含有重量はけい光体母体重
量に対して8ppmであることを確認した。 Quantitative analysis of aluminum in the calcium halophosphate phosphor thus obtained confirmed that the aluminum content was 8 ppm based on the weight of the phosphor matrix.
さらにこの実施例で得られたハロりん酸カルシ
ウムけい光体を既知通常のけい光ランプ製造方法
により40ワツト白色ノイズレスけい光ランプを製
作した。一方、アルミニウムを含有しないハロり
ん酸カルシウムけい光体を前記と同様にして製作
した比較用けい光ランプと比較した結果、本実施
例のハロりん酸カルシウムけい光体を用いたけい
光ランプはアルミニウムを含有していないハロり
ん酸カルシウムけい光体を用いた比較用けい光ラ
ンプに比較して、初期発光効率は1.5パーセント
向上、3000時間点灯後の働程特性は２パーセント
の向上が得られた。 Furthermore, a 40 watt white noiseless fluorescent lamp was fabricated using the calcium halophosphate phosphor obtained in this example by a known conventional fluorescent lamp manufacturing method. On the other hand, as a result of comparison with a comparative fluorescent lamp manufactured in the same manner as described above using a calcium halophosphate phosphor that does not contain aluminum, it was found that the fluorescent lamp using the calcium halophosphate phosphor of this example was made of aluminum. Compared to a comparative fluorescent lamp using a calcium halophosphate phosphor that does not contain phosphor, the initial luminous efficiency was improved by 1.5%, and the working characteristics after 3000 hours of lighting were improved by 2%. .
実施例 ３
前記実施例と同様にCaHPO4107.0ｇ、
CaCO333.4ｇ、CaF28.8ｇ、NH4Cl1.5ｇ、
Sb2O31.7ｇを秤量し、ボールミルで十分混合した
ものを８個準備する。この混合物８個それぞれに
Al2O3を0.0005ｇ、0.001ｇ、0.006ｇ、0.008ｇ、
0.01ｇ、0.012ｇ、0.016ｇ、0.02ｇ、0.05ｇ秤量
して投入し、さらにボールミルにて十分に混合す
る。この混合物８個をそれぞれ８組のふた付き石
英ルツボに投入したものを準備し、この８組の石
英るつぼをN2雰囲気中で1200℃の温度で1.5時間
焼成する。次にこのそれぞれの焼成物を乳鉢にて
粗粉砕後100メツシユを通過させ、さらにボール
ミルにて粉砕して通気法での平均粒度が６ミクロ
ンになるまで粉砕する。Example 3 CaHPO 4 107.0 g as in the previous example,
CaCO 3 33.4g, CaF 2 8.8g, NH 4 Cl 1.5g,
Weigh 1.7 g of Sb 2 O 3 and thoroughly mix it in a ball mill to prepare 8 pieces. For each of the 8 pieces of this mixture
Al 2 O 3 0.0005g, 0.001g, 0.006g, 0.008g,
0.01g, 0.012g, 0.016g, 0.02g, 0.05g were weighed and added, and further mixed thoroughly in a ball mill. Eight sets of quartz crucibles with lids are each charged with eight pieces of this mixture, and the eight sets of quartz crucibles are fired at a temperature of 1200° C. for 1.5 hours in an N 2 atmosphere. Next, each of the fired products was coarsely ground in a mortar, passed through 100 meshes, and further ground in a ball mill until the average particle size was 6 microns by aeration method.
このようにして得られた、それぞれのハロりん
酸カルシウムけい光体中のアルミニウムの定量分
析を行なつた結果アルミニウムの含有重量はけい
光体重量に対してそれぞれ２，４，25，30，40，
50，65，80，190ppmであることを確認した。 Quantitative analysis of aluminum in each of the calcium halophosphate phosphors thus obtained revealed that the weight of aluminum was 2, 4, 25, 30, and 40, respectively, relative to the weight of the phosphor. ，
It was confirmed that the levels were 50, 65, 80, and 190ppm.
さらにこの実施例で得られた、８種類及びアル
ミニウムを含有しないハロりん酸カルシウム螢光
体を用いて既知通常のけい光ランプ製造方法によ
り40ワツト白色ノイズレスけい光ランプを製作
し、それぞれの初期発光効率を測定した。その結
果を図に示す。 Furthermore, using the eight types of calcium halophosphate phosphors that did not contain aluminum obtained in this example, 40 watt white noiseless fluorescent lamps were fabricated by a known normal fluorescent lamp manufacturing method, and each initial luminescence was Efficiency was measured. The results are shown in the figure.
図の横軸はけい光体母体に含有するアルミニウ
ムの含有率を、縦軸はアルミニウムを含有しない
けい光体を使用したけい光ランプの初期発光効率
を基準としたときの、それぞれのアルミニウム含
有率に対応したけい光ランプの発光効率の向上率
を示す。したがつて＋は発光効率の向上を−は発
光効率の低下を意味する。 The horizontal axis of the figure is the aluminum content in the phosphor matrix, and the vertical axis is the aluminum content based on the initial luminous efficiency of a fluorescent lamp using a phosphor that does not contain aluminum. This shows the improvement rate of luminous efficiency of fluorescent lamps corresponding to Therefore, + means an improvement in luminous efficiency, and - means a decrease in luminous efficiency.
実線は初期の発光効率、破線は3000時間点灯後
の発光効率を示す。 The solid line shows the initial luminous efficiency, and the broken line shows the luminous efficiency after 3000 hours of lighting.
この図からわかるようにけい光体母体重量に対
してアルミニウム含有重量が２〜30ppmのもの
は発光効率が向上するが40ppm以上では逆に低
下する。 As can be seen from this figure, the luminous efficiency improves when the aluminum content is 2 to 30 ppm relative to the weight of the phosphor matrix, but it decreases when it is 40 ppm or more.
また上記実施例のけい光ランプの3000時間点灯
後の働程特性を測定したところアルミニウム含有
重量が２〜30ppmのものは働程特性が１〜1.5％
向上したが、アルミニウム含有重量が40ppm以
上のものは働程特性が向上しなかつた。 In addition, when the working characteristics of the fluorescent lamps of the above examples were measured after being lit for 3000 hours, those with an aluminum content of 2 to 30 ppm had working characteristics of 1 to 1.5%.
However, the working characteristics did not improve for those with an aluminum content of 40 ppm or more.
なお本実施例ではハロりん酸カルシウムけい光
体について述べたがカルシウム元素の一部を
Zn，Ba，Sr，Ca，Cd等で置換したけい光体でも
同様な効果を有することを確認した。 In this example, a calcium halophosphate phosphor was described, but some of the calcium elements
It was confirmed that phosphors substituted with Zn, Ba, Sr, Ca, Cd, etc. have similar effects.
図は本発明を説明するアルミニウム含有率と発
光効率の関係を示す図である。
The figure is a diagram showing the relationship between aluminum content and luminous efficiency to explain the present invention.
Claims (1)
のアルミニウムの含有重量がけい光体母体重量に
対し２〜30ppmであることを特徴とするハロり
ん酸カルシウムけい光体。1. A calcium halophosphate phosphor, characterized in that the matrix of the phosphor contains aluminum, and the aluminum content is 2 to 30 ppm based on the weight of the phosphor matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140980A JPS56109280A (en) | 1980-02-04 | 1980-02-04 | Calcium halophosphate fluorescent substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140980A JPS56109280A (en) | 1980-02-04 | 1980-02-04 | Calcium halophosphate fluorescent substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56109280A JPS56109280A (en) | 1981-08-29 |
| JPS6247228B2 true JPS6247228B2 (en) | 1987-10-07 |
Family
ID=11777212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1140980A Granted JPS56109280A (en) | 1980-02-04 | 1980-02-04 | Calcium halophosphate fluorescent substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56109280A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858277A (en) * | 1992-12-23 | 1999-01-12 | Osram Sylvania Inc. | Aqueous phosphor coating suspension for lamps |
| US6483234B1 (en) | 2000-08-30 | 2002-11-19 | Koninklijke Philips Electronics N.V. | Single-component arctic bright calcium halophosphate phosphor |
| US6683406B2 (en) * | 2002-06-24 | 2004-01-27 | Koninklijke Philips Electronics N.V. | Low pressure mercury vapor fluorescent lamps |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS601376B2 (en) * | 1974-07-20 | 1985-01-14 | 新日本製鐵株式会社 | Method for producing amorphous alloy with excellent strength and corrosion resistance |
| JPS53146983A (en) * | 1977-05-30 | 1978-12-21 | Hitachi Ltd | Production of fluorescent substance |
-
1980
- 1980-02-04 JP JP1140980A patent/JPS56109280A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56109280A (en) | 1981-08-29 |
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