JP2001098261A - Luminescent composition and color fluorescent lamp using the same - Google Patents
Luminescent composition and color fluorescent lamp using the sameInfo
- Publication number
- JP2001098261A JP2001098261A JP27425899A JP27425899A JP2001098261A JP 2001098261 A JP2001098261 A JP 2001098261A JP 27425899 A JP27425899 A JP 27425899A JP 27425899 A JP27425899 A JP 27425899A JP 2001098261 A JP2001098261 A JP 2001098261A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- lamp
- color
- composition
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 36
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims abstract description 23
- 229940043256 calcium pyrophosphate Drugs 0.000 claims abstract description 23
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims abstract description 23
- -1 europium-activated yttrium oxide Chemical class 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 13
- 230000004907 flux Effects 0.000 abstract description 42
- 238000012423 maintenance Methods 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- CJRWSNPGHPBPPH-UHFFFAOYSA-N [Ba+2].B([O-])([O-])[O-].[Ca+2] Chemical compound [Ba+2].B([O-])([O-])[O-].[Ca+2] CJRWSNPGHPBPPH-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Vessels And Coating Films For Discharge Lamps (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ユーロピウム付活酸化
イットリウム赤色発光蛍光体とピロリン酸カルシウム粉
末との混合物から成る発光組成物及びそれを用いたカラ
ー蛍光ランプに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-emitting composition comprising a mixture of europium-activated yttrium oxide red light-emitting phosphor and calcium pyrophosphate powder, and a color fluorescent lamp using the same.
【０００２】[0002]
【従来の技術】カラー蛍光ランプは単色蛍光物質を塗布
した蛍光ランプであり、淡いイメージの色光が得られる
ので、看板照明、電飾照明、ウインドー照明、色を活か
した雰囲気照明等に用いられている。従来、ピンク色発
光のカラー蛍光ランプ用としては、ピンク色発光の鉛、
マンガン付活ケイ酸カルシウム蛍光体、又はオレンジ色
発光のスズ付活リン酸ストロンチウムマグネシウム蛍光
体と深赤色発光のマンガン付活フッ化ゲルマン酸マグネ
シウム蛍光体の混合物から成る混合蛍光体が用いられて
いた。しかしながら、鉛、マンガン付活ケイ酸カルシウ
ム蛍光体の場合、発光色は白っぽいピンク色であり、色
純度が低く、ランプの光束維持率も低いという問題があ
った。また、スズ付活リン酸ストロンチウムマグネシウ
ム蛍光体とマンガン付活フッ化ゲルマン酸マグネシウム
蛍光体の混合蛍光体の場合、色純度を上げるには高価な
マンガン付活フッ化ゲルマン酸マグネシウム蛍光体の混
合割合を増やす必要からコスト高になり、ランプの光束
も低下するという問題があった。2. Description of the Related Art A color fluorescent lamp is a fluorescent lamp coated with a single-color fluorescent material, and can produce faint image color light. Therefore, it is used for signboard lighting, illumination lighting, window lighting, atmosphere lighting utilizing colors, and the like. I have. Conventionally, for pink fluorescent color fluorescent lamps, pink luminescent lead,
A manganese-activated calcium silicate phosphor or a mixed phosphor composed of a mixture of a tin-activated strontium magnesium phosphate phosphor emitting orange light and a manganese-activated magnesium fluorinated magnesium germanate phosphor emitting deep red light was used. . However, in the case of the lead and manganese-activated calcium silicate phosphor, there is a problem that the emission color is whitish pink, the color purity is low, and the luminous flux maintenance factor of the lamp is low. In the case of a mixed phosphor of a tin-activated strontium magnesium phosphate phosphor and a manganese-activated magnesium fluorogermanate phosphor, a mixing ratio of an expensive manganese-activated magnesium fluorogermanate phosphor is required to increase color purity. However, there is a problem that the cost is increased due to the necessity of increasing the number of lights, and the luminous flux of the lamp is also reduced.
【０００３】これに対し、白色物質の無機物質を蛍光体
重量に対し１０〜２３０％の範囲で混合希釈することに
より、高価な蛍光体の使用量が削減できることが特開昭
５７−１２８４５２号公報に開示されている。白色粉末
の無機物質としてはカルシウムのピロリン酸塩、或いは
オルソリン酸塩、或いは両者の混合物が使用できること
が記載されている。また、バルブ内面の蛍光層が蛍光体
と紫外線反射物質にて構成され、紫外線反射物質の占め
る割合が全体の３０〜９５重量％に設定される蛍光層を
具備した蛍光ランプについて特開昭５８−２１８７４５
号公報に開示され、高価な蛍光体の使用量を削減可能
で、紫外線反射物質は具体的には酸化チタン（Ｔｉ
Ｏ2）、アルミナ（Ａｌ2Ｏ3）、酸化マグネシウム（Ｍ
ｇＯ）、ピロリン酸カルシウム（Ｃａ2Ｐ2Ｏ7）などが
使用できることが記載されている。On the other hand, Japanese Patent Application Laid-Open No. 57-128452 discloses that the amount of expensive phosphor used can be reduced by mixing and diluting a white inorganic substance in the range of 10 to 230% based on the weight of the phosphor. Is disclosed. It is described that as the inorganic substance of the white powder, calcium pyrophosphate or orthophosphate, or a mixture of both can be used. A fluorescent lamp having a fluorescent layer in which the fluorescent layer on the inner surface of the bulb is composed of a fluorescent substance and an ultraviolet reflective substance and the ratio of the ultraviolet reflective substance is set to 30 to 95% by weight is disclosed in Japanese Patent Laid-Open No. 218745
No. 4,078,098, the amount of expensive phosphor used can be reduced, and the ultraviolet reflective material is specifically titanium oxide (Ti).
O 2 ), alumina (Al 2 O 3 ), magnesium oxide (M
gO), calcium pyrophosphate (Ca 2 P 2 O 7 ) and the like can be used.
【０００４】これらの手法を用い、ユーロピウム付活酸
化イットリウム赤色発光蛍光体に紫外線反射物質として
ピロリン酸カルシウムを混合し、蛍光ランプを作製した
ところ、ランプの発光色がピンク色の方に引き寄せられ
ることから、ピンク色発光のカラー蛍光ランプに使用で
きることがわかった。この色調の変化は、水銀蒸気放電
に基づく可視域の青紫色系発光の強度はほぼ変わらない
が、ピロリン酸カルシウムを混合することで赤色発光強
度が低下し、全体としてピンク色の発光色となることに
よる。When a fluorescent lamp is manufactured by mixing europium-activated yttrium oxide red light-emitting phosphor with calcium pyrophosphate as an ultraviolet reflecting material by using these techniques, the emission color of the lamp is drawn toward the pink color. It can be used for a color fluorescent lamp emitting pink light. This change in color tone shows that the intensity of blue-violet emission in the visible range due to mercury vapor discharge is almost unchanged, but the mixing of calcium pyrophosphate reduces the red emission intensity, resulting in a pink emission color as a whole. by.
【０００５】しかしながら、上記ピンク色発光のカラー
蛍光ランプを作製した場合、管端の色差の問題が新たに
発生した。これは、蛍光ランプの製造工程中、ガラス管
に発光組成物を塗布する工程で完全に均一に混合された
塗布懸濁液を用いても、乾燥され蛍光体層が形成される
時に、ガラス管の塗布上部と下部で、蛍光体層中の蛍光
体とピロリン酸カルシウムの成分比がずれてしまうこと
による。このように蛍光ランプの両端で発光色の色差が
発生することは、カラー蛍光ランプにおいて問題となる
ことから、改良が必要とされる。However, when the above-mentioned color fluorescent lamp emitting pink light is manufactured, a problem of a color difference at a tube end newly arises. This is because, even during the manufacturing process of the fluorescent lamp, even when a coating suspension that is completely uniformly mixed is used in the step of applying the luminescent composition to the glass tube, the glass tube is dried and the phosphor layer is formed. This is because the component ratio between the phosphor in the phosphor layer and the calcium pyrophosphate is shifted between the upper portion and the lower portion. Since the occurrence of the color difference between the emission colors at both ends of the fluorescent lamp is a problem in the color fluorescent lamp, improvement is required.
【発明が解決しようとする課題】従って、本発明は上述
した問題を解決することを目的とし、ピンク色発光のカ
ラー蛍光ランプに用いたとき、色純度が良く、ランプ光
束及び光束維持率が高く、管端の色差の少ない蛍光ラン
プを低コストで得ることのできる発光組成物及びそれを
用いたカラー蛍光ランプを提供することを目的としてい
る。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems, and when used in a pink fluorescent color fluorescent lamp, the color purity is good and the lamp luminous flux and the luminous flux maintenance rate are high. It is an object of the present invention to provide a luminescent composition that enables a fluorescent lamp having a small color difference at the tube end to be obtained at low cost, and a color fluorescent lamp using the same.
【０００６】[0006]
【発明を解決するための手段】本発明者等は上述した問
題を解決するために鋭意検討した結果、ピンク色発光の
カラー蛍光ランプ用として、ユーロピウム付活酸化イッ
トリウム赤色発光蛍光体とピロリン酸カルシウム粉末の
混合物から成る発光組成物を用いることにより、色純度
が良く、ランプ光束及び光束維持率が高く、管端の色差
の少ないカラー蛍光ランプが低コストで得られることを
新たに見いだし本発明を完成させるに至った。The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a europium-activated yttrium oxide red light-emitting phosphor and a calcium pyrophosphate powder are used for a color fluorescent lamp emitting pink light. It has been found that a color fluorescent lamp having a good color purity, a high lamp luminous flux and a high luminous flux maintenance ratio, and a small color difference at a tube end can be obtained at a low cost by using a luminescent composition comprising a mixture of the above. It led to.
【０００７】すなわち、本発明の発光組成物は、組成式
が（Ｙ1-k，Ｅｕk）2Ｏ3（ただし、ｋは０．０２１≦ｋ
≦０．０６６の範囲である。）で表され、平均粒径が２
〜６μｍの範囲のユーロピウム付活酸化イットリウム赤
色発光蛍光体とピロリン酸カルシウム粉末の混合物から
成る発光組成物であって、前記蛍光体の占める割合は発
光組成物全重量に対し１０〜５０重量％の範囲であり、
ピロリン酸カルシウム粉末の平均粒径ａと前記蛍光体の
平均粒径ｂとの比ａ／ｂは１≦ａ／ｂ≦１．５の範囲で
あり、該発光組成物が管壁に塗布されたカラー蛍光ラン
プのランプ色度は０．５０≦ｘ≦０．５９、０．３１≦
ｙ≦０．３４の範囲であることを特徴とする。Namely, the light emitting composition of the present invention, composition formula (Y 1-k, Eu k ) 2 O 3 ( however, k is 0.021 ≦ k
≦ 0.066. ) And the average particle size is 2
A light-emitting composition comprising a mixture of europium-activated yttrium oxide red light-emitting phosphor in the range of up to 6 μm and calcium pyrophosphate powder, wherein the proportion of said phosphor is in the range of 10 to 50% by weight based on the total weight of the light-emitting composition. And
The ratio a / b of the average particle size a of the calcium pyrophosphate powder to the average particle size b of the phosphor is in the range of 1 ≦ a / b ≦ 1.5, and the color obtained by applying the luminescent composition to a tube wall is used. The lamp chromaticity of the fluorescent lamp is 0.50 ≦ x ≦ 0.59, 0.31 ≦
It is characterized in that y ≦ 0.34.
【０００８】蛍光体中のＥｕの濃度ｋについては、蛍光
体１モルに対し、０．０２１モル以上、０．０６６モル
以下の範囲に調整する。０．０２１モルより少ないと光
吸収が悪くなり、その結果蛍光体の発光強度は低下し、
ランプ光束も低下する。０．０６６モルよりも多くなる
と、濃度消光を起こし、蛍光体の発光強度及びランプ光
束は低下する。また、蛍光体の平均粒径は２〜６μｍの
範囲が好ましい。２μｍ未満の場合、蛍光体の発光強度
は低く、ランプ光束は低下する。また、蛍光体粒子の分
散性が悪く、塗布特性が悪化する。逆に、６μｍを越え
ると、通常のカラー蛍光ランプの塗布重量（２〜４ｍｇ
／ｃｍ2）ではランプ光束が低下し、ランプ光束を上げ
るためには塗布重量を増加する必要があり、コスト面で
厳しくなる。ここで平均粒径は、空気透過法により比表
面積を測定し、一次粒子の粒径の平均値を求めたもので
あり、フィッシャーサブシーブサイザー（F.S.S.S.)を
用いて測定した値である。[0008] The concentration k of Eu in the phosphor is adjusted within a range from 0.021 mol to 0.066 mol per 1 mol of the phosphor. If the amount is less than 0.021 mol, the light absorption becomes poor, and as a result, the emission intensity of the phosphor decreases,
The lamp luminous flux also decreases. If it exceeds 0.066 mol, concentration quenching occurs, and the luminous intensity of the phosphor and the lamp luminous flux decrease. The average particle size of the phosphor is preferably in the range of 2 to 6 μm. If it is less than 2 μm, the emission intensity of the phosphor is low, and the lamp luminous flux is reduced. In addition, the dispersibility of the phosphor particles is poor, and the coating characteristics are deteriorated. Conversely, if it exceeds 6 μm, the coating weight of a normal color fluorescent lamp (2 to 4 mg)
/ Cm 2 ), the lamp luminous flux decreases, and in order to increase the lamp luminous flux, it is necessary to increase the coating weight, which is strict in cost. Here, the average particle diameter is a value obtained by measuring the specific surface area by an air permeation method and calculating the average value of the particle diameters of the primary particles, and is a value measured using a Fisher sub-sieve sizer (FSSS).
【０００９】ピロリン酸カルシウム粉末は可視域から紫
外域の範囲において反射率が９０％以上の白色物質から
成る紫外線反射物質であって、ピロリン酸カルシウム粉
末の平均粒径ａと蛍光体の平均粒径ｂとの比ａ／ｂが１
≦ａ／ｂ≦１．５の範囲となる粒径範囲のものを使用す
る。管端の色差が、粒径比ａ／ｂが１≦ａ／ｂ≦１．５
の範囲で最も小さく、粒径比ａ／ｂが１未満、又は１．
５を越えると大きくなるためである。The calcium pyrophosphate powder is an ultraviolet reflecting material composed of a white substance having a reflectance of 90% or more in the range from the visible region to the ultraviolet region, and has an average particle size a of the calcium pyrophosphate powder and an average particle size b of the phosphor. Ratio a / b is 1
A particle size range satisfying ≦ a / b ≦ 1.5 is used. The color difference at the end of the tube is such that the particle size ratio a / b is 1 ≦ a / b ≦ 1.5.
And the particle size ratio a / b is less than 1 or 1.
This is because when it exceeds 5, it becomes large.
【００１０】発光組成物中の蛍光体の割合は、発光組成
物全重量に対し１０〜５０重量％の範囲が好ましい。よ
り好ましくは、２０〜５０重量％の範囲である。１０重
量％未満では、ピンク色としての色純度が悪くなり、ラ
ンプ光束も低下する。逆に５０重量％を越えると、蛍光
ランプの発光色は赤みが強くなって色純度が悪くなり、
またコストも高くなる。The ratio of the phosphor in the light emitting composition is preferably in the range of 10 to 50% by weight based on the total weight of the light emitting composition. More preferably, it is in the range of 20 to 50% by weight. If the content is less than 10% by weight, the color purity as pink becomes worse, and the lamp luminous flux also decreases. Conversely, if it exceeds 50% by weight, the emission color of the fluorescent lamp becomes reddish and the color purity becomes poor,
Also, the cost is increased.
【００１１】上記した発光組成物を、水銀および希ガス
を含む封入ガスが充填された透光性ガラス管と、この透
光性ガラス管内壁面に設けられた蛍光体粒子を含む蛍光
体層と、封入ガス中で陽光中放電を維持するための手段
とを備える蛍光ランプに形成することで本発明のカラー
蛍光ランプを得ることができる。発光組成物の透光性ガ
ラス壁面への塗布は蛍光体を塗布する通常の方法を用い
て行うことができ、例えば、蛍光体層の脱落防止の目的
で、微粒子のアルミナ、及びカルシウムバリウムボレー
ト等の結着剤を使用することもできる。発光組成物の塗
布量も蛍光体単独を塗布する場合と同じ程度の量であ
る。A light-transmitting glass tube filled with a sealing gas containing mercury and a rare gas, a phosphor layer containing phosphor particles provided on the inner wall surface of the light-transmitting glass tube, The color fluorescent lamp of the present invention can be obtained by forming the fluorescent lamp including means for maintaining a discharge in sunlight in a sealed gas. The light-emitting composition can be applied to the wall surface of the light-transmitting glass using a usual method of applying a phosphor. For example, for the purpose of preventing the phosphor layer from falling off, fine particles of alumina, calcium barium borate, etc. Can also be used. The application amount of the light emitting composition is also about the same amount as when the phosphor alone is applied.
【００１２】図１に本発明のカラー蛍光ランプにおける
発光組成物中の（Ｙ0.965，Ｅｕ0.0 35）2Ｏ3蛍光体（平
均粒径４．０μｍ）の配合割合を種々に変化させ、ＦＬ
４０ＳＳ蛍光ランプを作製し、ランプ光束を測定した結
果を示す。ここで、発光組成物の塗布重量は３．５ｇに
固定している。発光組成物中ユーロピウム付活酸化イッ
トリウム赤色発光蛍光体が１０重量％未満では、コスト
削減メリットは大きいが、ランプ光束は大幅に低下す
る。逆に５０重量％を越えると、ランプ光束は高いもの
の、コスト削減メリットは小さくなる。[0012] Figure 1 to the light emitting composition in the color fluorescent lamp of the present invention (Y 0.965, Eu 0.0 35) 2 O 3 phosphor blend ratio of (average particle size 4.0 .mu.m) is changed variously, FL
The results of producing a 40SS fluorescent lamp and measuring the lamp luminous flux are shown. Here, the coating weight of the light emitting composition is fixed at 3.5 g. When the content of the europium-activated yttrium oxide red light-emitting phosphor in the light-emitting composition is less than 10% by weight, the cost reduction merit is great, but the lamp luminous flux is greatly reduced. On the other hand, if it exceeds 50% by weight, the lamp light flux is high, but the merit of cost reduction is small.
【００１３】図２は同ランプの色度点をＣＩＥ色度座標
上にプロットしたものである。発光組成物中ユーロピウ
ム付活酸化イットリウム赤色発光蛍光体が１０〜５０重
量％の範囲の場合、発光色は０．５０≦ｘ≦０．５９、
０．３１≦ｙ≦０．３４の範囲の色純度の良いピンク色
を示すが、１０重量％未満では、ｘ、ｙ値がともに小さ
くなり、発光色は青みが強くなる。逆に、５０重量％を
越えると、ｘ、ｙ値ともに大きくなり、発光色は赤みが
強くなって、ともにピンク色としての色純度が悪くな
る。FIG. 2 is a plot of chromaticity points of the lamp on CIE chromaticity coordinates. When the europium-activated yttrium oxide red light-emitting phosphor in the light-emitting composition is in the range of 10 to 50% by weight, the emission color is 0.50 ≦ x ≦ 0.59,
It shows a pink color with good color purity in the range of 0.31 ≦ y ≦ 0.34, but if it is less than 10% by weight, both x and y values become small, and the emission color becomes bluish. Conversely, if it exceeds 50% by weight, both the x and y values become large, the emission color becomes more reddish, and the color purity as pink becomes worse.
【００１４】このように、発光組成物中のユーロピウム
付活酸化イットリウム赤色発光蛍光体の配合割合を変え
ていくとカラー蛍光ランプの発光色が変化するのは、ラ
ンプの蛍光体層を透過する可視Ｈｇ線の強度はほぼ変わ
らないが、該蛍光体の配合割合を少なくしていった場
合、赤色発光強度が低下し、全体として発光色が青色方
向にシフトするためであり、逆に該蛍光体の配合割合を
多くしていった場合、赤色発光強度が増加し、全体とし
て発光色が赤色方向にシフトするためである。As described above, when the mixing ratio of the europium-activated yttrium oxide red light-emitting phosphor in the light-emitting composition is changed, the emission color of the color fluorescent lamp changes because visible light passing through the phosphor layer of the lamp is changed. Although the intensity of the Hg line is not substantially changed, when the blending ratio of the phosphor is reduced, the red light emission intensity decreases, and the emission color shifts in the blue direction as a whole. This is because when the compounding ratio of is increased, the red emission intensity increases, and the emission color shifts in the red direction as a whole.
【００１５】図３に、発光組成物中の（Ｙ0.965，Ｅｕ
0.035）2Ｏ3蛍光体（平均粒径４．０μｍ）の配合割合
が２０％、５０％の場合について、ピロリン酸カルシウ
ム粉末の平均粒径ａと前記蛍光体の平均粒径ｂとの比ａ
／ｂを種々に変化させ、ＦＬ４０ＳＳ蛍光ランプを作製
し、管端の色差を測定した結果を示す。ここで、発光組
成物の塗布重量は３．５ｇに固定している。また、管端
の色差は、ランプ上部の発光色（ｘ1，ｙ1）とランプ下
部の発光色（ｘ2，ｙ2）との色差を｛（ｘ1−ｘ2）2＋
（ｙ1−ｙ2）2｝×１０6で表したものである。発光組成
物中の蛍光体の配合割合がいずれの場合も、粒径比ａ／
ｂが１≦ａ／ｂ≦１．５の範囲において、管端の色差が
少ないことがわかる。FIG. 3 shows (Y 0.965 , Eu) in the luminescent composition.
0.035 ) The ratio a of the average particle size a of the calcium pyrophosphate powder to the average particle size b of the phosphor when the blending ratio of the 2 O 3 phosphor (average particle size is 4.0 μm) is 20% or 50%.
The results obtained by producing FL40SS fluorescent lamps with various / b values and measuring the color difference at the tube end are shown. Here, the coating weight of the light emitting composition is fixed at 3.5 g. The color difference at the end of the tube is obtained by calculating the color difference between the emission color (x 1 , y 1 ) above the lamp and the emission color (x 2 , y 2 ) below the lamp as ｛(x 1 −x 2 ) 2 +
(Y 1 −y 2 ) 2 ｝ × 10 6 . Regardless of the mixing ratio of the phosphor in the light emitting composition, the particle size ratio a /
It can be seen that when b is in the range of 1 ≦ a / b ≦ 1.5, the color difference at the tube end is small.
【００１６】[0016]
【実施例】［実施例１］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体２０ｇと平均粒径が５．
０μｍのピロリン酸カルシウム粉末８０ｇを乾式混合し
本発明の発光組成物を得た。この発光組成物をニトロセ
ルロース／酢酸ブチルバインダーに懸濁させた塗布液を
調製し、通常の方法により蛍光ランプ（ＦＬ４０ＳＳ）
用ガラス管に発光組成物を３．５ｇ塗布し、常法に従い
カラー蛍光ランプを作製した。このようにして得られる
蛍光層の成分比率は、塗布液の発光組成物の仕込み比率
にほぼ一致する。得られたカラー蛍光ランプを積分球と
分光光度計を用いて測定したところ、ランプ色度は、ｘ
＝０．５４９，ｙ＝０．３２５（ＣＩＥ色度座標）であ
り、ランプ光束は１８６１ルーメンであった。光束維持
率は、点灯初期（０時間）のランプ光束を１００％とし
て、１００時間点灯後のランプ光束を相対値％で示した
ものであり、９６％であった。また、管端の色差は、管
端から２０ｃｍの部分以外を黒い布等で覆い、ランプ上
部と下部の発光色を測定して求めたものであり、６８で
あった。[Example 1] (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 20 g of phosphor and average particle size of 5.
80 g of 0 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition of the present invention. A coating solution was prepared by suspending the luminescent composition in a nitrocellulose / butyl acetate binder, and a fluorescent lamp (FL40SS) was prepared by a usual method.
3.5 g of the luminescent composition was applied to a glass tube for use, and a color fluorescent lamp was produced according to a conventional method. The component ratio of the fluorescent layer obtained in this manner substantially matches the charging ratio of the light emitting composition in the coating solution. When the obtained color fluorescent lamp was measured using an integrating sphere and a spectrophotometer, the lamp chromaticity was x
= 0.549, y = 0.325 (CIE chromaticity coordinates) and the lamp luminous flux was 1861 lumens. The luminous flux maintenance ratio was 96%, assuming that the lamp luminous flux at the beginning of lighting (0 hour) was 100% and the lamp luminous flux after lighting for 100 hours was represented by a relative value%. The color difference at the tube end was 68, which was obtained by covering a portion other than 20 cm from the tube end with a black cloth and measuring the emission colors of the upper and lower portions of the lamp.
【００１７】［実施例２］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体５０ｇと平均粒径が５．
０μｍのピロリン酸カルシウム粉末５０ｇを乾式混合
し、発光組成物を得る以外は、実施例１と同様に行っ
た。ランプ色度は、ｘ＝０．５８０，ｙ＝０．３３２
（ＣＩＥ色度座標）であり、ランプ光束は２３８０ルー
メン、光束維持率は９７％であった。また、管端の色差
は１０であった。Example 2 (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 phosphor 50 g and average particle size 5.
The procedure was performed in the same manner as in Example 1 except that 50 g of 0 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition. The lamp chromaticity is x = 0.580, y = 0.332
(CIE chromaticity coordinates), the lamp luminous flux was 2380 lumens, and the luminous flux maintenance factor was 97%. The color difference at the tube end was 10.
【００１８】［比較例１］鉛、マンガン付活ケイ酸カル
シウム蛍光体１００ｇを発光組成物として使用する以外
は、実施例１と同様に行った。ランプ色度は、ｘ＝０．
４９３，ｙ＝０．３５９（ＣＩＥ色度座標）であり、ラ
ンプ光束は１７４１ルーメン、光束維持率は９２％であ
った。Comparative Example 1 The procedure of Example 1 was repeated, except that 100 g of a lead and manganese-activated calcium silicate phosphor was used as a light emitting composition. The lamp chromaticity is x = 0.
493, y = 0.359 (CIE chromaticity coordinates), the lamp luminous flux was 1741 lumens, and the luminous flux maintenance ratio was 92%.
【００１９】［比較例２］スズ付活リン酸ストロンチウ
ムマグネシウム蛍光体４０ｇとマンガン付活フッ化ゲル
マン酸マグネシウム蛍光体６０ｇを乾式混合し、発光組
成物を得る以外は、実施例１と同様に行った。ランプ色
度は、ｘ＝０．５１３，ｙ＝０．３４１（ＣＩＥ色度座
標）であり、ランプ光束は１３８７ルーメン、光束維持
率は９６％であった。Comparative Example 2 The procedure of Example 1 was repeated except that 40 g of tin-activated strontium magnesium phosphate phosphor and 60 g of manganese-activated magnesium fluorogermanate phosphor were dry-mixed to obtain a luminescent composition. Was. The lamp chromaticity was x = 0.513, y = 0.341 (CIE chromaticity coordinates), the lamp luminous flux was 1387 lumens, and the luminous flux maintenance factor was 96%.
【００２０】［比較例３］スズ付活リン酸ストロンチウ
ムマグネシウム蛍光体２５ｇとマンガン付活フッ化ゲル
マン酸マグネシウム蛍光体７５ｇを乾式混合し、発光組
成物を得る以外は、実施例１と同様に行った。ランプ色
度は、ｘ＝０．５４８，ｙ＝０．３２３（ＣＩＥ色度座
標）であり、ランプ光束は１１６９ルーメン、光束維持
率は９６％であった。Comparative Example 3 The same procedure as in Example 1 was carried out except that 25 g of a tin-activated strontium magnesium phosphate phosphor and 75 g of a manganese-activated magnesium fluorogermanate phosphor were dry-mixed to obtain a luminescent composition. Was. The lamp chromaticity was x = 0.548, y = 0.323 (CIE chromaticity coordinates), the lamp luminous flux was 1169 lumen, and the luminous flux maintenance factor was 96%.
【００２１】［比較例４］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体２０ｇと平均粒径が６．
５μｍのピロリン酸カルシウム粉末８０ｇを乾式混合
し、発光組成物を得る以外は、実施例１と同様に行っ
た。ランプ色度は、ｘ＝０．５４４，ｙ＝０．３２５
（ＣＩＥ色度座標）であり、ランプ光束は１８５７ルー
メン、光束維持率は９６％であった。また、管端の色差
は１０４であった。Comparative Example 4 (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 20 g of phosphor and average particle diameter of 6.
The procedure was performed in the same manner as in Example 1, except that 80 g of 5 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition. The lamp chromaticity is x = 0.544, y = 0.325
(CIE chromaticity coordinates), the lamp luminous flux was 1857 lumens, and the luminous flux maintenance factor was 96%. The color difference at the tube end was 104.
【００２２】［比較例５］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体２０ｇと平均粒径が３．
０μｍのピロリン酸カルシウム粉末８０ｇを乾式混合
し、発光組成物を得る以外は、実施例１と同様に行っ
た。ランプ色度は、ｘ＝０．５５０，ｙ＝０．３２５
（ＣＩＥ色度座標）であり、ランプ光束は１８６４ルー
メン、光束維持率は９６％であった。また、管端の色差
は１４８であった。Comparative Example 5 (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 phosphor 20 g and average particle size 3.
The procedure was performed in the same manner as in Example 1 except that 80 g of 0 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition. Lamp chromaticity is x = 0.550, y = 0.325
(CIE chromaticity coordinates), the lamp luminous flux was 1,864 lumens, and the luminous flux maintenance factor was 96%. The color difference at the tube end was 148.
【００２３】［比較例６］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体５０ｇと平均粒径が６．
５μｍのピロリン酸カルシウム粉末５０ｇを乾式混合
し、発光組成物を得る以外は、実施例１と同様に行っ
た。ランプ色度は、ｘ＝０．５７８，ｙ＝０．３３２
（ＣＩＥ色度座標）であり、ランプ光束は２３７９ルー
メン、光束維持率は９７％であった。また、管端の色差
は３７であった。Comparative Example 6 (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 50 g of phosphor and average particle diameter of 6.
The procedure was performed in the same manner as in Example 1 except that 50 g of 5 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition. The lamp chromaticity is x = 0.578, y = 0.332
(CIE chromaticity coordinates), the lamp luminous flux was 2379 lumens, and the luminous flux maintenance factor was 97%. The color difference at the tube end was 37.
【００２４】［比較例７］平均粒径が４．０μｍの（Ｙ
0.965，Ｅｕ0.035）2Ｏ3蛍光体５０ｇと平均粒径が３．
０μｍのピロリン酸カルシウム粉末５０ｇを乾式混合
し、発光組成物を得る以外は、実施例１と同様に行っ
た。ランプ色度は、ｘ＝０．５８１，ｙ＝０．３３２
（ＣＩＥ色度座標）であり、ランプ光束は２３７２ルー
メン、光束維持率は９７％であった。また、管端の色差
は３７であった。Comparative Example 7 (Y) having an average particle size of 4.0 μm
0.965 , Eu 0.035 ) 2 O 3 phosphor 50 g and average particle size 3.
The procedure was performed in the same manner as in Example 1 except that 50 g of 0 μm calcium pyrophosphate powder was dry-mixed to obtain a luminescent composition. The lamp chromaticity is x = 0.581, y = 0.332
(CIE chromaticity coordinates), the lamp luminous flux was 2372 lumens, and the luminous flux maintenance factor was 97%. The color difference at the tube end was 37.
【００２５】表１に実施例１、２及び比較例１、２、３
のカラー蛍光ランプの性能、発光組成物のコスト比をま
とめて比較する。この表から、本発明の実施例１、２の
場合、比較例１、２、３に比べ、ランプ光束、光束維持
率、コスト比のいずれにおいても優れていることがわか
る。特に、ランプ色度が比較例３とほぼ同じである実施
例１の場合、比較例３に比べ、ランプ光束は高く、コス
トは非常に低いことがわかる。Table 1 shows Examples 1 and 2 and Comparative Examples 1, 2, and 3.
The performance of the color fluorescent lamps and the cost ratio of the luminescent composition are summarized and compared. From this table, it can be seen that Examples 1 and 2 of the present invention are superior to Comparative Examples 1, 2, and 3 in all of the lamp luminous flux, the luminous flux maintenance ratio, and the cost ratio. In particular, in the case of Example 1 in which the lamp chromaticity is almost the same as that of Comparative Example 3, it can be seen that the lamp luminous flux is high and the cost is very low as compared with Comparative Example 3.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表２に実施例１、２及び比較例４、５、
６、７のカラー蛍光ランプのランプ上部の発光色
（ｘ1，ｙ1）、ランプ下部の発光色（ｘ2，ｙ2）及び管
端の色差をまとめて比較する。この表から、本発明の実
施例１と比較例４、５を比べた場合、また、実施例２と
比較例６、７を比べた場合、いずれにおいても本発明の
実施例が管端の色差が少ないことがわかる。Table 2 shows Examples 1 and 2 and Comparative Examples 4 and 5,
The emission colors (x 1 , y 1 ) at the top of the lamps, the emission colors (x 2 , y 2 ) at the bottom of the lamps, and the color difference at the tube end of the color fluorescent lamps 6 and 7 are compared together. From this table, it can be seen from the table that when Example 1 of the present invention is compared with Comparative Examples 4 and 5, and when Example 2 is compared with Comparative Examples 6 and 7, the Example of the present invention has a color difference at the tube end. Is small.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】本発明の発光組成物を用いることによ
り、ランプ色度が０．５０≦ｘ≦０．５９、０．３１≦
ｙ≦０．３４の範囲で色純度が良く、ランプ光束及び光
束維持率が高く、管端の色差の少ないカラー蛍光ランプ
を低コストで得ることができる。By using the light emitting composition of the present invention, the lamp chromaticity is 0.50 ≦ x ≦ 0.59, 0.31 ≦
A color fluorescent lamp having good color purity, a high lamp luminous flux and a high luminous flux maintenance ratio and a small color difference at the tube end can be obtained at a low cost in the range of y ≦ 0.34.
【００３０】[0030]
【図１】本発明の発光組成物中のユーロピウム付活酸化
イットリウム赤色発光蛍光体配合量とランプ光束の関係
を示すグラフ図FIG. 1 is a graph showing the relationship between the amount of europium-activated yttrium oxide red light-emitting phosphor in the light-emitting composition of the present invention and the lamp luminous flux.
【図２】本発明の発光組成物中のユーロピウム付活酸化
イットリウム赤色発光蛍光体配合量とランプ色度の関係
を示すグラフ図FIG. 2 is a graph showing the relationship between the amount of europium-activated yttrium oxide red light-emitting phosphor and the lamp chromaticity in the light-emitting composition of the present invention.
【図３】本発明の発光組成物中のピロリン酸カルシウム
粉末とユーロピウム付活酸化イットリウム赤色発光蛍光
体の粒径比と管端の色差との関係を示すグラフ図FIG. 3 is a graph showing the relationship between the particle size ratio of the calcium pyrophosphate powder and the europium-activated yttrium oxide red light emitting phosphor in the light emitting composition of the present invention and the color difference at the tube end.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堺 修 徳島県阿南市上中町岡491番地100 日亜化 学工業株式会社内 Ｆターム(参考） 4H001 CA07 XA08 XA39 YA63 5C043 AA03 AA11 AA20 CC09 CD01 DD28 EC06 EC18 EC20 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Osamu Sakai Inventor: 491-1 Kagaminakamachioka, Anan-shi, Tokushima Pref. EC18 EC20
Claims (2)
し、ｋは０．０２１≦ｋ≦０．０６６の範囲である。）
で表され、平均粒径が２〜６μｍの範囲のユーロピウム
付活酸化イットリウム赤色発光蛍光体とピロリン酸カル
シウム粉末の混合物から成る発光組成物であって、前記
蛍光体の占める割合は発光組成物全重量に対し１０〜５
０重量％の範囲であり、ピロリン酸カルシウム粉末の平
均粒径ａと前記蛍光体の平均粒径ｂとの比ａ／ｂは１≦
ａ／ｂ≦１．５の範囲であり、該発光組成物が管壁に塗
布されたカラー蛍光ランプのランプ色度は０．５０≦ｘ
≦０．５９、０．３１≦ｙ≦０．３４の範囲であること
を特徴とする発光組成物。1. The composition formula is (Y 1 -k , Eu k ) 2 O 3 (where k is in the range of 0.021 ≦ k ≦ 0.066).
And a light-emitting composition comprising a mixture of europium-activated yttrium oxide red light-emitting phosphor and calcium pyrophosphate powder having an average particle diameter in the range of 2 to 6 μm, wherein the proportion of the phosphor is the total weight of the light-emitting composition. 10-5
0% by weight, and the ratio a / b of the average particle size a of the calcium pyrophosphate powder to the average particle size b of the phosphor is 1 ≦
a / b ≦ 1.5, and the lamp chromaticity of the color fluorescent lamp having the luminescent composition applied to the tube wall is 0.50 ≦ x
≦ 0.59, 0.31 ≦ y ≦ 0.34.
ことを特徴とするカラー蛍光ランプ。2. A color fluorescent lamp comprising the luminescent composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27425899A JP3965838B2 (en) | 1999-09-28 | 1999-09-28 | Color fluorescent lamp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27425899A JP3965838B2 (en) | 1999-09-28 | 1999-09-28 | Color fluorescent lamp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001098261A true JP2001098261A (en) | 2001-04-10 |
| JP3965838B2 JP3965838B2 (en) | 2007-08-29 |
Family
ID=17539191
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27425899A Expired - Fee Related JP3965838B2 (en) | 1999-09-28 | 1999-09-28 | Color fluorescent lamp |
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| Country | Link |
|---|---|
| JP (1) | JP3965838B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2006051768A1 (en) * | 2004-11-11 | 2008-05-29 | 株式会社東芝 | Phosphor and method for producing the same, and light emitting device using the same and method for producing the same |
-
1999
- 1999-09-28 JP JP27425899A patent/JP3965838B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2006051768A1 (en) * | 2004-11-11 | 2008-05-29 | 株式会社東芝 | Phosphor and method for producing the same, and light emitting device using the same and method for producing the same |
| JP5329759B2 (en) * | 2004-11-11 | 2013-10-30 | 株式会社東芝 | Method for evaluating and selecting phosphor, LED lamp, and method for manufacturing light emitting device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3965838B2 (en) | 2007-08-29 |
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