JPS63268788A - Production of zinc silicate fluorescent substance activated with manganese - Google Patents
Production of zinc silicate fluorescent substance activated with manganeseInfo
- Publication number
- JPS63268788A JPS63268788A JP10534187A JP10534187A JPS63268788A JP S63268788 A JPS63268788 A JP S63268788A JP 10534187 A JP10534187 A JP 10534187A JP 10534187 A JP10534187 A JP 10534187A JP S63268788 A JPS63268788 A JP S63268788A
- Authority
- JP
- Japan
- Prior art keywords
- fluorescent substance
- zinc silicate
- manganese
- phosphor
- luminous flux
- 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
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000004110 Zinc silicate Substances 0.000 title claims abstract description 9
- 235000019352 zinc silicate Nutrition 0.000 title claims abstract description 9
- 239000011572 manganese Substances 0.000 title claims description 20
- 229910052748 manganese Inorganic materials 0.000 title claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000126 substance Substances 0.000 title abstract 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- -1 silicon nitride compound Chemical class 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 29
- 230000006866 deterioration Effects 0.000 abstract description 16
- 230000004907 flux Effects 0.000 abstract description 16
- 238000005507 spraying Methods 0.000 abstract description 3
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
この発明は、螢光ランプ用マンガン付活珪酸亜鉛螢光体
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a manganese-activated zinc silicate phosphor for fluorescent lamps.
[従来の技術とその問題点]
一般にマンガン付活珪酸亜鉛螢光体を螢光ランプに用い
ると、1ワット当り125ルーメンと非常に明るい輻射
をすることが知られているが、該マンガン付活珪酸亜鉛
螢光体の製造コストが極めて安価であるにもかかわらず
、実際には螢光ランプにほとんど用いられない。なぜな
ら、該マンガン付活珪酸亜鉛螢光体では、螢光ランプに
おける光束の劣化が極めて著しいからである。[Prior art and its problems] It is generally known that when a manganese-activated zinc silicate phosphor is used in a fluorescent lamp, it emits extremely bright radiation of 125 lumens per watt. Although zinc silicate phosphors are extremely inexpensive to manufacture, they are rarely used in fluorescent lamps. This is because, with the manganese-activated zinc silicate phosphor, the luminous flux in the fluorescent lamp deteriorates extremely.
このため、螢光ランプ点灯時におけるマンガン付活珪酸
亜鉛螢光体の光束の劣化を改善するための提案が成され
ている。例えば、第196回螢光体同学会講演予稿には
、マンガン付活珪酸亜鉛螢光体の粒子表面にシリカゲル
又はマグネシウムの硫化物をコートすることが提案され
ている。For this reason, proposals have been made to improve the deterioration of the luminous flux of the manganese-activated zinc silicate phosphor when the fluorescent lamp is turned on. For example, in the 196th Annual Conference on Fluorescent Materials Conference, it is proposed to coat the particle surface of a manganese-activated zinc silicate phosphor with silica gel or magnesium sulfide.
しかしながら、上述の提案にもかかわらず、従来、螢光
ランプ点灯時におけるマンガン付活珪酸亜鉛螢光体の光
束劣化を解消することができず、白色螢光ランプ用螢光
体、例えば、へロ燐酸カルシウム螢光体や三波長型螢光
ランプの緑色成分、例えば、セリウム及びテルビウム付
活燐酸ランタン螢光体に代わって、螢光ランプ用螢光体
としてマンガン付活珪酸亜鉛螢光体が用いられるまで至
らなかった。However, despite the above-mentioned proposals, conventionally it has not been possible to eliminate the luminous flux deterioration of manganese-activated zinc silicate phosphors during lighting of fluorescent lamps, and phosphors for white fluorescent lamps, for example, Manganese-activated zinc silicate phosphors are used as phosphors for fluorescent lamps in place of calcium phosphate phosphors and green components of three-wavelength fluorescent lamps, such as cerium- and terbium-activated lanthanum phosphate phosphors. I didn't get to the point where I was able to do it.
[発明が解決しようとする問題点]
この発明は、上述の事情に鑑みなされたものであって、
その目的とするところは、螢光ランプの点灯時光束劣化
の極めて少ないマンガン付活珪酸亜鉛螢光体を工業的に
安価に製造できるマンガン付活珪酸亜鉛螢光体の製造方
法を提供することにある。[Problems to be solved by the invention] This invention was made in view of the above circumstances, and
The purpose is to provide a method for producing a manganese-activated zinc silicate phosphor that can be industrially and inexpensively manufactured with extremely low luminous flux deterioration during lighting of a fluorescent lamp. be.
[発明の概要]
本発明者等は、マンガン付活珪酸亜鉛螢光体の組成が2
(ZnO) ・S i02 :Mnと表され、該組
成中の二酸化硅素(S i Ox )の一部が水洗時の
水と反応することにより吸着力の強いケイ酸(S i
02 ・nH2o)成分に変わることにより、螢光ラ
ンプ点灯時、該ケイ酸成分が螢光ランプの水銀(Hg)
等を吸着し、これにより、該螢光ランプの光束の劣化が
生起すると考えて、以下のような方法により、工業的に
簡単な方法で、螢光ランプの点灯時光束劣化の極めて少
ないマンガン付活珪酸亜鉛螢光体を得ることができるこ
とを新規に見い出した。[Summary of the Invention] The present inventors have discovered that the composition of the manganese-activated zinc silicate phosphor is 2.
(ZnO) ・S i02 :Represented as Mn, a part of silicon dioxide (S i Ox ) in the composition reacts with water during washing, resulting in silicic acid (S i Ox ) with strong adsorption power.
02 ・nH2o) component, when the fluorescent lamp is turned on, the silicic acid component becomes the mercury (Hg) of the fluorescent lamp.
Considering that this causes deterioration of the luminous flux of the fluorescent lamp, the following method was used to make a manganese-containing material with extremely low luminous flux deterioration when the fluorescent lamp is lit. It has been newly discovered that an active zinc silicate phosphor can be obtained.
即ち、この発明の方法は、マンガンを珪酸亜鉛の螢光体
母体に導入した後、マンガンを珪酸亜鉛の螢光体母体に
導入した後、該螢光体粒子を不活性ガスと共に1000
℃〜1300℃の温度範囲の還元性雰囲気中に噴霧する
ことを特徴としている。That is, the method of the present invention involves introducing manganese into a phosphor matrix made of zinc silicate, and then introducing the phosphor particles into the phosphor matrix made of zinc silicate.
It is characterized by being sprayed into a reducing atmosphere in a temperature range of 1300°C to 1300°C.
[作用]
螢光体粒子を不活性ガスと共に1000℃〜1300℃
の温度範囲の還元性雰囲気中に噴霧するにより、螢光体
表面には二酸化珪素でなく窒化珪素化合物の層が均一に
形成される。これにより、ランプ塗布時の劣化特性が改
善される。[Operation] Fluorescent particles are heated to 1000°C to 1300°C with an inert gas.
By spraying into a reducing atmosphere in a temperature range of , a layer of a silicon nitride compound instead of silicon dioxide is uniformly formed on the surface of the phosphor. This improves the deterioration characteristics during lamp application.
[実施例] 以下、この発明の実施例に基づいて説明する。[Example] Embodiments of the present invention will be explained below.
(実施例1)
まず、この発明の実施例1の説明に先立ち、この発明の
実施例に用いたマンガン付活珪酸亜鉛螢光体の製造方法
について説明する。(Example 1) First, prior to describing Example 1 of the present invention, a method for producing a manganese-activated zinc silicate phosphor used in the Example of the present invention will be described.
螢光体原料として酸化亜鉛、二酸化珪素及び弗化マンガ
ンを調量し、これら螢光体原料をボールミルで充分粉砕
混合し、アルミナルツボに充填し、1300℃2時間空
気中で焼成した。得られたマンガン付活珪酸亜鉛螢光体
中マンガン量は珪酸亜鉛の母体1モルに対し約0.05
モルで反応されたものである。Zinc oxide, silicon dioxide, and manganese fluoride were measured as phosphor raw materials, and these phosphor raw materials were thoroughly ground and mixed in a ball mill, filled into an alumina crucible, and fired in air at 1300° C. for 2 hours. The amount of manganese in the obtained manganese-activated zinc silicate phosphor is approximately 0.05 per mole of zinc silicate matrix.
It was reacted in moles.
次に、その表面に有機高分子としてポリビニルアルコー
ルを0.1重量%加えて乾燥され、このマンガン付活珪
酸亜鉛螢光体2kg (平均粒径16μm)を用いて噴
Mvt成した。不活性ガスとしTNzを10〜2017
分で直径1センチのアルミナ製バイブ内に送出させた。Next, 0.1% by weight of polyvinyl alcohol as an organic polymer was added to the surface and dried, and 2 kg of this manganese-activated zinc silicate phosphor (average particle size 16 μm) was used to form a spray Mvt. TNz from 10 to 2017 as inert gas
It was delivered into an alumina vibrator with a diameter of 1 cm in minutes.
該アルミナバイブ内は加熱手段により1200℃に加熱
されており、バイブの長さは2メートルであり、バイブ
内での螢光体の処理時間は3秒であった。The inside of the alumina vibrator was heated to 1200° C. by a heating means, the length of the vibrator was 2 meters, and the processing time of the phosphor in the vibrator was 3 seconds.
このようにして得られた本発明の螢光体と、焼成後、水
洗、篩、乾燥した従来の螢光体とを、夫々、1%ニトロ
セルロース酢酸ブチル溶液(バインダ)にて直径27セ
ンチのガラス直管内に5gの割合で厚さ10〜20μm
で塗布してランプを製作し、光束劣化試験を行った。The thus obtained phosphor of the present invention and the conventional phosphor which had been fired, washed with water, sieved, and dried were each mixed in a 1% nitrocellulose butyl acetate solution (binder) to a diameter of 27 cm. Thickness 10-20μm at a ratio of 5g in a straight glass tube
A lamp was manufactured by coating the product with the following methods, and a luminous flux deterioration test was conducted.
その結果、従来の螢光体では、初期光束に対する100
時間経過後の劣化特性が86.1%(図面中破線a)で
あったのに対し、本発明の螢光体では、初期光束に対す
る100時間経過後の劣化特性が92.1%(図面中実
1s1)であり、光束劣化特性が6.0%も向上した。As a result, with conventional phosphors, 100% of the initial luminous flux
While the deterioration characteristic after time elapsed was 86.1% (dashed line a in the drawing), in the phosphor of the present invention, the deterioration characteristic after 100 hours with respect to the initial luminous flux was 92.1% (in the drawing) In fact, the luminous flux deterioration characteristics were improved by 6.0%.
(実施例2)
バイブの温度を1000℃に保持すること、及びバイブ
内で5秒で螢光体を通過させること以外、実施例1と同
様に試作し、また、同様な光束劣化試験を行った。(Example 2) A prototype was produced in the same manner as in Example 1, except that the temperature of the vibrator was maintained at 1000°C and the phosphor was passed through the vibrator for 5 seconds, and the same luminous flux deterioration test was conducted. Ta.
その結果、従来の螢光体では、初期光束に対する100
時間経過後の劣化特性が86.】%(図面中破線a)で
あったのに対し、本発明の螢光体では、初期光束に対す
る100時間経過後の劣化特性が91.1%(図面中実
線2)であり、光束劣化特性が5.0%も向上した。As a result, with conventional phosphors, 100% of the initial luminous flux
Deterioration characteristics after time elapsed are 86. ]% (broken line a in the figure), whereas in the phosphor of the present invention, the deterioration characteristic after 100 hours with respect to the initial luminous flux was 91.1% (solid line 2 in the figure), and the luminous flux deterioration characteristic improved by 5.0%.
[発明の効果]
この発明の方法によれば、簡単な螢光体の噴霧工程によ
り、従来のコート法では、改善できなかった螢光ランプ
点灯時の光束劣化の改善したマンガン付活珪酸亜鉛螢光
体が得られる。[Effects of the Invention] According to the method of the present invention, a manganese-activated zinc silicate fluorescent material with improved luminous flux deterioration during lighting of a fluorescent lamp, which could not be improved with conventional coating methods, can be produced using a simple phosphor spraying process. A light body is obtained.
また、この発明の方法によれば、三波長型螢光ランプの
緑色成分として工業的に安価な螢光体が得られる。Further, according to the method of the present invention, an industrially inexpensive phosphor can be obtained as a green component of a three-wavelength fluorescent lamp.
図面は、この発明の螢光体を用いた螢光ランプにおける
時間に対する光出力の低下を示すグラフ図である。The drawing is a graph showing the decrease in light output over time in a fluorescent lamp using the phosphor of the present invention.
Claims (1)
光体粒子を不活性ガスと共に1000℃〜1300℃の
温度範囲の還元性雰囲気中に噴霧することを特徴とする
マンガン付活珪酸亜鉛螢光体の製造方法。Manganese-activated zinc silicate, characterized in that after manganese is introduced into a phosphor matrix of zinc silicate, the phosphor particles are sprayed together with an inert gas into a reducing atmosphere in a temperature range of 1000°C to 1300°C. Method of manufacturing phosphor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62105341A JPH0662944B2 (en) | 1987-04-28 | 1987-04-28 | Method for producing manganese-activated zinc silicate phosphor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62105341A JPH0662944B2 (en) | 1987-04-28 | 1987-04-28 | Method for producing manganese-activated zinc silicate phosphor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63268788A true JPS63268788A (en) | 1988-11-07 |
JPH0662944B2 JPH0662944B2 (en) | 1994-08-17 |
Family
ID=14405032
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62105341A Expired - Lifetime JPH0662944B2 (en) | 1987-04-28 | 1987-04-28 | Method for producing manganese-activated zinc silicate phosphor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0662944B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100456982B1 (en) * | 2002-02-28 | 2004-11-10 | 한국과학기술연구원 | Preparation of Green Phosphors for Plasma Display Panel |
US7465413B2 (en) | 2004-05-11 | 2008-12-16 | Panasonic Corporation | Phosphor and plasma display panel using the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5237581A (en) * | 1975-09-19 | 1977-03-23 | Toshiba Corp | Method of producing fluorescent substance |
-
1987
- 1987-04-28 JP JP62105341A patent/JPH0662944B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5237581A (en) * | 1975-09-19 | 1977-03-23 | Toshiba Corp | Method of producing fluorescent substance |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100456982B1 (en) * | 2002-02-28 | 2004-11-10 | 한국과학기술연구원 | Preparation of Green Phosphors for Plasma Display Panel |
US7465413B2 (en) | 2004-05-11 | 2008-12-16 | Panasonic Corporation | Phosphor and plasma display panel using the same |
Also Published As
Publication number | Publication date |
---|---|
JPH0662944B2 (en) | 1994-08-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1060942A (en) | Alumina coatings for mercury vapor lamps | |
JPH02283791A (en) | Method of baking and milling for manufacture of zinc silicate phosphor activated with manganese | |
JP4219514B2 (en) | Rare earth phosphate manufacturing method, rare earth phosphate phosphor, and rare earth phosphate phosphor manufacturing method | |
US5185180A (en) | Method of improving the maintenance of a fluorescent lamp containing europium-activated barium magnesium silicate phosphor | |
US4748391A (en) | Yellow green barium lanthanum silicate oxyapatite phosphor, a fluorescent lamp containing the same, and a method thereof | |
JPS63268788A (en) | Production of zinc silicate fluorescent substance activated with manganese | |
US5194332A (en) | Europium-activated barium magnesium silicate phosphor | |
JP2002212553A (en) | Lanthanum phosphate fluorophor for vacuum ultraviolet and rare gas discharge lamp | |
JPS6118952B2 (en) | ||
JP3832024B2 (en) | Vacuum ultraviolet-excited luminescent phosphor and method for producing the same | |
JP4199530B2 (en) | Fluorescent substance for mercury vapor discharge lamp and mercury vapor discharge lamp | |
JP2002015706A (en) | Gas discharge lamp with luminous layer | |
JPS5951105B2 (en) | Surface treatment method for fluorescent light tubes and other glass tubes | |
JPH11172244A (en) | Phosphor, manufacture thereof and fluorescent lamp | |
JPH03177491A (en) | Fluorescent substance and fluorescent lamp | |
KR960000475B1 (en) | Fluorescent material and method for preparing therof | |
NO115689B (en) | ||
US4757233A (en) | Efficient UV-emitting phosphors based on cerium-activated calcium pyrophosphate and lamps containing the same | |
US3555336A (en) | Cadmium vapor discharge lamp containing a europium activated phosphor | |
JPS63268787A (en) | Production of zinc silicate fluorescent substance activated with manganese | |
JPH02170888A (en) | Production of blue light-generating fluorescent material | |
JPS6014056B2 (en) | fluorescent material | |
JPS6244792B2 (en) | ||
EP0962514B1 (en) | Cation-treated silicate phosphor | |
US4594178A (en) | Process for producing a yellow emitting phosphor |