JP2543737B2 - Color television fluorescent - Google Patents
Color television fluorescentInfo
- Publication number
- JP2543737B2 JP2543737B2 JP62335976A JP33597687A JP2543737B2 JP 2543737 B2 JP2543737 B2 JP 2543737B2 JP 62335976 A JP62335976 A JP 62335976A JP 33597687 A JP33597687 A JP 33597687A JP 2543737 B2 JP2543737 B2 JP 2543737B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- tin
- silicate
- stripe
- amount
- 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 - Lifetime
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Description
この発明は、カラーテレビジョン用のブラウン管に使
用される蛍光体に係り、特にスラリー塗布法により蛍光
膜が形成されるカラーブラウン管用の蛍光体に関する。The present invention relates to a phosphor used in a cathode ray tube for a color television, and more particularly to a phosphor for a color cathode ray tube in which a phosphor film is formed by a slurry coating method.
一般に、カラーテレビジョンの蛍光膜の形成にはスラ
リー塗布法が採用されている。このスラリー塗布法は、
光印刷技術が用いられている。この方法は、まず、蛍光
体粒子が、例えば、ポリビニールアルコール(PVA)と
重クロム酸アンモニウムとを含む感光性樹脂溶液に分散
される。この蛍光体粒子を分散した感光性樹脂溶液は蛍
光体スラリー溶液と呼ばれている。この蛍光体スラリー
溶液はガラスパネル内面に均一に塗布され、その後、周
知の光印刷技術によって露光、現像することにより、規
則的に配列された所望形状のストライプ、又は、ドット
がガラスパネル内面に形成される。そして、これらの工
程が青色、緑色及び赤色の蛍光体に付いてそれぞれ繰り
返すことにより、蛍光膜が形成される。 このようなスラリー塗布法に用いられる蛍光体は、蛍
光体スラリー溶液中に於ける良好な分散性が特に大切で
ある。即ち、蛍光体の分散性が悪いと、ストライプ、又
は、ドットにおける端部形状が悪くなったり、蛍光膜が
均一に、あるいは緻密に形成できなくなり、蛍光膜の特
性が低下する。また、蛍光体の分散性によっては、スラ
リー溶液の露光感度が落ちて蛍光膜形成における作業性
が低下する。 このため、従来から、蛍光体の表面に、二酸化珪素、
珪酸亜鉛、珪酸アルミニウム等の珪素化合物を付着して
分散性を向上させている。蛍光体粒子表面に、特定の粒
子径の二酸化珪素、アルミニウム化合物および亜鉛化合
物を付着する技術が開発されている(特公昭61−46512
号公報)。 しかしながら、これ等の物質を付着した従来の蛍光体
でもって、高精細度のカラーブラウン管を製造する場
合、いずれも良好な分散性が得られず、均一にして緻密
で、しかも端部形成の優れた高精細度の蛍光膜を得るこ
とが難しい。即ち、ストライプ、あるいは、ドットの形
状を小さくする必要のある高精細度のカラーブラウン管
の蛍光膜は、蛍光体を極めて微細な、例えば、ドットピ
ッチが0.4mm以下となるように点状に付着する必要があ
るが、分散性が充分でない蛍光体は、微細なドットを奇
麗な輪郭で正確に付着できない。Generally, a slurry coating method is adopted for forming a fluorescent film of a color television. This slurry coating method is
Optical printing technology is used. In this method, first, phosphor particles are dispersed in a photosensitive resin solution containing, for example, polyvinyl alcohol (PVA) and ammonium dichromate. The photosensitive resin solution in which the phosphor particles are dispersed is called a phosphor slurry solution. This phosphor slurry solution is uniformly applied to the inner surface of the glass panel, and then exposed and developed by a well-known optical printing technique to form regularly arranged stripes or dots of a desired shape on the inner surface of the glass panel. To be done. Then, these steps are repeated for each of the blue, green and red phosphors to form the phosphor film. For the phosphor used in such a slurry coating method, good dispersibility in the phosphor slurry solution is particularly important. That is, when the dispersibility of the phosphor is poor, the end shape of the stripes or dots becomes poor, the phosphor film cannot be formed uniformly or densely, and the properties of the phosphor film deteriorate. Further, depending on the dispersibility of the phosphor, the exposure sensitivity of the slurry solution is lowered, and the workability in forming the phosphor film is lowered. Therefore, conventionally, silicon dioxide,
Silicon compounds such as zinc silicate and aluminum silicate are attached to improve dispersibility. A technique for adhering silicon dioxide, an aluminum compound and a zinc compound having a specific particle size on the surface of phosphor particles has been developed (Japanese Patent Publication No. 61-46512).
Issue). However, when a high-definition color cathode-ray tube is manufactured with conventional phosphors to which these substances are adhered, good dispersibility is not obtained in any of them, and it is uniform and dense and has excellent edge formation. It is difficult to obtain a high definition fluorescent film. That is, the stripe or the fluorescent film of the high-definition color cathode-ray tube that needs to have a small dot shape attaches the phosphor very finely, for example, in a dot shape so that the dot pitch is 0.4 mm or less. Although necessary, a phosphor having insufficient dispersibility cannot accurately attach fine dots with a clean contour.
この発明は、上述の事情を鑑みなされたものであっ
て、その目的とするところは、極めて優れた分散性を有
し、カラーブラウン管の蛍光膜形成時に、均一で、しか
も緻密な蛍光膜が能率良く形成できるテレビジョン用蛍
光体を提供することにある。The present invention has been made in view of the above circumstances, and an object thereof is to have an extremely excellent dispersibility, and to provide a uniform and dense fluorescent film at the time of forming a fluorescent film of a color cathode ray tube. Another object of the present invention is to provide a phosphor for television that can be well formed.
この発明の蛍光体は、上述の目的を達成する為に、蛍
光体粒子表面に、珪酸塩に加えて、更に、2価または4
価の錫化合物が付着されている。 錫化合物に含まれる錫の付着量は、蛍光体100重量部
に対して0.001〜0.5重量部以下に調整され、珪酸塩の付
着量は、2重量部以下に調整されている。錫化合物に含
まれる錫の付着量を前記の範囲にするのは、第1図に示
すように、多すぎても少なすぎても蛍光体の分散性が低
下するからである。 2価または4価の錫化合物には、好ましくは、水酸化
錫、錫酸、または、有機錫等が使用できる。 珪酸塩には、好ましくは、珪酸亜鉛、珪酸アルミニウ
ム、珪酸マグネシウム等が単独で、あるいは、これ等が
複数種混合して使用される。In order to achieve the above-mentioned object, the phosphor of the present invention has a divalent or tetravalent structure in addition to silicate on the surface of the phosphor particles.
Valuable tin compound is attached. The amount of tin contained in the tin compound is adjusted to 0.001 to 0.5 part by weight or less based on 100 parts by weight of the phosphor, and the amount of silicate attached is adjusted to 2 parts by weight or less. The reason why the amount of tin contained in the tin compound is set within the above range is that the dispersibility of the phosphor decreases if the amount of tin is too large or too small as shown in FIG. As the divalent or tetravalent tin compound, tin hydroxide, stannic acid, or organic tin can be preferably used. As the silicate, preferably, zinc silicate, aluminum silicate, magnesium silicate or the like is used alone, or a plurality of these are mixed and used.
2価または4価の錫化合物、例えば、錫酸は、酸化錫
(IV)水和物(SnO2・nH2O)であり、この酸化錫(IV)
水和物がアルカリを吸着したものは、コロイド溶液であ
って、一定の組成を持たない。この錫酸を、珪酸塩に加
えて表面に付着したこの発明の蛍光体粒子は、乾燥後、
蛍光体粒子表面がすべすべとした状態となり、そして、
スラリー塗布法における蛍光体スラリー溶液に蛍光体粒
子を懸濁させる場合、蛍光膜形成にとって極めて良好な
分散性を示す。 同様に、水酸化錫「Sn(OH)2]もコロイドを作り易
く、一定の組成を持たないが、水酸化錫を、珪酸塩に加
えて表面に付着した蛍光体粒子は、スラリー塗布法にお
ける蛍光体スラリー溶液に蛍光体粒子を懸濁させる場
合、蛍光膜形成にとって極めて良好な分散性を示す。 本発明の蛍光体は、珪酸塩に加えて、2価または4価
の錫化合物を付着しているが、この蛍光体は、珪酸塩を
単独で表面に付着し、あるいは、錫化合物を単独で付着
する蛍光体では実現できない優れた分散性を示す。その
理由は明確でないが、本発明の蛍光体は、珪酸塩と、2
価または4価の錫化合物の両方が表面に付着されること
によって、蛍光体が電価による反発を生じる為と考えら
れる。 又、水酸化錫、有機錫、錫酸を蛍光体粒子表面に付着
させても、良好な分散性が発揮されるのは言うまでもな
い。A divalent or tetravalent tin compound, such as stannic acid, is a tin (IV) oxide hydrate (SnO 2 · nH 2 O).
The hydrate adsorbed alkali is a colloidal solution and does not have a constant composition. This stannic acid, in addition to silicate, the phosphor particles of the present invention adhered to the surface, after drying,
The surface of the phosphor particles becomes smooth, and
When the phosphor particles are suspended in the phosphor slurry solution in the slurry coating method, the dispersibility is extremely good for forming the phosphor film. Similarly, tin hydroxide “Sn (OH) 2 ” is also easy to form a colloid and does not have a constant composition, but the phosphor particles in which tin hydroxide is added to the silicate and adhered to the surface are When the phosphor particles are suspended in the phosphor slurry solution, the dispersibility is extremely good for forming the phosphor film.The phosphor of the present invention has a divalent or tetravalent tin compound attached in addition to the silicate. However, this phosphor exhibits an excellent dispersibility that cannot be realized by a phosphor having a silicate alone attached to the surface or a tin compound alone attached to the surface. Phosphor is silicate and 2
It is considered that the phosphor causes a repulsion due to an electric value due to the fact that both the tin or tetravalent tin compound is attached to the surface. Needless to say, even if tin hydroxide, organic tin or stannic acid is attached to the surface of the phosphor particles, good dispersibility is exhibited.
以下、本発明の実施例に先立ち、蛍光体粒子表面に2
価または4価の錫化合物を付着する方法について説明す
る。 本発明に使用される2価または4価の錫化合物、即
ち、酸化錫や水酸化錫は、SnCl4、Sn(SO4)2、Sn(N
O)4等の錫塩を加水分解したものが使用でき、有機錫
には、Sn(CH−COO)4、Sn(C−O)4等が使用でき
る。 即ち、錫塩を加水分解することにより、水酸化錫を得
る方法では、先ず、被着させるべき蛍光体粒子を水中に
懸濁させ、錫塩水溶液、例えば、SnCl4水溶液を所定量
添加する。SnCl4水溶液を添加した蛍光体懸濁液を撹拌
しなが、アンモニア水、水酸化ナトリウム等のアルカリ
でpHを6〜8に調整することにより加水分解させる。こ
れにより、蛍光体粒子表面には2価の錫化合物、即ち、
水酸化錫[Sn(OH)2]が付着される。 錫有機酸塩の水溶液を添加すること以外、上述の方法
と同様な方法で行うことにより、蛍光体粒子表面には、
2価または4価の錫化合物、即ち、酸化錫及び/又は水
酸化錫が付着される。 乾燥は100℃未満の温度で行い、蛍光体表面に水酸化
錫または有機錫を吸着させる。 以下、この発明の実施例について説明する。Hereinafter, prior to the examples of the present invention, 2
A method of depositing a tin or tetravalent tin compound will be described. The divalent or tetravalent tin compound used in the present invention, that is, tin oxide or tin hydroxide, is SnCl 4 , Sn (SO 4 ) 2 , Sn (N
A hydrolyzed tin salt such as O) 4 can be used, and Sn (CH—COO) 4 , Sn (C—O) 4, etc. can be used as the organic tin. That is, in the method of obtaining tin hydroxide by hydrolyzing a tin salt, first, the phosphor particles to be adhered are suspended in water, and a tin salt aqueous solution, for example, SnCl 4 aqueous solution is added in a predetermined amount. While the phosphor suspension to which the SnCl 4 aqueous solution has been added is not stirred, it is hydrolyzed by adjusting the pH to 6 to 8 with an alkali such as aqueous ammonia or sodium hydroxide. As a result, the divalent tin compound, namely,
Tin hydroxide [Sn (OH) 2 ] is deposited. Except for adding an aqueous solution of tin organic acid salt, by performing the same method as described above, the surface of the phosphor particles,
A divalent or tetravalent tin compound is deposited, ie tin oxide and / or tin hydroxide. Drying is performed at a temperature of less than 100 ° C. to adsorb tin hydroxide or organic tin on the phosphor surface. Hereinafter, embodiments of the present invention will be described.
【実施例1】 銀付活硫化亜鉛蛍光体100gを純水250ml中に懸濁させ
た後、この蛍光体懸濁液にSnCl4水溶液(Sn2%含有溶
液)を2.5ml添加し、5分間撹拌した。撹拌を行いなが
ら、5%NaOH水溶液を滴下し、pHを6.5に調整した後、
撹拌を止め、蛍光体粒子を沈降させた。その後、濾別、
乾燥(90℃で3時間)して300メッシュのフルイを通す
ことにより、蛍光体粒子表面に錫化合物、即ち、水酸化
錫が付着された蛍光体を得た。 次に、表面に水酸化錫が付着された銀付活硫化亜鉛蛍
光体100gを、純水250ml中に懸濁させた後、この蛍光体
懸濁液にK2SiO3(SiO2を2%含有する溶液)を1ml撹拌
しながら添加し、更に、ZnSO4(Znを2%含有する溶
液)0.5ml添加して撹拌する。撹拌を行いながら、2%N
aOH水溶液を滴下し、pHを6.8に調整する。30分経過後、
SnCl4(Snを2%含有する溶液)2.5mlを添加混合し、5
%NaOH水溶液を滴下し、pHを6.5に調整して、蛍光体粒
子を沈降させた。 その後、濾別、乾燥(90℃で10時間)して300メッシ
ュのフルイを通すことにより、蛍光体粒子表面に水酸化
錫と珪酸亜鉛とが付着された蛍光体を得た。 得られた水酸化錫付着蛍光体を用いて、以下のような
通常のスラリー塗布法によるストライプを形成し、水酸
化錫を付着せずに珪酸亜鉛のみを付着させる以外実施例
1と同様な銀付活硫化亜鉛蛍光体と比較した。 水酸化錫付着銀付活硫化亜鉛蛍光体を、6g、PVA0.3g
と重クロム酸アンモニウム添加した感光性樹脂溶液220m
lに懸濁させて蛍光体スラリー溶液とした。この蛍光体
スラリー溶液をガラスパネル面に塗布し、第2図に示す
ように、シャドウマスク1を介してガラスパネル面に露
光し、その後、現像処理して約300μm幅のストライプ
を形成した。ストライプの端部の形状の良否を判定する
ため、第3図に示すように、ストライプの最大幅(A)
と最小幅(B)とを測定し、その差(A−B)をストラ
イプ値とした。 実施例1で得られた蛍光体が塗布されたストライプは
均一な厚さを有すると共に、緻密なものであった。 また、水酸化錫を付着せずに珪酸亜鉛のみを付着させ
る以外実施例1と同様の銀付活硫化亜鉛蛍光体(従来の
蛍光体)におけるストライプ形状の測定では、A=330
μm、B=300μmであり、ストライプ値は30μmであ
るのに対し、本発明の実施例1で得られた蛍光体は、A
=320μm、B=300μmであり、ストライプ値は20μm
と、従来の蛍光体に比べて50%も向上した。即ち、実施
例1で得られた蛍光体は、珪酸亜鉛に加えて水酸化錫を
付着することによって、ストライプの輪郭形状を著しく
向上できた。Example 1 After suspending 100 g of silver activated zinc sulfide phosphor in 250 ml of pure water, 2.5 ml of SnCl 4 aqueous solution (Sn 2% content solution) was added to this phosphor suspension and stirred for 5 minutes. did. 5% NaOH aqueous solution was added dropwise with stirring to adjust the pH to 6.5,
The stirring was stopped and the phosphor particles were allowed to settle. After that, filtration
After drying (90 ° C. for 3 hours) and passing through a 300-mesh sieve, a phosphor having a tin compound, that is, tin hydroxide, attached to the surface of the phosphor particles was obtained. Next, 100 g of silver-activated zinc sulfide phosphor having tin hydroxide on the surface was suspended in 250 ml of pure water, and K 2 SiO 3 (2% of SiO 2 was added to this phosphor suspension. (Containing solution) is added with stirring (1 ml), and 0.5 ml of ZnSO 4 (solution containing 2% Zn) is further added and stirred. 2% N while stirring
Aqueous aOH solution is added dropwise to adjust the pH to 6.8. After 30 minutes,
Add 2.5 ml of SnCl 4 (solution containing 2% Sn) and mix,
% NaOH aqueous solution was added dropwise to adjust the pH to 6.5 to precipitate phosphor particles. Then, it was separated by filtration, dried (at 90 ° C. for 10 hours), and passed through a 300-mesh sieve to obtain a phosphor in which tin hydroxide and zinc silicate were attached to the surface of the phosphor particles. The same silver as in Example 1 except that the obtained tin hydroxide-adhered phosphor was used to form stripes by the following ordinary slurry coating method, and only zinc silicate was adhered without adhering tin hydroxide. It was compared with an activated zinc sulfide phosphor. 6g of silver hydrated zinc sulfide phosphor with tin hydroxide attached, 0.3g of PVA
220m of photosensitive resin solution added with ammonium dichromate
It was suspended in l to prepare a phosphor slurry solution. This phosphor slurry solution was applied to the glass panel surface and, as shown in FIG. 2, the glass panel surface was exposed through the shadow mask 1 and then developed to form stripes having a width of about 300 μm. As shown in FIG. 3, the maximum width of the stripe (A) is used to judge whether the shape of the end of the stripe is good or bad.
And the minimum width (B) were measured, and the difference (AB) was taken as the stripe value. The stripe coated with the phosphor obtained in Example 1 had a uniform thickness and was dense. In addition, in the measurement of the stripe shape of the silver-activated zinc sulfide phosphor (conventional phosphor) similar to that of Example 1 except that tin silicate is not attached and only zinc silicate is attached, A = 330.
μm, B = 300 μm, and the stripe value is 30 μm, while the phosphor obtained in Example 1 of the present invention is A
= 320μm, B = 300μm, stripe value is 20μm
And, compared to the conventional phosphor, it is improved by 50%. That is, in the phosphor obtained in Example 1, the outline shape of the stripe could be remarkably improved by depositing tin hydroxide in addition to zinc silicate.
【実施例2】 銅及びアルミニウム共付活硫化亜鉛蛍光体100gを純水
250ml中に懸濁させた後、この蛍光体懸濁液にSn(SO4)
2水溶液(Sn2%含有液)を10ml添加し、5分間撹拌し
た。撹拌を行いながら、2%NH4OH水溶液を滴下し、pH
を6.5に調整した後、撹拌を止め、蛍光体粒子を沈降さ
せた。その後、濾別、乾燥して300メッシュのフルイを
通すことにより、蛍光体粒子表面に錫化合物、即ち、水
酸化錫が付着された蛍光体を得た。 次に、表面に水酸化錫が付着された銅およびアルミニ
ウム付活硫化亜鉛蛍光体100gを、純水250ml中に懸濁さ
せた後、この蛍光体懸濁液にK2SiO3(SiO2を2%含有す
る溶液)を1.5ml撹拌しながら添加し、更に、ZnSO4(Zn
を2%含有する溶液)を0.75ml添加して撹拌する。撹拌
を行いながら、5%NaOH水溶液を滴下し、pHを7.0に調
整する。30分経過後、Sn(SO4)2(Snを2%含有する
溶液)10mlを添加混合し、2%NaOH溶液を滴下し、pHを
6.5に調整して、蛍光体粒子を沈降させた。 その後、濾別、乾燥(90℃で10時間)して300メッシ
ュのフルイを通すことにより、蛍光体粒子表面に水酸化
錫と珪酸亜鉛とが付着された蛍光体を得た。 次に得られた水酸化錫付着蛍光体を用いて、実施例1
と同様なストライプ形状の値を測定した。 得られたストライプは均一な厚さを有して緻密なもの
であった。 また、水酸化錫を付着せずに珪酸亜鉛を付着させる以
外実施例2と同一の蛍光体(従来の蛍光体)におけるス
トライプ形状の測定では、A=340μm、B=300μmで
あり、ストライプ値は40μmであるのに対し、本発明の
実施例2で得られた蛍光体は、A=320μm、B=300μ
mであり、ストライプ値は20μmと、従来の半分に極減
した。Example 2 100 g of copper and aluminum co-activated zinc sulfide phosphor was added to pure water
After suspending in 250 ml, Sn (SO 4 ) was added to this phosphor suspension.
10 ml of 2 aqueous solution (Sn 2 % content liquid) was added and stirred for 5 minutes. While stirring, add 2% NH 4 OH aqueous solution dropwise to pH.
After adjusting to 6.5, stirring was stopped and the phosphor particles were allowed to settle. Then, it was filtered, dried, and passed through a 300-mesh sieve to obtain a phosphor in which a tin compound, that is, tin hydroxide, was attached to the surface of the phosphor particles. Next, 100 g of copper- and aluminum-activated zinc sulfide phosphor with tin hydroxide attached to the surface was suspended in 250 ml of pure water, and K 2 SiO 3 (SiO 2 was added to the phosphor suspension. 1.5% of a solution containing 2%) was added with stirring, and ZnSO 4 (Zn
(Solution containing 2%) was added and stirred. While stirring, 5% NaOH aqueous solution is added dropwise to adjust pH to 7.0. After 30 minutes, 10 ml of Sn (SO 4 ) 2 (solution containing 2% Sn) was added and mixed, and 2% NaOH solution was added dropwise to adjust the pH.
Adjusting to 6.5, the phosphor particles were allowed to settle. Then, it was separated by filtration, dried (at 90 ° C. for 10 hours), and passed through a 300-mesh sieve to obtain a phosphor in which tin hydroxide and zinc silicate were attached to the surface of the phosphor particles. Next, using the obtained tin hydroxide-adhered phosphor, Example 1
The value of the stripe shape similar to that was measured. The obtained stripe had a uniform thickness and was dense. In addition, in the measurement of the stripe shape of the same phosphor (conventional phosphor) as in Example 2 except that zinc silicate is adhered instead of tin hydroxide, A = 340 μm and B = 300 μm, and the stripe value is While 40 μm, the phosphor obtained in Example 2 of the present invention has A = 320 μm and B = 300 μm.
m, and the stripe value was 20 μm, which is a half of the conventional value.
【実施例3】 銀付活硫化亜鉛蛍光体100gを純水250mlに懸濁させた
後、先ず、この蛍光体懸濁液にアルミン酸コバルト2.0g
を添加し、アクリルエマルジョン(アクリル2%含有)
1mlを加え、酢酸でpHを5に調整し、沈降させ中性にな
るまでデカントした。 次に、Sn(SO4)2水溶液(Sn2%含有溶液)を50ml添
加し、5分間撹拌した。撹拌を行いながら、2%NH4OH
水溶液を滴下し、pHを6.0に調整した後、撹拌を止め、
蛍光体粒子を沈降させた。その後、濾別、乾燥(90℃で
10時間)して300メッシュのフルイを通すことにより、
蛍光体粒子表面に錫化合物、即ち、水酸化錫が付着され
た蛍光体を得た。 次に、表面に水酸化錫が付着された銀付活硫化亜鉛蛍
光体100gを、純水250ml中に懸濁させた後、この懸濁液
に、アルミン酸コバルト2gとアクリルエマルジョン(ア
クリル2%含有)1mlとを加え、酢酸でpHを5に調整
し、蛍光体を沈降させて中性になるまでデカントする。 更に、K2SiO3(SiO2を2%含有する溶液)を1ml撹拌
しながら添加し、更に、ZnSO4(Znを2%含有する溶
液)を0.5ml添加して撹拌する。撹拌を行いながら、NH4
OH2%水溶液を滴下し、pHを6.8に調整する。更にまた、
Sn(SO4)2(Snを2%含有する溶液)50mlを添加混合
し、5%NH4OH水溶液を滴下し、pHを6.0に調整して、蛍
光体粒子を沈降させた。 その後、濾別、乾燥(90℃6で10時間)して300メッ
シュのフルイを通すことにより、蛍光体粒子表面に水酸
化錫と珪酸亜鉛とが付着された顔料付蛍光体を得た。 次に、得られた蛍光体を用いて、実施例1と同様にし
てストライプ形状の値を測定した。 得られたストライプは均一な厚さを有して緻密なもの
であった。 また、水酸化錫を付着せずに珪酸亜鉛のみ付着させる
以外実施例3と同様の蛍光体(従来の蛍光体)を使用し
たストライプ形状の測定では、A=320μm、B=300μ
mであり、ストライプ値は20μmであるのに対し、本発
明の実施例3で得られた蛍光体を用いたストライプ形状
の測定では、A=310μm、B=300μmであり、ストラ
イプ値は10μmと半分に極減した。Example 3 After suspending 100 g of silver activated zinc sulfide phosphor in 250 ml of pure water, first, 2.0 g of cobalt aluminate was added to this phosphor suspension.
Acrylic emulsion (2% acrylic content)
1 ml was added, the pH was adjusted to 5 with acetic acid, sedimented and decanted until neutral. Next, 50 ml of Sn (SO 4 ) 2 aqueous solution (Sn 2 % content solution) was added and stirred for 5 minutes. 2% NH 4 OH with stirring
After dropping the aqueous solution and adjusting the pH to 6.0, stop stirring,
The phosphor particles were allowed to settle. Then, filter and dry (at 90 ℃
10 hours) and then pass through a 300 mesh screen,
A phosphor having a tin compound, that is, tin hydroxide, attached to the surface of the phosphor particles was obtained. Next, 100 g of silver-activated zinc sulfide phosphor having tin hydroxide adhered on its surface was suspended in 250 ml of pure water, and 2 g of cobalt aluminate and acrylic emulsion (acrylic 2%) were added to this suspension. 1 ml), pH is adjusted to 5 with acetic acid, the phosphor is allowed to settle and decanted until neutral. Further, 1 ml of K 2 SiO 3 (solution containing 2% of SiO 2 ) is added while stirring, and 0.5 ml of ZnSO 4 (solution containing 2% of Zn) is further added and stirred. NH 4 while stirring
A 2% OH aqueous solution is added dropwise to adjust the pH to 6.8. Furthermore,
50 ml of Sn (SO 4 ) 2 (solution containing 2% Sn) was added and mixed, a 5% NH 4 OH aqueous solution was added dropwise, the pH was adjusted to 6.0, and the phosphor particles were allowed to settle. Then, it was filtered and dried (at 90 ° C. for 6 hours) and passed through a 300-mesh sieve to obtain a pigmented phosphor having tin hydroxide and zinc silicate attached to the surface of the phosphor particles. Next, using the obtained phosphor, the stripe shape value was measured in the same manner as in Example 1. The obtained stripe had a uniform thickness and was dense. Further, in the stripe shape measurement using the same phosphor (conventional phosphor) as in Example 3 except that tin silicate is not adhered but only zinc silicate is adhered, A = 320 μm, B = 300 μm
m and the stripe value is 20 μm, whereas in the measurement of the stripe shape using the phosphor obtained in Example 3 of the present invention, A = 310 μm and B = 300 μm, and the stripe value is 10 μm. It was reduced to half.
【実施例4】 ユーロビウム付活酸硫化イットリウム蛍光体(Y2O2/E
u)100gを純水250ml中に懸濁させた後、この懸濁液に、
実施例1と同様にSnCl4水溶液(Sn2%含有溶液)を15ml
を添加して5分間撹拌した。撹拌をしながら、この蛍光
体懸濁液にアルギン酸ソーダ溶液(5%含有溶液)を5m
l添加し、酢酸でpHを5に調整し、2%NH4OH水曜得を滴
下し、pHを7.0に調整した後、撹拌を止め、蛍光体粒子
を沈降させた。その後、濾別、乾燥(90℃で3時間)し
て300メッシュのフルイを通すことにより、蛍光体粒子
表面にアルギン酸錫が付着された蛍光体を得た。 次に、この蛍光体を実施例1と同様の方法で、処理し
て、蛍光体粒子表面にアルギン酸錫と珪酸亜鉛とが付着
された蛍光体を得た。 以上の実施例は、珪酸塩に珪酸亜鉛を使用している
が、珪酸亜鉛に代わって、珪酸アルミニウム、または、
珪酸マグネシムウを使用することも可能である。 また、珪酸塩に代わって、燐酸亜鉛、燐酸アルミニウ
ム、燐酸マグネシウムを使用することも可能である。 本発明の蛍光体は、錫化合物に含まれる錫の付着量
を、蛍光体100重量部に対して、0.001〜0.5重量部の範
囲に調整する。錫化合物の付着量は、多すぎても少なす
ぎても蛍光体の分散性が低下する。錫化合物の錫付着量
に対する分散性を第1図に示す。 但し、第1図は、蛍光体の表面に、錫化合物に共に付
着する珪酸亜鉛量を0.5重量%一定とし、水酸化錫に含
まれる錫の被覆量を変化させた時の沈降容積を示してい
る。 沈降容積は、本発明の蛍光体をPVA−ADCスラリーとし
て、一定量を沈降管にとり、遠心分離機にて一定時間強
制沈降させて、その容積を測定している。 沈降容積が少ない程分散性が良いことを示し、分散性
の良い蛍光体は、接着力の目安となるストライプ幅が小
さくなっても、きちんとパネル面に付着される。 珪酸亜鉛の付着量が0.5重量%である蛍光体は、水酸
化錫に含まれる錫の量が、0.01〜0.05重量%のときに最
も分散性が良く、それ以上、又は、それ以下でも、沈降
容積は増加して、接着力は低下する。従って、錫化合物
の付着量は、蛍光体に要求される分散性を考慮して、上
述の範囲に調整される。 上述の実施例では、蛍光体粒子表面に付着される錫化
合物の添加物として4価の錫塩を使用して説明している
が、この発明によれば、これにかぎることでなく、2価
の錫塩を用いてもよい。なぜなら、2価の錫塩は化学的
に不安定であり、実質的には4価の錫塩に変化するから
である。 又、上述の実施例では、蛍光体粒子として硫化亜鉛蛍
光体を使用して説明しているが、この発明によれば、こ
れに限ることなく、酸硫化イットリウム蛍光体等の希土
類赤色発光蛍光体に適用してもよく、また、二酸化珪
素、アルミン酸コバルト、酸化鉄等の顔料を付着させた
顔料付赤色発光蛍光体および顔料付青色発光蛍光体にも
適用できる。Example 4 Eurobium activated yttrium oxysulfide phosphor (Y 2 O 2 / E
u) After suspending 100 g in 250 ml of pure water, in this suspension,
As in Example 1, 15 ml of SnCl 4 aqueous solution (Sn 2% content solution)
Was added and stirred for 5 minutes. While stirring, add 5 m of sodium alginate solution (5% content solution) to this phosphor suspension.
The pH was adjusted to 5 with acetic acid, 2% NH 4 OH Wednesday was added dropwise to adjust the pH to 7.0, stirring was stopped, and the phosphor particles were allowed to settle. Then, it was filtered, dried (90 ° C. for 3 hours), and passed through a 300-mesh sieve to obtain a phosphor having tin alginate attached to the surface of the phosphor particles. Next, this phosphor was treated in the same manner as in Example 1 to obtain a phosphor having tin alginate and zinc silicate attached to the surface of the phosphor particles. In the above examples, zinc silicate is used as the silicate, but instead of zinc silicate, aluminum silicate, or
It is also possible to use magnesium silicate. It is also possible to use zinc phosphate, aluminum phosphate, magnesium phosphate instead of silicate. The phosphor of the present invention adjusts the amount of tin contained in the tin compound in the range of 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the phosphor. If the amount of the tin compound attached is too large or too small, the dispersibility of the phosphor will decrease. The dispersibility of tin compounds with respect to the amount of tin deposited is shown in FIG. However, Fig. 1 shows the sedimentation volume when the amount of zinc silicate adhering to the tin compound on the surface of the phosphor was kept constant at 0.5% by weight and the coating amount of tin contained in tin hydroxide was changed. There is. As for the sedimentation volume, the phosphor of the present invention was used as a PVA-ADC slurry, a certain amount was taken in a sedimentation tube, and it was forcibly sedimented for a certain time by a centrifuge, and the volume was measured. The smaller the sedimentation volume is, the better the dispersibility is, and the phosphor having good dispersibility is properly attached to the panel surface even if the stripe width, which is a measure of the adhesive force, becomes small. Phosphors with a zinc silicate content of 0.5% by weight have the best dispersibility when the amount of tin contained in the tin hydroxide is 0.01 to 0.05% by weight. The volume increases and the adhesive strength decreases. Therefore, the amount of the tin compound deposited is adjusted within the above range in consideration of the dispersibility required for the phosphor. In the above-mentioned examples, the description has been made by using the tetravalent tin salt as the additive of the tin compound attached to the surface of the phosphor particles. You may use the tin salt of. The reason for this is that the divalent tin salt is chemically unstable and substantially changes to the tetravalent tin salt. Further, in the above-mentioned embodiments, the zinc sulfide phosphor is used as the phosphor particles for explanation, but the present invention is not limited to this, and rare earth red light-emitting phosphors such as yttrium oxysulfide phosphor can be used. In addition, the present invention can also be applied to a pigmented red light emitting phosphor and a pigmented blue light emitting phosphor to which pigments such as silicon dioxide, cobalt aluminate and iron oxide are attached.
この発明の蛍光体は、カラーテレビジョンの蛍光膜形
成におけるスラリーにとって優れた分散性を有する。従
って、本発明の蛍光体を使用して、カラーテレビジョン
用の蛍光膜を形成することによって、均一で、しかも緻
密な蛍光膜が形成できる。 また、本発明の蛍光体は、極めて作業性のよい状態で
分散特性を向上でき、微細なドットのストライプを有す
るテレビジョン用蛍光体が簡単に多量生産できる特長が
実現できる。 本発明の蛍光体が、微細のストライプ形成に優れた特
性を示すことが、第4図に示されている。この図は、露
光量に対するストライプ幅の関係を示している。分散性
が悪い蛍光体は、ストライプ幅が広くなり、周縁で接着
力が低下してストライプ値が大きくなる。反対に分散性
が良い蛍光体は、ストライプ幅が狭くなり、全体が強固
に付着される。この図に於て、曲線Aは実施例1で得ら
れた本発明の蛍光体の特性を有し、曲線Bは、錫化合物
が付着されない以外実施例1と同様である従来の蛍光体
の特性を示す。曲線Aで示されるように、本発明の蛍光
体は、従来の蛍光体に比べるとストライプ幅が狭く、微
細なストライプが鮮明に付着できることを示している。 ストライプ幅が狭い蛍光体が、優れた塗布特性を実現
することを第2図に基づいて説明する。第2図は、蛍光
面作成時の「光源2−シャドウマスク1−塗布面3」の
位置関係と、その露光量の分布を示す。露光光源2から
の光が、シャドウマス1クの電子ビーム通過孔を通って
感光結着剤の塗膜に投写されたとき、蛍光体の中央部
は、シャドウマスク1の孔を透過した光が、シャドウマ
スク1で遮られることなく照射される。ところが、シャ
ドウマスク1の孔から離れるに従って、光源2からの光
がシャドウマスク1で遮られ、露光量の分布は台形状を
呈する。中央部(a)が真影部、周辺部(a−b)が半
影部と呼ばれ、真影部から半影部にかけて順次硬化度が
低下する。従って、真影部をいかに有効ならしめるか
が、接着力及びストライプ形状の良し悪しを決定する重
要な要素となる。 分散性が良い蛍光体は、蛍光体粒子が奇麗に並べられ
て均一に分布し、真影部の蛍光体が確実にしかも強固に
付着されて、細幅のストライプが明瞭に形成される。反
対に分散性が悪い蛍光体は、蛍光体粒子が奇麗に並ば
ず、真影部と半影部との境界付近で不均一な状態に蛍光
体が付着されてストライプ幅が広くなり、ストライプ値
が大きくなる。 この発明の蛍光体は、第4図の曲線Aで示すように優
れた塗布特性を備え、ドットピッチが小さなストライプ
を鮮明に形成できる特長が実現できる。The phosphor of the present invention has excellent dispersibility for a slurry in forming a fluorescent film of a color television. Therefore, by using the phosphor of the present invention to form a phosphor film for a color television, a uniform and dense phosphor film can be formed. In addition, the phosphor of the present invention can improve the dispersion characteristics in an extremely workable state, and can realize a feature that a phosphor for television having a fine dot stripe can be easily mass-produced. It is shown in FIG. 4 that the phosphor of the present invention exhibits excellent characteristics for forming fine stripes. This figure shows the relationship between the exposure amount and the stripe width. A phosphor having a poor dispersibility has a wide stripe width, and the adhesive strength is reduced at the peripheral edge to increase the stripe value. On the other hand, a phosphor having good dispersibility has a narrow stripe width and is firmly adhered to the whole. In this figure, curve A shows the characteristics of the phosphor of the present invention obtained in Example 1, and curve B shows the characteristics of the conventional phosphor which is the same as that of Example 1 except that the tin compound is not attached. Indicates. As shown by the curve A, the phosphor of the present invention has a narrower stripe width than that of the conventional phosphor, and thus shows that fine stripes can be clearly attached. It will be described with reference to FIG. 2 that a phosphor having a narrow stripe width realizes excellent coating characteristics. FIG. 2 shows the positional relationship of “light source 2-shadow mask 1-coating surface 3” and the distribution of the exposure amount when the fluorescent screen is formed. When the light from the exposure light source 2 is projected on the coating film of the photosensitive binder through the electron beam passage hole of the shadow mask 1, the light transmitted through the hole of the shadow mask 1 is at the center of the phosphor. The light is irradiated without being blocked by the shadow mask 1. However, as the distance from the hole of the shadow mask 1 increases, the light from the light source 2 is blocked by the shadow mask 1, and the distribution of the exposure amount has a trapezoidal shape. The central part (a) is called a true shadow part, and the peripheral part (ab) is called a penumbra part, and the degree of curing gradually decreases from the true shadow part to the penumbra part. Therefore, how to make the true shadow area effective is an important factor for determining the goodness of the adhesive force and the stripe shape. In the phosphor having good dispersibility, the phosphor particles are arranged neatly and uniformly distributed, and the phosphor in the shadow area is firmly and firmly attached to form a narrow stripe clearly. On the other hand, phosphors with poor dispersibility do not have phosphor particles lined up neatly, and the phosphors are attached in a non-uniform state near the boundary between the shadow area and the penumbra area, resulting in a wide stripe width and a stripe value. Grows larger. The phosphor of the present invention has excellent coating characteristics as shown by the curve A in FIG. 4, and can realize the feature that a stripe having a small dot pitch can be clearly formed.
第1図はこの発明の蛍光体の錫付着量に対する沈降容積
を示すグラフ、第2図はストライプの形成状態を示す断
面図、第3図はストライプの状態を示す拡大図平面図、
第4図は露光量に対するストライプ幅を示すグラフであ
る。 1……シャドウマスク、2……光源、 3……塗布面。FIG. 1 is a graph showing the sedimentation volume of the phosphor of the present invention with respect to the amount of deposited tin, FIG. 2 is a cross-sectional view showing a stripe formation state, and FIG. 3 is an enlarged plan view showing the stripe state.
FIG. 4 is a graph showing the stripe width with respect to the exposure amount. 1 ... Shadow mask, 2 ... Light source, 3 ... Application surface.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−18677(JP,A) 特開 昭49−16689(JP,A) 特公 昭46−1627(JP,B1) 特公 昭49−43075(JP,B1) ─────────────────────────────────────────────────── --- Continuation of front page (56) References JP-A-56-18677 (JP, A) JP-A-49-16689 (JP, A) JP-B-46-1627 (JP, B1) JP-B-49- 43075 (JP, B1)
Claims (5)
または4価の錫化合物が付着されており、錫化合物に含
まれる錫の付着量は、蛍光体100重量部に対して0.001〜
0.5重量部に調整され、珪酸塩の付着量が、2重量部以
下に調整されていることを特徴とするカラーテレビジョ
ン用蛍光体。1. A divalent or tetravalent tin compound is attached to the surface of the phosphor particles in addition to the silicate, and the amount of tin contained in the tin compound is 100 parts by weight of the phosphor. 0.001 ~
A phosphor for a color television, wherein the amount of silicate deposited is adjusted to 0.5 parts by weight and the amount of silicate deposited is adjusted to 2 parts by weight or less.
の付着量を0.5重量%付近とし、錫の付着量を0.01〜0.0
5重量%とすることを特徴とする特許請求の範囲第1項
記載のカラーテレビジョン用蛍光体。2. Zinc silicate is used as a silicate, the amount of zinc silicate deposited is about 0.5% by weight, and the amount of tin deposited is 0.01 to 0.0.
The phosphor for a color television according to claim 1, characterized in that the amount is 5% by weight.
の範囲第1項記載のカラーテレビジョン用蛍光体。3. The phosphor for a color television according to claim 1, wherein the tin compound is organic tin.
求の範囲第1項記載のカラーテレビジョン用蛍光体。4. The phosphor for a color television according to claim 1, wherein the tin compound is tin hydroxide.
範囲第1項記載のカラーテレビジョン用蛍光体。5. The phosphor for a color television according to claim 1, wherein the tin compound is stannic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62335976A JP2543737B2 (en) | 1987-12-29 | 1987-12-29 | Color television fluorescent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62335976A JP2543737B2 (en) | 1987-12-29 | 1987-12-29 | Color television fluorescent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01178584A JPH01178584A (en) | 1989-07-14 |
JP2543737B2 true JP2543737B2 (en) | 1996-10-16 |
Family
ID=18294412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62335976A Expired - Lifetime JP2543737B2 (en) | 1987-12-29 | 1987-12-29 | Color television fluorescent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2543737B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1329945C (en) * | 2002-04-22 | 2007-08-01 | 皇家飞利浦电子股份有限公司 | Luminescent screen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS554793B2 (en) * | 1972-06-07 | 1980-01-31 | ||
JPS4943075A (en) * | 1972-08-29 | 1974-04-23 | ||
JPS5618677A (en) * | 1979-07-25 | 1981-02-21 | Hitachi Ltd | Surface treated phosphor |
-
1987
- 1987-12-29 JP JP62335976A patent/JP2543737B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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JPH01178584A (en) | 1989-07-14 |
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