JPH037712B2 - - Google Patents
Info
- Publication number
- JPH037712B2 JPH037712B2 JP63123695A JP12369588A JPH037712B2 JP H037712 B2 JPH037712 B2 JP H037712B2 JP 63123695 A JP63123695 A JP 63123695A JP 12369588 A JP12369588 A JP 12369588A JP H037712 B2 JPH037712 B2 JP H037712B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- zns
- slurry
- amount
- contamination
- 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
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 319
- 239000011701 zinc Substances 0.000 claims description 127
- 239000002002 slurry Substances 0.000 claims description 68
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000004381 surface treatment Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 zinc halide Chemical class 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical group [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 79
- 238000012864 cross contamination Methods 0.000 description 45
- 229910052782 aluminium Inorganic materials 0.000 description 33
- 239000010949 copper Substances 0.000 description 26
- 229910004298 SiO 2 Inorganic materials 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000035945 sensitivity Effects 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 21
- 239000000725 suspension Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 11
- 239000010931 gold Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000001054 red pigment Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000010908 decantation Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- NYZGMENMNUBUFC-UHFFFAOYSA-N P.[S-2].[Zn+2] Chemical compound P.[S-2].[Zn+2] NYZGMENMNUBUFC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- AQWXOQIDVKXZBZ-UHFFFAOYSA-N cadmium(2+) selenium(2-) sulfuric acid Chemical compound [Se-2].[Cd+2].S(=O)(=O)(O)O AQWXOQIDVKXZBZ-UHFFFAOYSA-N 0.000 description 1
- JLATXDOZXBEBJX-UHFFFAOYSA-N cadmium(2+);selenium(2-);sulfide Chemical compound [S-2].[Se-2].[Cd+2].[Cd+2] JLATXDOZXBEBJX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 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
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Description
本発明は蛍光膜作成用蛍光体スラリーに関す
る。さらに詳しくは本発明の混色の少ない蛍光膜
を与え、かつ露光感度の高い蛍光膜作成用蛍光体
スラリーに関する。
周知のように、カラーテレビジヨンブラウン管
の蛍光膜はそれぞれ青色、緑色および赤色発光成
分蛍光体からなる青色、緑色および赤色発光ドツ
トあるいはストライプをフエースプレート上に繰
返し規則的に配列したものである。このカラーテ
レビジヨンブラウン管の蛍光膜は光印刷法によつ
て作成される。すなわち、まず第１の発光成分蛍
光体を、例えば重クロム酸塩で活性されたポリビ
ニルアルコール水溶液のような感光性樹脂溶液に
分散せしめて蛍光体スラリーを調製する。得られ
る蛍光体スラリーを回転塗布法等の適当な塗布方
法でフエースプレート全面に塗布し（スラリー塗
布）、しかる後塗布面に所定のパターンに紫外線
等のエネルギー線を照射して、エネルギー線を照
射した部分の樹脂を硬化せしめ不溶性とする（露
光）。その後溶剤等によりエネルギー線末照射部
分（樹脂末硬化部分）を溶解し除去して（現像）、
第１の発光成分蛍光体からなるドツトあるいはス
トライプを形成する。第２および第３の発光成分
蛍光体についても上記と同じ一連のスラリー塗
布、露光および現像の作業を順次繰返し行ない第
２および第３の発光成分蛍光体からなるドツトあ
るいはストライプを形成する。この場合、第１、
第２および第３の発光成分蛍光体からなる各ドツ
トあるいはストライプは互に重なり合わず、フエ
ースプレート上に繰返し規則的に配列されるよう
にエネルギー線照射が制御されなければならない
ことは言うまでもない。次に上述のようにして得
た樹脂成分を含んだ蛍光膜を適当な温度で焼成し
て樹脂成分を分解揮発せしめ、目的とする蛍光膜
を得る。
上述の蛍光体スラリーを用いる光印刷法によつ
てカラーテレビジヨンブラウン管の蛍光膜を作成
するにあたつては
(1) 充分な厚さを有し、かつ緻密なドツトあるい
はストライプを形成すること、
(2) フエースプレート上の所定の位置に所定の形
状のドツトあるいはストライプを形成するこ
と、
(3) １つの発光成分蛍光体が他の発光成分蛍光体
に混入しないこと、すなわち混色が生じないこ
と、
(4) 蛍光体スラリーの露光感度が高く作業性がよ
いこと、
等が必要とされる。従来上記各事項を満足させる
ことを目的として蛍光体スラリーの組成、調製方
法等についてあるいは蛍光体スラリーに用いるカ
ラーテレビジヨン用蛍光体（青色、緑色および赤
色発光成分蛍光体）の表面処理について種々の研
究が行なわれてきた。そして現行の蛍光体スラリ
ーは上記各事項をある程度満足させるものであ
る。しかしながら商業的に常により高品質の蛍光
膜が要求されることから、上記各事項をさらに改
良することが望まれている。
本発明は上記事項のうち特に(3)および(4)をさら
に改良する蛍光膜作成用蛍光体スラリーを提供す
ることを目的とする。
すなわち、本発明は混色の少ない蛍光膜を与え
る蛍光膜作成用蛍光体スラリーを提供することを
目的とする。
また本発明は露光感度の高い蛍光膜作成用蛍光
体スラリーを提供することを目的とする。
尚、従来前記事項(1)に関する分散性を向上させ
るためにカリ水ガラスと硫酸亜鉛等の亜鉛イオン
を含む水溶液にて蛍光体の表面をメタケイ酸塩等
のケイ酸化合物で処理する方法が知られていた
（特公昭50−15747号公報、USP.2704726号公報参
照）。しかしながら、この表面処理方法は、本発
明に使用される処理と、構成も効果も異なる。
上記本発明の目的は特定の蛍光体スラリーによ
つて達成された。すなわち、本発明の蛍光膜作成
用蛍光体スラリーは、水溶性亜鉛化合物と水酸化
アルカリを用い水溶液中で表面処理して得られた
蛍光体と、重クロム酸塩及びポリビニールアルコ
ールを含む水溶液からなることを特徴とする。
また、従来カラーテレビジヨン用蛍光体に二酸
化珪素、マグネシウム、亜鉛、カルシウム、アル
ミニウム等の燐酸塩等を付着させてそのカラーテ
レビジヨン用蛍光体の蛍光体スラリー中における
分散性を改良し（これらカラーテレビジヨン用蛍
光体の分散性を改良する物質を本明細書において
は「分散剤」と呼ぶことにする）、これによつて
良好な蛍光膜を得ることが知られているが、本発
明の蛍光体スラリーに使用する蛍光体にこの分散
剤による表面処理を併用することができる。
本発明の蛍光体スラリーを用いて光印刷法でカ
ラーテレビジヨンブラウン管蛍光膜を作成する場
合、得られる蛍光膜は混色が著しく少ないもので
ある。また本発明の蛍光体スラリーは露光感度が
高く、従つて硬化のための紫外線照射時時間（露
光時間）を短縮することができ、作業能率を上げ
ることができる。
以下本発明を詳しく説明する。
本発明の蛍光体スラリーは例えば以下に述べる
ような工程からなる。
まず純水中に蛍光体を入れ、充分に懸濁させ
る。次にこの懸濁液に亜鉛イオンを含む水溶液を
適当量加え、しかる後にこの亜鉛イオンを含む懸
濁液にアルカリを加えて懸濁液のPH値を7.5乃至
11に調整し、水酸化亜鉛に代表される表面処理物
質［以下Zn（OH）2と略称する］を析出せしめる。
析出した微粒子のZn（OH）2は蛍光体表面に吸着
される。懸濁液を放置し、Zn（OH）2微粒子が付
着した蛍光体を沈降せしめ、しかる後デカンテー
シヨンにより上澄み液を除去する。水洗を数回繰
返して残留イオンを除去した後、脱水、乾燥す
る。乾燥後、得られる塊状の蛍光体を篩を通して
ほぐし、本発明に使用する蛍光体を得る。
亜鉛イオンを含む水溶液としては水溶性亜鉛化
合物、例えば硫酸亜鉛（ZnSO4）、酢酸亜鉛［Zn
（CH3COO）2］、硝酸亜鉛［Zn（NO3）2］、ハロゲ
ン化亜鉛（ZnX2、Ｘは弗素を除くハロゲン）等
の水溶液が用いられる。またPH値調整用のアルカ
リとしては水酸化アルカリが用いられ、例えば水
酸化ナトリウム（NaOH）、水酸化カリウム
（KOH）、水酸化アンモニウム（NH4OH）等が
水溶液として用いられる。NH4OHを使用する場
合、過剰に加えると可溶性のアンミン錯イオンが
生じZn（OH）2が析出しないので、PH値が10を越
えないように注意する必要がある。
乾燥は250℃以下の温度、好ましくは200℃以下
の温度で行なわれる。250℃よりも高い温度で乾
燥を行なう場合には蛍光体に付着したZn（OH）2
がすべて酸化亜鉛化合物（以下ZnOと略称する）
に変わるので本発明に使用する蛍光体は得られな
い。200乃至250℃で乾燥する場合にはZn（OH）2
の一部がZnOに変わるが（当然高温になる程ZnO
に変わる率は高くなる）、生じるZnOは蛍光体ス
ラリー特性に何ら悪影響をおよぼすものではな
い。200℃以下の温度で乾燥を行なう場合には
ZnOへの変換はほとんど起こらず、Zn（OH）2が
ほとんどそのまま残留する。
本発明に使用されるカラーテレビジヨンブラウ
用蛍光体に付けられるZn（OH）2の量はカラーテ
レビジヨン用蛍光体100重量部に対して０重量部
より多く0.7重量部以下である。Zn（OH）2付着量
が0.7重量部よりも多い場合には、得られる蛍光
体の蛍光体スラリー中に於ける分散性が次第に悪
くなるのに伴つて蛍光膜とした場合に混色が著し
く生じるようになるので好ましくない。より好ま
しいZn（OH）2付着量は0.01乃至0.5重量部である。
なお蛍光体に付着したZn（OH）2を定量するのに
は濃アンモニア水を用いるのが便利である。濃ア
ンモニア水は、主に硫化物あるいは酸化物である
カラーテレビジヨン用蛍光体、あるいは高い乾燥
温度を採用した場合に生じるZnOとは反応しない
が、Zn（OH）2と選択的に反応し、可溶性のアン
ミン錯イオンを生じる。従つて本発明の蛍光体を
濃アンモニア水で処理し、Zn（OH）2をアンミン
錯イオンとして溶解分離せしめ、このアンミン錯
イオンを定量することによつてZn（OH）2付着量
を知ることができる。
なお、本発明に使用される蛍光体において分散
剤を併用する場合、まず最初にカラーテレビジヨ
ン用蛍光体に従来の方法で分散剤を付着せしめ、
その後上述の方法でZn（OH）2を付着せしめても
よいし、あるいはその逆であつてもよい。分散剤
としては二酸化珪素（SiO2）、マグネシウム、亜
鉛、カルシウム、アルミニウム等のオルト、メタ
あるいはピロ燐酸塩［Mg3（PO4）2、Zn3（PO4）2、
Ca3（PO4）2、AlPO4、Mg（PO3）2、Zn（PO3）2、
Ca（PO3）2、Al（PO3）3、Mg2P2O7、Zn2P2O7、
Ca2P2O7等］が用いられるが、特にSiO2を用いる
のが好ましい。分散剤は従来知られている方法に
よつて蛍光体に付けられる。例えばSiO2の場合
には、まず水ガラス水溶液中に蛍光体を懸濁せし
め、次にこの懸濁液に硫酸亜鉛、硫酸アルミニウ
ム等の水溶液を添加してSiO2微粒子を析出させ
ると同時にこれを蛍光体表面に吸着させる等の方
法が採用される。
本発明に用いられる蛍光体は、例えばカラーテ
レビジヨン用蛍光体はカラーテレビジヨンブラウ
ン管蛍光膜の青色、緑色あるいは赤色発光成分蛍
光体として用いることができる蛍光体すべてを含
む。このカラーテレビジヨン用蛍光体は単一の蛍
光体であつてもよいし、あるいは最近実用化が進
んでいる銅およびアルミニウム付活硫化亜鉛蛍光
体（ZnS：Cu、Al）と金およびアルミニウム付
活硫化亜鉛蛍光体（ZnS：Au、Al）とを混合し
た緑色発光成分蛍光体のような混合蛍光体であつ
てもよい。また、最近高コントラストカラーテレ
ビジヨンブラウン管の蛍光膜には蛍光体表面を顔
料粒子で被覆した、いわゆる顔料付蛍光体が用い
られているが、本発明に用いられるカラーテレビ
ジヨン用蛍光体はこの顔料付蛍光体であつてもよ
い。従つて本明細書における「カラーテレビジヨ
ン用蛍光体」と言う表現は特別に断りがない限り
単一蛍光体、混合蛍光体および顔料付蛍光体のい
ずれをも意味するものとする。
特に実用的な点から好ましいカラーテレビジヨ
ン用蛍光体としては、青色発光蛍光体として銀付
活硫化亜鉛蛍光体（ZnS：Ag）、銀およびアルミ
ニウム付活硫化亜鉛蛍光体（ZnS：Ag、Al）、ア
ルミン酸コバルト青色顔料粒子付ZnS：Ag蛍光
体、アルミン酸コバルト青色顔料粒子付ZnS：
Ag、Al蛍光体等、緑色発光成分蛍光体として上
述のZnS：Cu、Al蛍光体とZnS：Au、Al蛍光体
の混合蛍光体、ZnS：Cu、Al蛍光体、金、銅お
よびアルミニウム付活硫化亜鉛蛍光体（ZnS：
Au、Cu、Al）、銅およびアルミニウム付活硫化
亜鉛・カドミウム蛍光体［（Zn、Cd）Ｓ：Cu、
Al］等、赤色発光蛍光体としてユーロピウム付
活酸硫化イツトリウム蛍光体（Y2O2S：Eu）、ユ
ーロピウム付活酸化イツトリウム蛍光体
（Y2O3：Eu）、べんがら赤色顔料粒子付Y2O2S：
Eu蛍光体、べんがら赤色顔料粒子付Y2O3：Eu蛍
光体、硫セレン化カドミウム赤色顔料粒子付
Y2O2S：Eu蛍光体、硫セレン化カドミウム赤色
顔料粒子付Y2O3：Eu蛍光体等が挙げられる。
次に本発明の効果をZnS：Ag青色発光成分蛍
光体を用いた蛍光体スラリーの場合を例に挙げて
説明する。
カラーテレビジヨンブラウン管蛍光膜における
各発光成分蛍光体間の混色には２つの種類があ
る。その１つは第１の発光成分蛍光体あるいは第
２の発光成分蛍光体がスラリー塗布、露光、現像
され、そのドツトあるいはストライプがフエース
プレート上に形成される時、その後に形成される
他の発光成分蛍光体のドツトあるいはストライプ
の位置に蛍光体が残留し、これによつて混色が生
じる場合であり、このような蛍光体の残留は「ヘ
イズ」と呼ばれる。もう１つは第２の発光成分蛍
光体あるいは第３の発光成分蛍光体がスラリー塗
布、露光、現像され、そのドツトあるいはストラ
イプが形成される時、すでに形成されている他の
発光成分蛍光体ドツトあるいはストライプ上に蛍
光体が付着し残留するもので、このような混色は
「クロスコンタミネーシヨン」と呼ばれる。ヘイ
ズは用いられる蛍光体スラリーの特性に依存して
生じるものであるが、クロスコンタミネーシヨン
は用いられる蛍光体スラリーの特性とすでに形成
されている下地のドツトあるいはストライプの特
性の両方に依存して生じるものである。
本発明の蛍光体スラリーは上述のヘイズおよび
クロスコンタミネーシヨンのいずれによる混色も
著しく改良するものである。
第１図はZn（OH）2付着ZnS：Ag蛍光体（付着
量０も含む）の蛍光体スラリーを用いた時、Zn
（OH）2付着量とヘイズとの間係を示すグラフで
ある。第１図のグラフは以下のようにして得られ
た。まずNnS：Ag蛍光体100重量部に対して0.15
重量部のSiO2が付着しているZnS：Ag蛍光体を
用いてZn（OH）2付着量がそれぞれ異なる７種類
のZn（OH）2付着量ZnS：Ag蛍光体を製造した。
この７種類のZn（OH）2付着ZnS：Ag蛍光体とZn
（OH）2が付着してないZnS：Ag蛍光体（0.15重量
％のSiO2は付着している）の８種類の蛍光体を
試料として用いた。なお、この８種類の蛍光体試
料は後に述べる第２図乃至第４図の各グラフを得
るのにも用いられた。次にこれら蛍光体試料を用
いて、以下のようにしてフエースプレート上にス
トライプを形成した。
まず、従来一般に用いられている重クロム酸ア
ンモニウム含有ポリビニルアルコール水溶液と各
蛍光体試料を用いて通常の方法で本発明の蛍光体
スラリーを調製した。次に得られる各蛍光体スラ
リーをそれぞれ16インチブラウン管のフエースプ
レート上に回転塗布し、乾燥し、しかる後シヤド
ウマスクを通して高圧水銀ランプにより紫外線を
照射して塗布面をストライプ状に露光し、温水に
より現像してストライプを形成した。なお、上記
ストライプの作成方法は第２図および第４図の各
グラフを得る場合にも適用された。上述のように
してストライプを形成したフエースプレートの一
部を拡大投映顕微鏡によつて100倍に拡大してス
クリーンに写し、末露光部、すなわちストライプ
とストライプの間〓部分のスクリーン上で20mm×
20mm（フエースプレート上では0.2mm×0.2mm）中
に残存している蛍光体粒子の数（ヘイズ）を数え
た。いずれの蛍光体スラリー試料についてもこの
蛍光体粒子数のカウントは２ケ所について行な
い、その平均値を各蛍光体試料のZn（OH）2付着
量（ZnS：Ag蛍光体100重量部に対する重量部）
に対してプロツトして第１図のグラフを得た。
第１図から明らかなように、Zn（OH）2付着量
が増加するに従つてヘイズは減少することが分か
る。特にZn（OH）2付着量が0.5重量部まではZn
（OH）2付着量増加に対するヘイズの減少は著し
く、Zn（OH）2付着量0.5重量部の場合のヘイズは
Zn（OH）2付着量０の場合の約1/10となる。
第２図はZn（OH）2付着ZnS：Ag蛍光体（付着
量０も含む）の蛍光体スラリーを用いた時のZn
（OH）2付着量とその蛍光体の他の発光成分蛍光
体とのクロスコンタミネーシヨンの関係を示すグ
ラフである。クロスコンタミネーシヨンは次の２
つの場合が考えられる。１つはすでに塗布されて
いる発光成分蛍光体へ付着するクロスコンタミネ
ーシヨンであり（「前塗布発光成分蛍光体とのク
ロスコンタミネーシヨン」と呼ぶことにする）、
もう１つはその後に塗布される発光成分蛍光体が
付着するクロスコンタミネーシヨンである（「後
塗布発光成分蛍光体とのクロスコンタミネーシヨ
ン」と呼ぶことにする）。第２図ＡはZn（OH）2付
着ZnS：Ag蛍光体（付着量０も含む）のZn
（OH）2付着量と、その蛍光体の前塗布ZnS：Cu、
Al緑色発光成分蛍光体とのクロスコンタミネー
シヨンの関係を示すグラフであり、第２図−Ｂは
Zn（OH）2付着ZnS：Ag蛍光体（付着量０も含む）
のZn（OH）2付着量と、その蛍光体の後塗布
Y2O2S：Eu績色発光成分蛍光体とのクロスコン
タミネーシヨンの関係を示すグラフである。第２
図−ＡおよびＢにおいて、クロスコンタミネーシ
ヨン（縦軸）はそれぞれ青色出力／緑色出力およ
び赤色出力／青色出力の値で表わされているが、
これらの値は以下のようにして測定された。
第２図−Ａについては、まずZnS：Cu、Al緑
色発光成分蛍光体［Zn（OH）2末処理］のストラ
イプがあらかじめ形成されているフエースプレー
ト上に、蛍光体スラリー試料を塗布し乾燥した
後、露光を行なわずに温水で現像を行なつた。上
記作業を行なつた後（当然ZnS：Ag蛍光体のス
トライプは形成されていない）、ZnS：Cu、Al蛍
光体のストライプを3650Åの紫外線で励起し、発
光をハーフミラーで分割し、分割された２つの光
をそれぞれ緑および青のラツテンフイルターを通
してフオトマルで受光し、それぞれの出力を測定
して青色出力／緑色出力の値を求めた。各蛍光体
試料について青色出力／緑色出力の値を求め、
Zn（OH）2付着量が０のものを１として規格化し、
各蛍光体試料のZn（OH）2付着量（ZnS：Ag蛍光
体100重量部に対する重量部）に対してプロツト
した。
また第２図−Ｂについては、まず蛍光体スラリ
ー試料を塗布、露光、現像してストライプを形成
した。次にこの試料のストライプが形成されてい
るフエースプレート上にY2O2S：Eu赤色発光成
分蛍光体［Zn（OH）2末処理］をスラリー塗布し
乾燥した後、露光を行なわずに温水で現像を行な
つた。上記作業を行なつた後（当然Y2O2S：Eu
蛍光体のストライプは形成されていない）、試料
のストライプを3650Å紫外線で励起し、発光をハ
ーフミラーで分割し、分割された２つの光をそれ
ぞれ青および赤のラツテンフイルターを通してフ
オトマルで受光し、それぞれの出力を測定して赤
色出力／緑色出力の値を求めた。各蛍光体試料に
ついて赤色出力／緑色出力の値を求め、Zn
（OH）2付着量が０のものを１として規格化し、
各蛍光体スラリー試料のZn（OH）2付着量（ZnS：
Ag蛍光体100重量部に対する重量部）に対してプ
ロツトした。
第２図−ＡおよびＢにおいて、青色出力／緑色
出力および赤色出力／青色出力の値が大きいほど
ZnS：Ag蛍光体の前塗布ZnS：Cu、Al蛍光体へ
のクロスコンタミネーシヨンおよびZnS：Ag蛍
光体への後塗布Y2O2S：Eu蛍光体のクロスコン
タミネーシヨンが多いことを意味する。
第２図−Ａから明らかなように、Zn（OH）2付
着量が増加するに従つて前塗布発光成分蛍光体へ
のクロスコンタミネーシヨンは減少することが分
かる。特にZn（OH）2付着量が0.5重量部まではZn
（OH）2付着量増加に対するクロスコンタミネー
シヨンの減少は著しい。
また第２図−Ｂから明らかなように、後塗布発
光成分蛍光体とのクロスコンタミネーシヨンは
Zn（OH）2付着量が0.2乃至0.3重量部まではZn
（OH）2付着量の増加に伴つて減少するが、Zn
（OH）2付着量がさらに増加すると逆に増加し始
め、Zn（OH）2付着量が約0.7重量部である場合に
Zn（OH）2付着量０の場合と同じになる。本発明
においてZn（OH）2付着量の上限を0.7重量部とし
たのはこのような知見に基づいてである。
上述のようにZn（OH）2付着量が多くなると後
塗布発光成分蛍光体とのクロスコンタミネーシヨ
ンが増加するようにになるのは、その１つの理由
としてZn（OH）2付着量がある値以上に大きくな
ると蛍光体の分散性が悪くなつてくるためである
と考えられる。すなわち、分散性が悪くなるとス
トライプを形成した場合ストライプの背面（後塗
布が行なわれる面）に凹凸が生じやすくなり、こ
のために後塗布発光成分蛍光体とのクロスコンタ
ミネーシヨンが生じやすくなる。Zn（OH）2付着
ZnS：Ag蛍光体（付着量０も含む）のZn（OH）2
付着量とその蛍光体の分散性との関係を第３図に
示す。
第３図において、分散性（縦軸）は沈降容積で
表わされている。この沈降容積の値は、蛍光体試
料５ｇを重クロム酸アンモニウム含有ポリビニル
アルコール水溶液30ｇ中に入れ、沈降管で24時間
沈降させて容積を読みとり、１ｇ当りの容積に換
算したものである。沈降容積の値か大きい程分散
性が悪いことを意味する。
第３図から明らかなように、分散性はZn
（OH）2付着量が約0.5重量部まではZn（OH）2付着
量が０の場合とほぼ同等であるが、Zn（OH）2付
着量が0.5重量部よりも多くなるとZn（OH）2付着
量が増加するに従つて悪くなることが分かる。先
に述べたように、後塗布発光成分蛍光体とのクロ
スコンタミネーシヨンの点から本発明における
Zn（OH）2付着量の上限を0.7としたが、この分散
性も考慮に入れるとZn（OH）2付着量は0.5重量部
以下とするのがより好ましい。なお、この分散性
は蛍光体スラリーへの界面活性剤あるいはその界
面活性剤を選択する等の手段によつてある程度改
良することができる。
本発明によつて得られた蛍光体スラリーは露光
感度を著しく高めるものである。
第４図はZn（OH）2付着ZnS：Ag蛍光体（付着
量０も含む）のZn（OH）2付着量と、その蛍光体
を使用した蛍光体スラリーを用いて一定幅
（230μｍ）のストライプを形成するに必要な露光
時間との関係を示すグラフである。第４図から明
らかなように、Zn（OH）2付着量が約1.2重量部ま
ではZn（OH）2付着量が０の場合よりも短かい露
光時間で同じストライプを得ることができる。す
なわち、Zn（OH）2付着量が０重量部より多く約
1.2重量部である場合に蛍光体スラリーの露光感
度が向上する。特にZn（OH）2付着量が0.05乃至
1.0重量部である時露光感度の向上が著しい。従
つてこのように露光感度が向上した蛍光体スラリ
ーを用いることによつて、露光時間を短縮するこ
とができ、作業能率を上げることができる。ま
た、露光時間をZn（OH）2付着量０の場合と同じ
にする時には、同じストライプを得るのに光源光
量を減らすことができ、従つて光源寿命を延ばす
ことができる。上述のように適当量のZn（OH）2
が付着した蛍光体を用いた蛍光体スラリーの露光
感度が向上する理由は明らかでないが、Zn
（OH）2あるいは一部溶解したZn++が蛍光体スラ
リー中で触媒的な作用をし、感光性樹脂の光重合
を促進するためであろうと考えられる。
以上本発明の効果をZnS：Ag蛍光体の場合を
例に挙げて説明したが、その他のカラーテレビジ
ヨン用蛍光体の場合も同じような効果が得られる
ことが確認された。また、分散剤処理を行なつた
カラーテレビジヨン用蛍光体あるいは分散剤処理
を行なつてないカラーテレビジヨン用蛍光体のい
ずれの場合も同じような効果が得られることが確
認された。
以上述べたように、本発明の蛍光体スラリーは
混色が著しく少ないカラーテレビジヨンブラウン
管蛍光膜を与え、またその露光感度を著しく高め
るものであつて、その工業的利用価値は、非常に
大きなものである。
次に実施例によつて本発明を説明する。
実施例 １
ZnS：Cu、Al蛍光体とZnS：Au、Al蛍光体を
重量比で７：３の割合で混合した緑色発光成分蛍
光体1000ｇを２の純水中に懸濁させた。この懸
濁液に水ガラス（東京応化製オーカシールＡ、
SiO220重量％含有）を15ｇ加えて撹拌し、さら
に硫酸亜鉛の10％水溶液90ｇを添加した。10分間
撹拌後撹拌を止めて蛍光体を沈降させ、上澄み液
をデカンテーシヨンにて除去した。その後蛍光体
を５の純水で２回水洗した。このようにして
SiO2による表面処理を完了し、SiO2が付着した
蛍光体を得た。
次に上述のようにして得たSiO2が付着した蛍
光体を２の純水中に懸濁させ、この懸濁液に硫
酸亜鉛10％水溶液28ｇを加え、その後撹拌しなが
らNaOH水溶液で懸濁液のPH値を10.0に調整し
た。PH値調整後さらに５分間撹拌を続けた。撹拌
を止め蛍光体を沈降させた後、上澄み液をデカン
テーシヨンにて除去し、さらに蛍光体を５の純
水で１回水洗した。その後蛍光体を吸引脱水し、
150℃で３時間乾燥した。乾燥後、蛍光体を250メ
ツシユの篩で篩つた。
上述のようにSiO2による表面処理およびZn
（OH）2による表面処理を行なつた蛍光体には、
SiO2とZn（OH）2が付着しており、Zn（OH）2の付
着量は混合緑色発光成分蛍光体100重量部に対し
て0.14重量部であつた。
次に上述のようにして得た蛍光体と通常の重ク
ロム酸アンモニウム含有ポリビニルアルコール水
溶液とを用いて通常の方法で蛍光体スラリーを調
製し、得られる蛍光体スラリーを用いて塗布試験
を行ない、混色（ヘイズおよびクロスコンタミネ
ーシヨン）および露光感度（露光時間）を調べ
た。その結果を第１表に上述のSiO2による表面
処理のみを行い、Zn（OH）2による表面処理を行
なわなかつた混合蛍光体の場合（第１表括弧内の
値）と比較して示す。なおクロスコンタミネーシ
ヨンは青色発光成分蛍光体としてZnS：Ag蛍光
体、赤色発光成分蛍光体としてY2O2S：Eu蛍光
体を用い［いずれもZn（OH）2末処理］、緑色、青
色および赤色発光成分蛍光体の順に塗布した場合
の後塗布ZnS：Ag青色発光成分蛍光体とのクロ
スコンタミネーシヨン（青色出力／緑色出力）お
よび後塗布Y2O2S：Eu赤色発光成分蛍光体との
クロスコンタミネーシヨン（赤色出力／緑色出
力）を測定した。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつた蛍光体は、Zn（OH）2による
表面処理を行なわなかつた蛍光体よりも蛍光膜に
おける混色が少なく、また蛍光体スラリーの露光
感度が高かつた。
実施例 ２
ZnS：Au、Cu、Al緑色発光成分蛍光体1000ｇ
を２の純水中に懸濁させ、この懸濁液に塩化亜
鉛の20％水溶液23.6ｇを加え、その後撹拌しなが
らNH4OH水溶液で懸濁液のPH値を8.0に調整し
た。PH調整後さらに５分間撹拌を続けた。撹拌を
止め蛍光体を沈降させた後、上澄み液をデカンテ
ーシヨンにて除去し、さらに蛍光体を５の純水
で２回水洗した。その後蛍光体を吸引脱水し、
100℃で８時間乾燥した。乾燥後蛍光体を250メツ
シユの篩で篩つた。
上述のようにしてZn（OH）2による表面処理を
行なつたZnS：Au、Cu、Al蛍光体には、Zn
（OH）2が付着しており、Zn（OH）2の付着量は
ZnS：Au、Cu、Al蛍光体100重量部に対して0.26
重量部であつた。
次に上述のようにして得た蛍光体を用いて実施
例１と同様にして蛍光体スラリーを調製し、得ら
れる蛍光体スラリーを用いて塗布試験を行ない、
混色（ヘイズおよびクロスコンタミネーシヨン）
および露光感度（露光時間）を調べた。その結果
を第１表に上述のZn（OH）2による表面処理を行
なわなかつたZnS：Au、Cu、Al蛍光体の場合
（第１表括弧内の値）と比較して示す。なおクロ
スコンタミネーシヨンの青色発光成分蛍光体とし
てZnS：Ag蛍光体、赤色発光成分蛍光体として
Y2O3S：Eu蛍光体を用い［いずれもZn（OH）2末
処理］、緑色、青色および赤色発光成分蛍光体の
順に塗布した場合の後塗布ZnS：Ag青色発光成
分蛍光体とのクロスコンタミネーシヨン（青色出
力／緑色出力）および後塗布Y2O3S：Eu赤色発
光成分蛍光体とのクロスコンタミネーシヨン（赤
色出力／緑色出力）を測定した。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつたZnS：Au、Cu、Al蛍光体
は、この処理を行なわなかつたZnS：Au、Cu、
Al蛍光体よりも蛍光膜における混色が少なく、
また蛍光体スラリーの露光感度が高かつた。
実施例 ３
ZnS：Ag青色発光成分蛍光体1000ｇを２の
純水中に懸濁させ、実施例１と同様にしてSiO2
による表面処理を行ない、SiO2が付着した蛍光
体を得た。
次に上述のようにして得たSiO2が付着した蛍
光体を２の純水中に懸濁させ、この懸濁液に酢
酸亜鉛の10％水溶液18.7ｇを加え、その後撹拌し
なながらNaOH水溶液で懸濁液のPH値を9.0に調
製した。PH調製後さらに５分間撹拌を続けた。撹
拌を止め蛍光体を沈降させた後、上澄み液をデカ
ンテーシヨンにて除去し、さらに５の純水で２
回水洗した。その後蛍光体を吸引し、200℃で３
時間乾燥した。乾燥後蛍光体を250メツシユの篩
で篩つた。
上述のようにしてSiO2による表面処理および
Zn（OH）2による表面処理を行なつたZnS：Ag蛍
光体には、SiO2とZn（OH）2が付着しており、Zn
（OH）2の付着量はZnS：Ag蛍光体100重量部に対
して0.08重量部であつた。
次に上述のようにして得た蛍光体を用いて実施
例１と同様にして蛍光体スラリーを調製し、得ら
れる蛍光体スラリーを用いて塗布試験を行ない、
混色（ヘイズおよびクロスコンタミネーシヨン）
および露光感度（露光時間）を調べた。その結果
を第１表に上述のSiO2による表面処理のみを行
ない、Zn（OH）2による表面処理を行なわなかつ
たZnS：Ag蛍光体の場合（第１表括弧内の値）
と比較して示す。なおクロスコンタミネーシヨン
は緑色発光成分蛍光体としてZnS：Cu、Al蛍光
体、赤色発光成分蛍光体としてY2O2S：Eu蛍光
体を用い、［いずれもZn（OH）2未処理］、緑色、
青色および赤色発光成分蛍光体の順に塗布した場
合の前塗布ZnS：Cu、Al緑色発光成分蛍光体と
のクロスコンタミネーシヨン（青色出力／緑色出
力）および後塗布Y2O2S：Eu赤色発光成分蛍光
体とのクロスコンタミネーシヨン（赤色出力／青
色出力）を測定した。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつたZnS：Ag蛍光体は、この処
理を行なわなかつたZnS：Ag蛍光体よりも蛍光
膜における混色が少なく、また蛍光体スラリーの
露光感度が高かつた。
実施例 ４
ZnS：Ag、Al青色発光成分蛍光体1000ｇを２
の純水中に懸濁させ、この懸濁液に硝酸亜鉛の
20％水溶液67ｇを加え、その後撹拌しながら
KOH水溶液で懸濁液のPH値を11.0に調整した。
PH調整後さらに５分間撹拌を続けた。撹拌を止め
蛍光体を沈降させた後、上澄み液をデカンテーシ
ヨンにて除去し、さらに蛍光体を５の純水で１
回水洗した。その後蛍光体を吸引脱水し、150℃
で３時間乾燥した。乾燥後、蛍光体を250メツシ
ユの篩で篩つた。
上述のようにしてZn（OH）2による表面処理を
行なつたZnS：Ag、Al蛍光体には、Zn（OH）2が
付着しており、そのZn（OH）2付着量はZnS：Ag、
Al蛍光体100重量部に対して0.51重量部であつた。
次に上述のようにして得た蛍光体を用いて実施
例１と同様にして蛍光体スラリーを調製し、得ら
れる蛍光体スラリーを用いて塗布試験を行ない、
混色（ヘイズおよびクロスコンタミネーシヨン）
および露光感度（露光時間）を調べた。その結果
を第１表に上述のZn（OH）2による表面処理を行
なわなかつたZnS：Ag、Al蛍光体の場合（第１
表括弧内の値）と比較して示す。なおクロスコン
タミネーシヨンは緑色発光成分蛍光体として
ZnS：Cu、Al蛍光体、赤色発光成分蛍光体とし
てY2O2G：Eu蛍光体を用い［いずれもZn（OH）2
未処理］、緑色、青色および赤色発光成分蛍光体
の順に塗布した場合の前塗布ZnS：Cu、Al緑色
発光成分蛍光体とのクロスコンタミネーシヨン
（青色出力／緑色出力）および後塗布Y2O2S：Eu
赤色発光成分蛍光体とのクロスコンタミネーシヨ
ン（赤色出力／青色出力）を測定した。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつたZnS：Ag、Al蛍光体は、こ
の処理を行なわなかつたZnS：Ag、Al蛍光体よ
りも蛍光膜における混色が少なく、また蛍光体ス
ラリーの露光感度が高かつた。
実施例 ５
Y2O2S：Eu赤色発光成分蛍光体1000ｇを２
の純水中に懸濁させ、この懸濁液に硫酸亜鉛の10
％水溶液112ｇを加え、その後撹拌しながら
NH4OH水溶液で懸濁液のPH値を9.0に調整した。
PH調整後さらに５分間撹拌を続けた。撹拌を止め
蛍光体を沈降させた後、上澄み液をデカンテーシ
ヨンにて除去し、さらに蛍光体を５の純水で３
回水洗した。その後蛍光体を吸引脱水し、130℃
で６時間乾燥した。乾燥後蛍光体を250メツシユ
の篩で篩つた。
上述のようにしてZn（OH）2による表面処理を
行なつたY2O2S：Eu蛍光体には、Zn（OH）2が付
着しており、そのZn（OH）2付着量はY2O2S：Eu
蛍光体100重量部に対して0.57重量部であつた。
次に上述のようにして得た蛍光体を用いて実施
例１と同様にして蛍光体スラリーを調製し、得ら
れる蛍光体スラリーを用いて塗布試験を行ない、
混色（ヘイズおよびクロスコンタミネーシヨン）
および露光感度（露光時間）を調べた。その結果
を第１表に上述のZn（OH）2による表面処理を行
なわなかつたY2O2S：Eu蛍光体の場合（第１表
括弧内の値）と比較して示す。なおクロスコンタ
ミネーシヨンは青色発光成分蛍光体としてZnS：
Ag蛍光体、緑色発光成分蛍光体としてZnS：Cu、
Al蛍光体［いずれもZn（OH）2未処理］、緑色、青
色および赤色発光成分蛍光体の順に塗布した場合
の前塗布ZnS：Cu、Al緑色発光成分蛍光体との
クロスコンタミネーシヨン（赤色出力／緑色出
力）および前塗布ZnS：Ag青色発光成分蛍光体
とのクロスコンタミネーシヨン（赤色出力／青色
出力）を測定した。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつたY2O2S：Eu蛍光体は、この
処理を行なわなかつたY2O2S：Eu蛍光体よりも
蛍光膜膜における混色が少なく、また蛍光体スラ
リーの露光感度が高かつた。
実施例 ６
べんがら赤色顔料粒子付Y2O2S：Eu赤色発光
成分蛍光体1000ｇを２の純水中に懸濁させ、実
施例１と同様にしてSiO2による表面処理を行な
い、SiO2が付着した蛍光体を得た。
次に上述のようにして得たSiO2が付着した蛍
光体を２の純水中に懸濁させ、この懸濁液に硫
酸亜鉛の10％水溶液56ｇを加え、その後撹拌しな
がらNaOH水溶液で懸濁液のPH値を8.0に調整し
た。PH調整後さらに５分間撹拌を続けた。撹拌を
止め蛍光体を沈降させた後、上澄み液をデカンテ
ーシヨンにて除去し、さらに５の純水で２回水
洗した。その後蛍光体を吸引脱水し、200℃で３
時間乾燥した。乾燥後蛍光体を250メツシユの篩
で篩つた。
上述のようにしてSiO2による表面処理および
Zn（OH）2による表面処理を行なつたべんがら赤
色顔料粒子付Y2O2S：Eu蛍光体には、SiO2とZn
（OH）2が付着しており、そのZn（OH）2付着量は
べんがら赤色顔料粒子付Y2O2S：Eu蛍光体100重
量部に対して0.30重量部であつた。
次に上述のようにして得た蛍光体を用いて実施
例１と同様にして蛍光体スラリーを調製し、得ら
れる蛍光体スラリーを用いて塗布試験を行ない、
混色（ヘイズおよびクロスコンタミネーシヨン）
および露光感度（露光時間）を調べた。その結果
を第１表に上述のSiO2による表面処理のみを行
ない、Zn（OH）2による表面処理を行なわなかつ
たべんがら赤色顔料粒子付Y2O2S：Eu蛍光体の
場合（第１表括弧内の値）と比較して示す。なお
クロスコンタミネーシヨンは青色発光成分蛍光体
としてZnS：Ag蛍光体、緑色発光成分蛍光体と
してZnS：Cu、Al蛍光体を用い［いずれもZn
（OH）2未処理］、緑色、青色および赤色発光成分
蛍光体の順に塗布した場合の前塗布ZnS：Cu、
Al緑色発光成分蛍光体とのクロスコンタミネー
シヨン（赤色出力／緑色出力）および前塗布
ZnS：Ag青色発光成分蛍光体とのクロスコンタ
ミネーシヨン（赤色出力／青色出力）を測定し
た。
第１表から明らかなように、Zn（OH）2による
表面処理を行なつたべんがら赤色顔料粒子付
Y2O2S：Eu蛍光体は、この処理を行なわなかつ
たべんがら赤色顔料粒子付Y2O2S：Eu蛍光体よ
りも蛍光膜における混色が少なく、また蛍光体ス
ラリーの露光感度が高かつた。
The present invention relates to a phosphor slurry for making a phosphor film. More specifically, the present invention relates to a phosphor slurry for producing a phosphor film that provides a phosphor film with less color mixture and has high exposure sensitivity. As is well known, the phosphor film of a color television cathode ray tube is a regular array of blue, green and red emitting dots or stripes made of blue, green and red emitting component phosphors, respectively, on a face plate. The fluorescent film of this color television cathode ray tube is produced by optical printing. That is, first, a phosphor slurry is prepared by dispersing the first luminescent component phosphor in a photosensitive resin solution such as a dichromate-activated polyvinyl alcohol aqueous solution. The resulting phosphor slurry is applied to the entire surface of the face plate using an appropriate coating method such as spin coating (slurry coating), and then the coated surface is irradiated with energy rays such as ultraviolet rays in a predetermined pattern. The resin in the exposed areas is cured and made insoluble (exposure). After that, the energy ray end irradiated part (resin end hardened part) is dissolved and removed using a solvent etc. (development).
Dots or stripes of the first luminescent component phosphor are formed. For the second and third luminescent component phosphors, the same series of slurry application, exposure and development operations as described above are repeated in sequence to form dots or stripes made of the second and third luminescent component phosphors. In this case, the first
It goes without saying that the energy beam irradiation must be controlled so that the dots or stripes of the second and third luminescent component phosphors do not overlap each other and are repeatedly and regularly arranged on the face plate. Next, the fluorescent film containing the resin component obtained as described above is fired at an appropriate temperature to decompose and volatilize the resin component, thereby obtaining the desired fluorescent film. When creating a phosphor film for color television cathode ray tubes by the optical printing method using the above-mentioned phosphor slurry, (1) it must have sufficient thickness and form dense dots or stripes; (2) Dots or stripes of a predetermined shape should be formed at predetermined positions on the face plate; (3) One luminescent component phosphor should not mix with other luminescent component phosphors, that is, color mixing should not occur. (4) The phosphor slurry must have high exposure sensitivity and good workability. Conventionally, in order to satisfy each of the above matters, various studies have been made regarding the composition, preparation method, etc. of phosphor slurry, and the surface treatment of color television phosphors (blue, green, and red emitting component phosphors) used in phosphor slurry. Research has been conducted. The current phosphor slurry satisfies each of the above items to some extent. However, since higher quality fluorescent films are always required commercially, it is desired to further improve each of the above points. The object of the present invention is to provide a phosphor slurry for forming a phosphor film that further improves especially (3) and (4) among the above matters. That is, an object of the present invention is to provide a phosphor slurry for forming a phosphor film that provides a phosphor film with less color mixture. Another object of the present invention is to provide a phosphor slurry for forming a phosphor film with high exposure sensitivity. In order to improve the dispersibility regarding the above-mentioned item (1), a method has been known in the past in which the surface of the phosphor is treated with a silicate compound such as metasilicate in an aqueous solution containing potassium water glass and zinc ions such as zinc sulfate. (See Japanese Patent Publication No. 50-15747 and USP.2704726). However, this surface treatment method differs in structure and effect from the treatment used in the present invention. The above objects of the present invention have been achieved by a specific phosphor slurry. That is, the phosphor slurry for making a phosphor film of the present invention is made from a phosphor obtained by surface treatment in an aqueous solution using a water-soluble zinc compound and an alkali hydroxide, and an aqueous solution containing a dichromate and polyvinyl alcohol. It is characterized by becoming. Furthermore, the dispersibility of the color television phosphor in the phosphor slurry has been improved by attaching phosphates such as silicon dioxide, magnesium, zinc, calcium, and aluminum to the conventional color television phosphor. It is known that a substance that improves the dispersibility of television phosphors (hereinafter referred to as a "dispersant") can be used to obtain a good phosphor film. The phosphor used in the phosphor slurry can be subjected to surface treatment with this dispersant. When a color television cathode ray tube phosphor film is produced by a photoprinting method using the phosphor slurry of the present invention, the resulting phosphor film has significantly less color mixture. Further, the phosphor slurry of the present invention has high exposure sensitivity, and therefore, the time during ultraviolet irradiation (exposure time) for curing can be shortened, and work efficiency can be increased. The present invention will be explained in detail below. The phosphor slurry of the present invention includes, for example, the steps described below. First, put the phosphor in pure water and suspend it thoroughly. Next, add an appropriate amount of an aqueous solution containing zinc ions to this suspension, and then add an alkali to the suspension containing zinc ions to adjust the pH value of the suspension to 7.5 to 7.5.
11, and a surface treatment substance represented by zinc hydroxide [hereinafter abbreviated as Zn(OH) 2 ] is precipitated.
The precipitated fine particles of Zn(OH) 2 are adsorbed on the surface of the phosphor. The suspension is allowed to stand to allow the phosphor to which the Zn(OH) 2 fine particles are attached to settle, and then the supernatant liquid is removed by decantation. After washing with water several times to remove residual ions, it is dehydrated and dried. After drying, the resulting lumpy phosphor is passed through a sieve to loosen it to obtain the phosphor used in the present invention. Examples of aqueous solutions containing zinc ions include water-soluble zinc compounds such as zinc sulfate (ZnSO 4 ), zinc acetate [Zn
(CH 3 COO) 2 ], zinc nitrate [Zn(NO 3 ) 2 ], zinc halide (ZnX 2 , where X is a halogen excluding fluorine), and the like are used. Further, as the alkali for adjusting the PH value, alkali hydroxide is used, and for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), etc. are used as an aqueous solution. When using NH 4 OH, care must be taken to ensure that the PH value does not exceed 10, since soluble ammine complex ions will be generated if NH 4 OH is added in excess and Zn(OH) 2 will not precipitate. Drying is carried out at a temperature below 250°C, preferably below 200°C. When drying at a temperature higher than 250℃, Zn(OH) 2 attached to the phosphor
are all zinc oxide compounds (hereinafter abbreviated as ZnO)
Therefore, the phosphor used in the present invention cannot be obtained. Zn(OH) 2 when drying at 200 to 250℃
(Of course, the higher the temperature, the more ZnO
The ZnO produced does not have any adverse effect on the phosphor slurry properties. When drying at temperatures below 200℃
Almost no conversion to ZnO occurs, and Zn(OH) 2 remains almost unchanged. The amount of Zn(OH) 2 added to the phosphor for color television viewing used in the present invention is more than 0 parts by weight and not more than 0.7 parts by weight based on 100 parts by weight of the phosphor for color televisions. When the amount of Zn(OH) 2 attached is more than 0.7 parts by weight, the dispersibility of the obtained phosphor in the phosphor slurry gradually deteriorates, resulting in significant color mixing when used as a phosphor film. This is not desirable because it becomes like this. A more preferable amount of Zn(OH) 2 deposited is 0.01 to 0.5 parts by weight.
Note that it is convenient to use concentrated ammonia water to quantify Zn(OH) 2 attached to the phosphor. Concentrated ammonia water does not react with color television phosphors, which are mainly sulfides or oxides, or with ZnO, which is produced when high drying temperatures are used, but it selectively reacts with Zn(OH) 2 . Generates soluble ammine complex ions. Therefore, the amount of Zn(OH) 2 attached can be determined by treating the phosphor of the present invention with concentrated ammonia water, dissolving and separating Zn(OH) 2 as ammine complex ions, and quantifying the ammine complex ions. Can be done. Note that when a dispersant is used in conjunction with the phosphor used in the present invention, the dispersant is first attached to the phosphor for color television by a conventional method,
Zn(OH) 2 may then be deposited in the manner described above, or vice versa. Dispersants include silicon dioxide (SiO 2 ), ortho, meta or pyrophosphates such as magnesium, zinc, calcium and aluminum [Mg 3 (PO 4 ) 2 , Zn 3 (PO 4 ) 2 ,
Ca 3 (PO 4 ) 2 , AlPO 4 , Mg (PO 3 ) 2 , Zn (PO 3 ) 2 ,
Ca ( PO3 ) 2 , Al ( PO3 ) 3 , Mg2P2O7 , Zn2P2O7 ,
Ca 2 P 2 O 7 etc.], but it is particularly preferable to use SiO 2 . The dispersant is applied to the phosphor by methods known in the art. For example, in the case of SiO 2 , the phosphor is first suspended in an aqueous water glass solution, and then an aqueous solution of zinc sulfate, aluminum sulfate, etc. is added to this suspension to precipitate SiO 2 fine particles. A method such as adsorption to the surface of the phosphor is adopted. The phosphors used in the present invention include, for example, phosphors for color televisions, including all phosphors that can be used as blue, green or red emitting component phosphors of color television cathode ray tube phosphors. This phosphor for color television may be a single phosphor, or it may be a copper- and aluminum-activated zinc sulfide phosphor (ZnS: Cu, Al), which has recently been put into practical use, and a gold- and aluminum-activated phosphor. A mixed phosphor such as a green light-emitting component phosphor mixed with a zinc sulfide phosphor (ZnS:Au, Al) may also be used. In addition, recently, so-called pigmented phosphors, in which the surface of the phosphor is coated with pigment particles, have been used in the phosphor films of high-contrast color television cathode ray tubes. It may also be a phosphor attached. Therefore, in this specification, the expression "phosphor for color television" means any of a single phosphor, a mixed phosphor, and a pigmented phosphor, unless otherwise specified. Preferred phosphors for color television from a practical standpoint include silver-activated zinc sulfide phosphors (ZnS:Ag) and silver- and aluminum-activated zinc sulfide phosphors (ZnS:Ag, Al) as blue-emitting phosphors. , ZnS with cobalt aluminate blue pigment particles: Ag phosphor, ZnS with cobalt aluminate blue pigment particles:
Ag, Al phosphor, etc. Green emitting component phosphor, mixed phosphor of ZnS:Cu, Al phosphor and ZnS:Au, Al phosphor, ZnS:Cu, Al phosphor, activated with gold, copper and aluminum Zinc sulfide phosphor (ZnS:
Au, Cu, Al), copper and aluminum activated zinc sulfide/cadmium phosphor [(Zn, Cd)S:Cu,
Europium-activated yttrium oxysulfide phosphor (Y 2 O 2 S: Eu), europium-activated yttrium oxide phosphor (Y 2 O 3 : Eu), Y 2 with red pigment particles as a red-emitting phosphor such as O2S :
Eu phosphor with red pigment particles Y 2 O 3 : Eu phosphor with cadmium selenide sulfate red pigment particles
Examples include Y 2 O 2 S: Eu phosphor, Y 2 O 3 : Eu phosphor with cadmium selenide sulfide red pigment particles, and the like. Next, the effects of the present invention will be explained using, as an example, a case of a phosphor slurry using a ZnS:Ag blue-emitting component phosphor. There are two types of color mixing between the luminescent component phosphors in the fluorescent film of a color television cathode ray tube. One is when the first luminescent component phosphor or the second luminescent component phosphor is slurried, exposed, and developed to form dots or stripes on the faceplate; This is a case where the phosphor remains at the position of the dots or stripes of the component phosphors, resulting in color mixing, and such residual phosphor is called "haze". The other is that when the second luminescent component phosphor or the third luminescent component phosphor is slurried, exposed, and developed to form dots or stripes, other luminescent component phosphor dots that have already been formed are removed. Alternatively, phosphor adheres to and remains on the stripes, and this type of color mixing is called "cross contamination." While haze occurs depending on the characteristics of the phosphor slurry used, cross-contamination depends on both the characteristics of the phosphor slurry used and the characteristics of the underlying dots or stripes that have already been formed. It is something that occurs. The phosphor slurry of the present invention significantly improves the color mixing caused by both the haze and cross-contamination described above. Figure 1 shows that when using a phosphor slurry of Zn(OH) 2 adhering ZnS:Ag phosphor (including 0 adhesion amount),
(OH) 2 is a graph showing the relationship between adhesion amount and haze. The graph in FIG. 1 was obtained as follows. First, NnS: 0.15 per 100 parts by weight of Ag phosphor
Seven types of ZnS: Ag phosphors with different amounts of Zn(OH) 2 adhesion were manufactured using ZnS:Ag phosphors to which a weight part of SiO 2 was attached.
These seven types of Zn(OH) 2 attached ZnS: Ag phosphor and Zn
Eight types of phosphors, including ZnS:Ag phosphor without (OH) 2 attached (0.15% by weight of SiO 2 attached), were used as samples. Note that these eight types of phosphor samples were also used to obtain each of the graphs shown in FIGS. 2 to 4, which will be described later. Next, using these phosphor samples, stripes were formed on the face plate in the following manner. First, a phosphor slurry of the present invention was prepared in a conventional manner using a commonly used polyvinyl alcohol aqueous solution containing ammonium dichromate and each phosphor sample. Next, each of the resulting phosphor slurries was spin-coated onto the face plate of a 16-inch cathode ray tube, dried, and then exposed to ultraviolet rays using a high-pressure mercury lamp through a shadow mask to expose the coated surface in stripes, and developed with warm water. to form stripes. Note that the above method for creating stripes was also applied to obtain the graphs shown in FIGS. 2 and 4. A part of the face plate on which stripes have been formed as described above is magnified 100 times and projected onto a screen using a magnifying projection microscope.
The number of phosphor particles (haze) remaining within 20 mm (0.2 mm x 0.2 mm on the face plate) was counted. For each phosphor slurry sample, the number of phosphor particles was counted at two locations, and the average value was calculated as the amount of Zn(OH) 2 deposited on each phosphor sample (parts by weight relative to 100 parts by weight of ZnS: Ag phosphor).
The graph shown in FIG. 1 was obtained by plotting against . As is clear from FIG. 1, the haze decreases as the amount of Zn(OH) 2 deposited increases. Especially when the amount of Zn(OH) 2 deposited is up to 0.5 parts by weight, Zn
The haze decreases significantly as the amount of Zn(OH) 2 increases, and the haze decreases when the amount of Zn(OH) 2 is 0.5 parts by weight.
It is about 1/10 of the case when the amount of Zn(OH) 2 attached is 0. Figure 2 shows Zn when using a phosphor slurry of Zn(OH) 2 adhering ZnS:Ag phosphor (including 0 adhesion amount).
It is a graph showing the relationship between the amount of (OH) 2 attached and the cross-contamination of the phosphor with other luminescent component phosphors. Cross contamination is caused by the following two
Two cases are possible. One is cross-contamination that adheres to the luminescent component phosphor that has already been applied (hereinafter referred to as "cross-contamination with the previously applied luminescent component phosphor").
The other type is cross-contamination where the luminescent component phosphor applied subsequently adheres (hereinafter referred to as "cross-contamination with the later-applied luminescent component phosphor"). Figure 2 A shows Zn(OH) 2 adhering ZnS: Zn of Ag phosphor (including 0 adhesion amount)
(OH) 2 deposition amount and its phosphor pre-coating ZnS:Cu,
FIG. 2-B is a graph showing the relationship of cross-contamination with Al green light-emitting component phosphor.
Zn(OH) 2 adhesion ZnS: Ag phosphor (including 0 adhesion amount)
Zn(OH) 2 deposition amount and its phosphor post-application
Y 2 O 2 S: is a graph showing the relationship of cross-contamination with Eu colorimetric luminescent component phosphor. Second
In Figures A and B, cross-contamination (vertical axis) is represented by the values of blue output/green output and red output/blue output, respectively.
These values were measured as follows. For Figure 2-A, first, a phosphor slurry sample was applied onto a face plate on which stripes of ZnS:Cu, Al green light-emitting component phosphor [Zn(OH) 2 powder treatment] had been formed and dried. Afterwards, development was carried out with warm water without exposure. After performing the above steps (obviously no ZnS:Ag phosphor stripes have been formed), the ZnS:Cu,Al phosphor stripes are excited with 3650 Å ultraviolet light, and the emitted light is split with a half mirror. The two lights were received as a photo through green and blue Wratten filters, and the respective outputs were measured to determine the value of blue output/green output. Determine the blue output/green output values for each phosphor sample,
The amount of Zn(OH) 2 adhesion is standardized as 1, and
It was plotted against the Zn(OH) 2 adhesion amount (parts by weight relative to 100 parts by weight of ZnS:Ag phosphor) of each phosphor sample. Regarding FIG. 2-B, first, a phosphor slurry sample was applied, exposed, and developed to form stripes. Next, a slurry of Y 2 O 2 S:Eu red light-emitting component phosphor [Zn(OH) 2 powder treatment] was coated on the face plate on which the stripes of this sample were formed, and after drying, it was soaked in hot water without exposure. I did the development. After performing the above operations (naturally Y 2 O 2 S: Eu
(no phosphor stripes are formed), the stripe of the sample is excited with 3650 Å ultraviolet light, the emitted light is split with a half mirror, and the two split lights are received as photomals through blue and red Ratten filters, respectively. The respective outputs were measured and the values of red output/green output were determined. Determine the red output/green output values for each phosphor sample, and
(OH) 2 The amount of adhesion of 0 is standardized as 1,
Zn(OH) 2 adhesion amount (ZnS:
It was plotted against (parts by weight relative to 100 parts by weight Ag phosphor). Figure 2 - In A and B, the larger the values of blue output/green output and red output/blue output
Pre-coating of ZnS:Ag phosphor means that there is a lot of cross-contamination with ZnS:Cu, Al phosphor and post-coating with Y2O2S :Eu phosphor of ZnS:Ag phosphor. do. As is clear from FIG. 2-A, it can be seen that as the amount of Zn(OH) 2 deposited increases, the cross-contamination to the pre-applied luminescent component phosphor decreases. Especially when the amount of Zn(OH) 2 deposited is up to 0.5 parts by weight, Zn
The decrease in cross-contamination is remarkable as the amount of (OH) 2 attached increases. Also, as is clear from Figure 2-B, cross-contamination with the post-applied luminescent component phosphor is
Zn(OH) 2The amount of Zn deposited is 0.2 to 0.3 parts by weight.
(OH) 2 decreases as the amount of adhesion increases, but Zn
When the amount of Zn(OH) 2 deposited increases further, it begins to increase, and when the amount of Zn(OH) 2 deposited is approximately 0.7 parts by weight,
It is the same as when the amount of Zn(OH) 2 attached is 0. It is based on this knowledge that the upper limit of the amount of Zn(OH) 2 deposited in the present invention is set to 0.7 parts by weight. As mentioned above, when the amount of Zn(OH) 2 attached increases, cross-contamination with the post-applied light-emitting component phosphor increases, and one of the reasons is the amount of Zn(OH) 2 attached. This is considered to be because the dispersibility of the phosphor deteriorates when the value exceeds this value. That is, if the dispersibility deteriorates, when stripes are formed, unevenness is likely to occur on the back surface of the stripes (the surface on which post-coating is performed), and therefore cross-contamination with the post-coated light-emitting component phosphor is likely to occur. Zn(OH) 2 adhesion
ZnS: Ag phosphor (including 0 adhesion amount) Zn(OH) 2
FIG. 3 shows the relationship between the amount of adhesion and the dispersibility of the phosphor. In FIG. 3, dispersibility (vertical axis) is represented by sedimentation volume. This sedimentation volume value was calculated by placing 5 g of the phosphor sample in 30 g of an aqueous polyvinyl alcohol solution containing ammonium dichromate, allowing it to settle in a sedimentation tube for 24 hours, reading the volume, and converting it into a volume per 1 g. The larger the settling volume value, the worse the dispersibility. As is clear from Figure 3, the dispersibility of Zn
When the amount of Zn(OH) 2 deposited is up to about 0.5 part by weight, it is almost the same as when the amount of Zn(OH) 2 deposited is 0, but when the amount of Zn(OH) 2 deposited exceeds 0.5 part by weight, Zn(OH) 2 It can be seen that as the amount of adhesion increases, it becomes worse. As mentioned above, in the present invention, from the viewpoint of cross-contamination with the post-applied luminescent component phosphor,
Although the upper limit of the amount of Zn(OH) 2 deposited is set to 0.7, taking this dispersibility into consideration, it is more preferable that the amount of Zn(OH) 2 deposited is 0.5 parts by weight or less. Note that this dispersibility can be improved to some extent by adding a surfactant to the phosphor slurry or by selecting the surfactant. The phosphor slurry obtained by the present invention significantly increases exposure sensitivity. Figure 4 shows the amount of Zn(OH) 2 attached on Zn(OH) 2 attached ZnS:Ag phosphor (including 0 amount attached) and the amount of Zn(OH) 2 attached on ZnS:Ag phosphor (including 0 amount attached) and the amount of Zn(OH) 2 attached on ZnS:Ag phosphor. It is a graph showing the relationship with the exposure time required to form stripes. As is clear from FIG. 4, when the amount of Zn(OH) 2 deposited is up to about 1.2 parts by weight, the same stripe can be obtained with a shorter exposure time than when the amount of Zn(OH) 2 deposited is 0. In other words, if the amount of Zn(OH) 2 deposited is more than 0 parts by weight,
When the amount is 1.2 parts by weight, the exposure sensitivity of the phosphor slurry is improved. In particular, the amount of Zn(OH) 2 deposited is 0.05 to
When the amount is 1.0 parts by weight, the exposure sensitivity is significantly improved. Therefore, by using a phosphor slurry with improved exposure sensitivity, the exposure time can be shortened and work efficiency can be increased. Furthermore, when the exposure time is the same as when the amount of Zn(OH) 2 deposited is 0, the amount of light from the light source can be reduced to obtain the same stripes, and the life of the light source can therefore be extended. Appropriate amount of Zn(OH) 2 as mentioned above
It is not clear why the exposure sensitivity of phosphor slurry using phosphor attached with Zn is improved, but
This is thought to be because (OH) 2 or partially dissolved Zn ++ acts as a catalyst in the phosphor slurry and promotes photopolymerization of the photosensitive resin. Although the effects of the present invention have been explained above using the ZnS:Ag phosphor as an example, it has been confirmed that similar effects can be obtained with other color television phosphors. It has also been confirmed that similar effects can be obtained with either a color television phosphor treated with a dispersant or a color television phosphor not treated with a dispersant. As described above, the phosphor slurry of the present invention provides a color television cathode ray tube phosphor film with significantly less color mixture and significantly increases its exposure sensitivity, and its industrial utility value is extremely large. be. Next, the present invention will be explained with reference to Examples. Example 1 1000 g of a green light-emitting component phosphor prepared by mixing a ZnS:Cu, Al phosphor and a ZnS:Au, Al phosphor at a weight ratio of 7:3 was suspended in 2 pure water. Add water glass (Oka Seal A manufactured by Tokyo Ohka Co., Ltd.) to this suspension.
15 g of SiO 2 (containing 20% by weight) was added and stirred, and further 90 g of a 10% aqueous solution of zinc sulfate was added. After stirring for 10 minutes, stirring was stopped to allow the phosphor to settle, and the supernatant liquid was removed by decantation. Thereafter, the phosphor was washed twice with pure water from Step 5. In this way
Surface treatment with SiO 2 was completed, and a phosphor with SiO 2 attached was obtained. Next, the phosphor with SiO 2 adhered to it obtained as described above was suspended in pure water from step 2, 28 g of a 10% zinc sulfate aqueous solution was added to this suspension, and then suspended in a NaOH aqueous solution while stirring. The pH value of the liquid was adjusted to 10.0. After adjusting the pH value, stirring was continued for an additional 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant liquid was removed by decantation, and the phosphor was further washed once with pure water from Step 5. After that, the phosphor is suctioned and dehydrated.
It was dried at 150°C for 3 hours. After drying, the phosphor was sieved through a 250 mesh sieve. Surface treatment with SiO2 and Zn as described above
Phosphors surface-treated with (OH) 2 have
SiO 2 and Zn(OH) 2 were attached, and the amount of Zn(OH) 2 attached was 0.14 parts by weight based on 100 parts by weight of the mixed green light-emitting component phosphor. Next, a phosphor slurry was prepared in a usual manner using the phosphor obtained as described above and a normal aqueous polyvinyl alcohol solution containing ammonium dichromate, and a coating test was conducted using the obtained phosphor slurry. Color mixture (haze and cross-contamination) and exposure sensitivity (exposure time) were investigated. The results are shown in Table 1 in comparison with the case of a mixed phosphor (values in parentheses in Table 1) in which only the surface treatment with SiO 2 was performed and no surface treatment with Zn(OH) 2 was performed. To prevent cross contamination, ZnS:Ag phosphor was used as the blue emitting component phosphor, and Y 2 O 2 S: Eu phosphor was used as the red emitting component phosphor [all treated with Zn(OH) 2 end treatment], green, and blue. Cross-contamination with the ZnS:Ag blue-emitting component phosphor (blue output/green output) and the post-coating Y2O2S :Eu red-emitting component phosphor when applied in the following order: Cross contamination (red output/green output) was measured. As is clear from Table 1, the phosphor whose surface has been treated with Zn(OH) 2 has less color mixture in the phosphor film than the phosphor whose surface has not been treated with Zn(OH) 2 , and The exposure sensitivity of body slurry was high. Example 2 ZnS: Au, Cu, Al green light emitting component phosphor 1000g
was suspended in pure water from step 2, 23.6 g of a 20% aqueous solution of zinc chloride was added to this suspension, and then the pH value of the suspension was adjusted to 8.0 with an aqueous NH 4 OH solution while stirring. After adjusting the pH, stirring was continued for an additional 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant liquid was removed by decantation, and the phosphor was further washed twice with purified water from Step 5. After that, the phosphor is suctioned and dehydrated.
It was dried at 100°C for 8 hours. After drying, the phosphor was sieved through a 250 mesh sieve. The ZnS:Au, Cu, Al phosphor surface-treated with Zn(OH) 2 as described above contains Zn.
(OH) 2 is attached, and the amount of Zn(OH) 2 attached is
ZnS: 0.26 per 100 parts by weight of Au, Cu, Al phosphor
It was by weight. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry.
Color mixing (haze and cross-contamination)
and the exposure sensitivity (exposure time) were investigated. The results are shown in Table 1 in comparison with the case of ZnS:Au, Cu, Al phosphors that were not subjected to the surface treatment with Zn(OH) 2 described above (values in parentheses in Table 1). In addition, ZnS:Ag phosphor is used as a blue-emitting component phosphor for cross-contamination, and ZnS:Ag phosphor is used as a red-emitting component phosphor.
When Y 2 O 3 S:Eu phosphor is used [all Zn(OH) 2 powder treated] and green, blue and red emitting component phosphors are applied in this order, the difference between post-coating and ZnS:Ag blue emitting component phosphor is Cross-contamination (blue output/green output) and cross-contamination with post-coated Y 2 O 3 S:Eu red emitting component phosphor (red output/green output) were measured. As is clear from Table 1, ZnS:Au, Cu, Al phosphors that have been surface-treated with Zn(OH) 2 are different from ZnS:Au, Cu, and Al phosphors that have not been subjected to this treatment.
Less color mixing in the phosphor film than Al phosphor,
Furthermore, the exposure sensitivity of the phosphor slurry was high. Example 3 1000 g of ZnS:Ag blue light emitting component phosphor was suspended in pure water of Step 2, and SiO 2 was added in the same manner as in Example 1.
A phosphor with SiO 2 attached was obtained. Next, the phosphor with SiO 2 adhered to it obtained as described above was suspended in pure water from step 2, 18.7 g of a 10% aqueous solution of zinc acetate was added to this suspension, and then a NaOH aqueous solution was added while stirring. The pH value of the suspension was adjusted to 9.0. After adjusting the pH, stirring was continued for an additional 5 minutes. After stopping the stirring and allowing the phosphor to settle, the supernatant liquid was removed by decantation, and the mixture was further diluted with pure water from Step 5.
Washed twice with water. After that, aspirate the phosphor and heat it at 200℃ for 3 hours.
Dry for an hour. After drying, the phosphor was sieved through a 250 mesh sieve. Surface treatment with SiO 2 and
ZnS:Ag phosphor surface-treated with Zn(OH) 2 has SiO 2 and Zn(OH) 2 attached, and Zn
The amount of (OH) 2 deposited was 0.08 parts by weight per 100 parts by weight of the ZnS:Ag phosphor. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry.
Color mixing (haze and cross-contamination)
and the exposure sensitivity (exposure time) were investigated. The results are shown in Table 1 for the case of ZnS:Ag phosphor that was subjected to the above-mentioned surface treatment with SiO 2 but not with Zn(OH) 2 (values in parentheses in Table 1).
A comparison is shown below. For cross-contamination, ZnS:Cu, Al phosphor was used as the green-emitting component phosphor, Y 2 O 2 S: Eu phosphor was used as the red-emitting component phosphor, [both untreated with Zn(OH) 2 ], green,
Cross-contamination with pre-coated ZnS:Cu, Al green-emitting component phosphor (blue output/green output) and post-coated Y 2 O 2 S: Eu red emission when blue and red emitting component phosphors are applied in order Cross contamination (red output/blue output) with component phosphors was measured. As is clear from Table 1, the ZnS:Ag phosphor that has been surface-treated with Zn(OH) 2 has less color mixture in the phosphor film than the ZnS:Ag phosphor that has not been subjected to this treatment, and The exposure sensitivity of body slurry was high. Example 4 ZnS: Ag, Al blue light emitting component phosphor 1000g
Zinc nitrate is suspended in pure water and added to this suspension of zinc nitrate.
Add 67g of 20% aqueous solution, then stir while stirring.
The pH value of the suspension was adjusted to 11.0 with a KOH aqueous solution.
After adjusting the pH, stirring was continued for an additional 5 minutes. After stopping stirring and allowing the phosphor to settle, the supernatant liquid was removed by decantation, and the phosphor was further dissolved in 5 parts of pure water.
Washed twice with water. After that, the phosphor was dehydrated by suction and heated to 150℃.
It was dried for 3 hours. After drying, the phosphor was sieved through a 250 mesh sieve. Zn(OH) 2 is attached to the ZnS:Ag, Al phosphor that has been surface-treated with Zn(OH) 2 as described above, and the amount of Zn(OH) 2 attached is equal to that of ZnS:Ag. ,
The amount was 0.51 parts by weight per 100 parts by weight of the Al phosphor. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry.
Color mixing (haze and cross-contamination)
and the exposure sensitivity (exposure time) were investigated. The results are shown in Table 1 for the case of ZnS:Ag, Al phosphor without the surface treatment with Zn(OH) 2 mentioned above (first
(values in parentheses). In addition, cross contamination can be prevented by using green light-emitting component phosphor.
ZnS: Cu, Al phosphor, Y 2 O 2 G: Eu phosphor as red emitting component phosphor [both Zn(OH) 2
Untreated], pre-coated ZnS: Cu, Al cross-contamination with green-emitting component phosphor (blue output/green output) and post-coated Y 2 O when green, blue and red emitting component phosphors are applied in order 2 S：Eu
Cross contamination (red output/blue output) with the red light-emitting component phosphor was measured. As is clear from Table 1, the ZnS:Ag, Al phosphor that has been surface-treated with Zn(OH) 2 has less color mixture in the phosphor film than the ZnS:Ag, Al phosphor that has not been subjected to this treatment. Moreover, the exposure sensitivity of the phosphor slurry was high. Example 5 Y 2 O 2 S: 1000 g of Eu red light emitting component phosphor
of zinc sulfate to this suspension.
Add 112g of % aqueous solution and then stir while stirring.
The pH value of the suspension was adjusted to 9.0 with an aqueous NH 4 OH solution.
After adjusting the pH, stirring was continued for an additional 5 minutes. After stopping stirring and allowing the phosphor to settle, the supernatant liquid was removed by decantation, and the phosphor was further dissolved in 3 parts of pure water.
Washed twice with water. After that, the phosphor was dehydrated by suction and heated to 130°C.
It was dried for 6 hours. After drying, the phosphor was sieved through a 250 mesh sieve. Zn(OH) 2 is attached to the Y 2 O 2 S:Eu phosphor that has been surface-treated with Zn(OH) 2 as described above, and the amount of Zn(OH) 2 attached is Y 2O2S ： Eu
The amount was 0.57 parts by weight per 100 parts by weight of the phosphor. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry.
Color mixing (haze and cross-contamination)
and the exposure sensitivity (exposure time) were investigated. The results are shown in Table 1 in comparison with the case of Y 2 O 2 S:Eu phosphor which was not subjected to the above-mentioned surface treatment with Zn(OH) 2 (values in parentheses in Table 1). Note that cross-contamination is caused by using ZnS as a blue-emitting component phosphor:
Ag phosphor, ZnS:Cu as green emitting component phosphor,
Al phosphor [all untreated with Zn(OH) 2 ], pre-coated ZnS:Cu when applied in order of green, blue and red emitting component phosphors, cross contamination with Al green emitting component phosphor (red output/green output) and cross-contamination with the precoated ZnS:Ag blue-emitting component phosphor (red output/blue output). As is clear from Table 1, the Y 2 O 2 S:Eu phosphor with surface treatment with Zn(OH) 2 is more fluorescent than the Y 2 O 2 S:Eu phosphor without this treatment. There was little color mixing in the film, and the exposure sensitivity of the phosphor slurry was high. Example 6 1000 g of Y 2 O 2 S:Eu red light-emitting component phosphor with red pigment particles was suspended in the pure water of step 2, and the surface was treated with SiO 2 in the same manner as in Example 1 . The attached phosphor was obtained. Next, the SiO 2 -attached phosphor obtained as described above was suspended in pure water (2), 56 g of a 10% aqueous solution of zinc sulfate was added to this suspension, and then suspended with an aqueous NaOH solution while stirring. The pH value of the suspension was adjusted to 8.0. After adjusting the pH, stirring was continued for an additional 5 minutes. After the stirring was stopped and the phosphor was allowed to settle, the supernatant liquid was removed by decantation, and the mixture was further washed twice with pure water from step 5. After that, the phosphor was dehydrated by suction and heated to 200℃ for 3 hours.
Dry for an hour. After drying, the phosphor was sieved through a 250 mesh sieve. Surface treatment with SiO 2 and
Y 2 O 2 S:Eu phosphor with red pigment particles surface treated with Zn(OH) 2 contains SiO 2 and Zn.
(OH) 2 was attached, and the amount of Zn(OH) 2 attached was 0.30 parts by weight based on 100 parts by weight of the Y 2 O 2 S:Eu phosphor with red pigment particles. Next, a phosphor slurry was prepared in the same manner as in Example 1 using the phosphor obtained as described above, and a coating test was conducted using the obtained phosphor slurry.
Color mixing (haze and cross-contamination)
and the exposure sensitivity (exposure time) were investigated. The results are shown in Table 1. In the case of a Y 2 O 2 S:Eu phosphor with red pigment particles, which was subjected to the above-mentioned surface treatment with SiO 2 but not with Zn(OH) 2 (Table 1). (values in parentheses). To prevent cross-contamination, ZnS:Ag phosphor was used as the blue-emitting component phosphor, and ZnS:Cu, Al phosphor was used as the green-emitting component phosphor [both Zn
(OH) 2 untreated], pre-coated ZnS:Cu, when green, blue and red emitting component phosphors are applied in order
Cross-contamination with Al green-emitting component phosphor (red output/green output) and pre-coating
Cross contamination (red output/blue output) with ZnS:Ag blue light emitting component phosphor was measured. As is clear from Table 1, red pigment particles with Zn(OH) 2 surface treatment were used.
The Y 2 O 2 S:Eu phosphor has less color mixing in the phosphor film than the Y 2 O 2 S:Eu phosphor that does not undergo this treatment and has red pigment particles, and the exposure sensitivity of the phosphor slurry is high. Ta.
【表】【table】
第１図はZn（OH）2付着ZnS：Ag蛍光体（付着
量０も含む）のZn（OH）2付着量とヘイズとの関
係を示すグラフである。第２図−ＡはZn（OH）2
付着ZnS：Ag蛍光体（付着量０も含む）のZn
（OH）2付着量と、その蛍光体スラリーの前塗布
ZnS：Cu、Al緑色発光成分蛍光体とのクロスコ
ンタミネーシヨンの関係を示すグラフである。第
２図−ＢはZn（OH）2付着ZnS：Ag蛍光体（付着
量０も含む）のZn（OH）2付着量と、その蛍光体
スラリーの後塗布Y2O2S：Eu赤色発光成分蛍光
体とのクロスコンタミネーシヨンの関係を示すグ
ラフである。第３図はZn（OH）2付着ZnS：Ag蛍
光体（付着量０も含む）のZn（OH）2付着量と、
その蛍光体の分散性との関係を示すグラフであ
る。第４図はZn（OH）2付着ZnS：Ag蛍光体（付
着量０も含む）のZn（OH）2付着量と、その蛍光
体を使用した蛍光体スラリーを用いて一定幅
（230μｍ）のストライプを形成する時の露光時間
との関係を示すグラフである。
FIG. 1 is a graph showing the relationship between the amount of Zn(OH) 2 attached and the haze of the Zn(OH) 2 attached ZnS:Ag phosphor (including the amount of 0 attached). Figure 2 - A is Zn(OH) 2
Adhered ZnS: Zn of Ag phosphor (including 0 adhesion amount)
(OH) 2 deposition amount and its pre-coating of phosphor slurry
ZnS: is a graph showing the relationship of cross-contamination with Cu and Al green light-emitting component phosphors. Figure 2 - B shows the amount of Zn(OH) 2 deposited on Zn(OH) 2 deposited ZnS:Ag phosphor (including 0 deposit amount) and the subsequent application of the phosphor slurry Y 2 O 2 S: Eu red emission It is a graph showing the relationship of cross-contamination with component phosphors. Figure 3 shows the Zn(OH) 2 adhesion amount of Zn(OH) 2 adhesion ZnS:Ag phosphor (including 0 adhesion amount), and
It is a graph showing the relationship with the dispersibility of the phosphor. Figure 4 shows the amount of Zn(OH) 2 attached on Zn(OH) 2 attached ZnS:Ag phosphor (including 0 amount attached) and the amount of Zn(OH) 2 attached on ZnS:Ag phosphor (including 0 amount attached) and the amount of Zn(OH) 2 attached on ZnS:Ag phosphor. It is a graph showing the relationship with exposure time when forming stripes.
Claims (1)
溶液中で表面処理して得られた蛍光体と、重クロ
ム酸塩及びポリビニールアルコールを含む水溶液
からなる蛍光膜作成用蛍光体スラリー。 ２ 上記重クロム酸塩が重クロム酸アンモニウム
であることを特徴とする特許請求の範囲第１項記
載の蛍光膜作成用蛍光体スラリー。 ３ 上記水溶性亜鉛化合物が、硫酸亜鉛、酢酸亜
鉛、硝酸亜鉛、ハロゲン化亜鉛（但し、ハロゲン
は弗素を除く）からなる群より選ばれた少なくと
も１種であることを特徴とする特許請求の範囲第
１項または第２項記載の蛍光膜作成用蛍光体スラ
リー。 ４ 上記水酸化アルカリが、水酸化ナトリウム、
水酸化カリウム、および水酸化アンモニウムから
なる群より選ばれた少なくとも１種であることを
特徴とする特許請求の範囲第１項〜第３項のいず
れか１項に記載の蛍光膜作成用蛍光体スラリー。 ５ 上記表面処理において分散剤を併用すること
を特徴とする特許請求の範囲第１項〜第４項のい
ずれか１項に記載の蛍光膜作成用蛍光体スラリ
ー。 ６ 上記分散剤が二酸化珪素であることを特徴と
する特許請求の範囲第５項記載の蛍光膜作成用蛍
光体スラリー。 ７ 上記分散剤で蛍光体の表面を処理した後、上
記表面処理をおこなうことを特徴とする特許請求
の範囲第５項または第６項記載の蛍光膜作成用蛍
光体スラリー。[Claims] 1. A phosphor for making a phosphor film comprising a phosphor obtained by surface treatment in an aqueous solution using a water-soluble zinc compound and an alkali hydroxide, and an aqueous solution containing a dichromate and polyvinyl alcohol. slurry. 2. The phosphor slurry for producing a phosphor film according to claim 1, wherein the dichromate is ammonium dichromate. 3 Claims characterized in that the water-soluble zinc compound is at least one selected from the group consisting of zinc sulfate, zinc acetate, zinc nitrate, and zinc halide (however, halogen excludes fluorine) The phosphor slurry for forming a phosphor film according to item 1 or 2. 4 The alkali hydroxide is sodium hydroxide,
The phosphor for making a fluorescent film according to any one of claims 1 to 3, characterized in that the phosphor is at least one member selected from the group consisting of potassium hydroxide and ammonium hydroxide. slurry. 5. The phosphor slurry for making a phosphor film according to any one of claims 1 to 4, characterized in that a dispersant is used in combination in the surface treatment. 6. The phosphor slurry for producing a phosphor film according to claim 5, wherein the dispersant is silicon dioxide. 7. The phosphor slurry for producing a phosphor film according to claim 5 or 6, wherein the surface treatment is performed after the surface of the phosphor is treated with the dispersant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12369588A JPH01213387A (en) | 1986-02-21 | 1988-05-20 | Fluorescent substance slurry for preparing fluorescent film |
| JP3338350A JPH0645784B2 (en) | 1988-05-20 | 1991-12-20 | Color cathode ray tube manufacturing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3657586A JPS61268789A (en) | 1986-02-21 | 1986-02-21 | Method for treating surface of fluorescent substance |
| JP12369588A JPH01213387A (en) | 1986-02-21 | 1988-05-20 | Fluorescent substance slurry for preparing fluorescent film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3657586A Division JPS61268789A (en) | 1986-02-21 | 1986-02-21 | Method for treating surface of fluorescent substance |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3338350A Division JPH0645784B2 (en) | 1988-05-20 | 1991-12-20 | Color cathode ray tube manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01213387A JPH01213387A (en) | 1989-08-28 |
| JPH037712B2 true JPH037712B2 (en) | 1991-02-04 |
Family
ID=26375648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12369588A Granted JPH01213387A (en) | 1986-02-21 | 1988-05-20 | Fluorescent substance slurry for preparing fluorescent film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01213387A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100189805B1 (en) * | 1991-08-21 | 1999-06-01 | 손욱 | Slurry composition for color braun tube |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867587A (en) * | 1954-11-01 | 1959-01-06 | Rca Corp | Water-stabilized zinc phosphate phosphors |
| US2909444A (en) * | 1957-12-10 | 1959-10-20 | Thomas Electronics Inc | Screen settling system |
| JPS4943075A (en) * | 1972-08-29 | 1974-04-23 | ||
| JPS5267569A (en) * | 1975-12-03 | 1977-06-04 | Hitachi Ltd | Fluorescent body slurry forming fluorescent face of colour receiving t ube |
| JPS6021675A (en) * | 1983-07-18 | 1985-02-04 | Toyota Motor Corp | Method and apparatus of automatic correction of position shift of television camera in measuring device |
-
1988
- 1988-05-20 JP JP12369588A patent/JPH01213387A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867587A (en) * | 1954-11-01 | 1959-01-06 | Rca Corp | Water-stabilized zinc phosphate phosphors |
| US2909444A (en) * | 1957-12-10 | 1959-10-20 | Thomas Electronics Inc | Screen settling system |
| JPS4943075A (en) * | 1972-08-29 | 1974-04-23 | ||
| JPS5267569A (en) * | 1975-12-03 | 1977-06-04 | Hitachi Ltd | Fluorescent body slurry forming fluorescent face of colour receiving t ube |
| JPS6021675A (en) * | 1983-07-18 | 1985-02-04 | Toyota Motor Corp | Method and apparatus of automatic correction of position shift of television camera in measuring device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01213387A (en) | 1989-08-28 |
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